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In this work, an innovative analytical approach focused on the use of advanced imaging techniques for the chemical mapping of degradation and/or restoration products is proposed. A representative cross-section showing a very complex stratigraphy from the Saint Wilgefortis Triptych (Hieronymus Bosch), exhibited in the Galleria dell'Accademia di Venezia, was investigated. Time-of-flight secondary ion mass spectrometry (ToF-SIMS) experiments were performed using a time-of-flight detector operating in the so-called delayed extraction mode. The time delay applied during the extraction of the secondary ions permitted mass spectra to be obtained with an excellent mass resolution and chemical maps with nanometer scale spatial resolution. The painting's cross-section was also analysed at the micrometer scale by micro-Fourier transform infrared spectroscopy (micro-FTIR). The combined analytical approaches highlighted the colocalization of lead chloride, oxychloride, and hydroxychloride ions, suggesting the transformation of lead white ((PbCO3)2Pb(OH)2) into laurionite (PbClOH). Furthermore, chlorine appears evenly diffused in the cinnabar (HgS) layer, inducing the alteration of its more external part into calomel (Hg2Cl2). In fact, from the chemical maps the presence in the sample of an unaltered portion of the cinnabar layer is evident. Such degradation products were probably due to the exposure of the painting to a chloride-rich atmosphere for a long time. This led to a global blackening of the painting. To protect the painting from aggressive chemical species, siloxane compounds were probably used as a modern restorative treatment. ToF-SIMS chemical maps revealed permeation of the silicon-based consolidants within the sample's cracks and no interaction products with the other constitutive materials of the painting were found. Finally, the presence of different lead soaps was detected in correspondence with the lead white layer.

Recent advances in the role played by dietary carbohydrates in human food webs during the Palaeolithic highlight that starchy foods were part of the diet well before crop domestication. Although certain plants can be eaten raw, intentional processing such as mechanical reduction using stone tools and thermal treatment readily increases the assimilation of nutrients for metabolic functions and for storing. We present a multi-techniques approach designed to combine micro to nanoscale analyses applied to percussive stones to identify their function using micro-wear traces and use-related biogenic residues. The starch grains extracted from functionally active areas of the ground stone tools were scanned using optical microscopy (OM) down to the nanoscale (SEM) and by applying different spectroscopic and spectrometric techniques like FTIR, ToF-SIMS, and IRMS. The combined analyses carried out at different resolutions–morpho-structural and molecular levels–contribute to an unprecedented methodological refinement regarding the intentional processing of starch-rich plants as early as 40,000 years ago at the boreal latitudes. Our preliminary data on pestles and grinding stones from Early Upper Palaeolithic sites of the Pontic steppe (Moldova and Russia) show the suitability of the analytical techniques involved and also the difficulties encountered in detailing authentication procedures of ancient starch candidates.

Detectors are a key feature of the contemporary scientific approach to cultural heritage (CH), both for diagnostics and conservation. INFN-CHNet is the network of the Italian National Institute of Nuclear Physics that develops and applies new instrumentation for the study of CH. This process results in both optimized traditional state-of-the-art and highly innovative detection setups for spectrometric techniques. Examples of the former are X-rays, gamma-rays, visible-light and particles spectrometers tailored for CH applications, with optimized performances, reliability, weight, transportability, cost, absorbed power, and complementarity with other techniques. Regarding the latter, examples are ARDESIA, the array of detectors at the DAΦNE-Light facility, the MAXRS detection setup at the Riken-RAL muon beamline and the imaging facilities at the LENA Laboratory. Paths for next-generation instruments have been suggested, as in the case of the X-ray Superconductive Detectors and X-ray Microcalorimeter Spectrometers, allowing astonishing improvement in energy resolution. Many issues in CH can now be addressed thanks to scientific techniques exploiting the existing detectors, while many others are still to be addressed and require the development of new approaches and detectors.

In the present paper, for the first time, non-invasive techniques have been employed to improve the knowledge of a Coronation of the Virgin dating back to 1560–70. This is an old master drawing by Giorgio Vasari, considered one of the major painters and art theoric of Italian late 16th Century. The adopted multi-technique approach, involving preliminary macroscopic and microscopic observations, and followed by X- ray fluorescence mapping (MA-XRF), μ-Raman, and Fourier Transform infrared spectroscopy (FTIR) analyses, along with the historical information, has allowed to identify the original materials and to understand the drawing's realization process. The results show that paper preparation has been realized by using a yellow mineral, namely goethite, in order to obtain a particular shade. Moreover, a proteinaceous component, likely animal gelatin, has been used as a binder for goethite or during the paper preparation process. Small white flakes, composed of lead white and massicot, have been randomly found on the surface of the drawing: the specific function and/or origin of these flakes is unknown. Finally, the use of black chalk for a preliminary sketch and iron gall ink for the final drawing has been observed.

