E-mail: cnr-ipcb.segreteria.ct@cnr.it |  Call: +39 095-7338111 |  Address: Via Paolo Gaifami 18, 9 -95126 Catania - Italy

PUBLICATIONS

IPCB NO ISI publications

 326 publications on ISI journals

1) 8.12 - Biodegradable Polymer-Based Items for Agriculture: Influence of Photo-Oxidation on the Performance, Soil Degradation and Environmental Issues

P.Rizzarelli, M.Rapisarda, F.P.La Mantia

Comprehensive Polymer Science  ,  234-281  - 2026

DOI: https://doi.org/10.1016/B978-0-323-95486-0.00079-X
In the last decades, the use of biodegradable polymers in the agricultural field has been investigated. book cover In agriculture, plastic items are widely employed and subjected to solar UV exposure. The effect of photo-oxidation or outdoor weathering on structures, performance, and biodegradation behavior in soil of macromolecular chains has been evaluated. This chapter aims to afford an overview of the studies dedicated to the influence of photo-degradation processes on chemical-physical properties and degradation in soil of biodegradable polymers or items designed for agricultural purpose, highlighting the recently emerged environmental issues.


2) Structural Insights into HSPG-Mediated SARS-CoV-2 Spike Remodeling and Integrin Engagement: An Integrative Mass Spectrometry and Molecular Dynamics Study

N.Scarano, B.Casini, A.De Palma, D.Romeo, A.Palmigiano, A.Messina, G.A.Trombetti, A.Manconi, P.Mauri, Y.Zheng, P.Fossa, P.D’Ursi

22nd Annual Conference of the Bioinformatics Italian Society Padova (Italy)   - 2026

Motivation:
COVID-19 symptoms include cough, fever, and shortness of breath, with additional extrapulmonary signs also possible. Severe cases can result in acute respiratory distress syndrome, involving microvascular endothelial cell (mEC) dysfunction, increased vascular permeability, inflammation, procoagulant activation, and alveolar-capillary barrier disruption. Common comorbidities such as hypertension, diabetes, and obesity involve endothelial dysfunction. Developing new therapies is vital to inhibit SARS-CoV-2 entry and COVID-19-related disease. SARS-CoV-2 infects ACE2-negative lung mECs via an Arg-Gly-Asp (RGD) motif in spike proteins (SP) binding to αvβ3 integrin, which is retained in all variants up to Omicron BA.1. Following its entry, SARS-CoV-2 remodels ECs phenotype and promotes angiogenesis even without productive viral replication. Additionally, the absence of spike/αvβ3 interaction, as seen in Omicron BA.5, which has the D405N mutation in the RGD motif, prevents HL-mECs infection and dysfunction [1]. The RGD motif is not exposed in the entire spike protein, and SARS-CoV-2 needs a cofactor to interact with αvβ3, and to enter into HL-mECs [1,2]. This abstract explores how heparan sulfate proteoglycans (HSPGs) act as cofactors, promoting an allosteric conformational change that aids endothelial infection and vascular complications.
Methods:
To investigate the heparins-Spike protein interaction, an integrated strategy was performed combining mass spectrometry (MS) using heparin oligomers at three different molecular weights as HSPG mimetics (8, 10, and 16mer), with glycan docking and molecular dynamics (MD). Non-denaturing MS experiments were used to investigate SP areas involved in heparin interaction, by digestion with trypsin, performed both in the absence and presence of heparin oligomers. The sequence regions protected from trypsin cleavage were identified and used to drive computational studies. The Omicron BA.1 variant (PDB 7TGW) was used as the starting model. Missing residues and glycosylation sites were modelled by SwissModel and assigned based on previously published LC-MS/MS data [3], respectively. N-glycosylations were added with the GlyCam web server. The fully glycosylated complex was simulated with Amber for a total of 1 µs to allow glycans relaxation. Global and local docking of heparin oligomers against this model were performed with GlycoTorch. MS information guided the selection of heparin docking poses. Their stability was further evaluated via classical MD. For each oligomer, stable poses were integrated into a (multi)heparinâ??SP model, which was further submitted to Gaussian accelerated MD (GaMD) simulations to explore large-scale conformational changes. Post-simulation analyses included hydrogen bond network characterization, Principal Component Analysis (PCA), and secondary structure persistence, among other metrics.
Results:
Potential heparin-binding sites were highlighted by MS analyses, which detected several peptide regions protected from trypsin cleavage upon heparin incubation. Site-specific MS data, mapped onto the trimeric Spike model, were aligned with in silico glycan-dynamics studies, confirming that these regions are exposed and not masked by the glycan shield. This convergence reinforces the validity of these integrated approaches, driving the docking of heparins, enabling a more accurate workflow, so overcoming the well-known uncertainties caused by the significant conformational flexibility of longer heparin chains. Heparin poses were then refined via cMD simulations, defining an accurate binding mode for heparin oligomers. GaMD simulations revealed that heparin binding affects the overall conformational dynamics of the SP trimer rather than the local flexibility of its residues. Comparison between apo and cofactor-bound systems showed that the presence of heparins reshapes the non-covalent interaction network within the SP. These modifications involve residues surrounding the RBD hinge and inter-domain interfaces, ultimately altering the stabilization pattern of the RBD. In parallel, analysis of global motions uncovered marked differences in the collective dynamics of the Spike, as well as local alterations of secondary structure, compatible with a heparin-induced remodelling. Overall, these results provide converging evidence that heparin engagement triggers a coordinated reorganization of both local contacts and long-range dynamics of the Spike trimer, suggesting a mechanistic basis by which HSPG-like molecules enhance the SPâ??integrin interaction. These insights deepen our understanding of alternative SARS-CoV-2 entry routes and could support the development of future therapeutic strategies.


3) Easy Non-Covalent Functionalization of PLA Film with Porphyrin for Heavy Metals Optical Sensing in Water: A Preliminary Study

C.Longo, I.Di Bari, G.Curcuruto, E.T.A.Spina, G.M.L.Messina, S.Carroccio

2025 IEEE International Workshop on Metrology for Green Technologies, Renewable Energy and Ecological Sustainability (MetroGREENST) 24-26 September 2025 Giardini Naxos (ME) - Italy   - 2025

DOI: https://doi.org/10.1109/MetroGREENST67435.2025.11428849
This study presents a holistic and sustainable, non-covalent method for fabricating a heterogeneous optical sensor for metal detection in water. The sensor consists of a biodegradable polylactic acid (PLA) thin film non-covalently functionalized with a porphyrin molecule. Meso-tetra (4-hydroxyphenyl) porphyrin has been chosen for its excellent optical properties and well-established metal chelation capability, which makes it an ideal candidate for optical sensing.Upon exposure to mercury ions solution, the sensor exhibits evident and typical variations in the Soret and in the Q bands, enabling effective detection. The heterogeneous configuration avoids porphyrin solubility issues, allowing direct sensor platform immersion in water samples. This simple approach overcomes the limitations of cost, time consumption, and the use of not sustainable functionalization methods to link active sites to the PLA. As a preliminary investigation, this work demonstrates the potential of the proposed system for water quality monitoring, paving the way for further optimization and application in environmental sensing.


4) Citrate Coated Maghemite Nanoparticles for Sustainable Nano-fertilization

V.Torrisi, V.Strano, G.Granata, L.Vitiello, S.Dattilo, S.Carroccio

2025 IEEE International Workshop on Metrology for Green Technologies, Renewable Energy and Ecological Sustainability (MetroGREENST) 24-26 September 2025 Giardini Naxos (ME) - Italy   - 2025

DOI: https://doi.org/10.1109/MetroGREENST67435.2025.11428819
High concentration of water colloidal solution based on maghemite Fe2O3 nanoparticles (NPs) was optimized for sustainable fertilization. Citrate surface functionalization method was carried out, together with size and morphological characterization of functionalized NPs and the investigation of total metal amount in the solution. Stability of colloidal solution containing 26 ppm of iron was checked once a month for a period of three months, in terms of iron content verified by Inductively Coupled Plasma Mass Spectrometry (ICP-MS), size of NPs aggregates by Scanning Electron Microscopy (SEM) and Dynamic Light Scattering (DLS), Z potential by Electrophoretic Light Scattering (ELS).


5) Chapter 3 - Extracellular vesicles for therapeutic and diagnostic applications

P.Ramani, H.Padinjarathil, S.Dattilo, C.Drago

Extracellular Vesicles for Therapeutic and Diagnostic Applications  ,  57-79  - 2025

DOI: https://doi.org/10.1016/B978-0-443-23891-8.00012-3
Early and precise disease diagnosis is still required in the medical world to establish diagnostic tools and boost a better epidemiological and therapy design.book cover Interpreting the condition becomes increasingly challenging as it worsens, despite improving diagnostic accuracy. Exosomes and extracellular vesicles (EVs) are essential components of intercellular communication enclosed by membranes. They have drawn interest as a novel diagnostic approach with excellent specificity, biocompatibility, minimal immunogenicity, and a marvelous cargo system that can aid in understanding different disease stages, therapeutic tracking, and target-based prognosis treatment. Moreover, exosomes possess the distinctive ability to unveil both the physiological and pathological condition of cells. The subsequent sections of this chapter provide a comprehensive analysis of the latest modifications implemented on EVs and exosomes to augment their diagnostic capabilities. Additionally, it explores their efficacy as biomarkers in different medical conditions.

IPCB graphical abstract



6) Antibacterial pvc blends based onimidazolium ionic liquids

D.Zampino, M.Mancuso, T.Ferreri, A.Borzacchiello, S.Zeppetelli, S.Dattilo, M.Ussia, L.Ferreri, D.Carbone, G.Recca, C.Puqlisi

XXIV Convegno Nazionale AIM - Trento 4-7 sett. 2022   - 2022

lonic Liquids (ILs), molten salts al temperature below 100°C, are interesting additives for polymeric materials due to their peculiar properties. In this work, antibacterial ILs (1-hexadecyl-3-methylimidazolium 1,3-dimethyl 5-sulfoisophthalate, HdmimDMSIP, and 1-octyloximethyl-3-methylimidazolium hexafluorophos­phate, OOMmimPF6) were synlhetized and characterized by 1HNMR, MALDI-TOF, DSC and TGA. Polyvi­nylchloride (PVC) blend films containing 0.1-10% (w/w) of the synthetized ILs were developed by solvent casting. Results proved that the loading of both ILs into PVC matrix made hydrophilic the blend films surface, induced antibacterial activity with ali ILs concentrations and marginally affected the PVC thermal and mechanical propertles. Moreover, low concentrations of both ILs in the blends were not cytotoxic for mouse fibroblast cells (L929), supporting their potenlial use in biomedical field.


7) Freestanding Photocatalytic Materials Based on 3D Graphene for Degradation of Organic Pollutants

M.Ussia, V.Privitera, S.Carroccio

Graphene-based 3D Macrostructures for Clean Energy and Environmental Applications  Chapter 13  - 2021

DOI: https://doi.org/10.1039/9781839162480
Heterogeneous photocatalysis holds enormous potential to transform a wide array of organic pollutants into relatively innocuous end products.

IPCB graphical abstract

Recently, 3D GBMs have emerged as a promising new class of metal-free photocatalysts, displaying semiconductor-like photoelectric properties and showing excellent photocatalytic performance owing to their unique interconnected structures, tunable porosity, ease of surface functionalization, outstanding electron-transfer efficiency and exceptional light-harvesting capabilities (from deep UV to the near-infrared). In this chapter, recent advances in the rational design of 3D GBM-based photocatalysts are highlighted and their applications in photocatalytic environmental remediation discussed. Additionally, the corresponding reaction mechanisms and pollutant transformation pathways are elucidated to fuel more disruptive and innovative research in this rapidly expanding field of industrial importance and practical relevance.


8) Tandem Mass Spectrometry in the Analysis of Biodegradable Polymers

P.Rizzarelli, M.Rapisarda

Mass Spectrometry: Theory and Applications  Chapter 2,  127-181  - 2021

IPCB graphical abstract

This book includes three chapters that discuss the analytical tool called mass spectrometry, which is used to measure the mass-to-charge ratio of ions. Chapter One describes the use of mass spectrometry in the determination of volatile organic compounds in natural matrices and in the characterization of wood extractives. Chapter Two summarizes the investigations by tandem mass spectrometry analysis in biodegradable polymers and the in formation achieved. Chapter Three discusses the most famous types of commercial Orbitrap analyzers, including LTQ Orbitrap, Orbitrap Elite, Q Exactive Orbitrap, and Orbitrap Fusion.


9) MALDI-MS cerebrospinal fluid (CSF) N-glycan profiles in neurodegenerative diseases

A.Palmigiano, A.Messina, F.Esposito, R.Barone, G.Mostile, A.Nicoletti, L.Sturiale, D.Romeo, C.Sanfilippo, M.Zappia, D.Garozzo

Workshop IPCB 27 - 29 October 2020  ,  47  - 2020

Glycosylation is a key post-translational protein modification in different biological functions such as cellular adhesion, recognition and signalling, and changes in protein glycosylation have been recognized in different neurodegeneration disorders [1]. Alzheimer’s Disease (AD) and Parkinson’s Disease (PD) are the most common neurodegenerative diseases. Both pathologies are multifactorial diseases presenting clinically heterogeneous symptoms and prognosis and ultimately resulting in neurons loss of functions and death. AD and PD are diagnosed by clinical and neuropsychological criteria, only proved by post-mortem autopsy. Therefore, there is a great need of diagnostic tools able of detecting the diseases in their early stages when preventative therapies could ameliorate patients’ conditions before irreversible neuronal damages. We performed Matrix-Assisted Laser Desorption/Ionization Mass Spectrometry (MALDI-MS) CSF N-glycosylation analysis of released and permethylated N-glycans from a cohort including 21 AD, 11 mild cognitive impairment (MCI), 19 PD patients and 19 control subjects (age- and gender-matched). PD-CSF spectra denoted a significant increase of high-mannose 5 (M5, m/z 1579.8), agalactosylated biantennary (G0, m/z 1661.8), agalactosylated bisected biantennary (G0B, m/z 1906.9) bisected, agalactosylated core fucosylated N-glycans (G0BF, m/z 2081.0). Although no unique profile emerged for AD and MCI, principal component analysis (PCA) allows to separate AD and MCI in two categories, according to bisecting-N-glycans relative intensities. AD1 and MCI1 showed significant increase of bisecting structures and an overall decrease of sialylated species compared to healthy controls, while AD2 and MCI2 showed a slightly reduction of those species. Interestingly, the observed divergences in MCI1 and MCI2 glycosylation profiles reflected the different clinical follow-up of the respective class of patients: 5 MCI1 patients out 5 converted to AD within 36 months from diagnosis, while all the MCI2 subjects (6 out 6) remained stable over the time, suggesting that increasing amount of N-glycans with bisected GlcNAc is a biochemical hallmark of AD in the pre-dementia phase [2]. MALDI-MS CSF N-glycome profiling enabled detection of peculiar changes in subject affected by neurodegenerative diseases, helpful in monitoring diseases development and progression, thus representing a source of potential biomarkers and therapeutic targets.


10) Synthesis and characterization of a series of copolymers with different percentages of PES and DPA units

A.Scamporrino, F.Samperi, C.Puglisi, D.Zampino, S.Dattilo, A.Spina

Polychar 27 World Forum on Advanced Materials. October 14-17, 2019 - Naples, Italy   - 2019



11) MS based approaches in the diagnosis of Congenital Disorders of Glycosylation

F.Esposito, A.Palmigiano, A.Messina, R. Barone, L. Sturiale, D. Garozzo

Workshop: Validazione dei metodi LC-MS e LC-MS/MS nella ricerca scientifica, 11-12 settembre, 2019, CNR-ICB Pozzuoli (NA)   - 2019



12) Evaluating multiple texture properties of gelatines by combining a new 3D printed tool and a universal testing machine

P.Rizzarelli, M.Rapisarda, G.Valenti, D.C. Carbone, G.Recca

AIMAT 2019, 21-24 luglio 2019, Ischia (NA)   - 2019



13) Analisi e contenimento dei prodotti di degradazione formati durante la lavorazione del PET

C.Gugliuzzo

Macrogiovani 2019, 1-2 luglio 2019 (AIM), Napoli   - 2019



14) UV and soil burial degradation of irrigation tubes based on biodegradable polymer blends

M.Rapisarda, S.La Carta, F.P.La Mantia, M.Ceraulo, C.Giuffrè, R.Pellegrino, G.Valenti, P.Rizzarelli

Eurofillers Polymer Blends, 23-26 aprile 2019, Palermo   - 2019



15) Analytical methods in resorbable polymer development and degradation tracking

P.Rizzarelli, S.La Carta, M.Rapisarda, G.Valenti

Materials for Biomedical Engineering  Chapter 13,  351-408  - 2019

A precise characterization of polymeric matrices and suitable degradation monitoring techniques is required to support the development of new materials or extend the applications of existing ones. In this context, polymer analysis plays an essential role for the innate relationship between structure and properties that establishes the industrial applications in different fields. It can involve many different features ranging from molecular weight determination to detailed characterization of chemical structures, compositions, and surface analysis. book cover In resorbable polymers, the role of analytical methods is doubled, since it must address both polymeric matrices and degradation tracking. In fact, the structural architectures, the mechanical and morphological properties, and the degradation rate are all of crucial importance for the specific application.
This chapter provides an overview of the analytical methods used to support research and development of resorbable polymers to investigate the structure and degradation mechanism. It focuses on the most significant studies concerning synthetic matrices (polylactide, polyglycolide and their copolymers, polyhydroxybutyrate, etc.) published in the last 10 years.


16) Influence of Cocatalysts and Polymerization Conditions On Properties of Polyesters from ROCOP of Epoxides and Cyclic Anhydride

M.Proverbio, N.Galotto, S.Losio, P.Rizzarelli, M.Rapisarda, L.Boggioni

Giornata Dipartimento DSCTM 2019, 28 - 30/10/2019, Bressanone   - 2019



17) Antimicrobial activity of polymeric ionic liquids

D.Zampino, F.Samperi, C.Zagni, C.Restuccia, L.Parafati, S.Dattilo, A.Scamporrino, C.Puglisi

Polychar 27 World Forum on Advanced Materials. October 14-17, 2019 - Naples, Italy   - 2019



18) Influence of cocatalysts and polymerization conditions on properties of polyesters from ROCOP using Salen complexes

M.Proverbio, N.Galotto, S.Losio, I.Tritto, P.Rizzarelli, M.Rapisarda, L.Boggioni

Polychar 27 World Forum on Advanced Materials. October 14-17, 2019 - Naples, Italy   - 2019



19) ALG12-CDG N-glycome discovers unusual hybrid and high mannose glycans

F.Esposito, S.Bianca, D.Garozzo, A.Messina, A.Palmigiano, L.Sturiale, C.Barone, A.Novelli, J.Jaeken, R.Barone

EurocabXX, June 30 - July 4, 2019 Leiden (Netherland)   - 2019



20) Drug-loaded nanoparticles from amphiphilic block copolymers synthesized by ATRP

G.Valenti, G.Granata, S.La Carta, G.Consoli, C.Geraci, P.Rizzarelli

Sixth International Symposium "Frontiers in Polymer Science", 5-8 maggio 2019, Budapest (Ungheria)   - 2019



21) Presentazione Benchmark Device "Comfort-In" (in collaborazione con azienda Gamastech s.r.l. )

A.Grasso, G.Recca

28/01/2019 - 01/02/2019 ArabHealth 2019, Dubai   - 2019



22) The cerebrospinal fluid (CSF) N-glycome as a novel biomarker of Parkinson’s disease. A mass spectrometry-based CSF n-glycosylation study of patients affected by Parkinson’s disease

A.Palmigiano, A.Messina, F.Esposito, R.Barone, G.Mostile, A.Nicoletti, L.Sturiale, D.Romeo, D.Garozzo, M.Zappia

Glycoconjugate journal   - 2019

Parkinson’s Disease (PD) is a clinically heterogeneous, multifactorial, age-related neurodegenerative disorder. PD is characterized by some pathological features such as cytoplasmic Lewy bodies accumulation in substantia nigra pars compacta, loss of dopaminergic neurons, inflammation, mitochondrial dysfunctions, that lead to neuronal degeneration and death. Glycosylation is a common post-translational protein modification with multiple biological functions. Glycosylation changes have been recently found in serum of patients with PD. However, N-glycosylation profiling in PD cerebrospinal fluid (CSF glycome) is still almost unexplored. We aimed to study CSF glycome in PD in order to identify potential glycosylation changes associated with PD. We performed Matrix-Assisted Laser Desorption/Ionization Mass Spectrometry (MALDI MS) CSF N-glycosylation analysis of released and permethylated N-glycans from a cohort including 19 PD patients and 19 control subjects (age- and gender-matched). Control CSF spectra were characterized by a base peak at 2792.4 Da, corresponding to a biantennary A2 complex N-glycan. Spectra from PD-CSF denote a significant increase of high-mannose 5 (M5, m/z 1579.8), agalactosylated biantennary (G0, m/z 1661.8), agalactosylated bisected biantennary (G0B, m/z 1906.9) bisected, agalactosylated core fucosylated N-glycans (G0BF, m/z 2081.0). CSF N-glycome could shed new light on the pathological mechanisms that lead to the disease development and progression in PD.


23) HILIC-MS based glycomics in the diagnosis of Congenital Disorders of Glycosylation

F.Esposito, A.Palmigiano, A.Messina, R.Barone, L.Sturiale, D.Garozzo

Glycoconjugate journal   - 2019

N-glycans are often studied to discover disease-associated biomarkers, as well as to identify changing in glycomic profiles supporting diagnosis of those disorders directly connected to impaired glycan biosynthesis of glycoconjugates, such as congenital disorders of glycosylation (CDG). Strategies based on liquid chromatography (LC) coupled preferentially to electrospray ionization (ESI) - mass spectrometry (MS) have emerged as powerful analytical methods for N-glycan identification and characterization. To enhance detection sensitivity, glycans are commonly functionalized with a tag prior to LC-MS analysis. Since the majority of the techniques used for glycan derivatization are notoriously time-consuming, some commercial analytical kits were developed to perform a rapid deglycosylation and labelling of N-glycans linked specifically to monoclonal antibodies (mAbs). Adopting one of these commercial kits, RapiFluor-MS (RFMS), through a slightly modified protocol, we performed the enzymatic release and the N-glycan labelling of total serum and single serum glycoproteins from selected CDG patients (MAN1B1-CDG, ALG12-CDG, MOGS-CDG, TMEM199-CDG). Hydrophilic Interaction Chromatography (HILIC)-UPLC-ESI-MS separation of derivatized N-glycans allowed us to differentiate either structural isomers and isomers differing for the linkage type, as hybrid glycan structures accumulating in N-glycan profile of MAN1B1-CDG and ALG12-CDG. According to patient immunological phenotype, serum IgG analysis of the Glucosidase 1-deficient patient (MOGS-CDG) showed significant N-glycosylation differences compared to control as the occurrence of the accumulating Glc3-Man7-GlcNAc2 glycoform (in accordance with the molecular defect) and, moreover, a generalized increase of sialylation. Serum N-glycan profiling of TMEM199-CDG showed, aside an increased amount of undersialylated biantennary structures, also an overall increase of the triantennary N-glycan component. All these applications demonstrated that RFMS method coupled to HILIC-UPLC-ESI-MS, represents a sensitive high throughput approach for serum N-glycome analysis and a valuable option for glycan detection and separation particularly for isomeric species.


24) Combined mass spectrometry methods for serum N-glycoprotein profiling enhance the awareness of the molecular patho-mechanism in ALG12-CDG

L.Sturiale, S.Bianca, A.Terracciano, E.Agolini, A.Messina, A.Palmigiano, F.Esposito, C.Barone, A.Novelli, A.Fiumara, D.Garozzo, J.Jaeken, R.Barone

Glycoconjugate journal   - 2019

Congenital disorders of glycosylation (CDG) are inherited metabolic diseases affecting the glycan biosynthesis of glycoconjugates. They represent an expanding group of multisystemic diseases with variable phenotypes and prevalent neurological involvement. More than 120 genetic disorders have been associated to defective glycosylation, mainly in the protein N-glycosylation pathway. Among these, CDG type I (CDG-I) occur in the cytosol or in the endoplasmic reticulum (ER) affecting dolichol-linked oligosaccharide synthesis, whereas CDG type II (CDG-II) involve the N-linked oligosaccharide processing in the Golgi. ALG12-CDG (MIM: 607143) is caused by mutations of the human orthologue of the yeast asparagine-linked glycosylation (ALG)12 gene, encoding the mannosyltransferase which adds in the ER an α-mannosyl residue to the core Man(α1-6) of the dolichol-PP-oligosaccharide precursor, thus ensuring its correct shape and branching before the oligosyltransferase (OST) complex action. Nine patients with ALG12-CDG have been reported so far. We investigated by MALDI MS and UHPLC-ESI MS the glyco-phenotype of a novel patient with unreported variants, sharing most of the clinical signs of patients with ALG12 deficiency, including severe recurrent infections with hypogammaglobulinemia and B cell dysfunction. MALDI MS analysis of native transferrin showed underoccupancy of N-glycosylation sites, a typical feature of CDG-I. N-glycome analysis by MALDI MS, either on total serum N-glycan pool and on IgG released N-glycans, revealed the abnormal occurrence of high-mannose and hybrid N-glycan species. These accumulating glycoforms, further analyzed by UHPLC-ESI MS, corresponded to unbranched structures with α1,2-terminal mannose residues, previously identified in serum of patients with MAN1B1-CDG (CDG-II defect). Glycosylation analyses on the observed ALG12-CDG patient revealed a combination of CDG-I and CDG-II defects, these last associated with abnormal IgG N-glycan profile, consistent with the immunophenotype. Glycan characterization of target glycoproteins may endorse the molecular defect unraveling the complex clinical phenotype of CDG patients.


25) CSF N-Glycoproteomics Using MALDI MS Techniques in Neurodegenerative Diseases

A.Messina, A.Palmigiano, R.O.Bua, D.Romeo, R.Barone, L.Sturiale, M.Zappia, D.Garozzo

Cerebrospinal Fluid (CSF) Proteomics  2044,  255-272  - 2019

CSF diagnostics has proved to be a formidable testing ground for N-glycoproteomic analysis of neurological diseases. book cover To characterize specific N-glycan profiles of CSF in early and advanced phases of Alzheimer’s disease, as well as in lysosomal storage disorders such as Tay-Sachs disease, we set up in our lab a robust and feasible protocol by coupling bioanalytical methods and mass spectrometry analysis.
Starting from a few microliters of CSF, after protein denaturation, reduction, and alkylation, N-glycans are released from glycoproteins using the peptide-N-glycosidase F (PNGase F) and purified. The analysis of permethylated N-glycans by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) and MALDI-TOF MS/MS allowed us to identify specific glyco-structures and also to distinguish between isobaric N-glycans.


26) Copolyethersulfones with pendant carboxylic groups for metal ions absorption

F.Samperi, A.Spina, S.Dattilo, E.F.Mirabella, A.Scamporrino, D.Zampino, C.Puglisi

Eurofillers Polymerblends - Palermo (Italy) April 23-26, 2019   - 2019

Aromatic thermoplastic poly(ether-sulfone)s (PES) have reached a remarkable scientific and industrial interests owing to their excellent mechanical, chemical and thermal stabilities (1,2). This class of polymers have found application as adhesives for metal-to-metal bonds, membranes for separating gases and solids from solution or isolation of proteins, matrices for fibre rein-forced composites and as toughening agents for thermosetting resins. It has been reported in the literature that a wide spectrum of thermal, chemical and mechanical properties and also morphological behaviour, can be obtained by varying the type of monomer units in the corresponding copolymers or by derivatization of preformed commercial PESs (1,2). In the present study the chelating properties of some functionalized PES copolymers against heavy metal ions will be investigated as a function of the composition of the functional monomers.


27) Poly(styrene/styrene sulfonate)/ionic liquid copolymers with antimicrobial activity

C.Puglisi, F.Samperi, C.Zagni, C.Restuccia, L.Parafati, S.Dattilo, A.Scamporrino, D.Zampino

Eurofillers Polymerblends - Palermo (Italy) April 23-26, 2019   - 2019

Ionic liquids (ILs) are molten salts at temperature below 100°C, containing of an organic cation and an anionic portion of various nature. Their structure as well as their chemical-physical properties, such as low vapor tension, high polarity, electrical conductivity and non-flammability, make them particularly versatile and interesting (1). It was reported that imidazole-based ILs display antimicrobial activity comparable to that of commercial antimicrobial agents. Their biocidal activity is due to the length of the alkyl chain of the cation, to the type of substituted functional groups and their position in the imidazole ring (2). Recent studies have concerned the synthesis of different poly-ionic liquids (PILs), in which the cation or anion portion has a polymeric structure with interesting characteristics such as high ionic conductivity and thermal stability. The aim of this study was the synthesis of ILs and PILs with antimicrobial activity.


28) Polymeric ionic liquids with antimicrobial activity

C.Zagni, F.Samperi, C.Restuccia, L.Parafati, S.Dattilo, C.Puglisi, D.Zampino

Frontiers in Polymer Science 5-8 May 2019, Budapest (Hungary)   - 2019

Polymeric ionic liquids (PILs) bearing imidazolium group have been extensively investigated as antimicrobial compounds due to their broad spectrum of activity and because do not easily induce bacterial resistance wìth low toxicity toward mammalian cells. With the aim to develop new antimicrobial compounds, we synthesized new ionic and polyionic liquids by metathesis reaction of 1-hexadecyl-3-methylimidazolium bromide, previously prepared by alkylation of 3-methylimidazole with 1-bromohexadecane, with different anions. The following compounds have been synthesized: 1-hexadecyl-3-methylimidazolium dimethyl-5-sulfoisophtalate (HDmim+ DMSIP-), 1-hexadecyl-3-methylimidazolium styrene sulfonate (HDmim+ SS-), 1-hexadecyl-3-methylimidazolium poly(styrene-styrene sulfonate 75:25) (HDmim+ PSS- 75:25) and 1-hexadecyl-3-methylimidazolium poly(styrene-styrene sulfonate 90:10) (HOmim+PSS- 90:10). In order to obtain PILs, two copolymers have been produced by reaction of styrene and sulfonate styrene mixed at different molar ratios (75:25 and 90:10) and then used as anions for the synthesis of polyionic liquids HDmim+ PSS- 75:25 and HDmim+ PSS- 90:10. All the synthesized compounds have been characterized by 1HNMR, MALDI, DSC and TGA analysis. The antimicrobial activity of cotton gauzes loaded with different concentrations of ionic and polyionic liquids was investigated by disk diffusion method. The synthesìzed compounds induced a good antimicrobial activity against both Gram positive (Listeria innocua and Bacillus subtilis) and Gram negatìve (Pseudomonas fluorescens) bacterial pathogens, thus resulting promising antimicrobial agents for future applications in different fields (medical, alimentary, textile, etc.).


29) Synthesis and characterization of copolyethersulfones with pendant carboxylic groups

A.Spina, S.Dattilo, E.F.Mirabella, C.Puglisi, F.Samperi, A.Scamporrlno, D.Zampino

Frontiers in Polymer Science 5-8 May 2019, Budapest (Hungary)   - 2019

Polyethersulfone based copolymers containing different percentages of 4,4'-bis(4-hydroxyphenyl)pentanoic acid (DPA) were synthesized and investigated in order to preparare membranes for removing heavy metals. The copolymers obtained contain 10, 20, 30, 50, 70% mol of DPA and were prepared by nucleophilic polycondensation reaction between DPA and 4,4’-sulfonyldiphenol (DHDPS) wlth 4,4’-dichlorodiphenyl sulfone (DCDPS). Chemical properties and thermal stability have been studied with particular attention to the influence of the diphenolìc acid moiety on the polyethersufone. The functional carboxylic group of the DPA unit of the PES-DPA copolymers was also used for the insertion of telechelic oligomers of polyethersulfone sulphonated (S-PES) with controlled degree of polymerization to synthesize grafted sulfonated copolymers with a comb structure and improved properties in terms of proton conductivity. The proposed idea is to develop filtration rnembranes with selective properties against heavy metal ions; preliminary tests were carried out in aqueous solutions containing known percentages of heavy metals (Pb, Cr, Cu, Cd, Zn,V). Copolymers were characterized by 1H-NMR spectrometry, MALDI-TOF mass spectrometry, FT­IR, thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The chemlcal-structural characterization by 1H-NMR and MALDI-TOF MS analysìs confirms the formation of macromolecular chaìns terminated with OH and CI functional groups. TGA analysis shows high thermal stability of the polymers, higher in the samples containing lower percentages of DPA. Preliminary studies revealed the ability of PES-DPA copolymers to adsorb some heavy metals in a selective manner, expecially Cr and Pb in aqueous solution.


