Supervisor: Dr. Ribechini Erika

Title: The role of tannin-based dyes in the degradation of historical textiles.

Abstract: The large number of historic textiles still preserved today represents an important field of our cultural heritage. The state of conservation of these examples of our historic handicraft may differ in dependence of numerous factors. Different kind of degradation effects can be observed, like fading or loss of material, occurring in the fibres unevenly. Particularly, it is possible to notice that tannin dyed textiles usually show more extended degradation phenomena than tissues dyed with other colouring materials, even in the same condition of preservation. In order to face the problems related to the occurrence of tannins in dyed textiles, the project The Short Life of Tannins has been founded by the Regione Toscana (FAS grants 2008-2013). The PhD project aims at creating a model describing the ageing processes taking place in textile fibres dyed with iron-tannin complexes. The final goal of the research is to appoint a conservation protocol to arrest or to slow degradation processes, on the basis of the developed predictive model. The project entails the study of textile reference specimens, also subjected to artificial ageing. Different analytical techniques will be used: spectrophotometry, SEM-EDX, chromatography and mass spectrometry. Particularly, HPLC-MS/MS and GC/MS will be used not only for the characterisation of lipids, proteins, dies, phenol, but also for the identification and quantification of degradation products. Results obtained by the characterisation of raw materials and textile reference specimens by optical and scanning electron microscope will be presented, discussed and compared to the data obtained by HPLC-DAD, DE-MS, GC/MS analysis.

Supervisor: Prof. Tinè Maria Rosaria

Title: Studies of artists' paint media by thermal analytical techniques.

Abstract: In this work of thesis I will study the effect of natural and artificial ageing on the media used by the artists in cultural heritage. In particular, proteinaceous binder and their interaction with inorganic pigments and studies of resins employ in modern and contemporary art, pluging in COPAC Project (Conservazione Preventiva dell’Arte Contemporanea, Regione Toscana 2011-2013). In this first year of work I studied ten samples of alkyd resins paint produced by Winsor & Newton- serie Griffin. Thermal analyses, specifically, differential scanning calorimetry (DSC) and thermogravimetric analysys (TGA), were used in this work to study the changes in properties of alkyd sample with age.
The cross-linking rate during ageing was observed with DSC by monitoring the exothermic reaction after the decomposition of peroxide groups, which form during auto-oxidation of the alkyd resin. TGA studies of aged flms permitted to evaluate the physical dry (solvent evaporation) and indicated an increase in film density with age, probably due to cross-linking and the loss of volatile dagradation species at first and then the possible formation of oxidative degradation products over time, such as carboxylate salts that increase the cohesive forces in the film.

Publications:
1) A highly pH-sensitive Zn(II) chemosensor
Carla Bazzicalupi, Andrea Bencini, Silvia Biagini, Enrico Faggi, Giovanna Farruggia, Giulia Andreani, Paola Gratteri, Luca Prodi, Alessio Spepi and Barbara Valtancoli Dalton Trans 39(30):7080-90 (2010)
2) A Novel Manganese Complex Effective as Superoxide Anion Scavenger and Therapeutic Agent against Cell and Tissue Oxidative Injury
Paola Failli, Daniele Bani, Andrea Bencini, Miriam Cantore, Lorenzo Di Cesare Mannelli, Carla Ghelardini, Claudia Giorgi, Massimo Innocenti, Francesco Rugi, Alessio Spepi, Roberto Udisti and Barbara Valtancoli J Med Chem 52(22):7273-83 (2009)
3) Exploring the Binding Ability of Phenanthroline-Based Polyammonium Receptors for Anions: Hints for Design of Selective Chemosensors for Nucleotides
Carla Bazzicalupi, Andrea Bencini, Silvia Biagini, Enrico Faggi, Stefano Meini, Claudia Giorgi, Alessio Spepi and Barbara Valtancoli J Org Chem 74(19):7349-7363 (2009)

Supervisor: Prof. Persico Maurizio

Title: Development of a new method for molecular dynamics simulations for photochemical and photophysical processes.

