Ntasi, Georgia (2021) Proteomics for ancient protein degradation. [Tesi di dottorato]

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Preservation of our cultural heritage is vital as it keeps alive the past that determines who we are, where we came from, and the human path's achievements over the years. Material culture, defined as every physical object, resource, and space that defines our culture, is powerful and appealing because it is probably more stable than human identity and social communities. Its preservation includes both cultural and economic processes. Chemistry has a very active role and contributes significantly to the preservation of our cultural heritage, helping to transmit this wealth to the next generations. The molecular characterization of archaeological objects and works of art replies to crucial questions such as: HOW and WHEN a masterpiece has been created, as also WHICH are the chemical degradation mechanisms that took place through the years. The answers to these questions are what determine how it will be kept alive in the future. However, chemistry is called upon to face immense challenges concerning the micro-invasiveness of the chemical approach, the high heterogeneity of the material encountered, and the tiny amount of samples in some of the cases. As a result, there is a demand for sensitive, versatile, and minimally invasive analytical approaches that can shed light on the origin of the material and its conservation state without provoking further deterioration. Mass spectrometry is an analytical tool that gained more and more attention in the last years because it includes fast analytical techniques of high sensitivity and accuracy that are micro destructive. Over the last 20 years, protein and mass spectrometry have been successfully adapted to the analysis of cultural heritage samples, actively contributing to the understanding of their origin and their preservation, a new scientific field known as palaeoproteomics. Proteins consist of a great target because of their high resistance over the years , giving us the possibility to recover information further back in time than previously thought possible. Palaeoproteomics is complementary to a variety of analytical techniques (physicochemical, geochemical, dating, microscopic etc.) That investigate components other than proteins in the archaeological object, aiming to the overall characterization of its origin, provenance and degradation state. The combination of these and proteomic approaches have obtained remarkable results in the field of cultural heritage, interpreting data related to the inorganic and organic material record of human cultural history. This Ph.D. project focused on developing proteomic analytical strategies with the use of mass spectrometry in archaeological objects and works of art. These strategies were used as such or combined with data obtained by other analytical approaches for a more in-depth insight of material origin and use and the chemical degradation mechanisms taking place over the years. After a brief introduction of the importance of cultural heritage, the types of cultural heritage materials and an overview on mass spectrometric analytical techniques herein used, chapter 2 explains the aim of the Ph.D. thesis and organizes the projects on the basis of the analytical techniques used in the single case of study. Chapter 3 reports a chemical review on palaeoproteomic analysis of bone and teeth as sources of collagen. Subsequently, the chapter reports proteomic strategies for the characterization of collagen-based materials ranging from archaeological bones to animal glues. Chapter 4 describes the development of novel micro-invasive techniques for the molecular characterization of proteins in archaeological objects and works of art. Chapter 5 reports the results of multidisciplinary approaches that combine proteomic strategies and mass spectrometry techniques with other analytical approaches such as microscopy and spectroscopy, with the final aim of characterizing organic materials in archaeological remains such as amphorae, historical paintings, and wooden coffins.All the data obtained from the aforementioned scientific projects have been later then organized in already published, under submission, or in preparation manuscripts.

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