30) Profilo glicomico delle sieroproteine in un paziente con deficit dell'enzima Glucosidasi I (MOGS-CDG)

F.Esposito, A.Palmigiano, A.Messina, R.Barone, L.Sturiale, G.Cantalupo, T.Lo Barco, G.Rodella, A.Fiumara, A.Bordugo, D.Garozzo

IX Congresso Nazionale SIMMESN - "Malattie Metaboliche Ereditarie: tra presente e futuro", 21-23 novembre 2018, Catania   - 2018



31) A new 3D printed tool to evaluate multiple texture properties of gelatine

M.Rapisarda, G.Valenti, D.Carbone, G.Recca, P.Rizzarelli

AIM2018 -XXIII Convegno Nazionale dell’Associazione Italiana di Scienza e Tecnologia delle Macromolecole, Catania 9-12 Settembre 2018   - 2018



32) Development and Application of an Analytical Method to Determine Polyethylene in Compostable Carrier Bags

P.Rizzarelli, M.Rapisarda, E.F.Mirabella, S.La Carta, C.Puglisi

Conferenza di Dipartimento DSCTM 2018, 24-26/09/2018, Assisi   - 2018



33) Characterization and Laser-Induced Degradation of Medical-Grade Polylactide

P.Rizzarelli, G.Piredda, S.La Carta, R.Bernet, G.Impallomeni

AIM2018 -XXIII Convegno Nazionale dell’Associazione Italiana di Scienza e Tecnologia delle Macromolecole, Catania 9-12 Settembre 2018 -Proceedings in atti di congresso ISBN 978-88-7751-449-3   - 2018



34) Composites of biobased Polyammide 11 and halloysite nanotubes filled thymol as photo protectors

G.Gorrasi, V.Bugatti, V.Vittoria, M.Ussia, R.Mendichi, D.Zampino, C.Puglisi, S.Carroccio

10th International Conference of Modification, Degradation and Stabilization of Polymers (MoDeSt 2018), 2-6 September 2018 Tokio (Japan)   - 2018

The formulation of cost-effectiveness sustainable materials is extensively growing and becoming an attractive approach for both industrial and academic fields. In this context, the bio-based aliphatic polyamide 11 (PA11) has acquired significant interest as environmentally friendly thermoplastic option. In addition, its formulation with selected natural antioxidant and/or reinforced compounds through green processing methods, might improve physical and mechanical properties without sacrificing the intrinsic bio-based nature of the matrix. In this work, we have investigated and compared the photo-oxidative degradation processes occurring on PA11 composites based on thymol and halloysite nanotubes prepared by using ball-milling method. In particular, halloysite nanotubes were used as green nano-container of a natural antioxidant molecule, and reinforced nano-filler as well. Molecular and structural information of photo-exposed samples were obtained by using size exclusion chromatography (SEC) (Figure 1) and matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF MS). Thermal and mechanical properties were also tested as well as thymol release. Data collected confirmed that PA11 filled with HNTs-Thymol nano-hybrid showed superior durability performance if compared to both pure PA11 and PA 11 blend realized by simply adding thymol and HNTs to polymer matrix. Furthermore, we found that HNTs and thymol combined in the nano-hydrid form exhibited an active and synergic role to achieve a major photo stabilization of PA11 biocomposite, without sacrificing its mechanical properties.


35) Liquidi ionici polimerici ad attività antimicrobica

D.Zampino, C.Zagni, F.Samperi, C.Restuccia, L.Parafati, S.Dattilo, C.Puglisi

AIM2018 -XXIII Convegno Nazionale dell’Associazione Italiana di Scienza e Tecnologia delle Macromolecole, Catania 9-12 Settembre 2018   - 2018

I liquidi ionici (ILs) sono composti costituiti da una porzione cationica organica ed una anionica di varia natura. La loro struttura così come le loro proprietà chimico fisiche, quali bassa tensione di vapore, elevata polarità, conduttività elettrica e noninfiammabilità, li rendono particolarmente versatili ed interessanti [1]. E’ stato osservato che ILs a base di imidazolo mostrano un’attività antimicrobica paragonabile a quella di agenti antimicrobici commerciali come il Triclosano e che la loro attività biocida è principalmente dovuta alla lunghezza della catena alchilica del catione, al tipo di gruppi funzionali sostituiti ed alla loro posizione nell’anello imidazolico [2]. Recentemente, sono stati sintetizzati diversi tipi di liquidi poli-ionici (PILs), in cui il catione o l’anione presentano una struttura polimerica con interessanti caratteristiche quali elevate conduttività ionica e stabilità termica. Scopo di questo studio è stato la realizzazione di fibre di cotone antimicrobiche ottenute additivando a garze di cotone liquidi ionici e poli-ionici di sintesi. Sono stati sintetizzati due liquidi ionici: l’1-metil-3-esadecil imidazolo dimetilsulfoisoftalato (EDmim+ DMSIP-) e l’1-metil-3-esadecil imidazolo stirene solfonato (EDmim+ SS-). Inoltre, sono stati sintetizzati due copolimeri salificati di stirene e stirene solfonato (PSS), a diversi rapporti molari, che sono stati utilizzati come anioni per la realizzazione dei PILs 1-metil-3-esadecil imidazolo polistirenestirene solfonato 75:25 (EDmim+ PSS- 75:25) e 1-metil-3-esadecil imidazolo polistirene-stirene solfonato 90:10 (EDmim+ PSS- 90:10). La scelta di utilizzare ILs e PILs è stata effettuata per verificare eventuali differenze nel rilascio dell’agente antimicrobico dalle fibre di cotone. In particolare, si è cercato di determinare l’influenza del diverso tipo di anione (ILs) e del diverso peso molecolare dei composti (ILs vs PILs). L’attività antimicrobica delle fibre di cotone additivate è stata testata nei confronti di batteri Gram positivi (Listeria innocua e Bacillus subtilis) e Gram negativi (Pseudomonas fluorescens) attraverso il metodo di diffusione in piastra.


36) Halloysite nanotubes filled thymol as photo protectors of biobased polyammide 11

M.Ussia, G.Gorrasi, V.Bugatti, R.Mendichi, D.Zampino, C.Puglisi, S.Carroccio

AIM2018 -XXIII Convegno Nazionale dell’Associazione Italiana di Scienza e Tecnologia delle Macromolecole, Catania 9-12 Settembre 2018   - 2018

The formulation of cost-effectiveness sustainable materials is extensively growing and becoming an attractive approach for both industrial and academic fields. In this context, the bio-based aliphatic polyamide 11 (PA11) has acquired significant interest as environmentally friendly thermoplastic option. In addition, its formulation with selected natural antioxidant and/or reinforced compounds through green processing methods, might improve physical and mechanical properties without sacrificing the intrinsic bio-based nature of the matrix. In this work, we have investigated and compared the photo-oxidative degradation processes occurring on PA11 composites based on thymol and halloysite nanotubes prepared by using ball-milling method. In particular, halloysite nanotubes were used as green nano-container of a natural antioxidant molecule, and reinforced nano-filler as well. Molecular and structural information of photo-exposed samples were obtained by using size exclusion chromatography (SEC) and matrix assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF MS). Thermal and mechanical properties were also tested as well as thymol release. Data collected confirmed that PA11 filled with HNTs-Thymol nano-hybrid showed superior durability performance if compared to both pure PA11 and PA 11 blend realized by simply adding thymol and HNTs to polymer matrix. Furthermore, we found that HNTs and thymol combined in the nano-hydrid form exhibited an active and synergic role to achieve a major photo stabilization of PA11 biocomposite, without sacrificing its mechanical properties.


37) Sintesi e caratterizzazione di copolieteresolfone aventi gruppi acidi pendenti

A.Spina, S.Battiato, S.Dattilo, C.Puglisi, F.Samperi, D.Zampino

AIM2018 -XXIII Convegno Nazionale dell’Associazione Italiana di Scienza e Tecnologia delle Macromolecole, Catania 9-12 Settembre 2018   - 2018

I poli(etere solfone) (PES) sono polimeri termoplastici ad elevate prestazioni con elevata temperatura di transizione vetrosa (Tg), elevata stabilità termica, ottima resistenza all’idrolisi ed all’ossidazione e interessanti proprietà meccaniche dal punto di vista ingegneristico [1-4]. A temperatura ambiente si presentano come resine dure e rigide. La loro resistenza al calore ed alla fiamma, nonchè a condizioni di esposizione prolungata a umidità e vapore, è di gran lunga superiore a quella delle plastiche convenzionali: sopportano temperature fino a 200°C senza mostrare significative variazioni dimensionali o deterioramento fisico anche nel lungo termine (fino a 20 anni).La loro diffusione è ancora limitata a causa dell’elevato costo delle materie prime e dei loro processi di lavorazione. Negli ultimi decenni sono stati prodotti e commercializzati un gran numero di PES aromatici per gli scopi più vari: come componenti per isolanti elettrici, utensili da cucina e dispositivi medicali, per applicazione in sensori elettrochimici e membrane a scambio protonico per celle a combustibile o, ancora, come agenti tenacizzanti di resine termoindurenti e adesivi per strati metallici. I PES si prestano per la produzione di membrane con proprietà riproducibili e dimensioni dei pori controllabili fino a 40 nanometri. Le membrane esclusivamente a base di polisolfoni sono tipicamente idrofobiche e quindi soggette a scarsa bagnabilità; variando la composizione ed, in particolare, funzionalizzando con gruppi maggiormente idrofilici possiamo ottenere migliorate proprietà.


38) Properties of dense films based on a poly(ether-block-amide) copolymer: effect of the preparation method and photo-oxidation

P.Bernardo, G.Clarizia, D.Zampino, S.Carroccio, G.Gorrasi

AIM2018 -XXIII Convegno Nazionale dell’Associazione Italiana di Scienza e Tecnologia delle Macromolecole, Catania 9-12 Settembre 2018   - 2018

Membrane gas separation processes represent energy-efficient and environmentally friendly solutions [1]. Today, membrane systems are successfully applied in several fields. The main applications are technologically relevant and include nitrogen production, hydrogen separation in refineries, recovery of volatile organics from gas streams and natural gas sweetening [1]. Typically, the gas separation membranes are based on polymeric materials. Indeed, polymers combine good processability and low cost with interesting separation properties. Pebax® polymers are commercial elastomeric poly(ether-block-amide) copolymers used for textile, medical and packaging applications. Different studies considered Pebax® for membrane preparation [2-4]. Interesting results were reported for the CO2/N2 separation, which is relevant to the CO2 capture from flue gas for greenhouse gas emission control. These block copolymers consist of polyether (PE) amorphous rubbery blocks and polyamide (PA) semi-crystalline segments. The soft PE blocks are gas permeable, while the hard PA segments provide mechanical stability. A change in the type of the PE and PA segments and their relative ratio [5, 6] results in different properties.
The present study focuses on dense films of Pebax®2533, investigating the effect of the casting solvent on their structure and transport properties. Films obtained in a solvent-free procedure by melting the polymer pellets in a hot press were prepared as another green alternative. Moreover, film samples were subjected to a photo-oxidative process under UV irradiation up to 11 hours and the oxidation level was monitored by means of matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI TOF MS). Their gas transport properties were evaluated and correlated with microstructure and surface properties.


39) Biophysical Approaches to Solve the Structures of the Complex Glycan Shield of Chloroviruses

C.De Castro, G.A. Duncan, D.Garozzo, A.Molinaro, L.Sturiale, M.Tonetti, J.L. Van Etten

Glycobiophysics  1104,  237-257  - 2018

The capsid of Paramecium bursaria chlorella virus (PBCV-1) contains a heavily glycosylated major capsid protein, Vp54. The capsid protein contains four glycans, each N-linked to Asn. book cover The glycan structures are unusual in many aspects: (1) they are attached by a Β-glucose linkage, which is rare in nature; (2) they are highly branched and consist of 8-10 neutral monosaccharides; (3) all four glycoforms contain a dimethylated rhamnose as the capping residue of the main chain, a hyper-branched fucose residue and two rhamnose residues with opposite absolute configurations; (4) the four glycoforms differ by the nonstoichiometric presence of two monosaccharides, L-arabinose and D-mannose; (5) the N-glycans from all of the chloroviruses have a strictly conserved core structure; and (6) these glycans do not resemble any structures previously reported in the three domains of life. The structures of these N-glycoforms remained elusive for years because initial attempts to solve their structures used tools developed for eukaryotic-like systems, which we now know are not suitable for this noncanonical glycosylation pattern. This chapter summarizes the methods used to solve the chlorovirus complex glycan structures with the hope that these methodologies can be used by scientists facing similar problems.


40) CSF N-Glycomics Using MALDI MS Techniques in Alzheimer’s Disease

A.Palmigiano, A.Messina, R.O.Bua, R.Barone, L.Sturiale, M.Zappia, D.Garozzo

Biomarkers for Alzheimer’s Disease Drug Development  ,  75-91  - 2018

In this chapter, we present the methodology currently applied in our laboratory for the structural elucidation of the cerebrospinal fluid (CSF) N-glycome. book cover N-glycans are released from denatured carboxymethylated glycoproteins by digestion with peptide-N-glycosidase F (PNGase F) and purified using both C18 Sep-Pak® and porous graphitized carbon (PGC) HyperSepTM HypercarbTM solid-phase extraction (SPE) cartridges. The glycan pool is subsequently permethylated to increase mass spectrometry sensitivity. Molecular assignments are performed through matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI TOF MS) analysis considering either the protein N-inked glycosylation pathway or MALDI TOF MS/MS data. Each stage has been optimized to obtain high-quality mass spectra in reflector mode with an optimal signal-to-noise ratio up to m/z 4800. This method has been successfully adopted to associate specific N-glycome profiles to the early and the advanced phases of Alzheimer’s disease.


41) Advanced LC-MS Methods for N-Glycan Characterization

A.Palmigiano, A.Messina, L.Sturiale, D.Garozzo

Comprehensive Analytical Chemistry . Chapter 6 (ISSN 0166-526X)  79,  147-172  - 2018

N-glycosylation is one of the main posttranslational modifications involving proteins that belong to all the three domains of life and plays a pivotal role in many biological functions, including intercellular signalling and recognition. book cover Glycosylation analysis in humans is an added value and a fundamental tool to characterize those genetic defects concerning glycan biosynthesis, such as congenital disorders of glycosylation. In addition, glycan alterations are associated with pathophysiology of major diseases as cancer and neurodegenerative dysfunctions. Concurrently, there is a growing interest of biopharmaceutical industries for the development of high-throughput methods for glycan analysis of therapeutic glycoproteins.N-linked glycans are commonly analyzed by liquid chromatography (LC) interfaced with fluorescence detection, but in the recent years a growing number of research laboratories extended the application by coupling LC with mass spectrometry (MS) techniques. Furthermore, LC-MS has become the primary device for smart high-throughput analyses.Here we report an outline of the prevailing LC-MS techniques set up for N-glycan analysis, paying special attention to N-glycomic characterization of human serum, as the most available and informative biological source for diagnosis and disease investigations.

Ion mobility MS analysis of the two disialo-biantennary linkage isomers from human serum transferrin



42) An Unexplained Congenital Disorder of Glycosylation-II in a Child with Neurohepatic Involvement, Hypercholesterolemia and Hypoceruloplasminemia

P.L.Calvo, M.Spada, I.Rabbone, M.Pino, F.Porta, F.Cisarò, S.Reggiani, A.B.Cefalù, L.Sturiale, D.Garozzo, D.J.Lefeber, J.Jaeken

JIMD Reports  35,  1-7  - 2017

We report on a 12-year-old adopted boy with psychomotor disability, absence seizures, and normal brain MRI. book cover He showed increased (but initially, at 5 months, normal) serum cholesterol, increased alkaline phosphatases, transiently increased transaminases and hypoceruloplasminemia with normal serum and urinary copper. Blood levels of immunoglobulins, haptoglobin, antithrombin, and factor XI were normal. A type 2 serum transferrin isoelectrofocusing and hypoglycosylation of apoCIII pointed to a combined N- and O-glycosylation defect. Neither CDG panel analysis with 79 CDG-related genes, nor whole exome sequencing revealed the cause of this CDG. Whole genome sequencing was not performed since the biological parents of this adopted child were not available.


43) Exchange Reaction Mechanisms in the reactive Extrusion of Condensation Polymers

C.Puglisi, F.Samperi

Reactive Extrusion: Principles and Applications . (Editors by Di Günter Beyer and Christian Hopmann)  Chapter 6,  135  - 2017

book cover



44) Imidazolium ionic liquids as antimicrobial additives of biomedical PVC

D.Zampino, D.Carbone, G.Recca, T.Ferreri, C.Puglisi, S.Dattilo, L.Ferreri, M.Mancuso, R.Zaccone

Materials2016 Sheraton Catania Hotel Aci Castello December 12-16 2016   - 2016

In the last years ionic liquids (ILs) have attracted research interest for their thermal stability, non-inflammability, negligible vapour pressure, solvation ability, biocompatibility, low toxicity, etc 1. ILs based on imidazolium salts have been used in a wide range of biological and material science applicationsas scaffold for biomimetic applications, oxygen transport membranes, surfactants, plasticizers, antimicrobial and anti-inflamatory agents2. It was reported that imidazolium ILs showed strong antimicrobial activity, comparable to that of commercial antimicrobial compounds such as Triclosan and that ILs biocidal activity is mainly due to the alkyl chain length in the cation3.
The aim of this study was the development of antimicrobial PVC compounds loaded with 1-10% (w/w) of 1,3-dimethyl5-sulfoisophthalate 1-hexadecyl-3-methyl imidazolium salt (PC4). PC4 was synthesised according to Colonna et al.4 and characterized by NMR and TGA. PVC-PC4 compounds were obtained by mixing, at 150 °C for 3 minutes, PVC pellets and PC4 powder (1-10% w/w ) in a Brabender mixer. Films of compounds were realized by compression moulding. Thermal and mechanical properties (elastic modulus E, tensile stress TS and elongation at break EB) of compounds were measured. Results demonstrated that the presence of PC4 in PVC formulation did not affect thermal and mechanical properties of compounds. The antimicrobial activity of PVC-PC4 compound films was determined by disk diffusion method. The inhibition zone (mm) surrounding the films, on TSA plates seeded with inocula of Escherichia coliand Staphylococcus epidermidisat an initial concentration of 103CFU/mL, was measured after 24 h of incubation at 37°C. Plates seeded with S.epidermidisshowed an inhibition zone (6 mm) around PVC film containing 10% (w/w) of PC4, whereas no inhibition zonewas observed against E. coligrowth, confirming a higher antimicrobial action against gram positive bacteria4. In all cases there was no growth of these strains on the PVC-PC4 compound films.


45) Antimicrobial PVC silver zeolite composites: plasticizers influence

D.Zampino, D.Carbone, G.Recca, T.Ferreri, C.Puglisi, S.Dattilo, L.Ferreri, E.Romeo, S.Milazzo, M.Mancuso, R.Zaccone

Materials2016 Sheraton Catania Hotel Aci Castello December 12-16 2016   - 2016

Polyvinyl chloride (PVC) is a polymer widely used in medical field to produce equipments for blood transfusion, medical devices, etc. The replacement of di-2-ethyl hexyl phthalate (DEHP) from PVC processing, reducing or eliminating the health risk caused by its release into environment together with theachievementof antimicrobial properties are undoubtedly important for the development of new PVC products relevant for health care applications.
In this study we used PVC plasticized with DEHP, di-isononyl phthalate (DINP) and tris-2-ethyhexyl trimellitate(TOTM) to test the influence of plasticizers on silver release from PVC silver composites. Polymer composites were prepared by mixing PVC pellets with a silver zeolite (SZ) in the amount of 10-20 wt%. The antibacterial activity of PVC SZ composites was tested on Escherichia coli and Staphylococcus epidermidisin culture broth, on agar plate and in sterile urine seeded with these strains for simulation purposes. The results indicate that the addition of large amount of SZ did not influence the processability and the formability of the composites as well as their thermal and mechanical properties, if compared to neat plasticized PVC. Composites showed antibacterial activity against S. epidermidis and E. coli in culture broth, direct inhibition on agar plate andin urine supplemented with bacteria. PVC-DEHP SZ composites exhibited a good antimicrobial activity at 10% wt of silver zeolite, while the best performance of composites of PVC plasticized with DINP and TOTM was at 20% wt of silver zeolite. In sterile urine, composites induced a significant reduction of viability of both strains already at 24 h, inhibiting E. coli growth up to 20 days, whereas their antimicrobial action against S. epidermidis vanished within 5 days. Data on silver release suggest that the different steric hindrance of plasticizers influence the migration and release of the antimicrobial agent from polymeric matrix to the environment.


46) Identification of N-glycan profiles in tears of vernal and atopic keratoconjunctivitis patients

A.Leonardi, A.Messina, A.Ruaro, A.La Gloria Valerio, D.Garozzo

Allergy  71(S102),  140  - 2016



47) Determinazione del contenuto in polietilene in miscele polimeriche biodegradabili e in sacchetti compostabili mediante PY-GC/MS e TGA

P.Rizzarelli, M.Rapisarda, S.Perna, E.F.Mirabella, S.La Carta, C.Puglisi, G.Valenti

XXII Convegno Nazionale Aim Genova, 11-14 settembre 2016   - 2016



48) Caratterizzazione strutturale di una poli(estere ammide) sintetizzata da acido sebacico e 3-ammino-1-propanolo mediante spettrometria di massa tandem

P.Rizzarelli, S.La Carta, G.Valenti, M.Rapisarda

XXII Convegno Nazionale Aim Genova, 11-14 settembre 2016   - 2016



49) Shelf Life Evaluation of Fresh-Cut Globe Artichoke Packaged in a Compostable Biobased Film

V.Rizzo, G.Sapienza, C.Restuccia, G.Mauromicale, S.Lombardo, G.R.Pesce, M.Rapisarda, S.Perna, P.Rizzarelli, G.Muratore

SLIM 2015, Shelf Life International Meeting -05 July 2016   - 2016



50) Controlled release of cortisone drugs from block copolymers synthetized by ATRP

G.Valenti, S.La Carta, S., G.Mazzotti, M.Rapisarda, S.Perna, R.Di Gesù, L.Giorgini, D.Carbone, G.Recca, P.Rizzarelli

8th International Conference on Times of Polymers and Composites: From Aerospace to Nanotechnology; Ischia, Naples; Italy; 19-23 June 2016   1736  - 2016

Diseases affecting posterior eye segment, like macular edema, infection and neovascularization, may cause visual impairment. Traditional treatments, such as steroidal-drugs intravitreal injections, involve chronic course of therapy usually over a period of years. Moreover, they can require frequent administrations of drug in order to have an adequately disease control. This dramatically reduce patient’s compliance. Efforts have been made to develop implantable devices that offer an alternative therapeutic approach to bypass many challenges of conventional type of therapy. Implantable drug delivery systems (DDS) have been developed to optimize therapeutic properties of drugs and ensure their slow release in the specific site. Polymeric materials can play an essential role in modulating drug delivery and their use in such field has become indispensable. During last decades, acrylic polymers have obtained growing interest. Biocompatibility and chemical properties make them extremely versatile, allowing their use in many field such as biomedical. In particular, block methacrylate copolymer with a balance of hydrophilic and hydrophobic properties can be suitable for prolonged DDS in biomedical devices. In this work, we focused on the realization of a system for controlled and long term release of betamethasone 17,21-dipropionate (BDP), a cortisone drug, from methacrylic block copolymers, to be tested in the treatment of the posterior eye’s diseases. Different series of methyl methacrylate/hydroxyethyl methacrylate (MMA/HEMA) block and random copolymers, with different monomer compositions (10-60% HEMA), were synthetized by Atom Transfer Radical Polymerization (ATRP) to find the best hydrophilic/hydrophobic ratio, able to ensure optimal kinetic release. Copolymer samples were characterized by NMR spectroscopy (1H-NMR, 13C-NMR, CosY), SEC, TGA and DSC. Monitoring of drug release from films loaded with BDP was carried out by HPLC analysis. Evaluation of different kinetic models allowed to deduce that release of BDP is controlled over time from PMMA-b-PHEMA 53/47. In particular, PMMA-b-PHEMA 53/47 showed the best release profile to achieve the therapeutic reference dose of 3 μg/die, employed in treatment of posterior eye disease, up to four months. Accordingly, PMMA-b-PHEMA 53/47 has been tested to prepare ocular inserts. Ocular inserts with different shape and the same area of polymer films have been obtained using silicon moulds made by a 3D printer.


51) Biobased compostable packaging for fresh-cut cherry tomatoes: performance evaluation and influence of UV sterilization treatment

P.Rizzarelli, M.Rapisarda, C.Patanè, A.Pellegrino, S.La Carta, A.Malvuccio, G.Valenti, V.Rizzo, G.Muratore

XXI IUPAC CHEMRAWN Conference - Solid Urban Waste Management - Rome, April 6-8, 2016   - 2016



52) Shelf life evaluation of fresh-cut globe artichoke packaged in a compostable biobased film

V.Rizzo, G.Sapienza, C.Restuccia, G.Mauromicale, S.Lombardo, R.Pesce, M.Rapisarda, S.Perna, P.Rizzarelli, G.Muratore

VII edizione di SLIM (Shelf Life International Meeting), Monza, Italy, 21-23 ottobre 2015   - 2015



53) Chapter 3. Recent Trends in the Structural Characterization and Degradation of Biodegradable Polymers By Modern Mass Spectrometry

P.Rizzarelli, S.Carroccio

Biodegradable Polymers. Volume 1: Advancement in Biodegradation Study and Applications (Editors: Chih-Chang Chu - Cornell University, Ithaca, NY, USA )   - 2015

Book Description:
These 2 volume books strive to provide to our readers the most up-to-date core information available in the published literature as well as our yet to be published studies with ample illustrations (total 416) on biodegradable polymers. book cover Much of the information used in this book is from the authors' own research activities over the past several decades. These 2 volume books contain a compilation of new developments in the creation and use of biodegradable polymers including the relatively new polymers designed from the ground up (i.e., designing new monomers), the modification of existing biodegradable polymers to achieve particular new goals and functions, new fabrication methods for better efficiency, purity and yields, new engineering methods to formulate existing biodegradable polymers into new physical forms, and new applications of existing or new biodegradable polymers in biomedical and environmental arenas.
These 2 volume books contain a total of 28 chapters grouped under 2 volumes. Volume 1 has a total of 14 chapters and 2 sections: Section I Basic degradation study and phenomenon (6 chapters), and Section II Biomedical and environmental applications (8 chapters). Volume 2 has also 14 chapters, and focuses on newly designed biodegradable polymers, and their formulation into different physical forms. The chapters in both volumes have both new original articles and information and review articles with updated and new information. Although the bulk of the chapters in this book (> 90%) deal with issues in biomedical fields which are far more challenging, demanding, and costly to resolve, two chapters deal with use of biodegradable materials for environmental impacts.
The books are designed for material and polymer scientists and engineers and biomedical engineers in both universities and in industries with an interest in the biomedical field. Biomaterial scientists and engineers, biomedical engineers and even medical professionals who have used implantable polymeric-based medical devices for their practice will find these books coverage of the latest developments and challenges useful either as a comprehensive review or an up to date report of the developments in the field of biodegradable polymers.
The contributors include both academic scientists and research scientists in industry, from 10 different countries in North (USA) and South America (Brazil, Argentina), Asia (China, Korea, Singapore) and Europe (Germany, Italy, Spain, Portugal). Therefore, these 2 volume books are truly internationally as well as multidisciplinary-oriented, covering science and engineering without borders.(Imprint: Nova)


54) Chapter 10. Role of Mass Spectrometry in the Elucidation of Thermal Degradation Mechanisms in Polymeric Materials

P.Rizzarelli, S.Carroccio

Reactions and mechanisms in thermal analysis of advanced materials (Editor(s): Atul Tiwari, Baldev Raj Print ISBN: 9781119117575 Online ISBN: 9781119117711 DOI: 10.1002/9781119117711 )   - 2015

Mass spectrometry (MS) is extensively used for the detection of products originated from degradation processes. book cover Most papers concerning thermal degradation of polymeric materials are based on traditional MS methods, such as pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) and direct pyrolysis mass spectrometry (DPMS). These analyses are based on the estimation of the volatile compounds evolved from pyrolytic reactions. They can be helpful for comparisons of the relative thermal stability, the effects of additives, studies of degradation kinetics, and to propose a degradation mechanism. However, these techniques fail to provide a direct observation of the chemical changes occurring during degradation on a molecular level within the polymer backbone. The more recent MS methods, especially matrix-assisted laser desorption ionisation mass spectrometry (MALDI-MS), revealed great potential in highlighting degradation pathways, since they provide the opportunity to explore the finest structural details. This chapter provides an overview of the MS analytical tools used to investigate thermal degradation mechanisms in macromolecules, trying to answer the crucial question one might ask "Why employ MS techniques for thermal degradation studies of polymeric materials?"


55) N-glycosylation of Chloroviruses: the end of a paradigm

C.De Castro, G.Duncan, I.Agarkova, I.Speciale, L.Sturiale, A.Palmigiano, R.Lanzetta, M.Parrilli, D.Garozzo, A.Molinaro, M.Tonetti, J.L.Van Etten

11th Jenner glycobiology and medicine Symposium, National Centre for Scientific Research (CNRS), Paris, France, 19-21 April 2015   - 2015



56) CSF N-glycan MS profiling may enable early diagnosis in some patients with Alzheimer Disease

L.Sturiale, R.Barone, A.Palmigiano, C.Sanfilippo, F.Le Pira, R.O.Bua, D.Romeo, M.Zappia, D.Garozzo

11th Jenner glycobiology and medicine Symposium, National Centre for Scientific Research (CNRS), Paris, France, 19-21 April 2015    - 2015



57) N-glycomics of tear fluid in patients with Vernal and Atopic Keratoconjunctivitis

A.Messina, C.L.Tosto, A.Palmigiano, L.Sturiale, A.Leonardi, D.Garozzo

11th Jenner glycobiology and medicine Symposium, National Centre for Scientific Research (CNRS), Paris, France, 19-21 April 2015   - 2015



58) Synthesis of block copolymers by ATRP for Drug Delivery System realization

S.La Carta, G.Mazzotti, S.Perna, L.Giorgini, R.Di Gesù, P.Rizzarelli, G.Valenti

XXI National Meeting of Italian Macromolecules Association (AIM),Torino, 14-19 Settembre 2014, Politecnico di Torino  ,  339-342  - 2014



59) Atti AIM 379-382

D.Zampino, G.Isaia, F.Ieva, D.Carbone, G.Recca, T.Ferreri, C.Puglisi, M.Mancuso, R.Zaccone

XXI Convegno Italiano di Scienza e Tecnologia delle Macromolecole (AIM). Torino, 14-19 Settembre 2014  Atti AIM,  379-382  - 2014



60) Tear Fluid N-Glycan Profiling To Investigate Biomarkers In Vernal Keratoconjunctivitis

C.L.Tosto, A.Messina, A.Palmigiano, R.O.Bua, A.Scamporrino, L.Sturiale, A.Leonardi, D.Garozzo

XIV Convegno-Scuola sulla Chimica dei Carboidrati, Pontignano (Si), 22-25 Giugno 2014   - 2014

The tears covering the ocular surface are an important component of the extracellular environment of the superficial epithelial cell layer. Secretory and plasma contributions result in a fluid containing lipids, carbohydrates, proteins, and electrolytes which can affect the activity of the cells of the ocular surface1. Different studies, based on proteomics and glycogene-chips, revealed several tear proteins are glycosylated, such as lacritin and proline rich protein 1. Mucins and carbohydrate-binding proteins were found to be among the most highly expressed glycogenes in human conjunctiva. These glycoproteins play a role in protection against pathogens and prevention of ocular surface desiccation2,3.

figura 1

Figure 1. MALDI-TOF analysis of permethylated N-glycans from control human tear sample

figura 2

Figure 2. MALDI-TOF analysis of permethylated N-glycans from pathological human tear sample

In the present study, we analyze the N-linked glycome of tear fluid from patients affected by vernal keratoconjunctivitis (VKC). VKC is a bilateral, chronic sight-threatening and severe inflammatory ocular disease mainly occurring in children and young male adults. Its predominant symptom is intense ocular itching, associated with tearing, mucous stringy discharge, severe photophobia, blepharospasm and foreign body sensation. Severe and inappropriately treated VKC can lead to severe ocular complications such as corneal ulcers and scarring, corticosteroids-induced glaucoma and visual impairment. To date, no specific laboratory test is suitable for VKC diagnosis and monitoring. Tear samples of VKC patients and control subjects were treated with N-glycosidase F (PNGase F), an enzyme which specifically deglycosylates N-glycoprotein. Released N-glycans are purified and chemically derivatized by permethylation to improve the sensitivity of detection of molecular ions. Samples are analyzed by matrix-assisted laser desorption/ionization-time of flight mass spectrometry (MALDI-TOF-MS). It is a valuable technique for biomarker detection and characterization of defective glycan structures. The eligibility of mass spectrometry for the study of glycosylation is due to its high sensibility and ability to analyze complex mixtures of glycans from biological samples. This approach allowed to distinguish tear fluid glycosylation pattern of VKC patients from control subjects (Figures 1 and 2).

relative area

Spectra show tear fluid is rich in N-glycan structures. Data analysis evidences changes in terms of relative intensities for some structures. Preliminary study suggests the most significant peaks are related to mass to charge ratios 1906.7, 2592.3 and 2765.9. Each one of these three structures to 2966.5 ratios reveal meaningful changes between healthy and pathological conditions, as evidenced by the following histogram: These peaks could be used as potential biomarkers for VKC disease. Further structural characterization of the disease-associated N-glycans could confirm these preliminary results and allow to discover additional biomarkers.