Abstract: The aim of my research work is the development of a new approach in the field of excited state dynamics methods that will be called “Parameterized Non-Adiabatic Dynamics” (PNAD). The PNAD strategy is based on the observation that the essential information about the excited state dynamics of a given chromophore is partially transferable among different environments. The procedure consists of three steps. First, we run a ”model dynamics” with the usual nonadiabatic trajectory methods such as TSH, in conditions that allow to reduce the computational burden by at least two orders of magnitude (one chromophore, normally in vacuo, and few trajectories, stopped shortly after reaching the ground state). Second, we extract from the results of the model dynamics the electronic energy differences, the nonadiabatic transition probabilities and possibly other dynamical quantities, and we fit them as functions of the most important nuclear space phase variables (internal coordinates, kinetic energies, etc). Third, we use a ground state force--field and the information obtained in the second step to compute also the excited state energies and the transition rates in order to run the PNAD simulations. The latter will have a computational cost close to standard ground state Molecular Dynamics, so it will be possible to treat more complex problems (many interacting chromophores, long simulation times covering (hot) ground state processes, many trajectories if needed to obtain statistically significant results, etc). As a test case, we choose the photoisomerization of trans-azobenzene excited in the n->pi* band, because of our previous results with classical molecular dynamics methods that can be good benchmark to check PNAD results.

Supervisor: Prof. Colombini Perla, Prof. Frediani Pier

Title: Synthesis and Characterization of Polyesters for Applications in Restoration and Conservation of Cultural Heritage.

Abstract: Cultural Heritage, particularly stone monuments exposed to the outdoor environment, are subjected to deterioration by natural causes (light, water, wind, microorganism) and by anthropological ones (pollutants like carbon dioxide, sulphur and nitrogen oxides). Recently, the use of bio-renewable materials, like polyesters obtained from natural sources, is increasing responding to environmental issues. However, the application of polyesters in the conservation field is still restricted and its expansion is limited by the lack of suitable materials: our aim is to synthesize a new class of conservation materials made from bio-renewable feedstocks, possessing high protective capability and durability. Polylactic acid (PLA) is one of the most promising polymer in this class, due to its high mechanical strength and workability easiness and the fact that it can be mass-produced from agricultural byproducts. Lactide (lactic acid cyclic dimer) polymerization to PLA can be catalyzed by metal complexes in the presence of oxidryl and amine compounds as initiators. The product characteristics can be controlled through functionalization, either by employing a specific initiator or by using substituted lactides, containing the desired functional group. While with the former method the functionalization is restricted only to chain ends, the latter lead to a more profound modification of PLA structure as the functional group is distributed along the chain; the proprieties changes can be tuned by copolymerization of lactide with variable amount of functionalized monomer. Our initial interest is focused on the improvement of protection capabilities (with the introduction of UV-visible chromophores and hydrophobic groups), light and thermal stability (benzotriazole, HALS) and resistance to biodeterioration (quaternary ammonium compounds). The polymers will be characterized by means of several techniques (NMR, GPC, DSC, Py-GC/MS, IR, UV, Vis and fluorescence spectroscopies) and specific tests will be conducted to evaluate the performance in conservation (water absorption, color change, accelerated aging chamber).

Supervisor: Prof. Di Bari Lorenzo

Title: Effects of chirality on optoelectronic properties of organic and inorganic dyes for photovoltaic devices.

Supervisor: Dr. Geppi Marco

Title: Nanometric and sub-nanometric structural properties of complex functional materials by means of solid-state NMR techniques.

Supervisor: Prof. Colombini Perla

Title: APCI-MS characterization of glycerolipids and polyphenols in complex matrices.

Abstract: The main goal of the project is to evaluate the performance of HPLC-APCI-MS and ESI-MS-QTOF in the complex archaeometric problem of resolving mixtures of aged lipid materials and reconstituting the original lipid component of ancient residues. The analytical protocol is set up using a comparative study based on the evaluation of triacylglycerol (TAG) compositions in raw natural lipid materials and in laboratory-reproduced formulation, prepared following recipes reported in historical treatises and used as reference materials. These reference materials are also subjected to stress treatments in order to evaluate the modification occurring in the TAG profiles as an effect of ageing. To differentiate the lipid materials on the basis of the TAG profiles, pattern analysis of the TAG distributions by means of principal components analysis (PCA) is applied. New markers, that can be used by the scientific community in the challenge of discriminating various oils and fats, are also investigated.

