University of Lille

Talk TitleInsoluble natural and synthetic polymers analysis for Cultural Heritage Science

Christian Rolando is a CNRS senior scientist working at the University of Lille and has been the Deputy director at the CNRS Institute for Chemistry in charge of scientific infrastructures. He has authored over 200 papers cited more than 6500 times (Google Scholar) and has supervised over 40 PhD theses. He has an h-index higher than 40 (Google Scholar). He has been President of the French Society for Mass Spectrometry, of the Group “Polyphénols” and of the Division of Analytical Chemistry of the French Chemical Society. He is a member of the Steering Committee of the Division of Analytical Chemistry of EuCheMS (European Association for Chemical and Molecular Sciences) and has organized several congresses, the last being EuroAnalysis 2015 in Bordeaux (France). He is the PI of just funded (start 1st January 2018) Horizon Infra for Starting Communities EU_FT-ICR_MS which includes 10 FT-ICR academic centers from nine European countries, an instrumentation companies and 2 SMEs.

Christian ROLANDO’s research is devoted to analytical and physical organic chemistry. He began his research career in 1977 at the Ecole Normale Supérieure (Paris, France) under the supervision of Prof. Marc Julia in organic synthesis and he defended his thesis in 1984. During this time he was acting as the director of the mass spectrometry facility and supervised 2 engineers. Mixing organic chemistry and analytical chemistry, he developed in cooperation with biologists specialised in wood biosynthesis a new method for depolymerizing lignin, the phenolic part of wood, called thioacidolysis, which is now a classical method in the field. In the 80’s he developed with the French mass spectrometer manufacturer Nermag many new devices for manipulating ions in RF-only quadrupole collision cells. With the pentaquadrupole he explored ion-molecule reactions and especially reactivity of transition metal cations. He proved that transition metal cations no only break but also catalyse bond formation in the gas phase. He moved from Paris to the University of Lille 1 in 2000. He created the Miniaturization for Synthesis, Analysis and Proteomics laboratory (USR CNRS 3290) and the proteomics platform of the Genopole of Lille. He developed miniaturized devices such as ESI tips with a nib design in polysilicon, which allows low ionization voltage and high sensitivity. Currently he develops method for the quantitative analysis of proteins in single starch granule. In 2006, he got funding for installing an FT-ICR mass spectrometer. In 2009 he started to revisit 2D FT-ICR with two NMR teams, topic which has been very fruitful and funded two times by the French National Research Agency.

Insoluble natural and synthetic polymers analysis for Cultural Heritage Science’

Pure natural, chemically modified and synthetic polymers are among the best preserved material in the Cultural heritage field. The first reason is due to their insolubility in water. The second one is that these polymers are often found enchased in an inorganic or organic matrix which protect them for millions of year. For example, collagen trapped in dinosaur bones has been identified. The inorganic matrix may be bones, shells, stucco or mortar for example and the polymeric matrix can be siccativated oil painting or natural resins. Very often the polymers can’t be analyzed directly by mass spectrometry and need to be cut either enzymatically or chemically in smaller chunks. In general the information increase with the size of the chunks analyzed. Since more than 30 years we developed such new methodologies based on a direct introduction high resolution GC/MS for the characterization of birch tars, the use of direct infusion ESI (ElectroSpray Ionization) for the characterization of polar compound such as bee wax,[1] a very successful proteomics approach for identifying proteins in art painting,[2] a direct infusion associated with very high resolution FT-ICR for characterization of lipids [3] and also sample miniaturization for proteomics in paintings [4] and glycomics for gums [5]. One of the major issue in the Cultural heritage field is the available quantity of samples. All our analyses were performed using nanoLC (Liquid Chromatography) with an 75 µm id column and nanoESI which requires one thousand less sample than conventional LC ESI MS protocol using either high resolution mass analyzer (Orbitrap MS) or ultra high resolution mass analyzer (FT-ICR MS). Furthermore, during the recent years all these techniques has been miniaturized using the eFASP (enhanced Filter-Aided Sample Preparation) protocol allowing to reach an unprecedented sensitivity. Over the years increased sensitivity has been equally related to the progress in instrumentation and to the refinement of sample preparation. Our more recent developments on paleoproteomics and on protocols for the identification of gums and crosslinks between proteins which are signature of the sample history as well as on new methods for the chemical depolymerization of art oil paint and resins will be presented. Examples of top down analysis in proteomics and 2D FT-ICR MS will be also given.

[1] Characterization of Archaeological Beeswax by Electron Ionization and Electrospray Ionization Mass Spectrometry. Anal. Chem. 2002, 74, 4868-4877.

[2] Identification of Proteins in Renaissance Paintings by Proteomics. Anal. Chem. 2006, 78, 1494-1502.

[3] Analysis of archaeological triacylglycerols by high resolution nanoESI, FT-ICR MS and IRMPD MS/MS: Application to 5th century BC-4th century AD oil lamps from Olbia (Ukraine). Int. J. Mass Spectrom. 2009, 284, 47-56.

[4] Identification of Animal Glue Species in Artworks Using Proteomics: Application to a 18th Century Gilt Sample. Anal. Chem. 2011, 83, 9431-9437.

[5] Plant gum identification in historic artworks. Scientific Reports 2017, 7, 44538.