  1. 1) Zhou L., Beuerman R. W., Foo Y., Liu S., Ang L. P., Tan D. T. "Characterisation of human tear proteins using high-resolution mass spectrometry". Ann. Acad. Med. Singapore 2006, 35 (6), 400-407
  2. 2) Li N., Wang N., Zheng J., Liu X. M., Lever O. W., Erickson P. M., Li L. A. "Characterization of human tear proteome using multiple proteomic analysis techniques". J. Proteome Res. 2005, 4 (6), 2052-2061
  3. 3) Argüeso P. "Glycobiology of the ocular surface: mucins and lectins". Jpn J Ophthalmol. 2013 Mar, 57(2), 150-155


61) Tay-Sachs CSF N-Glycan Profile by MALDI MS Reveals Incomplete Glycosylation

A.Scamporrino, A.Palmigiano, R.O.Bua, A.Messina, C.L.Tosto, A.Fiumara, R.Barone, L.Sturiale, D.Garozzo

XIV Convegno-Scuola sulla Chimica dei Carboidrati, Pontignano (Si), 22-25 Giugno 2014   - 2014



62) Red blood cell N-glycan profiling by MALDI-MS

R.O.Bua, C.L.Tosto, A.Palmigiano, A.Scamporrino, A.Messina, R.Barone, L.Sturiale, D.Garozzo

XIV Convegno-Scuola sulla Chimica dei Carboidrati, Pontignano (Si), 22-25 Giugno 2014   - 2014

Protein glycosylation is one of the most common post-translational modifications in mammalian cells, estimated to be found on over 50% of all human proteins. Changes in N-linked glycosylation have long been associated with disease development, and acquired glycan modifications have been described in multifactor diseases such as cancer and inflammatory disorders. The characterization of protein glycosylation is often a challenge due to the heterogeneity of glycoforms. MS-based methods are capable of structural characterization of unknown glycans and high-throughput analysis of known glycan structures. Due to the advancement in MS techniques, MALDI-TOF mass spectrometry has become an eligible technique for the study of glycan populations derived from biological samples (1). As red blood cell (RBC) glycosylated membrane proteins can be directly isolated from blood, purified and readily available, glycosylation analysis of erythrocyte membrane glycoproteins might be the key for detection of glyco-biomarkers for diagnostic and therapeutic purposes. There are few studies that investigated N-glycosylation of erythrocyte membrane glycoproteins using MS techniques, all referred to congenital dyserythropoietic anemia type II (CDA II), also called hereditary erythroblastic multinuclearity with positive acidified-serum test (HEMPAS). Fukunda et al. (2) in 1987 developed a method based on fast-atom bombardment (FAB) MS, whereas Denecke et al. (3) in 2008 compared erythrocyte band 3 mass mapping from HEMPAS with that from control by MALDI-TOF MS following SDS-PAGE and lectin-binding strategies. Both of these studies found accordingly unprocessed oligosaccharides (high mannose, hybrid, and truncated complex species) in the red blood cell membrane glycoproteins from HEMPAS patients suggesting the disease is caused by a defect disturbing Golgi processing in erythroblasts. In the present study, we reported the application of high-sensitivity MALDI MS-based glycomic methodologies to the analysis of N-linked glycans derived from human erythrocyte membrane proteins in order to produce a fingerprint of erythrocyte N-glycans. The obtained spectrum (see figure) contains a full complement of high-mannose type structures and a series of complex glycans comprising a mixture of bi- tri- and tetra-antennary structures. The main peaks correspond to fucosylated mono and disialo- biantennary oligosaccharides with bisecting N-acetylglucosamine (GlcNAc). Moreover, due to the extension of lactosamine repeating units, glycans larger than 8 kDa were detected. Our developed MS strategy led to a considerable improvement in upper mass range sensitivity and in signal-to-noise ratio, in addition to a substantive increases in resolution of MALDI-TOF mass spectra, allowing the detailed mapping of N-glycans derived from human erythrocyte membrane proteins. These results could provide a new tool to detect potential biomarkers, or allow the recognition of distinct glycosylation changes associated with disease conditions.
  • 1) Barone R, Sturiale L, Garozzo D. 2009. Mass spectrometry in the characterization of human genetic N- glycosylation defects. Mass Spectrometry Reviews 28:517-542.
  • 2) Fukuda MN, Dell A, Scartezzini P. 1987. Primary Defect of Congenital Dyserythropoietic Anemia Type II. Failure in glycosylation of erythrocyte lactosaminoglycan protein caused by lowered N-acetyl-glycosaminyltrasferase II. JBC 262:7195-7206
  • 3) Denecke J, Kranz C, Nimtz M, Conradt HS, Brune T, Heimpel H, Marquardt T. 2008. Characterization of N- glycosylation phenotype of erythrocyte membrane proteins in congenital dyserythropoietic anemia type II (CDA II/HEMPAS). Glycoconj J. 25:375-382



63) Cerebrospinal Fluid N-Glycomics May Enable Early Diagnosis in Alzheimer Disease

A.Palmigiano, R.O.Bua, A.Messina, C.L.Tosto, A.Scamporrino, L.Sturiale, R.Barone, F.Le Pira, M.Zappia, D.Garozzo

XIV Convegno-Scuola sulla Chimica dei Carboidrati, Pontignano (Si), 22-25 Giugno 2014   - 2014

The ability to predict the conversion from MCI to AD is one of the most important research topic in the field of neurodegenerative diseases; in particular it may represent an useful method for the diagnosis of early stages of AD. Several studies have been made in this regard by exploiting the diagnostic power of various predictors as: functional and neuropsychological measures, CSF biomarkers (ρTau, Aβ 42), magnetic resonance imaging data (MRI). In our study we compare MALDI MS CSF N-glycan profiles from eight control subjects, 11 MCI and 25 AD patients. Control spectra were characterized by a base peak at 2792 m/z corresponding to a biantennary A2 complex N-glycan. AD glycol-profiles were classified according to the ratio of NGA2FB/A2 glycans: we named AD1 profiles those characterized by a NGA2FB to A2 quotient over 50% (11 AD patients). AD2 profiles (14 AD patients) exhibited glycosylation patterns with a NGA2FB relative intensity below 50%. Of particular note, these last patients gave, in the majority of cases, a glycosylation ratio below the mean value from controls (36.06 ± 5.47). Interestingly, MCI patients exhibiting AD1 spectra profile conversed to AD (5 patients out of 6, the 6th patient refused monitoring) while MCI patients showing AD2 spectra profile don’t converse to AD (no conversion for 5 patients out of 5). CSF N-glycome profile could shed new light on the different mechanisms that lead to the development of AD even if those mechanism are still unclear.


64) N-Linked Glycans From PBCV-1 and Related Viruses Have A New Type Of Core Region

I.Speciale, D.Garozzo, J.R.Gurnon, R.Lanzetta, A.Molinaro, A.Palmigiano, M.Parrilli, F.Piacente, L.Sturiale, M.G.Tonetti, J.L.Van Etten, C.De Castro

XIV Convegno-Scuola sulla Chimica dei Carboidrati, Pontignano (Si), 22-25 Giugno 2014   - 2014



65) Glycomics of central nervous system diseases (CNS): from monogenic to multifactorial disorders

R.Barone

XIV Convegno-Scuola sulla Chimica dei Carboidrati, Pontignano (Si), 22-25 Giugno 2014   - 2014



66) Spettrometria di Massa MALDI ed ESI per l’analisi dei polimeri in soluzione

S.Carroccio, P.Rizzarelli

"CARATTERIZZAZIONE DI MATERIALI POLIMERICI. Tecniche per polimeri in soluzione". Nuova Cultura (Collana AIM quaderni, ISBN: 9788868123048. DOI: 10.4458/3048)   - 2014

book cover



67) Spettrometria di Massa MALDI ed ESI per l’analisi dei polimeri in soluzione - II parte

P.Rizzarelli

XXXV Convegno-Scuola AIM "Mario Farina" "CARATTERIZZAZIONE DI MATERIALI POLIMERICI: Tecniche per polimeri in soluzione". (19-23 Maggio 2014, Gargnano -Brescia)   - 2014



68) Reversible Polymerization Techniques Leading to π-Stacked Polymers

A.Cappelli , M.Paolino, G.Grisci, G.Giuliani, A.Donati, A.C.Boccia, F.Samperi, R.Mendichi, S.Vomero

π-Stacked Polymers and Molecules  ,  51-149  - 2013

Serendipity has often played a pivotal role in research and, in harmony with this function, it has had a fundamental responsibility in the discovery of the thermoreversible spontaneous polymerization of benzofulvene derivatives.book cover After a decade from the discovery of poly-BF1, the present chapter narrates the history of polybenzofulvene derivatives from the discovery to the latest developments. Now that more than 50 polymers belonging to this family have been synthesized and the relevant studies have been published in the most important journals dealing with polymer science, the spontaneous polymerization of benzofulvene monomers and the special features of the corresponding polymers appear to become a well-established topic. The chapter provides an in-depth analysis of the literature on the subject, from the preparation methods to the characterization of polybenzofulvene derivatives, the study of their properties, and the evaluation of the possible applications.


69) Imidazolium ionic liquigas as antimicrobial additives of biomedical PVC

D.Zampino, C.Prinzivalli, R.Di Gesù, G.Isaia, F.Ieva, D.Carbone, G.Recca, T.Ferreri, C.Puglisi, M.Mancuso, R.Zaccone

EUPOC 2013 on Polymers & Ionic Liquids. Gargnano-Lake Garda (Italy), 1-5 September 2013   - 2013



70) Plasticizer influence on silver release from PVC composites

D.Zampino, T.Ferreri, C.Puglisi, M.Mancuso, R.Zaccone

European Polymer Congress EPF 2013. Pisa - (Italy), 16-21 June 2013   - 2013



71) Antimicrobial PVC silver zeolite composites: Plasticizers influence

D.Zampino, T.Ferreri, C.Puglisi, M.Mancuso, R.Zaccone

Third International Symposium Frontiers in Polymer Science (21-23 May 2013, Sitges, Barcellona - Spagna)   - 2013



72) Functionalized bio-polyesters by nitroxide radical coupling

S.Coiai, F.Cicogna, I.Domenichelli, P.Rizzarelli, C.Gambarotti, N.Tz Dintcheva, G.Filippone, E.Passaglia

EPF (16-21 Giugno 2013 Pisa)   - 2013



73) Synthesis of Block Copolymers by ATRP for Biomedical application

L.Ferreri, P.Rizzarelli, S.Carroccio, S.Perna, S.La Carta

EPF (16-21 Giugno 2013 Pisa)   - 2013

Atom Transfer Radical Polymerization (ATRP) has emerged as a versatile and convenient synthetic techniques for the preparation of polymers and copolymers with predetermined molecular weights, low polydispersities (<1.3) and high degrees of chain end functionalities. ATRP permits to design multifunctional, nanostructured materials for a variety of applications in biology and medicine. Block methacrylate based copolymers having well defined structures are interesting for their morphological, phase, and mechanical properties. In particular, copolymer with a balance of hydrophilic and hydrophobic properties can be suitable for prolonged drug delivery systems in biomedical devices [1]. In this synthetic approach terminal bromine and/or chloride bearing polymethacrylates can be purified and used as macroinitiators for consecutive ATRP, yielding amphiphilic block copolymers. The synthesis of methacrylate macroinitators as well as block acrylate and methacrylate copolymers by ATRP were carried out using various combinations of catalyst systems (CuCl and CuBr), ligands (N,N,N’,N’’,N’’-Pentamethyldiethylenetriamine, PMDETA and Tris[2-(dimethylamino)ethyl]amine, Me6Tren) and initiators (Ethyl-α- bromoisobutyrate, Ethylene bis (2-bromo isobutyrate). The obtained materials were characterized by using Size Exclusion Chromatography (SEC), Matrix Assisted Laser Desorption Ionization Time of flight mass spectrometry (MALDI-ToF-MS) and Nuclear Magnetic Resonance (NMR). In addition, differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) measurements were also performed. SEC analysis confirmed a good correlation between the theoretical and experimental molar mass values (MMs) and a low PDI (1.1-1.3). Structural characterization performed by MALDI-ToF-MS has provided information about chain end functionalities and MMs. Experimental data were in agreement with SEC values for samples with molecular weights up to 15000. 1H-NMR was used to determine conversion, purity and composition of copolymers Atom Transfer Radical Polymerization (ATRP) has emerged as a versatile and convenient synthetic techniques for the preparation of polymers and copolymers with predetermined molecular weights, low polydispersities (<1.3) and high degrees of chain end functionalities. ATRP permits to design multifunctional, nanostructured materials for a variety of applications in biology and medicine. Block methacrylate based copolymers having well defined structures are interesting for their morphological, phase, and mechanical properties. In particular, copolymer with a balance of hydrophilic and hydrophobic properties can be suitable for prolonged drug delivery systems in biomedical devices [1]. In this synthetic approach terminal bromine and/or chloride bearing polymethacrylates can be purified and used as macroinitiators for consecutive ATRP, yielding amphiphilic block copolymers. The synthesis of methacrylate macroinitators as well as block acrylate and methacrylate copolymers by ATRP were carried out using various combinations of catalyst systems (CuCl and CuBr), ligands (N,N,N’,N’’,N’’-Pentamethyldiethylenetriamine, PMDETA and Tris[2-(dimethylamino)ethyl]amine, Me6Tren) and initiators (Ethyl-α- bromoisobutyrate, Ethylene bis (2-bromo isobutyrate). The obtained materials were characterized by using Size Exclusion Chromatography (SEC), Matrix Assisted Laser Desorption Ionization Time of flight mass spectrometry (MALDI-ToF-MS) and Nuclear Magnetic Resonance (NMR). In addition, differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) measurements were also performed. SEC analysis confirmed a good correlation between the theoretical and experimental molar mass values (MMs) and a low PDI (1.1-1.3). Structural characterization performed by MALDI-ToF-MS has provided information about chain end functionalities and MMs. Experimental data were in agreement with SEC values for samples with molecular weights up to 15000. 1H-NMR was used to determine conversion, purity and composition of copolymers Atom Transfer Radical Polymerization (ATRP) has emerged as a versatile and convenient synthetic techniques for the preparation of polymers and copolymers with predetermined molecular weights, low polydispersities (<1.3) and high degrees of chain end functionalities. ATRP permits to design multifunctional, nanostructured materials for a variety of applications in biology and medicine. Block methacrylate based copolymers having well defined structures are interesting for their morphological, phase, and mechanical properties. In particular, copolymer with a balance of hydrophilic and hydrophobic properties can be suitable for prolonged drug delivery systems in biomedical devices [1]. In this synthetic approach terminal bromine and/or chloride bearing polymethacrylates can be purified and used as macroinitiators for consecutive ATRP, yielding amphiphilic block copolymers. The synthesis of methacrylate macroinitators as well as block acrylate and methacrylate copolymers by ATRP were carried out using various combinations of catalyst systems (CuCl and CuBr), ligands (N,N,N’,N’’,N’’-Pentamethyldiethylenetriamine, PMDETA and Tris[2-(dimethylamino)ethyl]amine, Me6Tren) and initiators (Ethyl-α- bromoisobutyrate, Ethylene bis (2-bromo isobutyrate). The obtained materials were characterized by using Size Exclusion Chromatography (SEC), Matrix Assisted Laser Desorption Ionization Time of flight mass spectrometry (MALDI-ToF-MS) and Nuclear Magnetic Resonance (NMR). In addition, differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) measurements were also performed. SEC analysis confirmed a good correlation between the theoretical and experimental molar mass values (MMs) and a low PDI (1.1-1.3). Structural characterization performed by MALDI-ToF-MS has provided information about chain end functionalities and MMs. Experimental data were in agreement with SEC values for samples with molecular weights up to 15000. 1H-NMR was used to determine conversion, purity and composition of copolymers


74) A Snapshot of Thermo-Oxidative Degradation Products in Poly(bisphenol A carbonate) by ESI and MALDI Mass Spectrometry

S.Carroccio, P.Rizzarelli, D.Zampino

Third International Symposium Frontiers in Polymer Science (21-23 May 2013, Sitges -Barcellona, Spagna)   - 2013



75) CSF N-GLYCANS PROFILES TO INVESTIGATE BIOMARKERS IN ALZHEIMER’S DISEASE

A.Palmigiano, R.Barone, C.Tosto, R.O.Bua, L.Sturiale, F.Le Pira, M.Zappia, D.Garozzo

17th European Carbohydrate Symposium (July 7 -11 2013 Tel-Aviv, Israel)   - 2013

Alzheimer’s disease (AD) is the most common cause of dementia in the elderly, it’s a progressive, irreversible, degenerative brain disorder, resulting in memory, thinking and behavior impairments; the causes of AD are currently being researched but no definite answer exists yet, moreover there’s a lack of accurate diagnostic method for AD [1].
The composition of Cerebrospinal fluid (CSF) is rapidly and directly influenced by the brain, so CSF represents an appealing source for diagnostic biomarkers potentially able to describe neuropathological state and trajectory [2].
CSF N-glycans are characterized by large portions of bisecting N-acetylglucosammine while in blood such glycoforms cannot persist due to the existence of specific hepatic clearance mechanisms. Bisecting N-glycans are so called "brain type"[3]. Elevated expression levels of N-acetylglucosaminyl transferase III (GnT-III), the glycosyltransferase responsible for synthesizing a bisecting GlcNAc residue, may have a protective effect on β-amyloid production in AD [4].
We have analyzed a total of 35 individual CSF samples: 10 controls (from patients who underwent to minor orthopedic surgery), 13 AD samples and 12 from other neurodegenerative diseases such as mild cognitive impairment (MCI), Parkinson’s disease (PD) and Tay-Sachs disease. The number of analyzed samples is still limited but there are important differences between pathological and control spectra with a dramatic enhancement of bisecting structures in AD patients’ spectra expecially for the fucosylated ones. In particular NGA2FB glycan (asyalo, agalacto, bisected biantennary fucosylated) is over-expressed in AD patients. In order to differentiate between isobaric serum and brain type N-glycan structures we perform a target MALDI MSMS analysis.
[1] R. Barone et al. Journal of Proteomics 75, 5123-5139, 2012
[2] R.J. Perrin et al. PLoS ONE 6, 1, e16032
[3] A. Hoffmann et al. FEBS Letters 359, 164-168, 1995
[4] K. Akasaka-Manya et al. Glycobiology 20, 1, 99-106, 2010


76) CSF N-GLYCANS PROFILES TO INVESTIGATE BIOMARKERS IN ALZHEIMER’S DISEASE

A.Palmigiano, R.Barone, C.Tosto, R.O.Bua, L.Sturiale, F.Le Pira, M.Zappia, D.Garozzo

International symphosium on chemical glycobiology (June 29-July 1 2013 Shanghai, China)   - 2013

Alzheimer’s disease (AD) is the most common cause of dementia in the elderly, it’s a progressive, irreversible, degenerative brain disorder, resulting in memory, thinking and behavior impairments; the causes of AD are currently being researched but no definite answer exists yet, moreover there’s a lack of accurate diagnostic method for AD [1]. The composition of Cerebrospinal fluid (CSF) is rapidly and directly influenced by the brain, so CSF represents an appealing source for diagnostic biomarkers potentially able to describe neuropathological state and trajectory [2]. CSF N-glycans are characterized by large portions of bisecting N-acetylglucosammine while in blood such glycoforms cannot persist due to the existence of specific hepatic clearance mechanisms. Bisecting N-glycans are so called "brain type"[3]. Elevated expression levels of N-acetylglucosaminyl transferase III (GnT-III), the glycosyltransferase responsible for synthesizing a bisecting GlcNAc residue, may have a protective effect on β-amyloid production in AD [4]. We have analyzed a total of 35 individual CSF samples: 10 controls (from patients who underwent to minor orthopedic surgery), 13 AD samples and 12 from other neurodegenerative diseases such as mild cognitive impairment (MCI), Parkinson’s disease (PD) and Tay-Sachs disease. The number of analyzed samples is still limited but there are important differences between pathological and control spectra with a dramatic enhancement of bisecting structures in AD patients’ spectra expecially for the fucosylated ones. In particular NGA2FB glycan (asyalo, agalacto, bisected biantennary fucosylated) is over-expressed in AD patients. In order to differentiate between isobaric serum and brain type N-glycan structures we perform a target MALDI MSMS analysis.


77) Structure of very unusual N-Glycans Associated with the Major Capsid Protein of Chlorovirus PBCV-1: Nature can synthesize a different class of complex N-Glycans

C.De Castro, A.Molinaro, M.Tonetti, J.Gurnonc, L.Sturiale, A.Palmigiano, D.Garozzo, J. L. Van Etten

International symphosium on chemical glycobiology (June 29-July 1 2013 Shanghai, China)   - 2013

The envelope protein Vp54 from the prototype chlorovirus, Paramecium bursaria chlorella virus (PBCV-1) comprises ~40% of total virus protein and presents four N-glycosylated sites. In depth chemical, spectroscopical, and spectrometrical analysis has disclosed the structure of four different N-linked oligosaccharides and the type of substitution at each glycosylation site. Vp54 glycosylation is unusual in many respects: i) a β-glucose, and not an aminosugar, is connected to the protein, ii) N-linked glycans are not located in a typical N-X-(T/S) consensus site, iii) four glycoforms are present. The structure of four glycoforms share a common core region and differences are related to the non-stoichiometric presence of two monosaccharides. The more abundant species comprises nine neutral monosaccharide residues, organized in a highly branched fashion; among the most relevant features, a dimethylated rhamnose as capping residue of the main chain, a hyperbranched fucose unit, and two rhamnose residues with opposite absolute configuration deserve to be mentioned. This protein glycosylation is new and different from what so far reported in the three domains of life. Considering that Chloroviruses and other members of the family Phycodnaviridae have a long evolutionary history possibly dating back to the time when eukaryotes arose from prokaryotes, we suggest that the chlorovirus glycosylation pathway is ancient, possibly existing prior to the development of the ER and Golgi, and involves new and still unexplored mechanisms.


78) Mannosidase I deficiency: An unexpected CDG-II with intellectual disability and dysmorphic features

G.Matthijs, D.Rymen, R.Péanne, V.Race, L.Sturiale, D.Garozzo, P.Mills, P.Clayton, J.Jaeken, F.Foulquier

European Human Genetics Conference 2013 location:Paris, France (June 8-11, 2013)  21,  29-29  - 2013



79) Bone Dysplasia as a Key Feature in Three Patients with a Novel Congenital Disorder of Glycosylation (CDG) Type II Due to a Deep Intronic Splice Mutation in TMEM165

R.Zeevaert,F.De Zegher, L.Sturiale, D.Garozzo, M.Smet, M.Moens, G.Matthijs, J. Jaeken

JIMD Reports  8,  145-152  - 2013

Three patients belonging to two families presented with a psychomotor-dysmorphism syndrome including postnatal growth deficiency and major spondylo-, epi-, and metaphyseal skeletal involvement. book cover Other features were muscular hypotrophy, fat excess, partial growth hormone deficiency, and, in two of the three patients, episodes of unexplained fever. Additional investigations showed mild to moderate increases of serum transaminases (particularly of aspartate transaminase (AST)), creatine kinase (CK), and lactate dehydrogenase (LDH), as well as decreased coagulation factors VIII, IX, XI, and protein C. Diagnostic work-up revealed a type 2 serum transferrin isoelectrofocusing (IEF) pattern and a cathodal shift on apolipoprotein C-III IEF pointing to a combined N- and O-glycosylation defect. Known glycosylation disorders with similar N-glycan structures lacking galactose and sialic acid were excluded. Through a combination of homozygosity mapping and expression profiling, a deep intronic homozygous mutation (c.792 + 182G>A) was found in TMEM165 (TPARL) in the three patients. TMEM165 is a gene of unknown function, possibly involved in Golgi proton/calcium transport. Here we present a detailed clinical description of the three patients with this mutation. The TMEM165 deficiency represents a novel type of CDG (TMEM165-CDG). This disorder enlarges the group of CDG caused by deficiencies in proteins that are not specifically involved in glycosylation but that have functions in the organization and homeostasis of the intracellular compartments and the secretory pathway, like COG-CDG and ATP6V0A2-CDG.


80) Thermo-oxidative degradation products in poly(bisphenol A carbonate) by ESI and MALDI Mass Spectrometry

S.Carroccio, P.Rizzarelli, D.Zampino

MoDeSt (Praga 2-6 Settembre 2012)   - 2012



81) Polymers

M.S.Montaudo, S.Battiato

Mass Spectrometry Handbook  Chapter 45,  1079-1105  - 2012

book cover



82) Maldi mass spectrometry for the structural investigation of intact lipopolysaccharides

A.Silipo, A.Molinaro, R.Lanzetta, M.Parrilli, L.Sturiale, A.Messina, A.Palmigiano, D.Garozzo, A.Scamporrino

Atti XIII Convegno-Scuola sulla Chimica dei Carboidrati 24-27 giugno 2012 Certosa di Pontignano (Siena)  ,  PC-19  - 2012

Lipopoligosaccharides (LPS) are powerful Gram-negative glycolipids that evade the immune system and invade host animal and vegetal cells. The structural elucidation of LPS is pivotal to understanding the mechanisms of infection at the molecular level. The structural nature of LOS has been the main obstacle for structural analysis by matrix-assisted laser desorption/ ionization (MALDI) mass spectrometry (MS). Recently1,2, we have published strategies able to obtain MALDI mass spectra of Lipooligosaccharides (LOS) to reveal the fine chemical structure with minimal structural variations. The high-quality MALDI mass spectra show LOS species characteristic of molecular ions and defined fragments due to decay in the ion source. The in-source decay yields B-type ions, which correspond to core oligosaccharide(s), and Y-type ions, which are related to lipid A unit(s). MALDI tandem time-of-flight (TOF/TOF) MS of lipid A allowed for the elucidation of its structure directly from purified intact LOS without the need for any chemical manipulations. These findings constitute a significant advancement in the analysis of such an important biomolecule by MALDI MS. Here, we?ll show our preliminary results on MALDI MS of intact LPS. From these spectra (figure 1) it is possible to obtain the mw of the lipid a moiety, of the core oligosaccharides and of the o-chain repeating unit.

Graphical Abstract

Graphical Abstract



83) The Impact of Mass Spectrometry in the Diagnosis of Congenital Disorders of Glycosylation

L.Sturiale

Atti XIII Convegno-Scuola sulla Chimica dei Carboidrati 24-27 giugno 2012 Certosa di Pontignano (Siena)  ,  PL-5  - 2012

Congenital Disorders of Glycosylation (CDG) comprise an expanding group of autosomal inherited metabolic diseases due to defects in the biosynthesis of the glycan moiety of glycoproteins or glycolipids, in the attachment of these structures to the nascent glycoconjugates and in their processing. To date, some 45 CDG types have been described, based on their specific glycosylation defect. As this number is expected to rise in the short-term, a practical classification encompassing all the known and the upcoming CDG has been recently proposed. It includes four categories, namely (i) defects of protein N-glycosylation, (ii) defects of protein O-glycosylation, (iii) defects of lipid glycosylation and of GPI anchor glycosylation, (iv) defects in multiple glycosylation pathways and in other pathways [1; 2]. Deficiencies caused by mutations in the glycosylation pathway of glycoproteins are often associated to multisystemic phenotypes with a prominent nervous system involvement. CDG diagnosis is not straightforward for the clinicians, due to the heterogeneity of the clinical signs and to the large number of candidate genes involved. Moreover, secondary causes leading to defective glycosylation may complicate the identification of CDG affected patients. Thus, amelioration and diversification of the diagnostic tools, including the contribution of MS-based strategies, are among the primary requests. ESI MS and MALDI MS of intact serum glycoproteins are found effective to detect the partial or total absence of complete oligosaccharide moieties on N-glycosylation sites. These methods, when applied to plasma transferrin (the main glyco-biomarker for CDG, bearing two biantennary complex N-glycans) allow to identify glycosylation defects occurring in the cytosol or in the endoplasmic reticulum (CDG type I) [3, 4]. Also, MALDI MS profiling of N-linked glycans released from total plasma or from targeted biomarkers such as transferrin, provide an outstanding useful method to identify hypoglycosylation due to truncated oligosaccharide structures originated from an improper glycosylation processing in the Golgi apparatus (CDG type II) [3-5]. In some cases this analysis may reveal specific patterns with the accumulation of distinct Golgi glycan intermediates, thus suggesting a possible glycosylation defect [1, 5]. This lecture illustrates state-of-the-art, updates and compelling applications of the main mass spectrometric approaches utilized in the diagnosis and characterization of CDG.


84) Identification of N-Glycosylation in the CSF in Patients with Neurodegenerative diseases

A.Palmigiano, R.Barone, M.Zappia, L.Sturiale, D.Garozzo

Atti XIII Convegno-Scuola sulla Chimica dei Carboidrati 24-27 giugno 2012 Certosa di Pontignano (Siena)  ,  OC-15  - 2012

Neurodegenerative diseases are defined as hereditary and sporadic conditions which are characterized by progressive nervous system dysfunction. These disorders are often associated with atrophy of the affected central or peripheral structures of the nervous system. They include diseases such as Alzheimer’s Disease and other dementias, Brain Cancer, Degenerative Nerve Diseases, Encephalitis, Epilepsy, Genetic Brain Disorders, Head and Brain Malformations, Hydrocephalus, Stroke, Parkinson’s Disease, Multiple Sclerosis, Amyotrophic Lateral Sclerosis (ALS or Lou Gehrig’s Disease), Huntington’s Disease, Prion Diseases, Creutzfeld-Jakob disease (CJD) and others. The prevalence of neurodegenerative disorders is increasing, but diagnostic biomarkers and effective treatments are lacking. Cerebrospinal fluid (CSF) is produced from the choroid plexus within the ventricles of the brain and circulates through the ventricular system and around the outside of brain; because its composition is rapidly and directly influenced by the brain, CSF represents an appealing source for diagnostic biomarkers. Glycosylation is one of the most common and most complex post-translational modifications (PTMs) of secreted and cell surface proteins and plays a critical role in protein-protein, protein-cell, and cell-cell interactions including antibody binding, protein degradation, cellular endocytosis, and protease protection. Glycosylation is cell-type specific and reproducible for a given physiological state. Glycoproteins occur usually as a collection of glycoforms that differ in the structure of the component oligosaccharides. Glycoform abundance and glycan structures can be altered significantly in disease, resulting in a characteristic signature as a means of investigating complex pathophysiological processes and revealing novel biomarkers and drug targets. Here we describe a promising strategy for discovering N-glycan biomarkers in individual CSF in patients with neurodegenerative diseases based on analyzing total glycan profiles rather than the sugars on particular glycoproteins.


85) Identification of N-Glycosylation in the CSF in Patients with Alzheimer’s disease by MALDI Mass Spectrometry

A.Palmigiano, R.Barone, M.Zappia, L.Sturiale, D.Garozzo

Massa 2012 Congresso della Divisione di Spettrometria di Massa della Società Chimica Italiana (SCI) 1-5 Luglio 2012, Mondello (PA)   - 2012

Neurodegenerative diseases are defined as hereditary and sporadic conditions which are characterized by progressive nervous system dysfunction. These disorders are often associated with atrophy of the affected central or peripheral structures of the nervous system. They include diseases such as Alzheimer’s Disease and other dementias, Brain Cancer, Degenerative Nerve Diseases, Encephalitis, Epilepsy, Genetic Brain Disorders, Head and Brain Malformations, Hydrocephalus, Stroke, Parkinson's Disease, Multiple Sclerosis, Amyotrophic Lateral Sclerosis (ALS or Lou Gehrig's Disease), Huntington’s Disease, Prion Diseases, Creutzfeld-Jakob disease (CJD) and others. The prevalence of neurodegenerative disorders is increasing, but diagnostic biomarkers and effective treatments are lacking. Cerebrospinal fluid (CSF) is produced from the choroid plexus within the ventricles of the brain and circulates through the ventricular system and around the outside of brain; because its composition is rapidly and directly influenced by the brain, CSF represents an appealing source for diagnostic biomarkers. Glycosylation is one of the most common and most complex post-translational modifications (PTMs) of secreted and cell surface proteins and plays a critical role in protein-protein, protein-cell, and cell-cell interactions including antibody binding, protein degradation, cellular endocytosis, and protease protection. Glycosylation is cell-type specific and reproducible for a given physiological state. Glycoproteins occur usually as a collection of glycoforms that differ in the structure of the component oligosaccharides. Glycoform abundance and glycan structures can be altered significantly in disease, resulting in a characteristic signature as a means of investigating complex pathophysiological processes and revealing novel biomarkers and drug targets. Here we describe a promising strategy for discovering N-glycan biomarkers in individual CSF in patients with neurodegenerative diseases based on analyzing total glycan profiles rather than the sugars on particular glycoproteins.


86) Deficiency of Subunit 6 of the Conserved Oligomeric Golgi Complex (COG6-CDG): Second Patient, Different Phenotype

S.Huybrechts, C.De Laet, P.Bontems, S.Rooze, H.Souayah, Y.Sznajer, L.Sturiale, D.Garozzo, G.Matthijs, A.Ferster, J.Jaeken, P.Goyens

JIMD Reports  4,  103-108  - 2012

We describe a 27-month-old girl with COG6 deficiency. She is the first child of healthy consanguineous Moroccan parents. book cover She presented at birth with dysmorphic features including microcephaly, post-axial polydactyly, broad palpebral fissures, retrognathia, and anal anteposition. The clinical phenotype was further characterised by multiorgan involvement including mild psychomotor retardation, and microcephaly, chronic inflammatory bowel disease, micronodular liver cirrhosis, associated with lifethreatening and recurrent infections due to combined T- and B-cell dysfunction and neutrophil dysfunction. Mutation analysis showed the patient to be homozygous for the c.G1646T mutation in the COG6 gene. She is the second reported patient with a deficiency of subunit 6 of the COG complex. Although both patients are homozygous for the same mutation, they present a markedly different clinical picture. Indeed immunodeficiency as well as inflammatory bowel disease has not been described previously in patients with any COG-CDG.