Contatti:

Dr. Jacopo La Nasa 

PhD student

Dipartimento di Chimica e Ch. Industriale via Risorgimento, 35 - 56126 - Pisa

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Supervisor: Dr.ssa Francesca Modugno

Title: The chemistry of contemporary art: characterization of synthetic resins and study of their aging.

Abstract: A huge number of synthetic materials have been exploited by artists and restorers, and the wide variety of formulations of synthetics resins has allowed their extensive use as paint binders, plastic materials, consolidants, adhesives, coatings and varnishes and many other applications. The use of various and heterogeneous synthetic materials by contemporary artists in paintings, sculptures and installations, and their complex and partially unknown degradation patterns, is at the basis of the complexity of the conservation of contemporary art. The chemical knowledge of synthetic resins used in art and restoration and of their aging process, and the availability of effective analytical methods for their characterization in works of art, are of extreme importance for the proper conservation, to reduce the frequency of restorations, to make them less invasive and reversible while minimizing the risk of damage to the art works. The characterization and aging studies will be performed with the use of analytical techniques such as GC / MS, PY - GC / MS, LC / MS, SEC, FTIR and SEM-EDX. The experimental work will entail three steps:
• selection of materials to be object of the study, on the basis of the state of the art and of specific case studies related to unsolved conservation issues, with particular interest in the latest generation of materials widely used in the cultural heritage as paint and varnishes which, for the most part, have not yet been completely characterized for what concerns their stability;
• chemical analysis and characterization of reference materials and samples from artworks and natural and artificial aging of opportunely prepared and selected materials;
• evaluation of the data to gain a better knowledge of the artworks object of study and of the alteration pathways undergone by synthetic paint materials to contribute to the diagnosis of the state of alteration and to the selection of conservation approaches under a chemical aspects.

Journal publications

I. Bonaduce, M.P. Colombini, I. Degano, F. Di Girolamo, J. La Nasa, F. Modugno, S. Orsini, Mass spectrometric techniques to characterise low molecular weight resins used as paint varnishes, Analytical and Bioanalytical Chemistry, 2013, vol 405, p 1047–1065
Ilaria Degano, Jacopo La Nasa, Elisa Ghelardi, Francesca Modugno, Maria Perla Colombini, “Core shell stationary phases for a novel separation of triglycerides in plant oils by high performance liquid chromatography with electrospray-quadrupole-time of flight mass spectrometer”, Journal of Chromatography A, 2013, vol 1308, p 114-124
Sibilla Orsini, Jacopo La Nasa, Francesca Modugno, Maria Perla colombini, “Characterization of Aquazol polymers using techniques based on pyrolysis and mass spectrometry”, Journal of Analytical and Applied Pyrolysis, 2013, accepted for publication
Jacopo La Nasa, Ilaria Degano, Francesca Modugno, Maria Perla Colombini, “Alkyd paints in art: characterization using integrated mass spectrometry”, Analytica Chimica Acta, 2013, accepted for publication

Book chapters

D. Pellegrini, J. La Nasa, F. Modugno, F.a di Girolamo, M. P. Colombini, “Indagini scientifiche su Cette obscure clartè qui tombe des étoiles di Anselm Kiefer”, Il Master sulla conservazione delle opere contemporanee della Scuola di Alta Formazione dell'Opificio delle pietre dure. L'esperienza dei «cantieri didattici», Letizia Montalbano, EDIFIR, 2013, in press

Contribution in congress

Jacopo La Nasa, Francesca, Modugno, Sibilla Orsini, Maria Perla Colombini, "La protezione del murale Tuttomondo di K.Haring a Pisa (Italia): Innovativi sistemi di protezione a base di materiali polissilossanici", XIV congresso nazionale di Chimica dell'ambiente e dei beni culturali "la chimica nella società sostenibile", Rimini, 2-5 giugno 2013 - Poster

