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Supervisors: Dr. Ilaria Degano and Dr. Anna Lluveras Tenorio

Title: Ageing and fading of organic pigments in art: a multi-analytical study based on mass spectrometric techniques

Abstract: Since ancient times, man has tried to paint in colour using natural sources or, since the second half of the 19th century, by chemical synthesis. With the industrial progress, synthetic organic pigments have increasingly replaced natural inorganic and organic pigments due to their cheapness and wide availability. Thousands of these synthetic pigments have been introduced for a variety of applications including paints, printing inks, food and drink additives, plastics and textiles. Focusing on painting use, the introduction of ready to use tube colours radically changed the way in which artists approached painting and synthetic organic pigments have become the most important group of pigments used in modern art.
The characterization of synthetic organic pigments is challenging due to the high complexity of the matrix generally constituted by a mixture of traditional and modern paint materials, both organic and inorganic. In addition, the absence of information about the miscellaneous additives used by paint manufactures in the commercial formulations and the continual optimization of some pigments already synthetized lead to a general lack of knowledge of the chemistry of modern paints.
My PhD project aims to study the degradation and fading processes due to ageing and oxidation of some natural and synthetic organic pigments, less investigated until now, evaluating also the interaction mechanisms with the several binding media generally used. The analysis of paint model systems (naturally or artificially aged) will be fundamental in order to understand how to prevent or slow down deterioration processes and choose the most suitable procedures for preserving artworks.
I will develop and use methods based on High Performance Liquid Chromatography coupled with Diode Array or mass spectrometric detectors (HPLC-DAD-MS) and Pyrolisis-Gas Chromatography coupled with mass spectrometric detector (Py-GC/MS). Moreover, a multi-analytical approach, using also non-conventional analytical procedures and instrumentations, will be adopted in order to provide an exhaustive characterization of the degradation pathways of these synthetic organic pigments. The project will be performed in the frame of IPERION-CH, a European research infrastructure for restoration and conservation of Cultural Heritage, which will promote several collaborations with the members of the consortium.

Oral communications at congress:
•    F. Sabatini, R. Giugliano, R. Sokolová, I. Degano, M.P. Colombini, Investigating the degradation pathway of xanthene dyes in textiles, Dyes in History and Archeology (DHA) 36, London, 26-28/10/2017.
•     F. Sabatini, R. Giugliano, I. Degano, M.P. Colombini, Xanthene dyes: a study on fragmentation patterns and degradation pathways in textiles, 8th Mass Spectrometry and Chromatography (MaSC), Evora, 28-29/09/2017.
•     A. Chieli, A. Romani, B. Doherty, C. Anselmi, I. Degano, F. Sabatini, C. Miliani, Why does Geranium lake fade? Photochemical study of eosin-based pigments in oil paints, Colloquium Spectroscopicum Internationale XL, Pisa, 11-16/07/17.
•     F. Sabatini, P. Tognotti, C. Anselmi, A. Cheli, C. Miliani, I. Degano, Eosina: studio della degradazione di un pigmento storico di notevole importanza in campo artistico, XVI Congresso Nazionale di Chimica dell’Ambiente e dei Beni Culturali della SCI, Lecce, 26-29/07/16. Winner of the scholarship for the participation.
•     F. Sabatini, P. Tognotti, A. Lluveras Tenorio, I. Degano, Ageing and fading of eosin, a remarkable pigment in XIX-XX century paintings, 35th Dyes in History and Archeology, Pisa, 05-08/10/2016.

Poster communications at congress:
•    I. Degano, F. Sabatini, J. Wertz, A. Quye, Mass spectrometric analysis of arylcarbonium blue, violet and green dyes: unlocking structural differences though data mining, Dyes in History and Archeology (DHA) 36, London 26-28/10/2017.
•    F. Sabatini, I. Degano, R. Giugliano, C. Braccini, A. Lluveras-Tenorio, E. Ribechini, Ageing of mono-azo and β-naphthol red and yellow synthetic organic pigments in painting matrices and textiles, XXVI Congresso Nazionale della SCI, Paestum, 10-14/09/2017.
•    F. Sabatini, I. Degano, R. Giugliano, A. Lluveras-Tenorio, M.P. Colombini, Degradation of β-naphthol and mono-azo synthetic organic pigments in painting matrices and textiles, Convegno Tematico AIAr, Beni Culturali: grandi facilities, reti e networks di laboratori, Florence, 8-10/03/2017.
•    F. Sabatini, A. Lluveras-Tenorio, I. Degano, S. Kuckova, M.P. Colombini, HPLC-DAD-MS and MALDI strategies for anthraquinoid lakes identification in paint samples, 2nd International Conference of COLOURS 2015, Evora, 24-26/09/2015; and at 34th Dyes in History and Archeology, Thessaloniki, 21-24/10/2015.
•    F. Sabatini, A. Cardoso, R. Vaz Freire, A. Candeias, C. Barrocas Dias, Shedding light on Gregório Lopes’ palette: a multi-analytical approach for the characterization of painting materials used in the ‘Ressurreição do Mancebo’ 2nd International Conference of COLOURS 2015, Evora, 24-26/09/2015.
•    A. Lluveras-Tenorio, I. Bonaduce, F. Sabatini, I. Degano, C. Blaensdorf, E. Pouyet, M. Cotte, M. Linyan, B. Chongbin, H. Kejia, M. P. Colombini, Disclosing the Technologies of The Qing Dynasty Painters in Civil Buildings: the mural paintings in the Five Northern Provinces’ Assembly Hall, Ziyang China, 3rd International Congress on Chemistry for Cultural Heritage, Wien, 1/05/2014; and at XXV Congresso della Divisione di Chimica Analitica, Trieste, 13-17/09/2015.

Journal articles:
•    F. Sabatini, R. Giugliano, I. Degano, Photo-oxidation processes of Rhodamine B: A chromatographic and mass spectrometric approach, Microchemical Journal, vol. 140, pp. 114-122, 2018.
•    F. Sabatini, R. Giugliano, I. Degano, A. Lluveras-Tenorio, R. Sokolová, M. Thoury, M.P. Colombini (in press), Development of a multi-analytical approach to investigate the fading of eosin in painting matrices, IOP Conference Series: Materials Science and Engineering
•    F. Sabatini, A. Lluveras-Tenorio, I. Degano, S. Kuckova, I. Krizova, M. P. Colombini, A Matrix-Assisted Laser Desorption/Ionization Time-of-Flight Mass Spectrometry Method for the Identification of Anthraquinones:the Case of Historical Lakes, Journal of The American Society for Mass Spectrometry, vol. 27, no. 11, pp.1824-1834, 2016.
•    A. Lluveras-Tenorio, I. Bonaduce, F. Sabatini, I. Degano, C. Blaensdorf, E. Pouyet, M. Cotte, M. P. Colombini, The Organic Materials used in the Five Northern Provinces' Assembly Hall Mural Paintings (Ziyang, China): disclosing the painting technique of the Qing Dynasty Painters in Civil Buildings, Applied Physics A, vol. 121, no. 3, pp. 879-889, 2015.