87) Combined techniques for the characterization of linear hyperbranched hybrid PBA copolymers

L.Ascione, V.Ambrogi, C.Carfagna, S.Battiato, C.Puglisi, A.Scamporrino, F.Samperi

XX Convegno Italiano di Scienza e Tecnologia delle Macromolecole (AIM) TERNI 4 - 8 Settembre 2011   - 2011

Linear-hyperbranched hybrid poly(butylene adipate) copolymers (HPBA)s were synthesized through a branching reaction between the linear tailored pre-polymer terminated with methyl ester groups and different mol percents of the 1,1,1-tris(hydroxymethyl) propane (TMP) as branching agent, using the titanium(IV) isopropoxide (TIP) as catalyst, at 180 °C under vacuum for different time. All samples were characterized by NMR and MALDI-TOF Mass Spectrometry (MALDI-TOF MS). In particular, MALDI-TOF mass spectra of the unfractionated and SEC-fractionated hyperbranched (HB) samples gave information on their composition, on the end groups as well as on the TMP units present in each family of HB macromolecules. HB chains containing cyclic branches and ether bonds formed by inter-molecular trans-esterification and (intra and inter)-molecular trans-etherification side reactions, respectively, were also revealed by MALDI-TOF MS analysis. All samples were also investigated by size exclusion chromatography (SEC) and differential scanning calorimeter (DSC) tools. The average molar masses (MM) evaluated by SEC calibrated with the polystyrene (PS) narrow standards were overestimated with respect to those calculated by the SEC/MALDI-TOF MS self-calibration method, which gave reliable values. Moreover, it also showed that the hydrodynamic volume of the HPBA polymers was higher than that of the linear (PS)s with similar MM. DSC data showed that all (HPBA)s exhibited a glass transition (Tg) in the temperature range of linear poly(butylene adipate) (PBA) (-56 °C) and two melting points (Tm), whose values were dependent on the TMP content and the reaction time.


88) Synthesis and characterization of sulfonated copolyethersulphones (S-PES) having block of unsolfonated PES units

A.Scamporrino, F.Samperi, G.Cicala, R.Mendichi

XX Convegno Italiano di Scienza e Tecnologia delle Macromolecole (AIM) TERNI 4 - 8 Settembre 2011   - 2011

Polyethersulphones are a class of polyaromatics of high importance for special applications which includes toughening modifiers for epoxy resins, adhesives for metal to metal bonding, membranes for separate gaseous and solid substances and membranes for fuel cells (PEMFC). In the field of PEMFC perfluorosulfonic acid ionomers such as Nafion® and Flemion® have made a great breakthrough, and sulfonated polyethersulphones (S-PES) constitute an alternative promising class of materials owing of their high mechanical strength and high chemical, thermal and oxidative stabilities. The present contribute deals with the synthesis and characterization of some sulfonated copolyethersulphones. The synthetic approach differs from the post sulfonation approach traditionally reported in the literature, it is based on the use of sulfonated monomers which are then reacted with previously synthesized telechelic hydoxy-ended poly(ether sulphone)s. Combining the MALDI-TOF MS and 1H-NMR analyses, with SEC-Viscometry and TGA measurements, we demonstrate a powerful tool to characterize the chemical composition, end chains, degree of sulfonation and molecular mass distribution of disulfonated poly(arylene ether sulfone) copolymers


89) Combined techniques for the characterization of polyfluorene copolymers and correlaction whit their optical properties. Part 1

F.Samperi, S.Battiato, C.Puglisi, S.Destri, U.Giovanella, M.C.Pasini, R.Mendichi

XX Convegno Italiano di Scienza e Tecnologia delle Macromolecole (AIM) TERNI 4 - 8 Settembre 2011   - 2011

The energy demand is continuously growing up while the present energy sources are largely pollutant and limited. Hence, it is mandatory both to find out new alternative sources and try to reduce energy consumption. In this view the preparation of conjugated polymeric materials and their deep characterization becomes more and more important in order to correlate molecular properties with the optoelectronic ones. In this contribute polyfluorenes are considered because they are one of the most used materials for polymeric OLED fabrication. In particular these polyfluorenes allow for fabrication of white OLED which can be used for solid-state lighting and contribute to energy saving. Two series of fluorene based copolymers containing the benzothiadiazole units (Bzt; green chromophore) or the read chromophore (bis-thien-2yl)-benzothiadiazole units (T-Bzt-T) along the chains, were synthesized by Suzuki coupling reaction of tailored polyfluorene pre-polymers (PF) essentially terminated with propane boronic ester groups (PF sample) with the di-bromine derivative of the Bzt and T-Bzt-T monomers, in presence of tetrakis(triphenylphosphine) palladium ((Ph3P)4Pd) as catalyst. Two tailored PF pre-polymers constituted of alternated triphenylammino disubstituted fluorene units and dialkylsubstituted fluorine units were preliminary synthesized by Suzuki coupling reactions of equimolar ratio of 9,9-bis(4-diphenylaminophenyl)-2,7-dibromofluorene (1) and 2-(4,4,5,5-tetramethyl-1,3,2-dioxoborolane)-9,9-dioctylfluorene (2) in toluene solvent, using the same Pd catalyst, K2CO3 2 M and of a catalytic amount of Aliquat. After 6 or 10 h of reaction (depending on the run ) at 90°C, the bromine end group was quenched by adding phenylboronic acid pinacol ester in different ratios (1:1 or 1:3 with respect to the monomer equivalent) and stirring for 12 h or 18h at 90 °C in the two runs, respectively. Thus two PF samples with an weight average molar mass (Mw) of 5200 and 12700 g/mol, respectively, were obtained with the aim to better modulate the energy transfer to get white emission. These PFs were used to synthesize two series of polyfluorene based copolymers containing the green chromophore Bzt or the read chromophore one Tf-Bzt-Tf along the chains, by Suzuki coupling reaction with the di-bromine derivative of the Bzt and Tf-Bzt-Tf monomers respectively, in presence of ((Ph3P)4Pd) as catalyst. The average molar masses of all samples were calculated by SEC using THF as mobile phase, and two on-line detectors: (1) differential viscometer (DV); (2) differential refractometer (DRI model 2414). The chemical composition of the PFs and the copolymers (referred as PF-Bz and PF-(Tf-Bz-Tf)) were investigated by (1H and 13C) NMR and MALDI-TOF Mass Spectrometry tools (MALDI-TOF MS). In particular, the MALDI-TOF MS analysis of the neat polymers and copolymers and of the their narrow polydisperse fractions obtained by SEC fractionation gave peculiar information on their composition and on the side reactions occurring during the syntheses of the PF pre-polymers. The optical characterization (UV visible absorption and Photoluminescence) of the neat copolymers and of their SEC fractions were also performed and the data will be discussed in another contribute (see Combined techniques for the characterization of polyfluorene copolymers and correlaction whit their optical properties. Part 2 - Spectroscopy Measurements)


90) Characterization of Copoly(ester-amide)s From Reactive Blending of PET/MXD6 Blends in the Molten State

F.Samperi, M.S.Montaudo, S.Battiato, D.Carbone, A.Scamporrino, C.Puglisi

Advances in Polymer based Materials and Related Technologies (Capri -NA May 29th - June 1st, 2011)   - 2011

PET-MXD6 copolymers were prepared by reactive blending of equimolar PET/MXD6 blends at 285 °C for different time in presence of terephthalic acid (1 %w). Firstly, the partial hydrolysis of PET and MXD6 occurs, yielding oligomers terminated with reactive aromatic carboxyl groups. These oligomers quickly react with ester and amide inner groups producing a PET-MXD6 copolymer, that may be compatibilize the initial biphasic blend. In this homogeneous environment, the aliphatic carboxyl-terminated MCD6 chains, inactive in the initial biphasic blend, may promote the exchange reactions determining the formation of a random copolymer at longer reaction time (120 min). The progress of exchange reactions, and the microstructure of the formed copolyeteramides, versus the reaction time, was followed by (1H and 13C)-NMR analyses using a CDCl3/TFA-d/(CF3CO)2O mixture as solvent, and applying appropriate mathematical models. Dyads and triads sequences were thoroughly characterized by NMR. Block copolymers were formed at short reaction time; the average sequence lengths of each block decreases as increase the reaction time and random copolymers were formed at reaction time higher than 75 min. DSC data show that semi-crystalline block copolymers were obtained at reaction time lower than 45 min, while the other copolymers are amorphous. All PET-MXD6 copolymers shows a single Tg that changes as a function of the dyads molar composition in the copolymers. The measured Tg values match with those calculated by an proposed modified Fox equation that take into account the weight fraction of the four dyads components the PET-MXD6 copolymers. The composition of the randon copolymers was also investigated by MALDI-TOF MS analysis. PET and MXD6 were also heated with and without TA at the same processing conditions. MALDI-TOF analysis of the heated MXD6 and of the PET-MXD6 copolymers reveals also the formation of cyclopentanone ended chains, owing to the degradative reactions involving the adipic acids end groups.


91) Synthesis of PC-Ny6 block copolymers as a compatibilizers in Nylon6/Polycarbonate blends

S.Battiato, D.Carbone, A.Scamporrino, F.Samperi, C.Puglisi, A.Turturro, M.Castellano

Advances in Polymer based Materials and Related Technologies (Capri -NA May 29th - June 1st, 2011)   - 2011

PC-Ny block copolymers were prepared by reacting carboxyl-terminated Ny6 polymers (Ny6-COOH) with high molar mass PC at two different temperature (250-260 °C), for different tange time and with or without diphenylsulfone (DPSO) as solvent. The reaction produces block copolymers of the type PC-Ny6 (AB) plus a certain amount of un-converted PC degraded to lower molecular weights. The reaction products were separated by selective fractionation with solvents, obtaining three different fractions: THF soluble fraction (THF-SF), TFE soluble fraction (TFE-SF), and the TFE insoluble fraction (TFE-IF). Each fraction has been characterized by NMR and MALDI-TOF MS. All NMR spectra were recorded using CDCl3/(CF3CO)3O (90/10 v/v) mixture as solvent. The MALDI-TOF and NMR spectra of the THF-SF show that it is mainly constituted by unreacted and phenol terminated PC chains. The mass spectrum and 1H-NMR spectrum of the TFE-SF shows only the presence of typical Ny6-carboxyl terminated series of peaks. Both techniques show that all the TFE-IF were constituted of PC-Ny6 block copolymers. Two PC-Ny6 copolymer with a molar composition 80/20 and 70/30 were obtained. As expected, their DSC analysis shows that both block copolymers present two Tg values: at 47°C and 137çC for PC-Ny6 80/20 (Cop82); at 47°C and 131°C for PC-Ny6 70/30 (Copo73), due to the Ny6 and PC blocks, respectively. Blends of Ny6/PC 80/20 (w/w) with 2% phr of one of the two copolymers, as compatibilizers, were mixed in the Brabender mixer (250°C, 30 rpm) under N2 atmosphere for 5 and 10 min. The compatibilizing action of the two block copolymers have been invrstiagted by SEM analysis. SEM micrographies show that compatibilized Ny6/PC (80/20 mol/mol) blends were obtained when were processed in presence of the PC-co-Ny6 block copolymers (2%w). Blend mixed with 2%of PC-co-Ny6 80/20 present the better mechanical properties.


92) ENCEFALOPATIA EPILETTICA PRECOCE ASSOCIATA A DIFETTI CONGENITI DELLA GLICOSILAZIONE (CDG).

M.Falchi, M.A.Donati, E.Procopio, R.Barone, L.Sturiale, D.Garozzo, C.Barba, R.Guerrini

SINPIA 2011: la NEUROPSICHIATRIA dell’infanzia e dell’adolescenza: dalla ricerca alla clinica (Pisa 11-14 Maggio 2011)  ,  22  - 2011

I difetti congeniti della glicosilazione, (Congenital Disorder of Glycosylation CDG), sono patologie neurogenetiche dovute al difetto di enzimi implicati nella glicosilazione delle proteine. Il quadro clinico è eterogeneo con uno spettro di sintomi e segni variamente rappresentati nei singoli difetti. Scopo: descriviamo due pazienti con CDG-I, in cui la manifestazione principale è una encefalopatia epilettica precoce. La diagnosi di CDG-I posta in due pazienti affetti da encefalopatia epilettica, microcefalia acquisita, dismorfismi facciali, artrogriposi, scoliosi e tetraparesi spastica, sottolinea l’importanza di effettuare gli accertamenti specifici per questo gruppo di malattie genetiche rare. Metodologie e soggetti: Paziente 1: 2 anni e tre mesi; ritardo di crescita intrauterina e ipocinesia fetale, parto alla 34a settimana. Alla nascita parametri auxologici nella norma, severa ipotonia artrogriposi , distress respiratorio. Dai due mesi crisi epilettiche farmaco resistenti, microcefalia progressiva, grave ritardo psicomotorio, tetraparesi spastica, infezioni respiratorie frequenti con distress. Esame clinico: microcefalia, dismorfismi facciali, collo corto e grave scoliosi. Artrogriposi arti superiori e inferiori. Tetraparesi spastica. Esami strumentali RM: semplificazione della girazione con atrofia diffusa. EMG/ VCN: nella norma, BAEP e PEV: modesta alterazione della trasmissione centrale. Eco addome: fegato di dimensioni ed ecostruttura incrementate. Fondo oculare: iride stellata e atrofia ottica. EEG: scarsa organizzazione, anomalie parossistiche multifocali; crisi ad esordio emisferico destro o sinistro, con arresto psicomotorio, versione capo, manifestazioni toniche asimmetriche, talora clonie. Paziente 2: 16 mesi. Gravidanza normodecorsa, parto eutocico. Parametri auxologici nella norma. Alla nascita motricità povera. Ad un mese crisi parziali, pluriquotidiane farmacoresistenti, grave ritardo psicomotorio, infezioni respiratorie ricorrenti. Esame obiettivo: microcefalia, aplasia cutis dello scalpo. Dismorfismi facciali. Artrogriposi degli arti superiori e inferiori. Scoliosi. Tetraparesi spastica.Esami strumentali. RM encefalo: semplificazione della girazione con atrofia diffusa. EMG/ENG e PEV: nella norma, BAEP: bassa ampiezza con latenza conservata. Eco addome e fondo oculare nella norma. EEG: rallentato, anomalie parossistiche multifocali; numerose crisi ad esordio emisferico destro o sinistro, versione del capo, manifestazioni toniche asimmetriche, incostantemente clonie. Esami di laboratorio dei due pazienti: Isoelettrofocusing della transferrina sierica (IEF) : aumento di sialo-tranferrina con assenza di asialo-transferrina in entrambi. Analisi MALDI-TOF della transferrina sierica: in entrambi i pazienti difetto di glicosilazione in accordo con analisi IEF . Oligosaccaridi legati ai lipidi (LLO) su fibroblasti: profilo alterato nel primo paziente, in corso nel secondo. Analisi di mutazione del gene ALG3 (CDG-Id) in corso. Risultati e discussione: entrambi i pazienti presentano encefalopatia epilettica ad esordio precoce associata a microcefalia acquisita, dismorfismi facciali, artrogriposi e tetraparesi spastica. La RM encefalo in entrambi i casi mostra una semplificazione della girazione con progressiva e diffusa atrofia. Le crisi epilettiche ad esordio nei primi 3 mesi e farmacoresistenti, mostrano un pattern elettroclinico caratterizzato da coinvolgimento sincrono o asincrono dei due emisferi con manifestazioni cliniche prevalentemente di tipo motorio. L’IEF eseguita nel primo anno di vita ha mostrato in entrambi i pazienti, un pattern di CDG di tipo I. Le sindromi CDG sono un gruppo di difetti clinicamente e biochimicamente eterogeneo, probabilmente sotto diagnosticato. Si sottolinea l’importanza di eseguire l’analisi IEF su siero in pazienti affetti da encefalopatia epilettica da causa non nota specie in presenza di dimorfismi facciali, epatopatia e artrogriposi.


93) DISORDINI CONGENITI DELLA GLICOSILAZIONE: LA NOSTRA ESPERIENZA IN EUROGLYCANET (2005-2010)

R.Barone, L.Sturiale, D.Garozzo, D.Cocuzza, G.Sorge, A.Fiumara

SINPIA 2011: la NEUROPSICHIATRIA dell’infanzia e dell’adolescenza: dalla ricerca alla clinica (Pisa 11-14 Maggio 2011)  ,  19  - 2011

I disordini congeniti della glicosilazione (Congenital Disorders of Glycosylation - CDG) sono patologie neurometaboliche dovute a difetti di sintesi delle glicoproteine e altri glicoconiugati. Ad oggi, sono state identificate 25 forme di CDG dovute a difetti della N-glicosilazione. I disordini della glicosilazione sono caratterizzati da ritardo dello sviluppo di grado variabile e possibile presenza di anomalie malformative del sistema nervoso centrale (atrofia cerebellare), dismorfie, microcefalia, deficit sensoriali, epilessia, neuropatia periferica e patologia multisistemica. Euroglycanet è un network europeo finalizzato alla diffusione di strumenti adeguati per la diagnosi clinica dei pazienti affetti da CDG, per la identificazione dei difetti molecolari e per lo sviluppo di procedure terapeutiche. Scopo: riportiamo la nostra esperienza nella diagnosi dei disordini della glicosilazione e descriviamo i fenotipi clinici identificati attraverso un lavoro di screening per queste patologie svolto nel contesto di Euroglycanet. Pazienti e Metodi: durante gli ultimi 5 anni (2005-2010), presso il Dipartimento di Pediatria, Università di Catania, oltre 3000 campioni di pazienti Italiani con sospetto clinico per CDG, sono stati analizzati con esame isoelettrofocusing della transferrina sierica (test di primo livello per i difetti della N-glicosilazione). Sui campioni diagnosticati veniva ulteriormente effettuata caratterizzazione dello stato di glicosilazione tramite tecniche di spettrometria di massa, attraverso metodiche appositamente sviluppate presso l’ICTP-CNR di Catania. Successivamente tali campioni venivano inviati in altri laboratori Euroglycanet per analisi biochimica e molecolare. Risultati: sono stati identificati 21 pazienti con difetti molecolari della N-glicosilazione dovuti a deficit della sintesi del precursore glicoproteico dolicol-oligosaccaride nel citosol e reticolo-endoplasmico (CDG tipo I). Quattordici pazienti erano affetti da PMM2-CDG (CDG-Ia), che rappresenta la forma più frequente tra queste patologie. Rispetto alla forma classica, la presenza di pazienti con PMM2-CDG e fenotipo ’mild’ veniva definita in relazione al pattern di sviluppo, assenza di microcefalia e assenza di malformazione cerebellare tipo Dandy-Walker. In pazienti con fenotipo ’mild’ veniva osservata associazione genotipo-fenotipo per la ricorrenza in tutti questi soggetti di eterozigosi composta in presenza della mutazione p.L32R del gene PMM2. I sette pazienti non PMM2-CDG (38%), presentavano dismorfie (7/7), microcefalia (6/7), ritardo dello sviluppo di grado severo (6/7), epilessia farmaco-resistente con esordio nel primo anno di vita (6/7), deficit visivo (5/7) e assenza di atrofia cerebellare (6/7). In questi soggetti, i profili di glicosilazione della Tf osservati tramite spettrometria di massa MALDI-TOF erano significativamente differenti rispetto a quelli osservati in pazienti con PMM2-CDG. Conclusioni: la presenza di epilessia farmaco-resistente con esordio precoce, microcefalia e deficit visivo in pazienti identificati con CDG-I, definiscono nella popolazione studiata un fenotipo frequente e differente dalla forma classica (PMM2-CDG/CDG-Ia). Questi risultati indicano che la diagnosi di CDG dovrebbe essere considerata tra le malattie metaboliche causa di encefalopatia epilettica precoce.


94) Clinical and biochemical characterization of a CDG-I patient with fetal akinesia

L.Sturiale, R.Barone, L.Keldermans, A.Fiumara, M.Falchi, R.Guerrini, M.A.Donati, G.Matthijs, D.Garozzo

4th International Meeting on Congenital Disorders of Glycosylation (Leuven, Belgium, 13-14 January 2011)  ,  49  - 2011

This work reports on clinical and biochemical characterization of a CDG-I patient with arthrogryposis and developmental anomalies (fetal akinesia). Clinical data: the patient was born pre-term (34 weeks) to healthy unrelated parents, after a pregnancy complicated with intrauterine growth restriction between 20 and 32 weeks and decreased intrauterine fetal movement. At birth she had severe hypotonia, distinct facial features and multiple congenital contractures (arthrogryposis). Since the age 2 months she manifested drug-resistant epilepsy. At age 8 months microcephaly (OFC: 41 cm), severe and progressive kyphoscoliosis with thoracal deformity were recorded. There were absent psychomotor development, no visual fixation, axial hypotonia and reduction of active limb movements with normoactive deep tendon reflexes. Moderate hepatomegaly. Developmental anomalies included simplified gyral pattern and cerebellar hypoplasia. Laboratory investigations (age 8 months): increased serum transaminases levels (SGOT 106 IU/l, SGPT 103 IU/l). Blood CK levels, clotting times, plasma FVIII levels, thyroid hormones, karyotype, array CGH: normal.


95) Mass spectrometry contribution to the diagnosis and characterization of Congenital Disorders of Glycosylation (CDG): our experience in the EUROGLYCANET European network

L.Sturiale, R.Barone, A.Fiumara, G.Sorge, J.Jaeken, D.Garozzo

16th European Carbohydrate Symposium (July 3-7, Sorrento -Naples, Italy)  ,  538  - 2011

Congenital Disorders of Glycosylation (CDG) comprise an ever increasing group of inborn errors in the proteins glycosylation pathway, representing a paradigm as they disclose the direct connection between glycosylation changes and human diseases. Since the first description in 1980 [1], about 40 CDG forms were discovered, each with a variable clinical spectrum, from multisystem diseases to single organ involvements, causing high morbidity and even mortality. Sharing information and competences is an essential step in order to identify new CDG types and to promote awareness and early diagnosis. Mass spectrometry contributed significantly to this research field to identify possible underglycosylation profiles of intact individual glycoproteins and/or to map glycan population of the sample under study, typically serum or plasma. Here we report on serum glycosylation analyses by MALDI-MS in patients with CDG recruited in the context of Euroglycanet, an European network focused on diagnosis and understanding CDG [2]. During the last five years (2005-2010), almost 3000 samples of Italian patients with clinical suspicion of CDG were analyzed by serum Transferrin (Tf) isoelectric focusing (IEF) in a clinical setting at the University Paediatric Hospital in Catania. Patient with abnormal IEF pattern underwent MALDI MS glycosylation analyses at the ICTP-CNR in Catania, where a specific method for intact glycoprotein investigation and N-glycan analyses was set up [3]. Eighteen patients showed by MS the Tf abnormal glycosylation profile characteristic of type I CDG, encompassing defects in the assembly of dolichol-linked oligosaccharide in the Endoplasmic reticulum. Among these, PMM2-CDG (or CDGIa) was most frequently found (11 cases). Of particular importance, one patient affected with epileptic encephalopathy, had a newly identified CDG type due to DPM2 gene mutation [4]. Moreover, MS glycosylation analysis was performed on seventy-one serum samples with type II IEF pattern, collected from the Euroglycanet partners. Two of these samples showed recognizable glycan processing defects, respectively caused by gene mutations of subunit 5 and subunit 7 of the Conserved Oligomeric Golgi (COG) complex (COG5-CDG and COG7-CDG) [5-6]. Four more samples with combined Type I and Type II Tf MS profiles were also found; this significant information makes disease comprehension at molecular basis and diagnosis particularly challenging in these patients.


96) The MALDI TOF/TOF Mass Spectrometer as a Chemical Lab for the structural characterization of lipooligosaccharides

L.Sturiale, A.Palmigiano, A.Silipo, R.Lanzetta, M.Parrilli, A.Molinaro, D.Garozzo

16th European Carbohydrate Symposium (July 3-7, Sorrento -Naples, Italy)  ,  45  - 2011

Lipooligosaccharide (LOS) is a powerful Gram negative glycolipid involved in immune system elusion and invasion of host animal and vegetal cells. Its structural elucidation is pivotal to understand at molecular levels mechanisms of infections. Due to its amphiphilic nature, it has resisted structural matrix assisted laser desorption/ionization (MALDI) analysis. Our approach has now resolved this important issue, permitting us to obtain high resolution MALDI mass spectra that are rich of information. In fact, they show both LOS quasi-molecular ions, and also well defined fragments due to a in-source decay which yields B-type ions corresponding to core oligosaccharide(s), and Y-type ions relating to lipid A unit(s). Moreover, MALDI tandem Time of Flight (TOF/TOF) mass spectrometry (MS) of lipid A allows its complete structural elucidation straight from the purified intact LOS, without any chemical manipulation. These findings constitute a significant improvement in the analysis of such important biomolecule by MS.


97) Polymer Degradation

P.Rizzarelli, S.Carroccio, C.Puglisi

Mass Spectrometry in Polymer Chemistry  Chapter 13,  437-465  - 2011

Polymer degradation is one of the most important areas of polymer chemistry; being a major factor restraining application of these outstanding and versatile materials. book cover The idiom "polymer degradation" takes account of different processes, induced by one or more environmental factors such as heat, light, microorganisms, or chemicals that deteriorate polymers producing alterations in their properties. The degradation is the result of irreversible changes that are usually undesirable or, in some cases, required, as in biodegradation or recycling, or else induced to support structure determination. Degradation plays an important role in every life phase of a polymer, that is, during its synthesis, processing, use, and even after it has accomplished its planned purpose. As a result, stabilization is required to extend the life time of most polymers. Compounding with stabilizers is the preferred and well-established method for improving stability. However, monitoring and controlling degradation requires the understanding of many different phenomena, including the diverse chemical mechanisms underlying structural changes in macromolecules, the complex reaction pathways of additives, the interactions of fillers, as well as impurities, and the complicated relationship between molecular-level changes and macroscopic properties. Various schemes to classify polymer degradation exist. Because of its complexity, with regard to both the causes and the response of the polymer, classification is usually performed on the basis of the dominating features. We will refer to the classification based on the main factors responsible for degradation: thermal, thermo-oxidative, photo, photo-oxidative, hydrolytical, chemical, biological degradation, and so on. Modern mass spectrometry (MS) methods for their high sensitivity, selectivity, and speediness offer the opportunity to explore the finest structural details in polymer degradation. In fact, whatever the cause, the deterioration mainly yields degradation products frequently bearing characteristic end groups, which can be revealed and differentiated by MS, being indicative of specific degradation pathways [1-12]


98) From micro- to femto-moles, from small to giant molecules: the route of modern Mass Sectrometry

A.Palmigiano, D.Garozzo

Seminars in organic synthesis  SCI June 13-17, 2011 Gargnano (BS),  264-279  - 2011

The definition of a mass spectrometer from the America Society for Mass Spectrometry (ASMS) is: book cover "A mass spectrometer is an instrument that measures the masses of individual molecules thathave been converted to ions; i. e. molecules that have been electrically charged"; using simply words: a machine used to weigh molecules. This definition is obviously correct, but the mass spectrometer is much more than an instrument. It is a complete laboratory for the investigation of molecules, clusters, and other species under the environment-free conditions of the gas phase. For this reason Mass Spectrometry (MS) is widely used today by almost all chemists and many researchers from neighbouring disciplines such as physics, medicine, or biology as a powerful analytical tool. Today the mass spectrometer is more and more present in the pharmaceutical industry, in the biological labs, in the hospitals and in many other bio-labs, while until few years ago it was present only in specialized chemical lab. This revolution starts at the end of 1980s with the introduction of two different methods able to desorbs and ionize molecules with molecular weights in a range from few hundreds daltons to millions. Until then, a few techniques, fast atom bombardment (FAB), plasma desorption (PD) and desorption chemical ionization (DCI) were able to carry out in the gas phase and to ionize molecules with a molecular weight greater than one thousand, but they all required high concentrations of sample and they did not work at all for larger molecules such as proteins or polymers. Then, in 1988, Electrospray ionization (ESI) invented by John B. Fenn and Matrix assisted laser desorption (MALDI) introduced by Franz Hillenkamp and Michael Karas appeared almost simultaneously. These desorption-ionization methods revolutionized MS and are the main forms of ionization to this day. In the beginning the two techniques were not believed robust enough, but at the end of 1990s almost all MS instruments on the market were MALDI or ESI.


99) Two Argentinean Siblings with CDG-Ix: A Novel Type of Congenital Disorder of Glycosylation?

M.B.Bistuè Millòn, M.A.Delgado, N.B.Azar, N.Guelbert, L.Sturiale, D.Garozzo, G.Matthijs, J.Jaeken, R.Dodelson de Kremer, C.G.Asteggiano

JIMD Reports  1/2011,  65-72  - 2011

Congenital disorders of glycosylation (CDG) are genetic diseases caused by abnormal protein and lipid glycosylation. book cover In this chapter, we report the clinical, biochemical, and molecular findings in two siblings with an unidentified CDG (CDG-Ix). They are the first and the third child of healthy consanguineous Argentinean parents. Patient 1 is now a 11-year-old girl, and patient 2 died at the age of 4 months. Their clinical picture involved liver dysfunction in the neonatal period, psychomotor retardation, microcephaly, seizures, axial hypotonia, feeding difficulties, and hepatomegaly. Patient 1 also developed strabismus and cataract. They showed a type 1 pattern of serum sialotransferrin. Enzymatic analysis for phosphomannomutase and phosphomannose isomerase in leukocytes and fibroblasts excluded PMM2-CDG and MPI-CDG. Lipid-linked oligosaccharide (LLO) analysis showed a normal profile. Therefore, this result could point to a deficiency in the dolichol metabolism. In this context, ALG8-CDG, DPAGT1-CDG, and SRD5A3-CDG were analyzed and no defects were identified. In conclusion, we could not identify the genetic deficiency in these patients yet. Further studies are underway to identify the basic defect in them, taking into account the new CDG types that have been recently described.


100) Handbook of Engineering and Speciality Thermoplastics: Volume 3: Polyethers and Polyesters (chapter 12 "Polycarbonates")

F.Samperi, M.S.Montaudo, G.Montaudo

Sabu Thomas and Visakh P.M.  3,  493-529  - 2011

This chapter reviews the research and the most relevant progresses in polycarbonates (PC)s science and provides a comprehensive source of information on histoty, synthesis, processing and applications. book cover The application of different polymerization procedure of hte commercial aromatic bisphenol-A polycarbonate (referred herein as PC) and the innovative enzymatic catalysed polymerization of aliphatic polycarbonate are summarized. Due to the high engineering performance of PC polymer, an extensive section on mechanical, electrical, chemical and therma properties is included. The thermo and photo oxidative behaviours, the hydrolytic stability and the consequent modification on PC chemical structure are also discussed. The development of PC polymeric materials such as composites and blends are also addressed, emphasizing in particular the properties and the applications of impact modified PC blends and even of PC/Polyester systems.


101) Predicting and Measuring the Sequence Distribution of condensation Polymers (chapter 11 of "Mathematical approaches to polymer sequence analysis and related problems")

M.S.Montaudo

R.Bruni - Springer  Chapter 11,  227-246  - 2011

The sequence of polycarbonates polyesters polyamides and other condensation copolymers is discussed. book cover The theory predicts that the sequence is often radically different from addition polymers. One of the causes is the presence of a larger number of distinct monomers in the reaction vessel. Condensation copolymers from symmetric and asymmetric monomers involve a different number of parameters to be modeled, since asymmetric monomers require an additional parameter. A peculiar reaction is discussed, namely the synthesis of copolymers obtained by melt-mixing two different homopolymers. The sequence of copolymer fractions collected at the exit of a liquid chromatographic device is discussed as well. The measurement of condensation-polymer sequence distribution can be performed using nuclear magnetic resonance (NMR) and mass spectrometry (MS). Examples drawn from recent literature are discussed.


102) Predicting and Measuring the Sequence Distribution of Addition Polymers (chapter 10 of "Mathematical approaches to polymer sequence analysis and related problems")

M.S.Montaudo

R.Bruni Edito (Springer)  Chapter 10,  197-225  - 2011

The sequence distribution of poly(styrene), poly(methyl methacrylate) and other addition polymers can be predicted, starting from the knowledge of polymerization reaction conditions. book cover In many cases, the sequence distribution will be Markovian (of the first or second order), but in other cases, it cannot be described by Markovian statistics. Three examples of sequences falling in the latter class are discussed. All types of copolymers are considered: AB copolymers, ABC copolymers, ABCD copolymers. As reaction time increases, polymerization dynamics becomes less trivial. Additional parameters are required to describe how copolymer sequence varies as the reaction yield (or the reaction time) increases. Nevertheless, reaction products are conceptually simple points, and it is possible to follow their changes by drawing their trajectories in a multidimensional phase space. The task of measuring the sequence distribution is seldom trivial. Many examples of polymer sequencing using NMR spectroscopy have been collected and discussed by Randall. Mass spectrometry is also used. Often sequence distribution information must be extracted from experimental data. Flexible empirical models have been developed for this aim. Mixtures of two bernoullian chains and mixtures of two markovian chains are used. The pertubed markovianmodel features ε, a perturbation factor. Some experimental methods attempt to measure polymer sequence by partial degradation, i.e., by reducing the length of the chains until a mixture of tetramers, pentamers and hexamers is obtained. This procedure yields a new copolymer, with a new sequence distribution. The sequence of the undegraded polymer must be reconstructed from the knowledge of the sequence of the partially degraded one.