J. La Nasa, S.Orsini, I. Degano, F. Di Girolamo, F. Modugno, I. Bonaduce, M. P. Colombini, "Characterization of low molecular weight paint varnishes by analytical techniques based on mass spectrometry", MaSC Workshop and Meeting 2013, Pisa, 5-6 June 2013 – poster

F. Saliu, J. La Nasa, I. Degano, F. Modugno, E. Ribechini, M. P. Colombini, "TAG profiling by HPLC/MS for the identification of lipids in historical samples", MaSC Workshop and Meeting 2013, Pisa, 5-6 June 2013 – poster

J. La Nasa, I. Degano, F. Modugno, M.P. Colombini, "A study on alkyd paint media by GC/MS, HPLC and FIA-ESI-Q-ToF", 3-MS-J-Day, Firenze, Ospedale Meyer, 23 Novembre 2012 - presentazione orale

F.Di Girolamo, J. La Nasa, F.Modugno, M.P.Colombini, "Il contributo delle analisi chimiche allo studio delle opere d'arte contemporanea , Salone dell'Arte e del Restauro di Firenze" Fortezza da Basso, 9 Novembre 2012 – presentazione orale

J. La Nasa, S.Orsini, I. Degano, F. Di Girolamo, F. Modugno, I. Bonaduce, M. P. Colombini, Characterization of low molecular weight paint varnishes by analytical techniques based on mass spectrometry, XXIII Congresso Nazionale di Chimica Analitica, 16-20 Settember 2012, Isola d'Elba – poster

F. Saliu, J. La Nasa, I. Degano, F. Modugno, E. Ribechini, M. P. Colombini, "TAG profiling by HPLC/MS for the identification of lipids in historical samples", XXIII Congresso Nazionale di Chimica Analitica, 16-20 Settembre 2012, Isola d'Elba – poster

J. La Nasa, F. Modugno, I. Degano, M. P. Colombini, "A study on alkyd paint media by GC/MS and HPLC-ESI-Q-ToF", XXIII Congresso Nazionale di Chimica Analitica, 16-20 Settembre 2012, Isola d'Elba – presentazione orale

O. Chiantore, C. Riedo, A. Piccirillo, T. Poli, J. La Nasa, F. Di Girolamo, S. Orsini, F. Modugno, I.Bonaduce, M.P. Colombini, "Caratterizzazione dei materiali del murale Tuttomondo di Keith Haring preliminare al restauro dell'opera", XIII Congresso Nazionale di Chimica dell'Ambiente e dei Beni Culturali, 10-14 Settembre 2012, Taranto – poster

J. La Nasa, F. Di Girolamo, F. Modugno, S. Orsini, M.P. Colombini, "On the conservation of the mural Tuttomondo by Keith Haring in Pisa", VII congresso nazionale di Archeometria, 22-24 Febbraio 2012, Modena – presentazione orale

J. La Nasa, D. Pellegrini, F. Modugno, M.P. Colombini, F. Di Girolamo, "Die grosse fracht, by Anselm Kiefer: diagnosis and preventive conservation", VII congresso nazionale di Archeometria, 22-24 Febbraio 2012, Modena – presentazione orale

J. La Nasa, S.Orsini, F. DI Girolamo, F. Modugno, I.Bonaduce, M. P. Colombini, "Characterization of synthetic varnish and paint materials by analytical methods based on pyrolysis and mass spectrometry", Dalla scienza al restauro, le vernici nella pittura, Lucca, 2 Dicembre 2011 – presentazione orale

J. La Nasa, S.Orsini, F. DI Girolamo, F. Modugno, I.Bonaduce, M. P. Colombini, C. Duce, L. Ghezzi, V. Barone, V. Palleschi, E. Bramanti, S. Legnaioli, M. Picollo, G. Bartolozzi, C. Cucci, M. De Vita, V. Macchiafava, A. Ballerini, S. Carlesi, "Preventive Conservation of Contemporary Art (COPAC): a new Italian research project", Future Talks 011 (Technology and conservation of modern materials in desings), Monaco, 26-28 Ottobre 2011 – poster