103) COG5-CDG with a Mild Neurohepatic Presentation

C.W.Fung. G.Matthijs, L.Sturiale, D.Garozzo, K.Y.Wong, R.Wong, V.Wong, J.Jaeken

JIMD Reports  DOI 10.1007/8904_2011_61  - 2011

The conserved oligomeric Golgi (COG) complex is an eight subunit protein involved in the retrograde transport of Golgi components. book cover It affects the localization of several Golgi glycosyltransferases and hence is involved in N- and O-glycosylation. Genetic defects in this complex belong to the rapidly expanding family of congenital disorders of glycosylation (CDG). Patients have been reported with defects of subunit 1 (CDG1-CDG), subunit 4 (CDG4-CDG), subunit 5 (CDG5-CDG), subunit 6 (CDG6-CDG), subunit 7 (CDG7-CDG), and subunit 8 (CDG8-CDG). This paper is on the second reported patient with COG5-CDG. She showed a mild neurohepatic disease with central as well as peripheral neurological involvement while in the first reported patient (with a different mutation) only mild central neurological involvement was reported.


104) Polyetherimide

S.Carroccio, C.Puglisi, G.Montaudo

Book on Engineering and Specialty Thermoplastics   II chapter 4,  79-110  - 2011

This chapter reviews the researches and the most relevant progresses in polyetherimide (PEI) science and provides a comprehensive source of information on history, synthesis, processing and applications. book cover The ingenious application of nitro-displacement reaction on the synthesis of polyetherimide as well the existing one step polymerization methods, the new approaches and innovative solutions in processing operations are summarized. Due to the high engineering performance of PEI material, an extensive section on mechanical, electrical, chemical and thermal properties is included. The thermo and photo oxidative behaviours, the hydrolytic stability and the the consequent modifi cation on PEI chemical structure are also discussed. The new development of PEI materials such as blends, composites with particular attention to nano-composites, and the most recent patents and related commercial products are also addressed in the chapter.


105) Rhamnolipid biosurfactants from Brassica carinata oil: synthesis and characterization

M.G.Cambria, R.Bottari, A.Ballistreri, G.Impallomeni, S.Guglielmino

SIMGBM- 29th National Meeting, Pisa, September 21-23, 2011   - 2011

Aim of this work is the selection of rhamnolipid-producing strains that are able to synthesize monorhamnolipids or dirhamnolipids in preferential way. A panel of 39 isolates of P. aeruginosa was tested by a metabolic screening (methylene blue/CTAB agar plate method) and two strains, called L05 and L44, were selected as good rhamnolipids producers. To investigate the role of cultural conditions and carbon source, L05 and L44 were grown in two mineral media (Basal medium and E* medium, different for availability of N, Fe, Mg) and with two carbon sources: glycerol (three carbon atoms molecule) and Brassica carinata oil (very long chain fatty acids mixture). After 6 days fermentation, rhamnolipids were twice extracted with 2-fold volume of ethyl ether, were quantified by orcinol assay and were analyzed through 1 and 2D NMR spectroscopy. The data showed that in both tested media, only in reliance on carbon source, L05 exhibits a metabolic switch that allows to preferential production of about 80% of monorhamnolipids with Brassica carinata oil and 70% of dirhamnolipids with glycerol. L44, instead, produces a mixture of mono- and dirhamnolipids, in all tested conditions. This work shows the possibility to produce mono-rhamnolipids through a fermentation process by a selected strain; in this way, is possible avoid the production of complex mixtures, decreasing strongly the costs need for rhamnolipids separation. Moreover, by only changing the carbon source, it is possible to direct the production of rhamnolipids form.


106) Biosynthesis and structural characterization of biodegradable plastics from Brassica carinata oil and from very long chain fatty acids

A.Ballistreri, G.Impallomeni, G.M.Carnemolla, S.P.P.Guglielmino, M.S.Nicolò, M.G.Cambri

Eupoc2011 - Biobased Polymers and Related Biomaterials, Gargnano (I), 29 May - 3 June, 2011   - 2011

Agriculture and the industries connected frequently produce food surplus and byproducts that can be used as low-cost substrates in fermentation processes. One of the possible practical applications of this concept would be the production of bacterial polyesters by fermentation from such substrates, specifically the production of the biosynthetic polymers generically known as poly(hydroxyalkanoates) (PHAs)1,2. In some countries of the Mediterranean area, such as in Italy, particularly in Sicily, the production, collection, and pressing of Brassica carinata are being tested experimentally, with the aim to create a new chain of production for biofuels. The widespread and cheap production of B. carinata oil, intended for the production of biodiesel, brings about as a consequence a wide availability of said starting material at low cost, both as an alternative choice and as a means to dispose of the production surplus. Very long chain fatty acids (VLCFA), longer than C20, were employed for the production of medium chain length poly(3-hydroxyalkanoates) (mcl-PHA) by Pseudomonas aeruginosa. In order to keep the production costs low, Brassica carinata oil (erucic acid content 35 - 48%) was employed as the intact triglyceride containing VLCFA. As free fatty acids erucic acid (C22:1) and nervonic acid (C24:1) were employed. Weight average molecular weight, determined by GPC, varied from 56000 for PHA from B. carinata oil to about 120000 for those from erucic and nervonic acids. Monomeric units composition was obtained by GC analysis, while the structural characterization was performed by 1H- and 13C-NMR. The 3-hydroxyacids making up the repeating units of such polymers were saturated and unsaturated, with a higher content of the latter in the case of PHAs obtained from B. carinata oil. ESI MS of partially pyrolysed samples allowed the identification of oligomers up to heptamers and statistical analysis of the ion intensity in the mass spectra showed that these PHAs are random copolymers. The PHAs from erucic and nervonic acids were partially crystalline, with rubbery characteristics and a melting point (Tm) of 50°C, while the increase of unsaturation degree in the repeating units of PHA from B. carinata oil afforded a totally amorphous material, with a glass transition temperature (Tg) of -47 °C.


107) Advances in Polymer based Materials and Related Technologies

C.Puglisi, S.Battiato, D.Carbone, A.Scamporrino, F.Samperi

Advances in Polymer based Materials and Related Technologies (Capri -NA May 29th - June 1st, 2011)   - 2011

The molar composition of the copolymers produced during the melt mixing of equimolar PC/PEN blend, in presence of Ti(OBu)4 (0.5%w) as a catalyst, was monitored as a function of the reaction time by 1H-NMR. 1H-NMR spectra show a series of new signals with respect to the initial homopolymers, indicating the formation of copolymers. They show also that the intensity of methylene (-CH2-)protons decreass with respect that of the aromatic protons of the naphthalate units, as increases the reaction time, indicating the elimination of ethylene carbonate (ETC), as well as in the PC/PET blend melt mixed in the similar conditions. The exchange reactions were monitored by 13C-NMR following the intensity changes of signals corresponding to the -CH2- (62-68 ppm) and to the BPA (114-121 ppm). Applying an appropriate statistical model and using the intensities of these signals we have calculated the molar fractions of each copolymer component. We have found that after 2 min reactive blending the copolymer is essentially constituted of the expected four-component. With the progress of the reaction which occurring, this become a five- components from 5 min up to 10 min, and then become a six component after 15 min up to 45 min. After this time the sequences containing carbonate units disappear owing the elimination of CO2 and ETC, and a four-component copolymer is formed. The elimination of carbonate units was also followed looking the carbon signals due to the corresponding carbonyl that resonate between 153 and 155 ppm and was also confirmed by FT-IR analysis. The weight loss of ETC and CO2 was calculated from NMR data, ando also by isothermal TGA analysis at 280 °C. The DSC data show that the TG of the copolymers changes as a function of their composition and we have proposed and equation to predict this characteristic.


108) Fluorene Based Copolymers For Solid-State Lighting: Correlation Between Molecular Structure And Electro-Optical Properties

U.Giovanella, M.Pasini, A.Bolognesi, F.Samperi, S.Battiato, S.Destri

XX Convegno Italiano di Scienza e Tecnologia delle Macromolecole (AIM) TERNI 4 - 8 Settembre 2011   - 2011

Efficient white electroluminescence can be obtained from a fully miscible blend of a polyfluorene-based copolymers emitting with the three fundamental colours and their chemical composition is a key factor to tune the emission properties. By combining physical and chemical characterization techniques it is possible to correlate copolymer molecular structures and electro-optical properties.


109) Identification of tear fluid biomarkers in vernal keratoconjunctivitis syndrome using iTRAQ quantitive proteomics

A.Palmigiano, E.Mazzola, A.Messina, S.Milazzo, A.Leonardi, D.Garozzo

58th ASMS Conference on Mass Spectrometry and Allied Topics - May 23-27 2010 Salt Lake City, Utah   - 2010



110) Identification of tear fluid biomarkers in vernal keratoconjunctivitis using iTRAQ quantitive proteomics

M.Bortolotti, A.Palmigiano, A.Messina, E.Mazzola, S.Milazzo, D.Garozzo, A.Leonardi

Annual meeting ARVO 2010 - May 2-6 2010 Fort Lauderdale, Florida   - 2010



111) La Spettrometria di Massa nella Caratterizzazione delle Bioplastiche

P.Rizzarelli

Giornata Tecnologica AIM: "Materiali Polimerici per la produzione di manufatti ecocompatibili". S. Piero a Grado (Pisa) 07/05/2010    - 2010



112) Soil burial degradation test of aliphatic poly(ester amide)s

P.Rizzarelli, M.Cirica, G.Pastorelli, C.Puglisi

BIOPOLPACK - 1° Congresso Nazionale sugli imballaggi in polimeri biodegradabili. (Parma 15/04/10 - 16/04/10)    - 2010



113) Synthesis and Characterization of Linear Hyperbranched PBA Block Copolymers

L.Ascione, V.Ambrogi, C.Carfagna, C.Puglisi, S.Battiato, F.Samperi

5th International conference on times of polymers (top) & composites (Ischia)   - 2010



114) Sintesi e caratterizzazione di copolieterisolfoni solfonati

S.Battiato, C.Puglisi, V.Asarisi , A.Recca, G.Cicala, R.Mendichi

10 Convegno nazionale AIMAT (Capo Vaticano)   - 2010



115) Compositi di PVC-Ag con proprietà antimicrobiche

D.Zampino, T.Ferreri, C.Puglisi, D.Carbone, M.Mancuso, R.Zaccone, R.Scaffalo, A.Fiaccabrino

Atti del Convegno Congiunto delle Sezioni Calabria e Sicilia della Società Chimica Italiana (SCI Aci Castello, 1-2 dicembre 2009) P28   - 2009

Negli ultimi decenni c’è stata una crescente domanda di materiali con proprietà antimicrobiche da usare in vari campi di applicazione (biomedicale, industriale, prodotti di largo consumo). Il poli(vinil cloruro) (PVC) è un polimero largamente usato per le possibilità di additivazione, la facilità di lavorazione, la versatilità applicativa e il prezzo contenuto. L’inclusione di metalli, come ad esempio l’argento, è un metodo efficace per aumentare l’idrofilicità di un polimero e per renderlo antimicrobico [1]. Recentemente le zeoliti d’argento hanno avuto larga diffusione come agenti antimicrobici, in particolare nell’imballaggio alimentare e nel biomedicale, in quanto la funzione di scambiatore ionico rende la zeolite il vettore ideale per gli ioni di argento [2]. L’obiettivo di questo studio è stato lo sviluppo di compositi in PVC contenenti zeoliti d’argento come agente antimicrobico. La caratterizzazione termogravimetrica e calorimetrica dei compositi ha fatto rilevare che le loro proprietà termiche non sono influenzate dalla presenza delle zeoliti d?argento nella matrice del PVC rispetto ai campioni di PVC commerciale. I test meccanici hanno messo in evidenza solo un lieve incremento del modulo elastico e una leggera diminuzione della tensione di rottura dei compositi e ciò indica che la presenza di zeoliti d’argento non causa cambiamenti sensibili in tutta la performance meccanica dei compositi. Per quanto riguarda il comportamento reologico, la viscosità dei compositi non cambia se comparata con quella del PVC commerciale. I compositi hanno mostrato una promettente attività antibatterica fino a 7 giorni verso Escherichia coli and Staphylococcus epidermidis in brodo coltura (TSB), mentre l’inibizione diretta in piastra (TSA) di E. Coli ha fatto rilevare aloni d’inibizione fino a 30 giorni. L’attività dei compositi in urina sterile contenente i ceppi batterici ad alta concentrazione iniziale ha prodotto già a 24 h una forte riduzione della crescita batterica. La determinazione della quantità di argento rilasciato dai compositi in urina sterile ha permesso di osservare un continuo rilascio nel tempo di ioni argento, che risulta promettente ai fini dello sviluppo di dispositivi medicali e di altri prodotti a base di PVC antimicrobici.


116) Compositi di PVC-Ag con proprietà antimicrobiche

D.Zampino, T.Ferreri, C.Puglisi, D.Carbone, M.Mancuso, R.Zaccone, R.Scaffalo, A.Fiaccabrino

Atti del XIX Convegno Italiano di Scienza e Tecnologia delle Macromolecole (AIM MI 13-17 settembre 2009) P4.27 e 4.109-4.110   - 2009

This study was aimed to the development of poly(vinyl chloride) (PVC) composites containing silver nanoparticles or zeolites to prevent the bacterial colonization of polymeric surfaces. Polymer composites were prepared by mixing plasticised PVC pellets with silver nanoparticles and silver zeolite in the amount of 1-8 wt% and 2-20 wt%, respectively. The results indicate that the thermal and mechanical properties of PVC composites were not affected by the presence of both silver additives, with respect to the pure plasticised PVC. The antibacterial activity of PVC zeolites composites, examined on Escherichia coli and Staphylococcus epidermidis, in Trypticase Soy Broth and in Trypticase Soy Agar resulted promising both in culture broth and in agar plate, while PVC composites containing silver nanoparticles showed low antimicrobial activity.


117) Antimicrobial activity of Ag based PVC composites

D.Zampino, T.Ferreri, C.Puglisi, D.Carbone, M.Mancuso, R.Zaccone, R.Scaffalo, A.Fiaccabrino

Atti Polymerfest Proceedings: 169-170 (Palermo, August 30-September 2, 2009 )   - 2009

The growing demand of materials with antimicrobial properties to be used in many industrial fields has produced an increasing research interest to the development of antimicrobial termoplastics [1]. Among polymers, poly(vinyl chloride) (PVC) has been extensively used in different industrial applications for its ease of processing, compatibility with different additives, versatility (building products, cosmetics, medical and paramedical fields). The inclusion of metals into polymers represents till now an effective method to develop polymers with antimicrobial properties. Silver is a well known and long used metal to inhibit the growth of a broad spectrum of bacterial strains on medical and industrial processes [2, 3 ]. The aim of this study was the development of silver nanoparticles-PVC and silver zeolite? PVC composites with antimicrobial activity.


118) Quantitative proteomic analysis of human tear fluids using differentially labelled tags iTRAQ with LC-MALDI MS and MS/MS in VKC Patients

D.Garozzo

Quantitative Techniques in Mass Spectometry-Based Proteomics 12th 13th October 2009 Vienna: IMP/IMBA   - 2009



119) LC MALDI MS nell’analisi del fluido lacrimale

D.Garozzo

Cromatografia Nano Capillare e Spettrometria di Massa Applicazioni di Proteomica - Pisa 22 Aprile 2009 (Area della Ricerca del CNR)   - 2009



120) Microbial synthesis and structural characterization of biodegradable polyesters from faty acids with odd number of carbon atoms

A.Ballistreri, G.Impallomeni, G.M.Carnemolla, S.P.P.Guglielmino, M.Nicolò, M.G.Cambria

XXIII Congresso Nazionale della Società Chimica Italiana (Sorrento)   - 2009



121) PHA synthesis by Pseudomonas aeruginosa ATCC 27853 in magnesium and nitrogen starvation

C.Frezza, A.Ferreri, G.Impallomeni, A.Ballistreri, G.M.Carnemolla, S.P.P.Guglielmino

28° CONVEGNO SIMGBM SPOLETO2009   - 2009



122) Synthesis and Characterization of disulfonated Poly(arylene ether sulphone) Copolymers

F.Samperi, G.Cicala, V.Asarisi, I.Blanco

Atti del XIX Convegno Italiano di Scienza e Tecnologia delle Macromolecole - AIM pp.2.59-2.60 (MI 13-17 Settembre 2009)   - 2009



123) Frazionamento, Analisi e caratterizzazione di Sistemi macromolecolari Complessi

R.Mendichi, A.Giacometti Schieroni, D.Piovani, F.Samperi

Atti del XIX Convegno Italiano di Scienza e Tecnologia delle Macromolecole - AIM pp.2.5-2.6 (MI 13-17 Settembre 2009)   - 2009



124) Synthesis and Characterization of Oligo-(ethylene glicol) Conjugated Benzofulvene Macromonomers

R.Mendichi, A.C.Boccia, F.Bertini, L.Zetta, F.Samperi, A.Cappelli

Atti del XIX Convegno Italiano di Scienza e Tecnologia delle Macromolecole - AIM pp.1.32-1-33 (MI 13-17 Settembre 2009)   - 2009



125) Characterization of New Copolymers Formed by Reactive Blending of PC/PEN Blends in the Molten State

F.Samperi, S.Battiato, C.Puglisi

Atti del XIX Convegno Italiano di Scienza e Tecnologia delle Macromolecole - AIM pp. 3.34-3-35 (MI 13-17 Settembre 2009)   - 2009



126) Synthesis of Block Copolymers as Compatibilizers in Nylon6/Polycarbonate Blends

C.Puglisi, F.Samperi, A.Turturro

Atti del XIX Convegno Italiano di Scienza e Tecnologia delle Macromolecole - AIM pp.3.30 (MI 13-17 Settembre 2009)   - 2009



127) Caratterizzazione dei Copolimeri PET-MXD6 Ottenuti per Miscelazione Reattiva del PET con MXD6 allo Stato Fuso

S.Battiato, F.Samperi, C.Puglisi, D.Carbone

Atti del XIX Convegno Italiano di Scienza e Tecnologia delle Macromolecole - AIM pp.3.1-3-2 (MI 13-17 Settembre 2009)   - 2009



128) Chemical Reactions occurring in the molten state between Ny6 and Oxazoline groups linked to a cyclophosphazene moiety

F.Samperi, S.Battiato, R.Scaffaro, L.Botta, M.C.Mistretta, R.Bertanti, R.Milani

Atti del XIX Convegno Italiano di Scienza e Tecnologia delle Macromolecole - AIM pp. 3.3-3-4 (MI 13-17 Settembre 2009)   - 2009



129) Characterization of new copolymers formed by reactive blending of pc and pen

F.Samperi, S.Battiato, C.Puglisi

Atti del Convegno "Polymerfest " pp. 251-252 ( PA 30 Agosto- 2 Settembre 2009)   - 2009



130) Characterization of pet-mxd6 copolymers formed by reactive blending of pet/mxd6 blends in the molten state

S.Battiato, F.Samperi, C.Puglisi, D.Carbone

Atti del Convegno "Polymerfest " pp. 100-101 ( PA 30 Agosto- 2 Settembre 2009)   - 2009



131) Chemical Reactions occurring in the molten state between Ny6 and Oxazoline groups linked to a cyclophosphazene moiety

F.Samperi, S.Battiato, R.Scaffaro, L.Botta, M.C.Mistretta, R.Bertanti, R.Milani

Atti del Convegno "Polymerfest " pp. 98-99 ( PA 30 Agosto- 2 Settembre 2009)   - 2009



132) Structural relaxation of statistical Syndiotactic PMMA Copolymers

M.Penco, G.Spagnoli, S.Della Sciucca, R.Mendichi, M.S.Montaudo

Atti del XIX Convegno Italiano di Scienza e Tecnologia delle Macromolecole - AIM pp. 2.11-2.12 (MI 13-17 Settembre 2009)   - 2009



133) Caratterizzazione di copolimeri ottenuto per miscelazione reattiva di PET e MXD6

M.S.Montaudo, F.Samperi, S.Battiato

Giornata Tecnologica "Materie Plastiche per il Packaging: Novità dal mondo della Ricerca" (MI 27 Marzo 2009)   - 2009



134) Clinical, Biochemical and Molecular studies of two siblings with cdg-ix in the context of the first program for congenital disorders of glycosylation studies in Argentina

M.B.Bistué Millón, M.A.Delgado, N.B.Azar, N.Guelbert, L.Sturiale, G.Matthijs, J.Jaeken, R. Dodelson de Kremer, C.G.Asteggiano

11th International Congress of Inborn Errors of Metabolism (ICIEM 2009)   - 2009



135) Mass Spectrometry: Instrumentation, Interpretation, and Applications (Cap.15 Polymers)

M.S.Montaudo

Wiley Publications  cap.15,  299  - 2009

With contributions from noted experts from Europe and North America, Mass Spectrometry Instrumentation, Interpretation, and Applications serves as a forum book cover to introduce students to the whole world of mass spectrometry and to the many different perspectives that each scientific field brings to its use. The book emphasizes the use of this important analytical technique in many different fields, including applications for organic and inorganic chemistry, forensic science, biotechnology, and many other areas. After describing the history of mass spectrometry, the book moves on to discuss instrumentation, theory, and basic applications.



136) Ag-composites with antimicrobial properties

D.Zampino, T.Ferreri, C.Puglisi, M.Mancuso, R.Zaccone, R.Scaffalo

IV International Conference on Times of Polymers (TOP) and Composites, Ischia 21-24 settembre 2008. Atti AIP  1042,  240  - 2008

Polymer composites with antimicrobial properties were prepared by mixing plasticised poly(vinyl chloride) (PVC) pellets with silver nanoparticles and silver zeolite in the amount of 8 wt% and 10 wt%, respectively. Thermal and mechanical properties of PVC composites were obtained by tensile and calorimetric (TGA and DSC) measurements. Rheological characterization was also performed by a parallel plates rheometer. The results indicate that the thermal and mechanical properties of PVC composites were not affected by the presence of both silver additives, with respect to the pure plasticised PVC. The antibacterial activity of PVC composites was examined on Escherichia coli and Staphylococcus epidermidis in Trypticase Soy Broth and in Trypticase Soy Agar for the direct inhibition. PVC composite with Ag-zeolite exhibited antibacterial activity against S. epidermidis and E. coli in culture broth and direct inhibition in agar plate (inhibition zone: 2-4 mm), for more than 7 days. PVC composites containing silver nanoparticles showed very low antimicrobial activity.


137) Structural and chemical characterization of melted PET/MXD6 blends

S.Battiato, F.Samperi, C.Puglisi

XVII Congresso Nazionale di Chimica Industriale, Energia, materiali e prodotti da tecnologie e processi eco-sostenibili, Genova, 30 Giugno - 3 Luglio 2008  PLO-C05  - 2008

Exchange reactions occurring in the melt mixing processes of poly(ethylene terephthalate) (PET) with poly(m-xylene adipamide) (MXD6) blends at 290°C, in presence of p-TolueneSulfonic Acid (p-TsOH) or Terephthalic Acid (TA) as promoter reaction have been investigated by viscometry and 13C NMR tools. Equimolar mixtures (with respect to the repeat units) of PET/MXD6 blends were reacted in a glass reactor for different times (from 0 up to 100 min) under stirring and N2 flow. The inherent viscosity decrease with the reaction time until 60 min indicating that the molar mass of the blend decrease. After this reaction time the viscosity shows an increase slightly anomalous. This behavior may be due to the increase of the hydrodinamic volume of the formed copoly-(esteramide) and or an increase of the molar mass of the blend components owing of the condensation reactions which can occur during the melt mixing. On the base of the exchange reactions mechanism a four components PETMXD6 copolymers are expected. Their molar composition in terms of the molar fraction of dyads and triads sequences in the formed PET-MXD6 copolymers were monitored by 13C NMR analyses. These reveal the formation of copoly-(esteramide) PET/MXD6 with different degree of randomness as a function of mixing time as well as of the type and % (w/w) of the promoter reaction. For the same conditions of time and % of promoter reaction the greater degree of randomness was obtained with TA respect to p-TsOH. Up to 60 min of reaction time with the 1% of TA a block copoly-(esteramide) whit degree of randomness of about 0.5 was formed, while the blends processed until 100 min give a statistical copolymer (degree of randomness of about 0.9). Hand the other hand, increasing the percentage of TA up to 5% (w/w), for 60 min mixing, a random copolymers with similar degree of randomness of the Blend at 1% TA at 100 min was formed, but with less molar mass as showed the inherent viscosity measurements.


138) Reactive melt mixing of PEN/PC blends

F.Samperi, C.Puglisi

XVII Congresso Nazionale di Chimica Industriale, Energia, materiali e prodotti da tecnologie e processi eco-sostenibili, Genova, 30 Giugno - 3 Luglio 2008  PLO-C05  - 2008

Exchange reactions occurring in the melt mixing processes of poly(ethylene naphthalate) (PEN) with poly(Bisphenol-A carbonate) (PC) blends at 280°C in presence of Ti(OBu)4 as a catalyst, and under N2 flow, have been investigated by DSC and NMR (1H and 13C) tools. Equimolar mixtures (with respect to the repeat units) of PC/PEN blends were reacted in a mixer brabender for different times (from 0 up to 60 min). DSC analysis showed that products formed at 2 and 5 min heating present two glass transition (Tg) with temperature values intermediate to those of the homopolymers; materials formed at reaction time higher that 5 min show only one Tg value that increase as raise the mixing time. The molar composition, the molar fraction of dyads and triads sequences of PCPEN formed copolymers were monitored by 13C and 1H-NMR analyses. Besides the four component expected on the base of the exchange reactions stoichiometry, were also revealed the ether groups along the copolymer chains. These can be formed by elimination of CO2 from aliphatic carbonate units formed in the exchange reactions between PEN and PC. These aliphatic carbonate units can be also eliminate ethylene carbonate (ETC) generating a thermally stable aromatic ester units. NMR analyses showed that a random aromatic copolyester-ether with a very low amount of PEN (2% mol) units was formed at mixing time higher than 30 min. The weight loss of ETC and CO2, was monitored by NMR analyses and also by isothermal thermogravimetric analysis at 280°C of a PEN/PC sample in the presence of catalyst. Selective extraction of the melt mixed materials with specific solvents showed that 45%w and 90%w of PC-PEN copolymer was formed at 2 and 5 min of mixing, respectively.


139) Multiplexed glycoproteomic analysis of glycosylation disorders by sequential IgY immunoseparation and MALDI TOF MS

L.Sturiale, R.Barone, A.Messina, A.Palmigiano, D.Garozzo

XI Convegno-Scuola sulla Chimica dei Carboidrati, Pontignano (Si), 22-26 Giugno 2008   - 2008

The physiological roles of glycan structures in the fine-tuning of multiple biological processes is depicted in the congenital disorders pf glycosylation (CDG) clinical spectrum which is broad and virtually involves all organ systems. A major challenge in CDG research concerns the possibility to screen different native intact glycoproteins for their possible macroheterogeneity due to site glycosylation underoccupancy which is mandatory for characterization of CDG-I defects. In addition, the investigation of glycoprotein microheterogeneity (structural abnormalities of N-glycan structures at glycosylation sites) is required for detecting CDG-II disorders. Glycoproteomics of CDG and secondary glycosylation disorders such as galactosemia (GALT deficiency) and hereditary fructose intolerance or HFI, is aimed to investigate glycosylation changes of proteins with the following purposes: 1) biomarker detection for diagnosis and treatment monitoring (whenever possible); 2) characterization of defective glycan structures to pinpoint possible enzyme/gene defects in patients with unknown basic defect; 3) insight into the pathogenesis by elucidating structure-function relationships. We applied IgY immunoaffinity separation and MALDI MS for clinical proteomics of post-translational modification (glycosylation) as schematised in figure, with the aim to set up a high-throughput method to analyze macroheterogeneity and microheterogeneity of protein glycoforms. The method was validated by the analyses of human underglycosylated serum glycoproteins in CDG-I, CDG-II and secondary glycosylation disorders and applied for biomarker detection in the diagnostic procedure (CDG-I and II) and treatment monitoring (galactosemia and HFI).



140) Clinical characteristics and mass spectrometry glycosylation profile in two CDG-I patients

R.Barone, L.Sturiale, M.D.Cocuzza, G.Rapicavoli, G.Sorge, A.Fiumara, D.Garozzo

IV Euroglycanet Meeting, Worms, 1-4 ottobre 2008   - 2008

We report on two unrelated Sicilian patients which share some clinical features and have a similar and peculiar mass spectrometry (MS) glycosylation profile of native Transferrin (Tf) and alpha1-antitrypsin (AAT).
Clinical data
Two unrelated girls aged 9 month (patient 1) and 20 month (patient 2) presented with almost absent psychomotor development and marked hypotonia. They both were born pre-term from healthy non-consanguineous parents, after a pregnancy complicated with polyhydramnios. The two patients had congenital microcephaly, craniofacial dysmorphy, limb anomalies with joint restrictions. Malformation anomalies were more severe in patient 1. Brain MRI documented a decrease of cerebral white matter and thinning of the corpus callosum. They presented increased serum transaminases levels (<110 UI/l) and coagulopathy. Serum Transferrin (Tf) isoelectric focusing (IEF) showed a type I pattern with a very faint asialo band in the two patients, while it was normal in their respective parents. CDG-Ia and CDG-Ib were ruled out in as PMM and PMI enzyme activities were found in the normal ranges. Mass Spectrometry analyses MALDI spectra of native Tf showed in these patients in addition to the main normal peak at ˜79,5 kDa (di-glycosylated Tf), a significant component at ˜77,4 kDa (mono-glycosylated Tf). Hypoglycosylation profiles were observed in the AAT mass spectra from both the patients. MALDI analyses of the acidic N-glycans from Tf did not reveal truncated and/or abnormal species.
Conclusions
The reported patients have common clinical features. MS glycosylation analyses of serum Tf is also similar between these patients and it suggests the increase of mono-glycosylated but not a-glycosylated Tf species.


141) Multiplexed glycoproteomic analysis of glycosylation disorders by sequential IgY immunoseparation and MALDI TOF MS

L.Sturiale, R.Barone, A.Messina, A.Palmigiano, D.Garozzo

XXI Congresso Nazionale di Chimica Analitica, Arcavacata di Rende (CS), 21 - 25 Settembre 2008   - 2008

The physiological roles of glycan structures in the fine-tuning of multiple biological processes is depicted in the congenital disorders pf glycosylation (CDG) clinical spectrum which is broad and virtually involves all organ systems. A major challenge in CDG research concerns the possibility to screen different native intact glycoproteins for their possible macroheterogeneity due to site glycosylation underoccupancy which is mandatory for characterization of CDG-I defects. In addition, the investigation of glycoprotein microheterogeneity (structural abnormalities of N-glycan structures at glycosylation sites) is required for detecting CDG-II disorders. Glycoproteomics of CDG and secondary glycosylation disorders such as galactosemia (GALT deficiency) and hereditary fructose intolerance or HFI, is aimed to investigate glycosylation changes of proteins with the following purposes: 1) biomarker detection for diagnosis and treatment monitoring (whenever possible); 2) characterization of defective glycan structures to pinpoint possible enzyme/gene defects in patients with unknown basic defect; 3) insight into the pathogenesis by elucidating structure-function relationships. We applied IgY immunoaffinity separation and MALDI MS for clinical proteomics of post-translational modification (glycosylation) as schematised in figure, with the aim to set up a high-throughput method to analyze macroheterogeneity and microheterogeneity of protein glycoforms. The method was validated by the analyses of human underglycosylated serum glycoproteins in CDG-I, CDG-II and secondary glycosylation disorders and applied for biomarker detection in the diagnostic procedure (CDG-I and II) and treatment monitoring (galactosemia and HFI).



142) Stimuli-responsive poly(ampholyte)s containing L-histidine residues: synthesis and protonation thermodynamics of methacrylic polymers in the free and in the cross-linked gel forms

M.Casolaro, Y.Ito, T.Ishii, S.Bottari, F.Samperi, R.Mendichi

Express Polymer Letters  2,  165  - 2008

Abstract. Methacrylate-structured poly(ampholyte)s were synthesized in the homopolymer and copolymer forms starting from the N-methacryloyl-L-histidine (MHist) and the N-isopropylacrylamide (NIPAAm). They were also obtained in the cross-linked (hydrogel) form, showing a close thermodynamic behaviour as that shown by the corresponding soluble free polymer analogues. Viscometric data revealed that the minimum hydrodynamic volume of the polymer at its isoelectric point (pH 5) shifted to lower pHs as the NIPAAm content increased, and beyond a critical low MHist content the reduced viscosity decreased, even at low pHs. The phenomenon was attributed to hydrophobic forces between the isopropyl groups outweighing the repulsive electrostatic interactions of the polymer in the positively charged form. A similar behaviour was shown by the corresponding hydrogel. The latter also revealed a different phase transition phenomenon induced by external stimuli (temperature, pH, ionic strength, electric current) when compared to the acrylate-structured analogues. The polyMHist, as well as the corresponding monomer, was found for two days to be non toxic against the mouse osteoblasts (MC3T3-E1).