J. La Nasa, S. Orsini, F. di Girolamo, F.Modugno, I. Bonaduce, M.P. Colombini, "Characterization of synthetic varnishes and paint materials by analytical methods based on pyrolysis and mass spectrometry", XXIV Congresso Nazionale della Società Chimica Italiana, Lecce 11-16 Settembre 2011

L. Ghezzi, J. La Nasa, S. Orsini, F. di Girolamo, F. Modugno, C. Duce, I. Bonaduce, M. Tiné, M.P. Colombini, "Study on the curing and ageing of alkyd paints layers", XXIV Congresso Nazionale della Società Chimica Italiana, Lecce 11-16 Settembre 2011 - poster

J. La Nasa, S.Orsini, F. DI Girolamo, F. Modugno, I.Bonaduce, M. P. Colombini, "Characterization of synthetic varnish and paint materials by analytical methods based on pyrolysis and mass spectrometry", Safeguard of cultural heritage: a challenge from the past for the Europe of tomorrow, COST strategic workshop, Firenze 11-13 Luglio 2011 - Presentazione orale

Maria Perla Colombini, Francesca Di Girolamo, Ilaria Bonaduce, Francesca Modugno, Jacopo La Nasa, Vincenzo Barone, Marcello Picollo, "The COPAC project: Preventive Conservation of Contemporary Art in Tuscany: Preliminary results", VIII INSTM Conference, Catania, 26-29 Fiugno 2011 - presentazione orale

I. Bonaduce, F. Modugno, S. Orsini, J. La Nasa, M.P. Colombini, " GC/MS study of curing of alkyd paints under artificial ageing", MaSC Workshop and Meeting 2011, Harvard Art Museums, Cambridge MA, 9-13 Maggio 2011 - poster

S.Orsini, J. La Nasa, F. Modugno, I.Bonaduce, M. P. Colombini, Studio molecolare dell'essiccamento ed invecchiamento di stesure di pittura alchidica, AiAr meeting: "Science for contemporary art"., Ferrara, Castello Estense, 1-4 Marzo 2011 - poster

Supervisor: Prof. Anna Maria Raspolli

Title: Catalytic exploitation of lignocellulosic biomass to give fine chemicals and biofuels

Contatti:
Dr. Tommaso Lomonaco
PhD student
Dipartimento di Chimica e Ch. Industriale via Risorgimento, 35 - 56126 - Pisa
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Supervisor: Prof. Roger Fuoco, Dott. Fabio Di Francesco

Title: Measurement of drug concentration in alternative biological fluids for therapeutic monitoring.

Abstract: Aim of the project is the development of methods for the analysis of non traditional biological fluids such as saliva to be used for a non invasive therapeutic drug monitoring. Therapeutic Drug Monitoring (TDM) consists in the measurement of drug concentrations in biological fluids (typically plasma, serum or blood) to obtain useful information to personalize dosage, keep concentrations within a target range, increase efficacy or decrease toxicity. TDM is particularly useful for drugs showing large inter-individual dose/effect variations, having a narrow target range or a concentration-dependent pharmacokinetics. In these cases, a frequent monitoring is necessary to achieve the best therapeutic effect and reduce risks of adverse effects. In the last decade, alternative biological fluids like breath, saliva, hair and sweat have gained importance as sources of clinical information, both for diagnosis and therapy monitoring. Toxicology and assay of drugs of abuse have become other important application fields. In comparison with blood and its derivates, these fluids are easily and painlessly collected. Furthermore, chemical analysis are generally less complex and potentially provide physiological information in real time. In the case of drugs, saliva and sweat are suitable for therapeutic monitoring because the concentration in these alternative fluids only mirrors the free plasma concentration, i.e. the biologically active fraction. The main disadvantage of such approach is that drugs are only present at very low concentrations (100-1000 times lower than blood) and this implies that accurate methods with adequate sensitivity and specificity are needed for their measurement. Gas or liquid chromatography combined with mass spectrometry (GC/MS or LC/MS), ultraviolet (LC/UV) and fluorescence (LC/FP) detection are the reference techniques in this field.

Publications:  http://arp.unipi.it/listedoc.php?ide=486092&ord=C