143) Synthesis and characterization of novel polyamides from new aromatic phosphonate diamine monomer

S.Bazzano, F.Samperi, C.Puglisi, P.Finocchiaro, G.A.Consiglio, A.Imbrogiano, S.Failla.

Atti del XVIII Convegno Italiano di Scienza e Tecnologia delle Macromolecole, Catania 16-20 Settembre 2007  ,  211  - 2007



144) Pirolisi di materiali da imballaggio in tetrapack per la preparazione di carboni attivi

F.Samperi, T.Ferreri, C.Puglisi, D.Zampino, A.Bonaccorso, C.Crisafull

Atti del XVIII Convegno Italiano di Scienza e Tecnologia delle Macromolecole, Catania 16-20 Settembre 2007  ,  211  - 2007



145) Effect on structural relaxation of the pmma copolymers chain flexibility

S.Della Sciucca, G.Spagnoli, M.Penco, L.Sartore, F.Samperi, S.D’Antone

Atti del XVIII Convegno Italiano di Scienza e Tecnologia delle Macromolecole, Catania 16-20 Settembre 2007  ,  211  - 2007



146) Rilascio di plasticizzanti durante i cicli di dialisiI: linee classiche in pvc-dehp e nuove linee in pvc-totm

D.Zampino, G.Scaltro, C.Puglisi, M.R.Di Francesca, A. M.Zoccolo, P.Castellino, A.Fiaccabrino

Atti del XVIII Convegno Italiano di Scienza e Tecnologia delle Macromolecole, Catania 16-20 Settembre 2007  ,  210  - 2007



147) MALDI Investigation OF NY6 AND NY66 Thermo-Oxidation Products

S.Carroccio, G.Scaltro, T.Ferreri, G.Montaudo, C.Puglisi

Atti del XVIII Convegno Italiano di Scienza e Tecnologia delle Macromolecole, Catania 16-20 Settembre 2007  ,  209  - 2007



148) Synthesis, characterization and soil burial degradation of aliphatic poly(ester amide)

P.Rizzarelli, M.Cirica, G.Pastorelli, C.Puglisi

Atti del XVIII Convegno Italiano di Scienza e Tecnologia delle Macromolecole, Catania 16-20 Settembre 2007  ,  208  - 2007



149) MALDI TOF/TOF and MALDI TOF/TOF MS/MS analysis of synthetic poly(ester amide) from sebacic acid and 4-amino-1-butanol

P.Rizzarelli, C.Puglisi

Atti del XVIII Convegno Italiano di Scienza e Tecnologia delle Macromolecole, Catania 16-20 Settembre 2007  ,  207  - 2007



150) Mechanism of Reactions Occurring in PEN/PC Blends During The Melt

C.Puglisi F.Samperi

Mixing Process MoDeSt 2007. Workshop on DEGRADATION AND STABILIZATION OF POLYMER BLENDS Palermo, 9 September 2007    - 2007



151) Characterization of Nylons -Based Copolymer Prepared by Reactive Melt-Mixing

C.Puglisi, F.Samperi

Atti del 9th EUROPEAN SYMPOSIUM Polymer Blends, September 9-12, 2007, Palermo, Italy  ,  18  - 2007



152) Exchange Mechanisms in the Reactive Melt-Mixing of Polyester and Polyamide Blends

F.Samperi, C.Puglisi

Atti del 9th EUROPEAN SYMPOSIUM Polymer Blends, September 9-12, 2007, Palermo, Italy   - 2007



153) Compatibilization of polymer blends by using a ciclophosphazene additive

R.Scaffaro, L.Botta, M.C.Mistretta, F.Samperi, S.Bazzano, C.Puglisi

Atti del 9th EUROPEAN SYMPOSIUM Polymer Blends, September 9-12, 2007, Palermo, Italy  ,  17  - 2007



154) Reactivity of cyclophosphazenes with end functionalised Ny6 samples and EEA Copolymer

F.Samperi, C.Puglisi, S.Bazzano, R.Scaffaro, L.Botta, M.C.Mistretta

Atti del 9th EUROPEAN SYMPOSIUM Polymer Blends, September 9-12, 2007, Palermo, Italy  ,  16  - 2007



155) Differences in disease severity reflect diversity of glycoproteome in two sibs with CDG-Ia

R.Barone, L.Sturiale, V.Sofia, A.Ignoto, A.Fiumara, D.Garozzo, M.Zappia

3rd International Meeting on Congenital Disorders of Glycosylation. 18-19 October, 2007, Paris, France   - 2007



156) Multiplexed glycoproteomic analysis of glycosylation disorders by sequential IgY immunoseparation and MALDI TOF MS

L.Sturiale, R.Barone, A.Messina, A.Palmigiano, D.Garozzo

3rd International Meeting on Congenital Disorders of Glycosylation. 18-19 October, 2007, Paris, France   - 2007



157) Proteomic analysis of human tear fluids using LC-MALDI MS and MS/MS

A.Messina, L.Sturiale, R.Barone, A.Palmigiano, MG.Mazzone, A.Leonardi, D.Garozzo

Italian Proteomic Association. 2nd Annual National Conference. 26-29 Giugno 2007, Acitrezza (CT). Italy   - 2007



158) Differences in severity of clinical phenotype reflect diversity of glycoproteome in two sibs with CDG-Ia

L.Sturiale, R.Barone, V.Sofia, A.Messina, A.Palmigiano, A.Fiumara, M.Zappia, D.Garozzo

Italian Proteomic Association. 2nd Annual National Conference. 26-29 Giugno 2007, Acitrezza (CT). Italy   - 2007



159) Glycoproteomics of congenital disorders of glycosylation and secondary glycosylation disorders

R.Barone, L.Sturiale, A.Messina, A.Palmigiano, D.Garozzo

Italian Proteomic Association. 2nd Annual National Conference, 26-29 Giugno 2007, Acitrezza (CT), Italy   - 2007



160) Exopolysaccharides as Bacterial Defence Tools: the Case of Burkholderia cepacia complex

P.Cescutti, Y.Herasimenka, G.Impallomeni, L.Sturiale, A.Palmigiano, D.Garozzo, R.Rizzo

14th European Carbohydrate Symposium (EUROCARB 2007), Lubeck (Germania), 2-7 Settembre, 2007   - 2007



161) Structure-Function Relationships in Cepacian Biofilm Formation

P.Cescutti, Y.Herasimenka, G.Impallomeni, R.Rizzo

14th European Carbohydrate Symposium (EUROCARB 2007), Lubeck (Germania), 2-7 Settembre, 2007   - 2007



162) Structural Analysis of the Polysaccharides from Echinacea angustifolia Radix

R.Cozzolino, P.Malvagna, E.Spina, A.Giori, N.Fuzzati, A.Anelli, D.Garozzo, G.Impallomeni

XVIII Convegno Italiano di Scienza e Tecnologia delle Macromolecole, Catania, 16-20 Settembre, 2007   - 2007



163) Caratterizzazione Strutturale di Copolitioesteri Batterici Mediante NMR ed ESI-MS

G.Impallomeni, A.Steinbuchel, T.Lutke-Eversloh, T.Barbuzzi, A.Ballistreri

XVIII Convegno Italiano di Scienza e Tecnologia delle Macromolecole, Catania, 16-20 Settembre, 2007   - 2007



164) Sodium Alginates and Glycerol Based Films: Influence of Different Polymeric Microstructures on Chemical-Physical Properties of the Films

M.Malinconico, B.Immirzi, E.Di Pace, M.Avella, G.Santagata, G.Impallomeni

XVIII Convegno Italiano di Scienza e Tecnologia delle Macromolecole, Catania, 16-20 Settembre, 2007   - 2007



165) Valutazione Tecnologica di Nuovi Copolimeri per il Drug Delivery

T. Musumeci, G. Carnemolla, G.Impallomeni, A. Ballistreri, R. Pignatello, G. Puglisi

XVIII Convegno Italiano di Scienza e Tecnologia delle Macromolecole, Catania, 16-20 Settembre, 2007   - 2007



166) A Spectroscopic Study of the Interaction of New Water solubile Bis-Porphyrin Tweezers with L-Amino Acids

V.Villari, N.Micali, N.Angelini, P.Mineo, E.Scamporrino, D.Vitalini

Atti del XVIII Congresso Società Italiana di Biofisica Pura e Applicata. Città del Mare (Terrasini - Palermo), 17 - 21 settembre 2006  ,  66  - 2006



167) Sintesi e Caratterizzazione di Derivati Fullerenici Idrosolubili Non-Ionici con Proprietà Anfifiliche .

E.Spina, P.Mineo, E.Scamporrino, D.Vitalini

Atti del Convegno intitolato XXII Congresso Nazionale della Società Chimica Italiana, Firenze, 10 - 15 settembre 2006  ,  107  - 2006



168) Determinazione di plasticizzanti rilasciati da linee in PVC durante i cicli di dialisi

D.Zampino, G.Scaltro, C.Puglisi, M.R.Di Francesca, A.M.Zoccolo, P.Castellino, Fiaccabrino

Atti del Convegno intitolato XXII Convegno Nazionale della Società Chimica Italiana - Firenze 10 - 15 Settembre 2006  ,  256  - 2006



169) Sintesi e Caratterizzazione di un Sensore Molecolare di Ammino Acidi Aromatici Costituito da un Complesso Co(II)-Porfirina Idrosolubile

P.Mineo, N.Angelini, N.Micali, E.Scamporrino, V.Villari, D.Vitalini

Atti del XXII Convegno Nazionale della Società Chimica Italiana, Firenze 10 -15 Settembre 2006  ,  255  - 2006



170) Biodegradation of aliphatic polyesters: comparative evaluation in soil burial tests and enzymatic degradation in solution

C.Puglisi, P.Rizzarelli, G.Montaudo

Atti del Convegno intitolato Fourth International Conference on Polymer Modification, Degradation and Stabilization, MODEST 2006, 10-14 September 2006, San Sebastian Spain  ,  263  - 2006



171) Photo-degradation mechanisms in aliphatic polyesters

C.Puglisi, S.Carroccio, P.Rizzarelli, G.Montaudo

Atti del Convegno intitolato Fourth International Conference on Polymer Modification, Degradation and Stabilization, MODEST 2006, 10-14 September 2006, San Sebastian Spain  ,  262  - 2006



172) Comparison of photo and thermal-oxidation processes in poly(ethereimide)

C.Puglisi, S.Carroccio, G.Montaudo

Fourth International Conference on Polymer Modification, Degradation and Stabilization, MODEST 2006, 10-14 September 2006, San Sebastian, Spain  ,  261  - 2006



173) Characterization of Synthetic Polymers by MALDI

M.S.Montaudo

17th International Mass Spectrometry Conference. Aug 27 - Sep 1, 2006, Prague/Czech  ,  31  - 2006



174) Structural characterisation of synthetic polymers BY MALDI and MALDI-TOF/TOF-MS/MS

P.Rizzarelli, C.Puglisi, G.Montaudo

20th Bratislava International Conference on Macromolecules - ADVANCED POLYMERIC MATERIALS (APM-2006), June 11 - 15, 2006 Bratislava, Slovakia   - 2006



175) Dall’analisi dei monosaccaridi all’analisi del glicoma; dalle micromoli alle femtomoli: i progressi della spettrometria di massa nell’analisi dei carboidrati

D.Garozzo

X Convegno-scuola sulla chimica dei carboidrati, 25-29 Giugno 2006, Certosa di Pontignano - Siena   - 2006



176) Silver-Russell syndrome-like features in a patient with abnormal transferrin glycosylation

R.Barone, A.Fiumara, E.Pasquini, MA.Donati, L.Sturiale, D.Garozzo, G.Sorge

EUROGLYCANET meeting, 28-29 April, 2006, Porto, Portugal.   - 2006



177) Advances in purification methods of serum glycoproteins for MALDI-MS analysis of N-glycome in CDG patients and in galactosemia

L.Sturiale, R.Barone, D.Garozzo

EUROGLYCANET meeting, 28-29 April, 2006, Porto, Portugal   - 2006



178) Differences in severity of clinical phenotype reflect diversity of glycosylation status in two sibs with phosphomannomutase deficiency (CDG-Ia) due to V129M/R141H mutations

R.Barone L.Sturiale, V.Sofia, A.Ignoto, L.Pavone, D.Garozzo, M.Zappia

XXXVII Congresso Società Italiana di Neurologia. 14-18 Ottobre 2006. Bari   - 2006



179) Analisi del glicoma del fluido lacrimale in pazienti affetti da disordini congeniti della glicosilazione (CDG)

L.Sturiale, R.Barone, A.Messina, A.Scuderi, A.Leonardi, M.Santocono, MG.Mazzone, D.Garozzo

X Convegno-scuola sulla chimica dei carboidrati. 25-29 Giugno 2006. Certosa di Pontignano - Siena   - 2006



180) Microstructure Determination of 3-Hydroxybutyrate/3-Mercaptoalkanoate Copolymer by NMR and ESI-MS

G.Impallomeni, A.Steinbuchel, T.Lutke-Eversloh, T.Barbuzzi, A.Ballistreri

COFEM 2006, Giornate di Chimica Organica Fisica e Meccanicistica, Catania, 21-23 Settembre, 2006   - 2006



181) Miscelazione reattiva di polimeri allo stato fuso: meccanismi di reazione e caratterizzazione dei copolimeri formati.

C.Puglisi

Dipartimento di Chimica Industriale, Università di Genova, 29 Novembre 2005, Genova, Italy   - 2005



182) Optical Selective Recognition Behavior of a Molecular Functional Material

A.Gulino, P.Mineo, M.M.Purrazzo, E.Scamporrino, D.Vitalini, I.Fragalà

Atti del Convegno intitolato SAMIC 2005 - Syntheses And Methodologies In Inorganic Chemistry. Trends in Nanoscience. Bressanone (BZ), 4 - 7 dicembre 2005. Book of Abstracts  ,  P33  - 2005



183) Sensori Molecolari Costituiti da Monostrati Molecolari di Derivati Porfirinici e Fullerenici Covalentemente Legati a Superfici di Quarzo

P.Mineo, E.Scamporrino, D.Vitalini, A.Gulino, G.Condorelli, S.Giuffrida, G.Ventimiglia, I.Fragalà

Atti del Convegno intitolato Società Chimica Italiana - Convegno Congiunto delle Sezioni Calabria e Sicilia.Catania, 5 - 6 dicembre 2005.  ,  8  - 2005



184) A Self-Assembled Fullerene Monolayer for Molecular Oxygen Optical Recognition

A.Gulino, I.Fragalà, P.Mineo, E.Scamporrino, D.Vitalini, S.Giuffrida, G.Ventimiglia

Atti del Convegno intitolato V Convegno Nazionale sulla Scienza e Tecnologia dei Materiali.Geremeas, Maracalagonis (CA), 26 - 29 settembre 2005.  ,  H12  - 2005



185) Sensori molecolari costituiti da monostrati molecolari di derivati porfirinici e fullerenici covalentemente legati a superfici di quarzo

P.Mineo, E.Scamporrino, D.Vitalini, A.Gulino, I.Fragalà

Atti del XVII Convegno Italiano di Scienza e Tecnologia delle Macromolecole, Napoli 11-15 settembre 2005  ,  334  - 2005



186) Meccanismi termo-ossidativi della polietereimmide ULTEM

C.Puglisi, S.Carroccio, G.Montaudo

Atti del XVII Convegno Italiano di Scienza e Tecnologia delle Macromolecole, Napoli 11-15 settembre 2005  ,  95  - 2005



187) Photo-oxidation of Poly(Butylene Succinate)

S.Carroccio, P.Rizzarelli, G.Montaudo, C.Puglisi

Atti del XVII Convegno Italiano di Scienza e Tecnologia delle Macromolecole, Napoli 11-15 settembre 2005  ,  91  - 2005



188) Sequence analysis in synthetic aliphatic poly(ester amide)s by PSD-MALDI/TOF and MALDI-TOF/TOF-MS/MS

P.Rizzarelli, G.Montaudo, C.Puglisi

XVII Convegno Italiano di Scienza e Tecnologia delle Macromolecole, AIM 2005, Napoli 11-15 Settembre 2005  ,  18  - 2005



189) Sintesi e caratterizzazione di copoliammidi NY6/NY6,10 e NY6/NY4,6

C.Puglisi, F.Samperi, G.Montaudo

Atti del XVII Convegno Italiano di Scienza e Tecnologia delle Macromolecole, Napoli 11-15 settembre 2005  ,  81  - 2005



190) Sintesi e caratterizzazione di polieterisolfoni PES-PEES

G.Cicala, G.Magnano, A.Recca, C.L.Restuccia, F.Samperi, C.Puglisi.

Atti del XVII Convegno Italiano di Scienza e Tecnologia delle Macromolecole, Napoli 11-15 settembre 2005  ,  77  - 2005



191) Structural characterisation of aliphatic poly(ester amide)s by MALDI/TOF, PSD-MALDI/TOF and MALDI-TOF/TOF-MS/MS

P.Rizzarelli, C.Puglisi, G.Montaudo

2nd Workshop of Young European Scientists - YES 2005, September 13-18, 2005 Cracow, Poland   - 2005



192) Caratterizzazione strutturale di copolimeri ottenuti mediante miscelazione reattiva controllata

F.Samperi, C.Puglisi, G.Montaudo

XVII Convegno Italiano di Scienza e Tecnologia delle Macromolecole, 11-15 settembre 2005, Napoli  ,  73  - 2005



193) Used Cooking Oils as Renewable Source for Polyhydroxyalkanoates Production

R.Alicata, A.Ballistreri, V.Catara, E.Conte, S.Di Silvestro, A.Ferreri, S.Greco, S.Guglielmino, G.Impallomeni, S.La Porta, M.Russo, A.Catara

3rd European Symposium on Biopolymers ESBP05, Madrid (Spagna), 24-25 Novembre, 2005.   - 2005



194) Isolamento e Caratterizzazione di una Liasi Attiva sul Polisaccaride Cepaciano

P.Cescutti, S.Scussolin, Y.Herasimenka, G.Impallomeni,R.Rizzo

XVII Convegno Italiano di Scienza e Tecnologia delle Macromolecole, Napoli, 11-15 Settembre, 2005.   - 2005



195) Advances in purification methods of serum glycoproteins for MALDI_MS analysis of N-Glycome in patients with glycosylation disorders.

L.Sturiale, R.Barone, D.Garozzo

2005 Annual Meeting of the Society for Glycobiology. 9-12 November, 2005. Boston   - 2005



196) Mass spectrometric approaches for the N-glycosylation analysis in congenital disordrs of glycosylation (CDG) and galactosemia

L.Sturiale, R.Barone, M.Perez, G.Sorge, J.Jaaken, D.Garozzo

Italian Human Proteomic Organization (IHUPO). Terzo Congresso Nazionale. 29-Settembre- 1 Ottobre 2005, Lodi-Milano   - 2005



197) Mass spectrometry strategies for the N-glycosylation analysis of serum glycoproteins in patients with congenital disorders of glycosylation (CDG) and galactosemia

L.Sturiale, R.Barone, G.Sorge, M.Perez, A.Messina, S.Tortorelli, J.F.O&rsquoBrien, J.Jaeken, D.Garozzo

Glycoproteomics - Protein Modifications for Versatile Functions. June 28 - 30, 2005, Dubrovnik, Croatia   - 2005



198) Hypoglycosylation with increate fucosylation and branching of serum transferrin N-glycans in untreated galactosemia

L.Sturiale, R.Barone, A.Fiumara, M.Perez, M.Zaffanello, G.Sorge, L.Pavone, J.Jaeken, D.Garozzo

1st Euroglycanet meeting, March, 28-30, 2005, Athens, Greece   - 2005



199) Size-exclusion chromatography/matrix-assisted laser desorption ionization and SEC/NMR techniques for polymer characterization

M.S.Montaudo

ACS Symposium Series   893,  152  - 2005

Measurements on a series of random copolymers with units of Me methacrylate (MMA), Bu acrylate (BA), styrene (St), and maleic anhydride (MAH) are performed. A characterization method is used which consists in fractionating the copolymer by size-exclusion chromatog. (SEC), collecting 30-40 fractions and then recording both the NMR (NMR) spectroscopy and matrix-assisted laser desorption ionization (MALDI) spectra of the fractions. In a successive step, Bivariate Distribution of chain sizes and compn. maps are derived from knowledge of the molar mass, wt., and compn. of the copolymer fractions.


200) Identificazione rapida di batteri mediante spettrometria di massa MALDI-TOF: dallo spettro del lipooligosaccaride all’individuazione di batteri gram-negativi

L.Sturiale, R.Cozzolino, M.Perez, A.Messina, D.Garozzo

Convegno finale del progetto Trattamento di prodotti freschi altamente deperibili per garantirne qualità, sicurezza e salubrità . 16-19 Marzo, 2005, Ariano Irpino (AV)   - 2005



201) Mass spectrometric strategies for the N-glycosylation analysis of serum glycoproteins in patients with congenital disorders of glycosylation (CDG) and galactosemia

L.Sturiale, R.Barone, M.Perez, G.Sorge, J.Jaeken, D.Garozzo

GLYCO XVIII. XVIII International Symposium on Glycoconjugates, September 4-9, 2005, Firenze, Italy   - 2005



202) Proteomic Analysis of Human Tear Fluids in Healthy and Pathological Conditions

R.Cozzolino, M. Perez, A.Messina, L.Sturiale, D.Garozzo, M.G.Mazzone, M.Santocono

53rd ASMS Conference (June 5-9 2005)   - 2005

The ocular tear film is a complex mixture of ions, small molecules, glycoproteins and proteins, which form a thin film over the surface of the cornea and conjunctiva. Since directly in contact with the environment, it plays a critical role in protecting against microbial challenge and preserving visual acuity. Changes in tear film composition are usually related to several eye diseases like dry eye, Sjögren syndrome, conjunctivitis, blepharitis and so on. To elucidate compositional differences between healthy subjects and patients affected by different eye diseases, we thoroughly studied their tear proteomic profiles by MALDI-TOF MS, focusing in particular the low mass range region, in which defensins and bioactive peptides are present in order to find biomarkers for disease diagnosis.


203) Increased fucosylation and branching of serum transferrin N-glycans in long-term untreated galactosemic patients

L.Sturiale R.Barone, G.Sorge, M.Zaffanello, A.Fiumara, G.Impallomeni, D.Garozzo

US/Japan Glyco 2004 - Joint meeting of the society for glycobiology and the japanese society of carbohydrate research. November 17-20, 2004, Honolulu, Hawaii   - 2004



204) Microbial Synthesis of Poly(hydroxyalkanoates) by Pseudomonas aeruginosa from Fatty Acids: Identification of Higher Monomer Units and structural Characterization

A.Ballistreri, T.Barbuzzi, G.Impallomeni, M.Giuffrida, S.Carnazza, S. P. P.Guglielmino, A.Ferreri

2nd European Symposium on Biopolymers ESBP04, EMPA St. Gallen (Svizzera), 13-14 Maggio, 2004    - 2004



205) Sintesi e caratterizzazione mediante NMR 1H e 13C del metil-6-O-[2-(6-metossi-2-naftil)propanoil]-D-glucofuranoside del S-Naproxen

G.Impallomeni, R.Saletti, S.Foti

XXIX Convegno Nazionale della Divisione di Chimica Organica della Società Chimica Italiana, Potenza, 31 Agosto - 4 Settembre, 2004   - 2004



206) Sintesi e caratterizzazione strutturale di copoliesteri biodegradabili da Pseudomonas aeruginosa coltivata su acidi grassi

A.Ballistreri, T.Barbuzzi, G.Impallomeni, M.Giuffrida, S. P. P.Guglielmino, S.Carnazza, A.Ferreri

XXIX Convegno Nazionale della Divisione di Chimica Organica della Società Chimica Italiana. Potenza, 31 Agosto - 4 Settembre, 2004   - 2004



207) Glycomics: a frontier in proteomics

D.Garozzo

Primiero discussion group on mass spectrometry. New frontiers in proteomics . November 7-10, 2004. Fiera di Primiero (TN)   - 2004



208) New Fragmentation Mechanisms in MALDI-TOF/TOF MS/MS of Carbohydrates

D.Garozzo

International Symposium on Mass Spectrometry in Proteomics and Molecular Profiles. 29th January 2004. Università della Calabria   - 2004



209) Variability of enzymatic activities in the Ionian Sea

R.Zaccone, L.S.Monticelli, D.Zampino

Rapp. Comm. Int. Mer Médit  37,  298  - 2004



210) Determination of living and active bacterioplankton: a comparison of methods

D.Zampino, R.Zaccone, R.La Ferla

Chemistry and Ecology  20(6),  411  - 2004

The purpose of this study was the quantification, through the comparison of different methods, of viable and metabolically active bacteria in marine environments. To quantify the living and active bacterioplankton fractions, we compared the total cell count (TC using DAPI staining), plate count on marine agar (CFU), and three viability-staining methods: nucleoid-containing cell count (NuCC), Live/Dead staining procedure (L/D) and direct viable count (DVC). With respect to TC (mean value 3.0 ± 2.3 × 10 5 cell ml -1 ) CFU represented less than 0.1% and DVC cells 1%, both showing significant differences. NuCC and L/D cells were 18.0% and 15.9% of TC, respectively, showing no significant differences and higher percentages in the Ionian Sea than the Adriatic Sea. Moreover, NuCC and L/D were two orders of magnitude greater than the culturable fraction, while active cells (DVC) exceeded CFU by one order of magnitude. The comparison of different staining methods allowed us to confirm the simultaneous presence of different physiological states within the bacterial population in natural marine environments. The NuCC and L/D methods gave comparable values to those of other authors, while the DVC procedure gave lower values than previously reported. This research provides information on the fraction of living and/or metabolically active bacteria in aquatic ecosystems. Since each method has its own detection limits, the study highlights the need to simultaneously compare the different methods to validate their results.


211) Full copolymer characterization by SEC-MALDI and SEC-NMR

M.S.Montaudo

MACRO2004: World Polymer Congress . 4-9 July 2004, Parigi, Francia  ,  2449  - 2004



212) Hybrid Molecular Materials for Optical NO2 Gas Sensing

E.Scamporrino, D.Vitalini

Atti del Convegno intitolato SAMIC 2004 – Syntheses And Methodologies In Inorganic Chemistry. Trends in Nanoscience. Bressanone (BZ), 4-7 dicembre 2004. Book of Abstracts  ,  38  - 2004



213) Effect of Delay Time and Grid Voltage Changes on the Average Molecular Mass of Polymers and Polymeric Blends Determined by DE MALDI-TOF

E.Scamporrino, D.Vitalini

Atti del Convegno intitolato MASSA 2004. An International Symposium on Mass Spectrometry.Bari, 26-30 settembre 2004. Book of Abstracts  ,  19  - 2004



214) Sintesi di Macromolecole Porfiriniche e loro Assemblaggio su Superfici Inorganiche per Sensoristica Molecolare

R.Alicata, S.Bazzano, I.Fragalà, A.Gulino, P.Mineo, E.Scamporrino, D.Vitalini

Atti del Convegno intitolato XXVI Convegno Scuola AIM su Tecniche Avanzate e Nuovi Sviluppi nella Caratterizzazione dei Materiali Polimerici .Gargnano (BS), Palazzo Feltrinelli, 24-28 maggio 2004  ,  4  - 2004



215) Exchange reactions occurring through active chain ends. MALDI-TOF characterization of copolymers from Nylon 6,6 and Nylon 6,10

C.Puglisi, F.Samperi, S.Di Giorgi, G.Montaudo

Atti del The 2nd International Conference on Times of Polymers (TOP) Ischia (Na) 20-23 giugno 2004  ,  34  - 2004



216) Structural characterization of copolyamides synthesized via the facile blending of polyamides

F.Samperi, M.S.Montaudo, C.Puglisi, S.Di Giorgi, G.Montaudo

Atti del The 2nd International Conference on Times of Polymers (TOP) Ischia (Na) 20-23 giugno 2004  ,  33  - 2004



217) Essential role of chain ends in the Nylon6/Poly(ethyleneterephthalate) exchange

F.Samperi, C.Puglisi, R.Alicata, G.Montaudo

Atti del The 2nd International Conference on Times of Polymers (TOP) Ischia (Na) 20-23 giugno 2004  ,  32  - 2004



218) Essential role of chain ends in the Ny6/ PBT exchange a combined NMR and MALDI approach

F.Samperi, Maurizio Montaudo, C.Puglisi, Rossana Alicata, Giorgio Montando

Atti del The 2nd International Conference on Times of Polymers (TOP) Ischia (Na) 20-23 giugno 2004  ,  3  - 2004



219) Microbial community dynamics during assays of oil spill bioremediation : study in micro- and mesoscale

S.Cappello, G.Caruso, M.M.Yakimov, L.Monticelli, D.Zampino, G.Maimone, C.Tamburini, B.Tripodo, M.Mancuso, M.Trousselier, L.Giuliano

IV Convegno Nazionale CoNISMa - XVI Congresso AIOL. Città del Mare - Terrasini (PA), 18-22 ottobre 2004, abstract  ,  100  - 2004



220) Rapid analytical approaches for Escherichia coli monitoring in coastal waters of Messina straits

G.Caruso, F.De Pasquale, M.Mancuso, D.Zampino, E.Crisafi

IV Convegno Nazionale CoNISMa - XVI Congresso AIOL. Città del Mare- Terrasini (PA), 18-22 ottobre 2004, abstract  ,  223  - 2004



221) Caratterizzazione strutturale di polisaccaridi mediante spettrometria di massa

D.Garozzo, G.Impallomeni, D.Romeo, E.Spina, L.Sturiale

XXVI Convegno Scuola dell’Associazione Italiana di Scienza e Tecnologia delle Macromolecole, Gargnano (BS) 24-28 Maggio, 2004   - 2004



222) Analisi del Glicoma del Siero di Pazienti Affetti da Disordini Congeniti della Glicosilazione (CDG) e da Galattosemia

L.Sturiale, R.Barone, A.Fiumara, G.Sorge, G.Impallomeni, D.Garozzo

IX Convegno sulla Chimica dei Carboidrati, Certosa di Pontignano (Siena), 21-23 Giugno, 2004   - 2004



223) Glycomics of human serum: mass spectrometry investigations of serum glycoproteins in patients with congenital disorders of glycosylation (CDG) and glactosemia

L.Sturiale, R.Barone, A.Fiumara, G.Sorge, G.Impallomeni, D.Garozzo

2nd Italian Human Proteome Organization National Meeting. Proteomics impact in basic and clinical research. 16-18 September, 2004 - Chieti, Italy   - 2004



224) Preliminary results on proteomics of human tear fluids : Lack of bioactive peptides and defensins in disease subjects

M.Perez, A.Messina, R.Cozzolino, L.Sturiale, MG.Mazzone, D.Garozzo

2nd Italian Human Proteome Organization National Meeting. Proteomics impact in basic and clinical research. 16-18 September, 2004 - Chieti, Italy   - 2004



225) Proteomic of human tear fluids in healthy and pathological conditions

MG.Mazzone, M.Santocono, M.Perez, A.Messina, R.Cozzolino, L.Suriale, D.Garozzo

4th International Conference on the lacrimal gland, tear film, ocular surface and dry eye syndromes: basic science and clinical relevance. November17-20, 2004. Fajardo, Puerto Rico   - 2004



226) Deep-chlorophyll maximum time series in the Augusta Gulf (Ionian Sea): microbial community structures and functions

R.Zaccone, C.Caroppo, R.La Ferla, D.Zampino, G.Caruso, M.Leonardi, G.Maimone, M.Azzaro, R.Sitran

Chemistry and Ecology  20 (suppl.1),  S267  - 2004

An integrated study was carried out to follow the temporal evolution of microbiological parameters during a 48 h period, in relation to the deep chlorophyll maximum (DCM) at a coastal station. The micro-organisms showed an active role in the environment and a different distribution, without a clear diel cycle. The phytoplankton community, responsible for the DCM, consisted mainly of diatoms. Their distribution in relation to pycnocline showed an opposite trend with respect to picophytoplankton. Total bacterioplankton contributed to enzymatic degradation of particulated organic carbon (by producing β-glucosidase and aminopeptidase), with peaks related to changes in the main water current. We estimated that about 25% of particulate organic carbon per day may be hydrolysed by bacteria. The living bacterioplankton represented 20% of the total. The picophytoplankton fraction contributed significantly to the high values of alkaline phosphatase, suggesting a fast P regeneration. Respiration showed significant correlations with the physical and chemical parameters as well as with the different planktonic fractions.


227) Early detection of Vibrio anguillarum in waters: a challenge experience on Dicentrarchus labrax in microcosm

R.Zaccone, G.Caruso, D.Zampino, M.Mancuso, L.Genovese, R.Adone, F.Ciuchini, A.Manfrin

European Aquaculture Society  34,  849  - 2004



228) Exopolysaccharides produced by Burkholderia cenocepacia recA lineages IIIA and IIIB

L.Chiarini, P.Cescutti, L.Drigo, G.Impallomeni, Y.Herasimenka, A.Bevivino, C.Dalmastri, S.Tabacchioni, G.Manno, F.Zanetti, R.Rizzo

Journal of Cystic Fibrosis   3(3),  165  - 2004

Clin. and environmental strains of Burkholderia cenocepacia belonging to the recA lineages IIIA and IIIB were examd. for exopolysaccharide (EPS) prodn. The exopolysaccharides structure was detd. using mainly gas chromatog. coupled to mass spectrometry and NMR spectroscopy. All the strains produced Cepacian, a highly branched polysaccharide constituted of a heptasaccharide repeating unit, composed of one rhamnose, one glucose, one glucuronic acid, one mannose and three galactose residues. This polymer is the most common exopolysaccharide produced by strains of the Burkholderia cepacia (Bcc) complex. One clin. strain produced also another polysaccharide constituted of three galactose units and one 3-deoxy-d-manno-2-octulosonic acid residues, a polymer that was previously isolated from two strains of B. cepacia genomovar I and B. cenocepacia IIIA.


229) Size- Exclusion Chromatography/Matrix - Assisted Laser Desorption Ionization and SEC/NMR Techniques for Polymer Characterization

M.S.Montaudo

Multiple Detection in Size-Exclusion Chromatography. Andre M.Striege, Editor the Florida State University ACS SYMPOSIUM SERIES 893   Chapter 9  - 2004

Measurements on a series of random copolymers with units of methyl methacrylate (MMA), butyl acrylate (BA), styrene (St), and maleic anhydride (MAH) are performed. book cover A characterization method is used which consists in fractionating the copolymer by size-exclusion chromatography (SEC), collecting 30-40 fractions and then recording both the nuclear magnetic resonance (NMR) spectroscopy and matrix-assisted laser desorption ionization (MALDI) spectra of the fractions. In a successive step, Bivariate Distribution of chain sizes and composition maps are derived from knowledge of the molar mass, weight, and composition of the copolymer fractions.



230) The "half-monomer" concept for sequence analysis of condensation copolymers by NMR

M.S.Montaudo

Polymer News  29(7),  228  - 2004

The "half-monomer" concept was introduced in 1982 by Devaux et al. [1]. The authors used Nuclear Magnetic Resonance (NMR) to characterize the copolymer obtained when mixing and heating at 290¼C poly(butylene terephthalate) (PBT for brief) together with poly(bisphenol A carbonate) (PC for brief). They noted that the repeat unit of PBT and of PC can be ideally split in two parts and thus they introduced four half-monomers A, B, C, D namely


231) Variations occurring in microbial activities in the Ionian Sea: observations during the SINAPSI cruises

R.Zaccone, L.S.Monticelli, R.La Ferla, D.Zampino, M.Azzaro, G.Maimone

Workshop SINAPSI Climate, variability, circulation and effects on marine ecosystem in the Eastern Mediterranean. Pisa 16-17 Novembre 2003.   - 2003



232) Enzymatic activities in water masses of the Ionian Sea

R.Zaccone, L.S.Monticelli, D.Zampino

2° Convegno Internazionale Enzymes in the environment: Activity Ecology and Applications, Praha 14-17 luglio 2003  ,  94  - 2003



233) News About Exopolysaccharides Produced by Burkholderia cepacia Strains

P.Cescutti, Y.Herasimenka, G.Impallomeni, A.Bevivino, C.Dalmastri, S.Tabacchioni, L.Chiarini, G.Manno, C.Lagatolla, E. A.Tonin, R.Rizzo

International Burkholderia cepacia Working Group, 8th Annual Meeting, London, March 21-23, 2003   - 2003



234) MALDI-TOF Mass Spectrometry Characterization of Biodegradable Copolymers Obtained by Exchange Reactions

A.Ballistreri, T.Barbuzzi, G.Impallomeni, M.Giuffrida

Workshop on MALDI and ESI Mass Spectrometry after 2002 Chemistry Nobel Prize, Catania, 11-12 Febbraio, 2003   - 2003



235) HPLC/ESI-MS Studies on Enzymatic Hydrolysis of Synthetic Aliphatic Polyesters

P.Rizzarelli, G.Impallomeni, G.Montaudo

16th International Mass Spectrometry Conference, Edimburgo, August 31-September 5, 2003   - 2003



236) HPLC/ESI-MS studies on enzymatic hydrolysis of synthetic aliphatic copolyesters

G.Impallomeni, G.Montaudo, P.Rizzarelli

Workshop on MALDI and ESI Mass Spectrometry after the 2002 Chemistry Nobel Prize, Catania 11-12 Febbraio 2003.   - 2003



237) Determination of linkage positions and sequence of complex carbohydrates by MALDI TOF-TOF mass spectrometry.

E.Spina, L.Sturiale, G.Impallomeni, D.Garozzo, D.Waidelich, M.Glueckmann

Primo congresso Nazionale IHUPO, 26-27 Settembre 2003. Napoli, Italy   - 2003



238) Analysis of human tear proteins by capillary LC/ESI-MS

R.Cozzolino, V.Enea, MG.Mazzone, D.Garozzo

Primo congresso Nazionale IHUPO, 26-27 Settembre 2003. Napoli, Italy   - 2003



239) Structural characterization of the O-specific lipopolisaccharide chains by MALDI-MS

L.Sturiale, A.Molinaro R.Lanzetta, D.Garozzo

12th European Carbohydrate Symposium, July 6-11, 2003, Grenoble, France   - 2003



240) Insertion of Cu-diimine Complexes or Porphyrin Units in Commercial Polycarbonate by Thermal Processes

P.Mineo, E.Scamporrino, D.Vitalini

Atti del IV Convegno Nazionale sulla Scienza e Tecnologia dei Materiali.Ischia Porto (NA), 29 giugno - 2 luglio 2003  ,  B28  - 2003



241) Inserimento di Unità Diimminiche e Porfiriniche in Policarbonati Commerciali mediante Processi Termici

R.Alicata, S.Bazzano, P. Mineo, E.Scamporrino, D.Vitalini

Atti del XVI Convegno Italiano di Scienza e Tecnologia delle Macromolecole.Pisa, 22 - 25 settembre 2003  ,  70  - 2003



242) Recent advances in the analysis of polymers and copolymers by MALDI

M.S.Montaudo

Atti dell’ Ibaraki Regional Workshop on MALDI dell’Advanced Industrial Science and Technology (AIST), 4-5 Marzo 2003, Tsukuba, Japan.   - 2003



243) Full copolymer characterization by SEC-MALDI and SEC-NMR

M.S.Montaudo

Atti del Workshop on MALDI and ESI Polymer mass spectrometry. Catania, 11-12 Febbraio 2003  ,  4  - 2003



244) Thermal degradation of PET and PBT at the processing temperature

F.Samperi, C.Puglisi, R.Alicata, G.Montaudo

Atti del XVI Convegno Italiano di Scienza e Tecnologia delle Macromolecole, Pisa 22-25 settembre 2003  ,  26  - 2003



245) Caratterizzazione mediante MALDI-MS del gel formato per riscaldamento del Ny66.

F.Samperi, C.Puglisi, S.Di Giorgi, G.Montaudo

Atti del XVI Convegno Italiano di Scienza e Tecnologia delle Macromolecole, Pisa 22-25 settembre 2003  ,  25  - 2003



246) Degradazione termica del policaprolattone

C.Puglisi, F.Samperi, N.Tasca, G.Montaudo

Atti del XVI Convegno Italiano di Scienza e Tecnologia delle Macromolecole, Pisa 22-25 settembre 2003  ,  23  - 2003



247) HPLC/ESI-MS studies on lipase-catalysed preferential cleavage of synthetic aliphatic copolyesters

P.Rizzarelli, G.Impallomeni, G.Montaudo

Atti del XVI Convegno Italiano di Scienza e Tecnologia delle Macromolecole, Pisa 22-25 settembre 2003  ,  21  - 2003



248) Photo-oxidation mechanisms of nylon 6

S.Carroccio, G.Montaudo, C.Puglisi

Atti del XVI Convegno Italiano di Scienza e Tecnologia delle Macromolecole, Pisa 22-25 settembre 2003, pagina 18  ,  18  - 2003



249) Proprietà Strutturali di Polisaccaridi Prodotti dal Batterio Patogeno Opportunista Burkholderia cepacia

P.Cescutti, Y. Herasimenka, R.Urbani, P.Sist, R.Rizzo, G.Impallomeni, L.Sturiale, D.Garozzo

XVI Convegno Italiano di Scienza e Tecnologia delle Macromolecole, Pisa, 22-25 Settembre, 2003   - 2003



250) Ruolo dei gruppi terminali nelle reazioni di scambio in miscele Ny6/PBT allo stato fuso

F.Samperi, C.Puglisi, R.Alicata, G.Montaudo

Atti del XVI Convegno Italiano di Scienza e Tecnologia delle Macromolecole, Pisa 22-25 settembre 2003  ,  15  - 2003



251) Sintesi e caratterizzazione di copoliammidi Ny66/Ny6,10

F.Samperi, C.Puglisi, G.Montaudo

Atti del XVI Convegno Italiano di Scienza e Tecnologia delle Macromolecole, Pisa 22-25 settembre 2003  ,  14  - 2003



252) Meccanismi di reazione in miscele di polimeri di condensazione allo stato fuso.

F.Samperi, C.Puglisi, G.Montaudo

Atti del XVI Convegno Italiano di Scienza e Tecnologia delle Macromolecole, Pisa 22-25 settembre 2003  ,  10  - 2003



253) Analisi di Copolimeri mediante cromatografia ad esclusione sterica accoppiata alla spettrometria di massa MALDI-TOF ed alla risonanza magnetica nucleare.

M.S.Montaudo

Atti del XVI Convegno Italiano di Scienza e Tecnologia delle Macromolecole, Pisa 22-25 settembre 2003  ,  9  - 2003



254) MALDI-TOF and ESI mass spectrometry of biodegradable copolymers obtained by exchange reactions

A.Ballistreri, T.Barbuzzi, M.Giuffrida, G.Impallomeni

Atti del XVI Convegno Italiano di Scienza e Tecnologia delle Macromolecole, Pisa 22-25 settembre 2003  ,  8  - 2003



255) Identification of some adulteration in milk and in water buffalo mozzarella cheese by MALDI TOF MS

R.Cozzolino, S.Passalacqua, S.Salemi, D.Garozzo

Abstracts of the 51st Conference on Mass Spectrometry and Allied Topics, Montreal, June 2003  ,  1704  - 2003

Water buffalo mozzarella cheese and "Pecorino" cheese are two of the most typical Italian products. Because water buffalo milk and ewe milk are more expensive than bovine milk, this is some times fraudulently added to raw ovine and water buffalo milk samples leading to products that are sold to the same prize of the authentic cheese. Several analytical methodologies have been developed in order to detect this kind of adulteration but the slowness of these methods makes them of limited value in the diary industry routine screening of milk. Recently, matrix-assisted laser desorption/ionisation mass spectrometry has shown to be a powerful analytical tool in providing a valid fingerprint of milk protein profiles. The method, in fact, has been successful employed for monitoring structural damages caused by thermal industrial processes, like pasteurisation and sterilisation, as well as to reveal differences in the protein pattern of milk samples coming from various mammal species.


256) Sequencing underivatized oligosaccharides using a MALDI-TOF/TOF tandem mass spectrometer

D.Garozzo, E.Spina, F.J.Mayer-Posner, V.Sauerland

Abstracts of the 51st Conference on Mass Spectrometry and Allied Topics, Montreal, June 2003  ,  1300  - 2003

Analysis of carbohydrates is an important problem in biochemical analysis but the structural elucidation of a complex carbohydrate molecule is analytically difficult because it requires the knowledge of several parameters such as sugar sequence, reducing end, linkage type between the monosaccharides and the anomeric configuration. Because of its large mass range and high sensitivity, matrix-assisted laser desorption time-of-flight (MALDI-TOF) mass spectrometry is now widely used in the molecular mass determination of underivatized oligo- and polysaccharides (1-5) and since the introduction of the postsource decay (PSD) technique, providing fragmentation spectra, some papers dealing with the PSD of oligosaccharides have been published


257) Advances in MALDI-MS methods to investigate the structure of bacterial Lipopolysaccharides

L.Sturiale, A.Molinaro, R.Lanzetta, D.Garozzo

Abstracts of the 51st Conference on Mass Spectrometry and Allied Topics, Montreal, June 2003  ,  1293  - 2003

Lipopolysacchrides (LPSs) are the main components of the outer membrane of bacterial cells and contribute significantly to patho-physiological effects and virulence of these organisms. Such glycoconjugates, also known as endotoxin of gram-negative bacteria, are comprised of three distinct regions covalently bound: a lipid A moiety (which acts as hydrophobic anchor of LPSs in the bacterial membrane) an acidic oligosaccharide core, and an O-antigen, a long chain of oligosaccharide repeating units extending out into the external environment. The LPSs structures vary greatly among different bacterial species, particularly, O-antigen changes also between diverse strains and exhibits moreover a remarkable polydispersity due to the presence of molecules differing in the number of repeating units. This work presents some improved MALDI-MS approaches to elucidate the structure of these high complex species.


258) Photooxidation mechanisms of polyetherimide Ultem investigated by MALDI-TOF-MS

C.Puglisi, G.Montaudo, S.Carroccio

Abstracts of Papers, 225th ACS National Meeting, New Orleans, LA, United States, March 23-27, 2003   - 2003

Poly (2,2'bis (3,4-dicarboxyphenoxy) phenylpropane)-2 phenylendiimide (ULTEM) was subjected to photo aging in the attempt to find evidence on the structure of the species formed in the oxidative degrdn. The oxidative process was followed as a function of the exposure time by MALDI and SEC/MALDI techniques. The SEC curves showed extensive degrdn., with the formation of low molar mass oligomers having different end groups. Highly valuable structural information on the photoxidized ULTEM species was extd. from the MALDI spectra of the photoxidized ULTEM samples.These showed the presence of polymer chains contg. acetophenone, Ph acetic acid, phenols, benzoic acid, phthalic anhydride and phthalic acid end groups. The mechanisms accounting for the formation of photoxidn. products of Ultem involve the operation of several simultaneous reactions: i) photo-cleavage of Me groups of the N-Me phthalimide terminal units; ii) photoxidative degrdn. of the isopropylidene bridge of BPA units; iii) photoxidn. of phthalimide units to phthalic anhydride end groups: iiii) hydrolysis of phthalic anhydride end groups. The kinetic behavior of all the species detected is in agreement with the predictions of the reaction mechanisms hypothesized.


259) Exchange reactions occurring through active chain ends: MALDI-TOF characterization of copolymers from nylon 6,6 and nylon 6,10

C.Puglisi, F.Samperi, G.Montaudo

Abstracts of Papers, 225th ACS National Meeting, New Orleans, LA, United States, March 23-27, 2003   - 2003

A study on the sequence and compn. of copolyamides formed by activated exchange reactions occurring in the melt mixing of Ny6,10 and Ny6,6 is reported. Equimolar mixts. of Ny6,10, Ny6,6 and carboxyl terminated Ny6,6 samples were melt mixed at different temps. (290-310°C) for different times (10-180 min). MALDI-TOF mass spectra allowed the detection of the copolyamides formation and the detn. of their sequence and compn. The results can be reconciled within the overall scheme of exchange reaction occurring through active chain ends.The compn. of the copolyamides formed by the exchange of Ny6,6-COOH/Ny6,10 mixts. showed a higher amt. of Ny6,6 units, with respect to the initial blends compn., and a higher value of the Ny6,6 av. block length, at the beginning of the reaction (10 min). The compn. of the copolyamides was found to be equal to the feed compn. (50/50), after 30 min of heating, with a random distribution of sequences. The compn. and the sequence distributions of the copolyamides remained unaffected even at higher heating time (180 min) although some degrdn. reactions also occurred.


260) Photoxidation mechanisms of polyetherimide Ultem investigated by MALDI-TOF-MS

S.Carroccio, C.Puglisi, G.Montaudo

Polymeric Materials Science and Engineering  88,  183  - 2003

The photooxidative degrdn. of ULTEM (i.e., poly(2,2'-bis(3,4-dicarboxyphenoxy)phenylpropane)-2-phenylenediimide) was studied by MALDI-TOF mass spectrometry (matrix assisted laser desorption ionization time-of-flight). According to the identified oxidn. products, the photooxidn. process is characterized by 4 main processes: photo-cleavage of Me-groups of the N-Me phthalimide terminal units, photooxidative degrdn. of the isopropylidene bridge of BPA units, photooxidn. of phthalimide units to phthalic anhydride end groups, and hydrolysis of the phthalic anhydride end groups


261) Exchange reactions occurring through active chain ends. MALDI-TOF characterization of copolymers from nylon 6,6 and nylon 6,10

C.Puglisi, F.Samperi, G.Montaudo

Polymeric Materials Science and Engineering  88,  336  - 2003

A study on the sequence and compn. of copolyamides formed by activated exchange reactions occurring in the melt mixing of Nylon 6,10 and Nylon 6,6 is reported. Equimolar mixts. of Nylon 6,10, Nylon 6,6 and carboxyl terminated Nylon 6,6 samples were melt mixed at different temps. (290 - 310 °C) for different times (10 - 180 min). MALDI-TOF mass spectra allowed the detection of the copolyamides formation and the detn. of their sequence and compn. The results can be reconciled within the overall scheme of exchange reaction occurring through active chain ends. The compn. of the copolyamides formed by the exchange of Nylon 6,6-COOH/Nylon 6,10 mixts. showed a higher amt. of Nylon 6,6 units, with respect to the initial blends compn., and a higher value of the Nylon 6,6 av. block length, at the beginning of the reaction (10 min). The compn. of the copolyamides was equal to the feed compn. (50/50), after 30 min of heating, with a random distribution of sequences. The compn. and the sequence distributions of the copolyamides remained unaffected even at higher heating time (180 min) although some degrdn. reactions also occurred


262) Copolymer characterization by SEC-NMR and SEC-MALDI

M.S.Montaudo

ACS Symposium Series  834,  358  - 2003

Off-line SEC-NMR and SEC-MALDI measurements are performed on a series of random copolymers of methyl methacrylate, butyl acrylate, styrene and maleic anhydride.book cover First, a method is used, consisting of fractionating the copolymer by SEC and recording both the NMR and MALDI spectra of the fractions, In a successive step, the bivariate distribution of chain sizes and composition maps are derived from a knowledge of the molar mass, weight and composition of the copolymer fractions. The compositional distribution is obtained by summation of the sections of the bivariate distribution which belong to a narrow compositional range. Secondly, a model for SEC fractionation of copolymers is developed. It permits the prediction of the composition and dispersity of each SEC fraction. Thirdly, offline SEC-MALDI measurements are performed, in order to measure dispersity experimentally for the random copolymer, The agreement between theoretical and experimental values for dispersity and for the composition of the SEC fraction (as derived from SEC-NMR measurements) is good. The predictions of the model also compare favorably with literature SEC fractionation data of a copolyester of butylene adipate and butylene sebacate.


263) MALDI Mass Spectrometry as a Tool for Characterizing Glycosaminoglycan Oligosaccharides and their Interaction with Proteins

L.Sturiale, A.Naggi, G.Torri

50th ASMS Conference on Mass Spectrometry and Allied Topics, Orlando, Florida, June 2-6, 2002   - 2002

The increasing interest in analytic techniques that are able to manage very small amount of samples, like those coming into play at the physiological level, has recently brought matrix assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI TOF-MS) to an amazing development in the field of glycobiology. This trend has allowed us to overcome some of the problems that only few years ago were hard to solve. An important example is the application of the MALDI approach to the structural investigations of a biologically-relevant class of very acidic polysaccharides, such as the glycosaminoglycans (GAGs), and their fractions and fragments.


264) Thermal oxidation products of nylon-6 determined by MALDI-TOF mass spectrometry

G.Montaudo, C.Puglisi, F.Samperi, D.Chionna

Abstracts of Papers, 224th ACS National Meeting, Boston, MA, United States, August 18-22, 2002   - 2002

Thermal oxidative degrdn. products of Nylon 6 samples, generated at 250°C under atm. air were analyzed by Matrix Assisted Laser Desorption Ionization-Time of Flight (MALDI-TOF) Mass Spectrometry. This technique possesses a high sensitivity, allowing the desorption and the ionisation of large mols., even in complex mixts., and therefore is widely used with increasing success for the characterization of synthetic polymers. The anal. of the MALDI-TOF spectra of thermally oxidized Nylon 6 samples showed the presence of polymer chains contg. aldehyde, amide,N-formamide, and Me end groups, which appear to be generated from primary oxidn. processes. The MALDI-TOF spectra show also the presence of carboxyl end groups, most likely formed by the further oxidn. of aldehyde contg. compds. Also the formation of azomethynes, from further reaction of aldehydes with amino terninated Ny6 chains, is also supported by the appearance of specific peaks in the MALDI spectra


265) Mechanisms of thermal oxidation of poly(bisphenol a carbonate)

G.Montaudo, S.Carroccio, C.Puglisi

Abstracts of Papers, 224th ACS National Meeting, Boston, MA, United States, August 18-22, 2002   - 2002

Thermal oxidn. products of Poly(Bisphenol A carbonate) (PC), generated by heating at 300 and 350°C under atm. air as a fuction of the exposure time, were investigated by SEC, 1H-NMR , MALDI-TOF mass spectrometry techniques. The MALDI-TOF spectra of thermal oxidized PC samples showed the presence of polymer chains contg. acetophenone, phenyl-substituted acetone, phenols, benzyl-alc. and biphenyl terminal groups. Formation of acetophenone and phenol end groups was confirmed by 1H-NMR anal. The mechanisms accounting for the formation of thermal oxidn. products of PC involve the operation of several simultaneous reactions: i) hydrolysis of carbonate groups of PC to form free Bisphenol A end groups; ii) oxidn. of the isopropenyl groups of PC; iii) oxidative coupling of phenols end groups to form biphenyl groups. The presence of biphenyl units among the thermal oxidn. products confirmed the occurrence of crosslinking processes, which is responsible for the formation of the insol. gel fraction


266) Direct pyrolysis of polymers into the ion source of a mass spectrometer (DP-MS)

G.Montaudo, C.Puglisi

Mass Spectrometry of Polymers  ,  181  - 2002

book cover A review on the principles and methodol. as well as selected applications (poly(styrene sulfide), evolution of aroms. in the thermal degrdn. of poly(vinyl chloride), nylon 6.6, poly(ethylene terephthalate), poly(bisphenol-A carbonate), poly(ether imide), and polymer blends) of DP-MS



267) Identification of High Molecular Mass Proteins in Tear Fluid by MALDI MS

R.Cozzolino, V.Enea, M.G.Mazzone, D.Garozzo

50th ASMS Conference on Mass Spectrometry and Allied Topics, Orlando, Florida, June 2-6, 2002   - 2002

Tear fluid, a complex mixture of ions, small molecules, glycoproteins and proteins, refers to fluid present as the precorneal film and in the conjunctival sac. As it is directly in contact with the environment, it mainly serves to protect the eye from exogenous antigenic substances and to maintain the structural integrity of the cornea and the conjunctival sac [1]. Regarding to this, tear proteins play an important role in the maintenance of the eye surface integrity, in fact in patients with external eye diseases, the level of certain tear proteins may be altered [2-4]. Consequently, many attempts have been made to correlate any qualitative and/or quantitative change in tear protein with eye disorders, but at the moment problems are habitually encountered finding appropriate, sensitive and yet rapid and simple techniques for the analysis of tear proteins. SDS-PAGE has been demonstrated to be a useful methods for the analysis of tear protein composition, as the major tear proteins sIgA, lactoferrin, TSPA and lysozyme can be separated with high resolution [5]. Furthermore, up to now with the two-dimensional electrophoretic technique at least 60 components have been detected in tears [6]. Recently, MALDI-TOF MS has been proposed in the ocular environment as a diagnostic tool for evaluating the pattern of low molecular weight peptide species (<20kDa) in tears [8-9]. On the contrary, there are no published data on the detection of the high molecular mass tear proteins. In view of these results, the aim of this study has been to build a biochemical profile of high molecular mass proteins in tears and to determine its repeatability by MALDI-TOF MS. A total of 90 tear samples were collected from 20 subjects. In particular, figure 1 presents the MALDI TOF spectrum of a tear sample using sinapinic acid as matrix. In figure 1, besides the peaks due to peptide species [8-9], it is possible to clearly detect two intense mass signals at m/z 14690 Da and 17443 Da which, according to the data reported in literature and in particular to some study obtained by SDS-PAGE [10-11], can be due to Lysozyme and Tear Specific Prealbumin (TSPA), respectively, while at m/z around 35kDa there are some peaks which can be attributed to the so called Protein G (TSPA dimmer). Comparable data were obtained with other MALDI matrices, as DHB, THAP, DHAP, a-ciano etc. and for all the samples studied. These data have demonstrated that tear samples, opportunely diluted and analysed by MALDI TOF using sinapinic acid as a matrix, give rise to spectra showing peaks only up to about 35 KDa. On the contrary, the same studies have shown the difficulty in obtaining molecular ion signals corresponding to the high molecular mass tear proteins such as Albumin and Lactoferrin. In view of the fact that Lactoferrin is soluble at lightly basic pH, it was thought to dilute tear samples with 0.05M NH3 and analyse the so treated samples using different matrices. As shown in figure 2 this way of proceeding allowed to observe a peak at about m/z 82000, if DHB was employed as matrix, the MW of which corresponds to Lactoferrin. Unfortunately, the dilution with 0.05M NH3 did not permit to reveal the albumin and other high molecular weight tear proteins mass signals. In order to overcome this problem, tear samples were treated with Centri/Por Centrifughe Concentrators which allow to concentrate, fractionate and desalt the high molecular mass proteins. Following this kind of procedure it can be obtained two fractions called filtrate (which contains compounds that can pass the membrane) and retentate (which is the aliquot containing the high MW species). Figure 3 presents the MALDI spectrum of the retentate of a tear sample, gained with Centri/Por Centrifughe. This analysis shows that treating the sample in that way, other two peaks at m/z about 67kDA and 92KDa can be detected, using sinapinic acid as a matrix. According to the data reported in literature [10-11], these two mass signals can be attributed to Albumin and Progelatinase B, respectively. The approach for a rapid, simple and accurate detection of human tear protein profile proposed here has demonstrated that the majority of high molecular mass proteins in tears are repeatedly present. Thanks to the successful data obtained, this method can be considered a first attempt in order to characterize tear high molecular protein species and to identify qualitative changes in tear protein patterns coming from healthy people and subject affected by eye diseases.


268) New Results on MALDI MS of Widely Polydisperse Hydrosoluble Polymers

P.Malvagna, G.Impallomeni, R.Cozzolino, E.Spina, D.Garozzo

50th ASMS Conference on Mass Spectrometry and Allied Topics, Orlando, Florida, June 2-6, 2002   - 2002

Since its introduction in 1988 (1), Matrix Assisted Laser Desorption Mass Spectrometry (MALDI MS) has become an important analytical tool in the analysis of macromolecules. However, while it was found that average molecular mass (MM) and molecular mass dispersion (MMD) estimates by MALDI MS for narrowly dispersed polymers were in agreement with those obtained by conventional methods of MM determination (size exclusion chromatography (SEC), end group titration, light scattering), on the contrary, several authors reported that for polymers with a broad MMD (synthetic polymers and polysaccharides) MALDI yielded erroneous results. Specifically, when the polydispersity index reached values around 1.10 the MM obtained by SEC and the MM calculated by MALDI might differ up to about 20%. With broader MMDs, which are quite common, MALDI spectra failed to give reliable MM values, these being much lower than those obtained by classical methods (2-4). To overcome these difficulties, it was introduced the so-called SEC-MALDI technique (7-10), wherein the samples are fractionated by SEC, in order to reduce the polydispersity of the original sample to values compatible with MALDI analysis (i.e., < 1.1) (2-12). The collected SEC fractions are then analyzed by MALDI MS, and the mass spectra of these nearly monodisperse samples allow the computation of reliable values of the number-average and weight-average molecular weight (Mn and Mw) corresponding to each fraction. When the MM of each fraction is plotted vs. the elution volume, an accurate calibration of the chromatogram may be obtained. The SEC trace and the calibration constants are fed into the SEC software, which outputs the Mn and the Mw of the polymer. On the other hand, it must be remembered that the quality of a MALDI mass spectrum, even of simple molecules, is highly dependent from the morphology of the irradiated matrix/sample crystals, with the consequence that significant variations in peaks presence, intensity, resolution and mass accuracy are often obtained by focusing the laser on different regions of the same sample (13-14). To alleviate this problem, considerable efforts have been made toward the development of new sample preparation techniques able to conduct to the formation of a homogeneous "solid solution" following the matrix/sample mixture. However, these procedures can improve the quality of MALDI mass spectra of monodisperse samples, but fail in the case of polydisperse polymers. The main problem in the co-crystallization of a polydisperse polymer with the solid matrix is, in fact, the phase separation due to the difference in the interactions between the species in solution, which occurs during solvent evaporation. These considerations may explain why it is not possible to obtain the correct MM and MMD of polydisperse polymers and the suppression of desorption and ionization of heavier molecules by the lighter, which, in general, can better mix with the matrix. On this subject, it is known that polyvynilpyrrolidone (PVP) is a material which can form complexes with many small molecules, including DHB, increasing the solubility of these in water. The formation of complexes between the polymer and DHB assures the intimate sample and matrix mixing, that is essential in order to obtain good MALDI spectra. Furthermore, it guarantees that all the polymer molecules, independently from their dimension, are deeply mixed with the matrix. For these reasons, it represented a good candidate to obtain a MALDI mass spectrum of a polydisperse sample, and we analyzed PVP with Mw of 40000 and 160000 using DHB as the solid matrix. The MALDI mass spectra of PVP with Mw of 40000 is reported in figure 1. This spectrum shows a broad molecular weight distribution from which it is possible to calculate the values of Mn and Mw, which are 26000 and 48000, in good agreement with those obtained by SEC in our lab and those reported by the manufacturer.Similar results have been achieved for the analysis of PVP 160000. In fact, also in this second case the Mn and Mw obtained are the ones expected for this polymer (data not shown). These results are absolutely different from those gained for all other synthetic polymers and shown by many authors (2-12), who, on the contrary, observed a relevant difference between the real MM and MMD and those measured by MALDI MS. A possible explanation of this failure is the polymer and/or matrix phase separation during the drying process, with the consequence that the spectrum obtained is representative only of the lower molecular weight species present in the polymer sample. The exception discussed in the present paper relative to PVP, a molecule which interacts with the matrix, seems to confirm this hypothesis. In view of these first and encouraging results, we decided to test a completely different method of sample preparation of polydisperse polymers. Instead of the "dried drop" technique, in which the slow crystallization of the matrix/sample mixture produces phase separation and fractionation of the polymer sample, as recently demonstrated (15), we used freeze drying of the matrix/sample solution where it may be expected that the original dispersed state of the polymer is maintained, provided that the cooling process by which the solution is solidified is fast enough. The first sample we checked was dextran, a polysaccharide constituted by glucose units linked alpha 1-6 . The MALDI mass spectrum of a dextran with a MW of 150000 Daltons prepared by freeze drying the solution containing the sample and the matrix (DHB) is reported in figure 2. From the MMD here presented the Perseptive computer software calculated Mn and Mw values of 100000 and 150000, which are in good agreement with the values obtained by conventional techniques and reported by the manufacturer. After this experiment, we studied other two polysaccharides: Lichenan and Nigeran which, because of their low solubility in water, are difficult to analyze by SEC. The MALDI mass spectra obtained by the 'freezedrying preparation' give, also in this case, the correct molecular weight distribution for these polymers. In particular, figure 3 presents the MALDI analysis of Nigeran The last sample we analyzed was a synthetic hydrosoluble polymer, polyethyleneoxide (PEO) Mw 100000. The MALDI mass spectrum obtained by the 'freeze drying preparation' (data not shown), shows a MMD from mass 10000 to above mass 250000. The Mn and Mw calculated are in good agreement with those reported by the manufacturer. Our results demonstrate that this method allows to obtain, for the first time, reliable spectra of the molecular weight distribution of polydisperse samples, extending the usefulness of MALDI MS. Including DHB, increasing the solubility of these in water. The formation of complexes between the polymer and DHB assures the intimate sample and matrix mixing, that is essential in order to obtain good MALDI spectra. Furthermore, it guarantees that all the polymer molecules, independently from their dimension, are deeply mixed with the matrix. For these reasons, it represented a good candidate to obtain a MALDI mass spectrum of a polydisperse sample, and we analyzed PVP with Mw of 40000 and 160000 using DHB as the solid matrix. The MALDI mass spectra of PVP with Mw of 40000 is reported in figure 1. This spectrum shows a broad molecular weight distribution from which it is possible to calculate the values of Mn and Mw, which are 26000 and 48000, in good agreement with those obtained by SEC in our lab and those reported by the manufacturer.Similar results have been achieved for the analysis of PVP 160000. In fact, also in this second case the Mn and Mw obtained are the ones expected for this polymer (data not shown). These results are absolutely different from those gained for all other synthetic polymers and shown by many authors (2-12), who, on the contrary, observed a relevant difference between the real MM and MMD and those measured by MALDI MS. A possible explanation of this failure is the polymer and/or matrix phase separation during the drying process, with the consequence that the spectrum obtained is representative only of the lower molecular weight species present in the polymer sample. The exception discussed in the present paper relative to PVP, a molecule which interacts with the matrix, seems to confirm this hypothesis. In view of these first and encouraging results, we decided to test a completely different method of sample preparation of polydisperse polymers. Instead of the "dried drop" technique, in which the slow crystallization of the matrix/sample mixture produces phase separation and fractionation of the polymer sample, as recently demonstrated (15), we used freeze drying of the matrix/sample solution where it may be expected that the original dispersed state of the polymer is maintained, provided that the cooling process by which the solution is solidified is fast enough. The first sample we checked was dextran, a polysaccharide constituted by glucose units linked alpha 1-6 . The MALDI mass spectrum of a dextran with a MW of 150000 Daltons prepared by freeze drying the solution containing the sample and the matrix (DHB) is reported in figure 2. From the MMD here presented the Perseptive computer software calculated Mn and Mw values of 100000 and 150000, which are in good agreement with the values obtained by conventional techniques and reported by the manufacturer. After this experiment, we studied other two polysaccharides: Lichenan and Nigeran which, because of their low solubility in water, are difficult to analyze by SEC. The MALDI mass spectra obtained by the 'freezedrying preparation' give, also in this case, the correct molecular weight distribution for these polymers. In particular, figure 3 presents the MALDI analysis of Nigeran The last sample we analyzed was a synthetic hydrosoluble polymer, polyethyleneoxide (PEO) Mw 100000. The MALDI mass spectrum obtained by the 'freeze drying preparation' (data not shown), shows a MMD from mass 10000 to above mass 250000. The Mn and Mw calculated are in good agreement with those reported by the manufacturer. Our results demonstrate that this method allows to obtain, for the first time, reliable spectra of the molecular weight distribution of polydisperse samples, extending the usefulness of MALDI MS.


269) Copolymer Characterization by SEC-NMR and SEC-MALDI

M.S.Montaudo

Polymer News  27,  115  - 2002

Measurements on a series of random copolymers with units of methylmethacrylate, butylacrylate, styrene, and maleic anhydride are performed. A characterization method is used that consists in fractionating the copolymer by SEC, collecting 30-40 fractions, and then recording both the NMR and MALDI spectra of the fractions. In a successive step, bivariate distribution of chain sizes and composition maps afe derived from knowledge of the molar mass, weight, and composition of the copolymer fractions. The compositional distribution is obtained by summation of the sections of the bivariate distribution which belong to a narrow compositional range.


270) Copper (II) Assisted Self-Assembly of Functionalized Beta-Cyclodextrins with Beta-Alanyl-L-Histidine

P.Mineo, D.Vitalini, D.La Mendola, E.Rizzarelli, E.Scamporrino, G.Vecchio

Journal of Supramolecular Chemistry  1/3,  147  - 2002

A combined UV-visible, CD and ESI-MS spectroscopic approach has been followed to obtain the speciation and the bonding details of copper(II) complexes with β-cyclodextrins functionalized by means of the bio-active peptide β-alanyl- -histidine (carnosine). A new metal-assisted self-assembled system of bifunctionalized β-cyclodextrins has been shown to exist.


271) Copolymer characterization by SEC-NMR and SEC-MALDI

M.S.Montaudo

Abstracts of Papers of the American Chemical Society  221,  375  - 2001

Proteins that belong to the fibroblast growth factor (FGF) family regulate proliferation, migration, and differentiation of many cell types. Several FGFs, including the prototype factors FGF-1 and FGF-2, depend on interactions with heparan sulfate (HS) proteoglycans for activity. We have assessed tissue-derived HS fragments for binding to FGF-1 and FGF-2 to identify the authentic saccharide motifs required for interactions. Sequence information on a range of N-sulfated HS octasaccharides spanning from low to high affinity for FGF-1 was obtained. All octasaccharides with high affinity for FGF-1 (¦0.5 M NaCl required for elution) contained an internal IdoUA(2-OSO3)-GlcNSO3(6-OSO3)-IdoUA(2-OSO3)-trisaccharide motif. Octasaccharides with a higher overall degree of sulfation but lacking the specific trisaccharide motif showed lower affinity for FGF-1. FGF-2 was shown to bind to a mono-O-sulfated HS 6-mer carrying a single internal IdoUA(2-OSO3)-unit. However, a di-O-sulfated -IdoUA(2-OSO3)-GlcNSO3-IdoUA(2-OSO3)-trisaccharide sequence within a HS 8-mer gave stronger binding. These findings show that not only the no. but also the positions of individual sulfate groups det. affinity of HS for FGFs. Our findings support the notion that FGF-dependent processes can be modulated in vivo by regulated expression of distinct HS sequences.


272) Matrix-Assisted Laser Deserption Ionization Mass Spectrometry of Polymers (MALDI-MS)

G.Montaudo, M.S.Montaudo, F.Samperi

G.Montaudo, R.P.Lattimer (EDS) CRC Press  Chapter 10,  419  - 2001

book cover



273) Fast Atom Bombardment of Polymers

G.Montaudo, F.Samperi

G.Montaudo, R.P.Lattimer (EDS) CRC Press  Chapter 7,  269  - 2001

book cover



274) Direct Pyrolysis of Polymers into the Ion Source of a Mass Spectrometer (DP-MS)

G.Montaudo, C.Puglisi

G.Montaudo, R.P.Lattimer (EDS) CRC Press  Chapter 5,  181  - 2001

book cover



275) Polymer Characterization Methods

G.Montaudo, M.S.Montaudo

G.Montaudo, R.P.Lattimer (EDS) CRC Press  Chapter 2,  41  - 2001

book cover



276) Mass Spectrometry of Polymers

G.Montaudo, R.P.Lattimer

CRC Press   - 2001

book cover



277) Solute-solvent interaction strength of disaccharide aqueous solutions: trehalose primate

C.Branca, A.Faraone, S.Magazu, G.Maisano, P.Migliardo, P.Mineo, V.Villari

AIP Conference Proceedings  513,  47  - 2000

Results of d., ultrasonic velocity, and DSC measurements performed on aq. solns. of the homologous disaccharides trehalose, maltose and sucrose, are reported. To get some insight into the mechanisms of cryopreservation that characterize these systems, and to clarify the reasons that make trehalose the most effective bioprotector, we investigate the volumetric and thermic properties of trehalose, maltose and sucrose aq. solns. as a function of concn. and temp. What conclusively emerges is the presence of a more collapsed conformation for trehalose in respect with the other disaccharides, indicative of a much more marked solute-solvent interaction strength. Moreover, DSC findings indicate a greater effectiveness of trehalose in destroying the tetrahedral network of water compatible with the formation of ice and support the hypothesis of a higher "fragile" thermodn. character of the trehalose-water system at high diln.


278) Molar mass distributions and hydrodynamic interactions in random copolyesters investigated by SEC/MALDI

G.Montaudo, C.Puglisi, F.Samperi, M.S.Montaudo

Abstracts of Papers of the American Chemical Society  219,  432  - 2000

Results of d., ultrasonic velocity, and DSC measurements performed on aq. solns. of the homologous disaccharides trehalose, maltose and sucrose, are reported. To get some insight into the mechanisms of cryopreservation that characterize these systems, and to clarify the reasons that make trehalose the most effective bioprotector, we investigate the volumetric and thermic properties of trehalose, maltose and sucrose aq. solns. as a function of concn. and temp. What conclusively emerges is the presence of a more collapsed conformation for trehalose in respect with the other disaccharides, indicative of a much more marked solute-solvent interaction strength. Moreover, DSC findings indicate a greater effectiveness of trehalose in destroying the tetrahedral network of water compatible with the formation of ice and support the hypothesis of a higher "fragile" thermodn. character of the trehalose-water system at high diln.


279) Thermal degradation mechanisms of polyetherimide investigated by direct pyrolysis MS

G.Montaudo, C.Puglisi, S.Carroccio

Abstracts of Papers of the American Chemical Society  219,  431  - 2000



280) MALDI-TOF investigation of polymer degradation: Pyrolysis of Poly(Bisphenol A carbonate)

G.Montaudo, C.Puglisi, F.Samperi, S.Carroccio

Abstracts of Papers of the American Chemical Society  219,  429  - 2000



281) Bivariate distribution in PMMA/PBA copolymers by combined SEC/NMR and SEC/MALDI measurements

M.S.Montaudo

Abstracts of Papers of the American Chemical Society  219,  245  - 2000



282) SEC/MALDI analysis of poly(bisphenol a carbonate): Self-association due to end-groups

G.Montaudo, C.Puglisi, F.Samperi, S.Carroccio

Abstracts of Papers of the American Chemical Society  219,  241  - 2000



283) Control of polyester chain scission by lipase-catalysis

M.Bankova, A.Kumar, R.A.Gross, G.Impallomeni, A.Ballistreri

Abstracts of Papers of the American Chemical Society  204,  U305  - 2000



284) Spettrometria di Massa MALDI TOF di Macromolecole

D.Garozzo, E.Spina, R.Cozzolino

AIM Magazine  54(1),  33  - 2000



285) Structure analysis of underivatized oligosaccharides using postsource decay with collision-induced fragmentation, in matrix-assisted laser desorption ionization mass spectrometry

D.Garozzo, E.Spina, R.Cozzolino

47th ASMS Conference on Mass Spectrometry and Allied Topics, Dallas, Texas, June 13-17, 1999   - 1999

In this paper we show the PSD spectra of some underivatized oligosaccharides obtained using collision induced decomposition (CID) by using helium as the collision gas. We observe some relevant differences with the spectra of the same oligosaccharides obtained without a collision gas or by using argon and recently reported. The most important difference is the presence of X1,5 fragments which are highly diagnostic allowing to obtain the sequence of the oligosaccharides analyzed. We have observed that CID spectra of underivatized oligosaccharides, unlike other compounds as peptides are quite different from that observed without CID. The most important difference is the presence of intense X1,5 ions containing the reducing end. By the presence of these ions in the CID PSD spectra we can now distinguish the Y ions from all others and in this way, sequence the oligosaccharide (in terms of Hex, HexNAc, etc.) by the CID PSD spectrum alone. This constitutes a big improvement respect the PSD spectra obtained without CID where, although a lot of information on the sequence of the oligosaccharides analyzed are obtained, the presence of "internal" fragments and the difficulty of discriminate B and C fragments from Y and Z can originate some problems in unequivocal assign the sequence from a PSD spectrum alone


286) Il profilo composizionale degli oligosaccaridi potrebbe differenziare il latte delle diverse specie animali

D.Beccati, B.Casu, A.Naggi, L.Sturiale, G.Torri, G.Coppa, S.Bruni

Caseus, Anno IV, Luglio 1999   - 1999

The introduction of size-exclusion chromatography (SEC) analysis of polysaccharides prior to MALDI mass spectroscopy accounts for the determination of the molecular mass of the repeating unit when neutral homopolymers are investigated. In the case of natural polysaccharides characterised by more complicated structural features (presence of non-carbohydrate substituents, charged groups, etc.), this mass value usually is in agreement with more than one sugar composition. Therefore, it is not sufficient to give the correct monosaccharidic composition of the polysaccharide investigated. To solve this problem, MALDI spectra were recorded on the permethylated sample and post-source decay experiments were performed on precursor ions. In this way, the composition (in terms of Hex, HexNAc, etc.), size and sequence of the repeating unit were determined. (C) 2000 Elsevier Science Ltd. All rights reserved


287) Copolymer Composition: a Key to the Mechanisms of Exchange in Reactive Polymer Blending

G.Montaudo, C.Puglisi, F.Samperi

S.Fakirov(Ed)WILEY-VCH.  Chapter 4,  159  - 1999



288) Recent Advances in Mass Spectrometry of Polymers, in Experimental Methods in Polymer Characterization

E.Scamporrino, D.Vitalini

R.A.Pethrick Editor - P.233 - John Wiley & Sons - Ltd - Publisher   - 1999



289) Computer tool for the speciation of natural fluids

C.De Stefano, S.Sammartano, P.Mineo, C.Rigano

A. Gianguzzo et al. (eds) - Marine Chemistry  1997,  71  - 1997

Some computer tools, useful in speciation studies, are examined in this paper. In particular problems related to the calculation of formation constants and free concentrations in multicomponent system are described, together with some subsidiary calculations. A new general computer program for fitting linear and non linear equations (LIANA) is reported.


290) The Discovery of Tetrahedral Carbon: Contributions of Paterno and Cannizzaro

G.Montaudo

Gazzetta Chimica Italiana  127(12),  837  - 1997

Although the discovery of stereoisomerism is due to van't Hoff and Le Eel (1875), the hypothesis of tetrahedral carbon, on which the stereoisomerism is actually based, is older. The latter is due to Kekule (1862), who then built the tetrahedral carbon molecular models, and applied them to solve the problem of the structure of benzene. The molecular models of Kekule were used by the most talented pupils of his school (Dewar, Koemer, van't Hoff), and were applied to diverse structural problems. Among: these contributions, of great relevance is the work of Emanuele Paterno, who grew up in the laboratory of S. Cannizzaro in Palermo, and who came also in contact with the school of Kekule. Paterno, using the molecular models of Kekule, in 1869 applied for the first time the theory of the tetrahedral carbon to aliphatic organic compounds, and discussed the conformational isomerism of these compounds. Only a few years later, van't Hoff and Le Eel succeeded in applying the hypotesis of Kekule to the problem of optical antipodes, and discovered stereoisomerism. [References: 16]


291) Maldi Ms of oligo and polysaccharides in Mass Spectrometry in the Biomolecular Sciences, R. M. Caprioli et al (eds)

D.Garozzo

Kluwer Academic Publishers  1997,  477  - 1997



292) Time-of-Flight SIMS Characterization of Nylon6/polycarbonate blends in Secondary Ion Mass Spectrometry-SIMS X

A.Licciardello, C.Puglisi, E.Niehuis, A.Benninghoven

A. Benninghoven, F. Linton, H. Werner, Eds. John Wiley & Sons.   - 1997



293) MALDI-TOF AS GPC Detector For MW & MWD Measurements In Polydisperse Polymers and Copolymers

G.Montaudo

Polym. Prep. (A.C.S., Div.Polym.Chem.)  211,  261  - 1996



294) Microstructure of Copolymers by Statistical Modeling of Their Mass-Spectra

G.Montaudo, M.S.Montaudo

Macromolecular Reports   31,  1053  - 1994



295) Microstructure of Copolymers by Statistical Modeling of Their Mass Spectra

M.S.Montaudo, G.Montaudo

Makromol. Chem. Makromol. Symp.  65,  269  - 1993

A novel method for the determination of the microstructure of copolymers is presented here. Statistical modeling of the mass spectral intensities of copolymers has been used to derive information on the distribution of monomers along the copolymer chain, and an automated procedure to find the composition and the sequence of the copolymers analyzed has been developed. [References:9]


296) Structural Characterization of Synthetic Polymers and Copolymers by FAB-MS

G.Montaudo, E.Scamporrino, D.Vitalini

In Applied polymer Analysis and Characterization , J.Mitchell Ed., Hanser, Munich  Vol 2,  79  - 1992

A review with 51 refs.


297) Thermal Degradation of Condensation Polymers

G.Montaudo, C.Puglisi

Comprehensive Polymer Science, First Supplement. Pergamon Press, Oxford  1992,  227  - 1992



298) Microstructure of Copolymers by Statistical Modeling of Their Mass-Spectra

M.S.Montaudo, G.Montaudo

Abstracts of Papers of the American Chemical Society  203,  288  - 1992

Detn. of sequence distribution and compn. of copolymers via statistical modeling of their mass spectra was briefly discussed.


299) Negative-Ion Fab Ms of 3-O-Branched Oligosaccharides

D.Garozzo, G.Impallomeni, G.Montaudo, F.Spina

Abstracts of Papers of the American Chemical Society  204,  78  - 1992



300) Recent advances in mass spectrometry of polymers

G.Montaudo

Polym. Sci. (Symp.Proc.Polym.)  2,  552  - 1991

The application of mass spectrometry to polymers is discussed with particular attention to sequencing copolymer structures and to direct pyrolysis mass spectrometry of condensation polymers.


301) Linkage Analysis in Disaccharides by Electrospray Mass-Spectrometry (Es Ms)

D.Garozzo, G.Impallomeni, E.Spina

Abstracts of Papers of the American Chemical Society  202,  48  - 1991



302) Microstructure of Bacterial Poly(B-hydroxybutirate-co-B-hydroxyvalerate) by Fast Atom Bombardment Mass SpectrometryAnalysis of their Partial Degradation Products

A.Ballistreri, D.Garozzo, M.Giuffrida, G.Montaudo

Novel Biodegradable Microbial Polymers ,E.A.Dawes Ed., Kluwer  1990,  49  - 1990

The partial methanolysis and the partial pyrolysis of bacterially synthesized .beta.-hydroxybutyric acid-.beta.-hydroxyvaleric acid copolymers were performed and the oligomers produced were analyzed by fast-atom-bombardment mass spectrometry. An algorithm was developed to distinguish pure random copolymers from mixts. of random copolymers, using the relative abundances of the oligomers which could be deduced from the mass spectra.


303) Sequential analysis of condensation copolymers by FAB-MS

G.Montaudo

Polym. Prep. (A.C.S., Div.Polym.Chem.)  30  - 1989

The application of fast-atom-bombardment mass spectrometry to sequence anal. of polyesters and polyamides was described. Structural anal. of .beta.-hydroxybutyric acid-.beta.-hydroxyvaleric acid copolymer, piperazine-truxillic acid-adipic acid copolymer, and ethylene glycol-terephthalic acid-truxillic acid copolymer was shown.


304) Polymerization of nitro compounds on silver surfaces during surface-enhanced Raman scattering

W.H.Tsai, F.J.Boerio, S.J.Clarson, G.Montaudo

Report   - 1989

Surface-enhanced Raman scattering was obsd. from thin films formed by 1,4- dinitrobenzene (I) and 1,3-dinitrobenzene (II) spin-coated onto Ag island films from dil. solns. During laser irradn. of I films on Ag substrates at relatively high laser powers, new bands appeared near 152, 1350, 1412, and 1460 cm-1 and bands near 1118, 1358, and 1372 cm-1 decreased in intensity. Bands near 1152 and 1412 cm-1 were assigned to stretching modes of Ph-N and -N=N- bonds of azo compds., resp., indicating that polymn. of I had occurred. The extent of polymn. was greatest when the surface coverage of absorbed I was greatest and when the SERS expts. were carried out in a N atm., indicating that reducing conditions were required for the polymn. No polymn. was obsd. for II under similar circumstances. The difference was attributed to orientation of the adsorbed species. Thus, it was concluded that I was adsorbed with a horizontal configuration in which the arom. rings were parallel to the substrate surface and both nitro groups were in contact with the surface, whereas II was adsorbed with a vertical configuration in which the rings were perpendicular to the surface and only one nitro group was in contact with the surface.


305) Formation of cyclic oligomers

P.Maravigna, G.Montaudo

Comprehnsive Polymer Science G.C.Eastmond, A.Ledwith, S.Russo, S.Sigwalt Eds. Pergamon Press Oxford  5,  63  - 1989



306) Thermal degradation mechanisms in condensation polymers

G.Montaudo, C.Puglisi

Dev. Polym. Degrad.  7,  35  - 1987

A review with 187 refs.


307) Mass spectrometric detection of cyclic sulfides in the polycondensation of dibromoalkanes with dithiols

G.Montaudo, E.Scamporrino, C.Puglisi, D.Vitalini

J. Polym. Sci., Polym. Symp.  74,  285  - 1986

Mass spectrometry was used to identify the cyclic oligomers formed in the polycondensation of .alpha.,.omega.-dibromoalkanes with .alpha.,.omega.-alkanedithiols contg. the same no. of C atoms. Cyclic oligomers with only an even no. of repeating units were detected among the polycondensation products.


308) Direct mass spectrometry of polymers

S.Foti, G.Montaudo

"Mass Spectrometry of Large Molecules" S. Facchetti Ed. Elsevier Science Pub.Amsterdam  1985,  283  - 1985

A review with 54 refs. on the use of 4 mass spectrometry methods in polymer identification, identification of volatile additives in polymer samples, differentiation of isomeric structures, detn. of copolymer compn., and sequential anal.


309) Studio dei meccanismi di degradazione termica e di inibizione della combustione dei materiali polimerici

A.Ballistreri, C.Puglisi

Tecnopolimeri e resine  1,  66  - 1984

La scienza e la tecnologia dei polimeri sintetici hanno avuto una crescita notevole negli scorsi decenni, ed il numero dei materiali polimerici prodotti aumenta di giorno in giorno. Tutti i polimeri organici bruciano e così la loro diffusione commerciale incrementa i pericoli di incendio, già tanto gravi nel nostro tempo. Il problema della loro stabilizzazione al fuoco è divenuto quindi di primaria importanza. La pericolosità d'incendio è regolata, nei paesi piùsviluppati, da leggi che fissano degli standard per l'applicazione dei materiali polimerici nelle diverse aree di consumo, come ad esempio nel settore del tessili, dei trasporti e dell'edilizia. Si può facilmente prevedere che tali limitazioni diverranno più severe in futuro provocando una pressante richiesta di metodi di stabilizzazione al fuoco dei polimeri. Già da qualche tempo sono state introdotte sul mercato delle formulazioni aventi lo scopo di rendere i polimeri autoestinguenti ed anche di sopprimere i fumi che si sviluppano durante la. combustione. L'efficacia di queste formulazioni varia da caso a caso, mentre la richiesta di agenti antifiamma più efficienti si fa sempre più stringente. In figura 1, sono schematizzate le tre operazioni principali nel lavoro di stabilizzazione alla fiamma dei polimeri. Gli additivi usati nel formulati commerciali sono per lo più a base di composti alogenati e fosforati ed il loro impiego è stato spesso proposto sulla base di ricerche empiriche. Molto rimane quindi da imparare sul modo di azione di questi inibitori, e negli ultimi anni si sono sviluppati studi tendenti a razionalizzare i meccanismi di inibizione della combustione dei polimeri mediante l'impiego delle metodologie analitiche più avanzate. Lo studio dei meccanismi di inibizione della combustione richiede la conoscenza preliminare dei processi di degradazione termica dei materiali polimerici come indicato in fig. 1. Infatti, la temperatura e la velocità di decomposizione termica in condizioni di riscaldamento e di atmosfere controllate, nonché la composizione dei prodotti di pirolisi e di combustione sono alcuni dei parametri più importanti che determinano l'infiammabilità dei polimeri. Una loro appropriata valutazione si può ottenere tramite una serie di metodologie analitiche che descriveremo nel presente articolo.


310) Direct mass spectrometry of polymers. Primary thermal fragmentation processes in aromatic polyesters

S.Foti, M.Giuffrida, P.Maravigna, G.Montaudo

Polym. Prep. (A.C.S., Div.Polym.Chem.)  25,  88  - 1984

The thermal fragmentation of polyesters (m-COC6H4CO2C6H4O-m)n, (m-COC6H4O)n, (CO(CH2)xCO2C6H4O-m)n (x = 2, 4), and (m-COC6H4CO2(CH2)yO)n (y = 2, 4, 6) was investigated by direct mass spectrometry. The primary fragmentation process was the formation of cyclic oligomers and the secondary process was the hydrolytic cleavage of the cyclic compds.


311) Acid-catalyzed photoreactions: photolytic behavior of polyamides containing truxillic and truxinic units

G.Montaudo, E.Scamporrino

Dev. Polym. Degrad.  5,  121  - 1984

A review with 45 refs. of acid-catalyzed photoreactions in the title photodegradable polymers with a view to producing polymers with controlled degrdn. times.


312) Synthesis of polycondensates by interfacial and dispersion polymerizations

S.Foti, P.Maravigna, G.Montaudo

La Chimica e L’industria  65,  337  - 1983

Polyurethanes, polyureas, polycarbonates, and polyamides having sterically hindered centers are prepd. by dispersion polymn. Dispersion polymn. gives higher conversion and viscosity for the polymers than interfacial polymn., except for polycarbonates, where the two types with comparable results.


313) Identification of polymers by library search of mass spectra

S.Foti, D.Garozzo, G.Montaudo

La Chimica e L’industria  65,  641  - 1983

The generation of a data bank of mass spectra of polymers obtained by direct pyrolysis-mass spectrometry and a computer retrieval procedure based on this data bank were described. The use of the retrieval system allowed the identification of unknown polymers.


314) Dispersion and interfacial polycondensation. Synthesis of polyurethanes, polyureas, polyamides and polycarbonates

S.Foti, P.Maravigna, G.Montaudo

Conv. Ital. Sci. Macromol. [Atti]  2,  331  - 1983

Differences in the prepn. of polyurethanes, polyureas, polyamides, and polycarbonates by dispersion and interfacial polymn. are discussed.


315) Intumescent flame retardants for polymers. The polypropylene-ammonium polyphosphate-polyurea system

G.Montaudo, E.Scamporrino, D.Vitalini

Conv. Ital. Sci. Macromol. [Atti]  2,  327  - 1983

Polyureas are charring promoters in flame retardant polypropylene [9003-07-0] compns. contg. NH4 polyphosphate (I). The thermal decompn. of polyureas on burning produces oligomers with reactive end groups, e.g. isocyanate, which are quickly hydrolyzed by I to amines which, in the form of phosphide salts, are the active species.


316) Reorganization of polycarbonates with piperazine. Synthesis of copoly(carbonate-urethanes)

S.Foti, M.Giuffrida, P.Maravigna, G.Montaudo

Conv. Ital. Sci. Macromol. [Atti]  2,  335  - 1983

Polycarbonate-polyurethanes are prepd. by depolymn. of bisphenol A polycarbonate [24936-68-3] or resorcinol polycarbonate [32473-32-8] with piperazine [110-85-0] and repolymg. the reaction mixt. in the presence of COCl2.


317) Primary thermal fragmentation processes in aromatic polyesters

S.Foti, M.Giuffrida, P.Maravigna, G.Montaudo

Conv. Ital. Sci. Macromol. [Atti]  2,  313  - 1983

The mass spectral data of isophthalic acid (I)-resorcinol (II) copolymer [26637-46-7], poly(m-hydroxybenozic acid) [25302-76-5], II-succinic acid copolymer [90386-92-8], adipic acid-II copolymer [32200-90-1], ethylene glycol-I copolymer [26948-62-9], 1,4-butanediol-I copolymer [28087-45-8], and 1,6-hexanediol-I copolymer [59199-93-8] indicated that cyclic oligomers formed in the primary thermal fragmentation processes.


318) Metodologie per lo studio della combustione e della stabilizzazione al fuoco dei materiali polimerici

E.Scamporrino, D.Vitalini

Tecnopolimeri e resine  5,  31  - 1982

La facilità con cui i materiali polimerici si infiammano nonché la quantità e la tossicità dei fumi generati quando bruciano, hanno determinato negli ultimi anni un interesse crescente verso il problema del ritardo di fiamma e della soppressione del fumo generato nella combustione dei polimeri. Contrariamente ai composti organici a basso peso molecolare, che possono evaporare indecomposti nella regione della fiamma, i polimeri non hanno tensione di vapore apprezzabile e possono produrre specie volatili solo attraverso un processo di decomposizione termica. Quando la superficie di un materiale polimerico viene esposta a una sorgente di calore, la temperatura del solido aumenta gradualmente fino a un valore critico in corrispondenza del quale comincia la decomposizione del polimero. La velocità di questo processo dipende dal bilancio energetico tra l'endotermicità delle reazioni pirolitiche e la quantità di calore fornito al materiale, ivi compreso quello svio luppato dalle reazioni ossidative, quasi sempre presenti alla superficie del materiale. Vengono a formarsi specie volatili che, diffondendo attraverso la superficie polimerica fusa, passano nell'atmosfera. La maggiore o minore infiammabilità del polimero dipenderà dalla quantità e dalla natura dei composti volatili prodotti nella pirolisi. Se la temperatura della miscela gas com. bustibili-aria è sufficientemente alta, si potrà avere l'ignizione. La combustione puòavvenire in due diversi modi: con sola evoluzione di fumo (smoldering) o con fiamma (flaming). In ogni caso, il calore s'viluppato dalle reazioni chimiche nella fase gassosa e/o alla superficie viene in parte trasmesso al restante materiale polimerico determinando così ulteriori processi di decomposizione. Si viene a creare un ciclo di trasporto di calore (figura 1) tra la zona di combustione e la zona polimerica non decomposta, il cui bilancio determinerà la propagazione della combustione. Durante il processo i prodotti di pirolisi vengono trasformati in gas (CO, CO, e incondensabili) e fumo. Nella combustione in flaming viene generato un fumo nero costituito da particelle carboniose più o meno aggregate e da composti catramosi (soot), mentre durante ir fenomeno di smoldering il fumo generato è bianco ed è costituito da microgoccioline di liquido formatesi per condensazione dei composti incombusti. Il processo di combustione è molto com. plesso e per la sua comprensione bisogna tener conto anche di fattori fisici che, sovrapponendosi ai processi chimici sopra descritti, influenzano in maniera rilevante il fenomeno. Diffusione gassosa, flusso di calore (conduttivo, convettivo e radiativo), fusione, gocciolamento, rapporto superficie/volume, sono soltanto alcuni dei fattori che regolano l'ignizione, la velocità di combustione e di propagazione della fiamma. L'inibizione della combustione può quindi essere ottenuta agendo sia su parametri chimici che fisici; può inoltre aver luogo nella fase gassosa o in quella condensata, oppure in entrambe simultaneamente.


319) Smoke suppression by ferrocene in PVC combustion

A.Ballistreri, G.Montaudo, C.Puglisi, E.Scamporrino, D.Vitalini

La Chimica e L’industria  64,  403  - 1982

Addn. of 1 and 5 phr finely ground ferrocene (I) [102-54-5] to PVC [9002-86-2] suppressed the smoke formation and increased the char yield compared to pure PVC in the entire range of temps. explored (400-800.degree.). In smoldering conditions the smoke d. decreased by .apprx.20%, whereas in flaming conditions the amt. of smoke decreased by .apprx.50%. The smoke evolution occurred almost immediately, whereas the evolution of CO2 occurred at a later combustion stage and was accompanied by char yield redn. due to char oxidn. I, which is otherwise volatile, was maintained in PVC and apparently acted as a crosslinking catalyst in PVC combustion.


320) Making polymers resist fire

G.Montaudo

Shell Polymers  6,  84  - 1982



321) Analysis of polymers by mass spectrometry

S.Foti, G.Montaudo

Applied Science  1982,  103  - 1982



322) Effects of N-methyl substitution on the thermal stability of polyurethanes and polyureas

S.Foti, P.Maravigna, G.Montaudo

Proc. IUPAC, I. U. P. A. C., Macromol. Symp. 28th.   - 1982

The thermal degrdn. N-disubstituted polyurethanes contg. O-aliph. linkages occurred selectively in a 6-membered cyclic transition state. Polyurethanes contg. N-aliph. and O-arom. linkages underwent degrdn. via cyclic oligomer formation. Totally arom. N-disubstituted polyureas did not form cyclic oligomers, but evolved MeNCO and arom. amines, suggesting a C-H transfer decompn. pathway of high activation energy.


323) A comparative approach to the determination of the smoke emission from burning polymers

A.Ballistreri, G.Montaudo, C.Puglisi, E.Scamporrino, D.Vitalini

La Chimica e L’industria  63,  167  - 1981

Smoke d. and scattering increase linearly with temp. in the 400-500.degree. range, where the PVC [9002-86-2] combustion is in smoldering conditions. At 500.degree. self-ignition of PVC occurs with a decrease of the both smoke d. and scattering. At 600.degree. the smoke d. increases again and remains const. up to


324) Analysis of polymers by mass spectrometry

S.Foti, P.Maravigna, G.Montaudo

Atti Conv.-Sc. Caratt. Mol. Polim.  1981,  319  - 1981

A review with 6 refs.


325) Use of MIKE spectra for polymer studies using mass spectrometry

S.Foti, A.Liguori, P.Maravigna, G.Montaudo

Conv. Ital. Sci. Macromol. [Atti] 5th  ,  305  - 1981

Ion-kinetic-energy mass spectra were used in anal. of thermal oligomeric poly(carboxypiperazine) [32006-42-1] prepd. at >270.degree. by direct pyrolysis-mass spectrometry. The mass spectra recorded at increasing temp. confirmed an identical spectral pattern for the total temp. range of oligomer formation. The peaks of spectra corresponding to mol. ions of thermal oligomers were confirmed using prepd. model compds.


326) Determination and characterization of some new cyclic oligomers in polyurethanes and polyureas using mass spectrometry

S.Foti, P.Maravigna, G.Montaudo

Conv. Ital. Sci. Macromol. [Atti] 5th  ,  307  - 1981

A cyclic urethane and 3 cyclic ureas, formed during the prepn. of polymers of corresponding structures, were identified and characterized without sepn. by mass spectrometry. The mass-spectrometric data obtained for (I) [81019-31-0] and other cyclic compds. suggested a possible application of the method in the identification of cyclic oligomers in polymer samples.


go to the top of the pageTop

Valid HTML5 | IPCB CT Web Site | Cookie Policy | Trasparency |