Hybrid biomaterials allow for the improvement of the biological properties of materials and have been successfully used for implantology in medical applications. The covalent and selective functionalization of materials with bioactive peptides provides favorable results in tissue engineering by supporting cell attachment to the biomaterial through biochemical cues and interaction with membrane receptors. Since the functionalization with bioactive peptides may alter the chemical and physical properties of the biomaterials, in this study we characterized the biological responses of differently functionalized chitosan analogs. Chitosan analogs were produced through the reaction of GRGDSPK (RGD) or FRHRNRKGY (HVP) sequences, both carrying an aldehyde-terminal group, to chitosan. The bio-functionalized polysaccharides, pure or “diluted” with chitosan, were chemically characterized in depth and evaluated for their antimicrobial activities and biocompatibility toward human primary osteoblast cells. The results obtained indicate that the bio-functionalization of chitosan increases human-osteoblast adhesion (p &lt, 0.005) and proliferation (p &lt, 0.005) as compared with chitosan. Overall, the 1:1 mixture of HVP functionalized-chitosan:chitosan is the best compromise between preserving the antibacterial properties of the material and supporting osteoblast differentiation and calcium deposition (p &lt, 0.005 vs. RGD). In conclusion, our results reported that a selected concentration of HVP supported the biomimetic potential of functionalized chitosan better than RGD and preserved the antibacterial properties of chitosan.

This study focusses on the development and application of an innovative protocol which combines chemical data, GIS (geographical information system) and PCA, involving numeric (chemical composition) and categorical (typology of object, archaeological context, chronology and geographical areas) variables, as a simple tool to help in the visualisation and interpretation of large multidisciplinary datasets on Cu-based alloy archaeological artefacts influenced by Phoenician-Punic contacts. The protocol is a useful tool for highlighting existing connections between specific alloy chemical compositions, the location of the original settlement where the artefact had been produced and the proximity to mining resources, waterways, and allochthonous presence such as, in the specific case of this study, the Phoenician and Punic influence in the Iberian bronze production during the Late Bronze Age-Iron Age. The protocol was tested successfully in a case study concerning the precise dating and provenance of bronze statuettes of unknown age and provenance from the Evora Museum collection in Southern Portugal where it confirmed and further refined earlier hypotheses based solely on archaeological and/or chemical studies. The results were interpreted with a unique perspective, to validate the GIS system in combination with experimental chemical-physical data to yield the identification of metallurgical sites of bronze production.

Inter-observer variability and cancer over-diagnosis are emerging clinical problems, especially for follicular patterned thyroid lesions. A very recent paradigm change versus the reduced thyroid cancer overtreatment necessitates for a new clinical tool to reliably identify neoplastic lesions and to improve the efficiency in differentiation between benign and malignant neoplasms, especially what regards small carcinomas and growing number of thyroid nodules. Raman spectroscopy (RS) is a promising label-free non-invasive technique capable to increase diagnostic reliability, providing specific information on biochemical composition. The combined histological and Raman microscopy analyses approach could allow clear-cut integration of morphological and biochemical observations, with dramatic improvement of efficiency and reliability in the differential diagnosis of neoplastic thyroid nodules. In this work, we applied RS microscope to investigate frozen thyroid tissues, in order to support histologic analysis. Our aim was to investigate the ability of RS to discriminate between healthy and Papillary Thyroid Carcinoma (PTC) tissues, between the two PTC variants (classical and follicular); between normal parenchyma and pathologic follicular patterned thyroid nodules, and between benign and malignant follicular lesions (adenoma versus carcinoma). Our Raman database of various thyroid pathologies includes 30 thyroid patient cases, containing reach biochemical information. To generate tissue classification models, a supervised statistical analysis of the obtained Raman spectra was performed. It consisted in the sequential data treatment by Principal Component Analysis and Linear Discriminant Analysis, followed by internal (leave-one-out) and external (independent) dataset validation. The obtained results allow to affirm that RS is able to discriminate between healthy and PTC tissues of thyroid with 100% of sensitivity, specificity and accuracy and between classical and follicular variants of PTC with 93% of sensitivity, 100% of specificity and 95% of accuracy [1]. The achieved diagnostic sensitivity, specificity and accuracy are compatible with the clinical use, both for the PTC diagnosis and for the differential diagnosis between classical and follicular variants of PTC, the latter being a significant challenging point for thyroid nodules evaluation. Furthermore, the achieved results demonstrate 92% of accuracy for RS based diagnosis in distinguishing between healthy and neoplastic follicular patterned thyroid tissues, while for the very challenging follicular lesions (carcinoma versus adenoma) approximately 90% of accuracy can be assured [2]. In comparison, for this latter result, histopathology provides about 70% of reliability. The 20% increase of diagnosis reliability for follicular lesions demonstrates the great potential of RS biochemical fingerprints to contribute to clinical decision-making. Moreover, our study demonstrates that RS translation into intra-operative diagnosis on frozen sections and in pre-operative analysis of biopsy samples can be helpful to reduce unnecessary surgery in patients with indeterminate cytological reports. Furthermore, RS biochemical information allows the identification of molecular species involved in thyroid tumorigenesis and progression. The combination of histological and Raman microscopy analyses, yielding improved diagnostic accuracy and reduced inter-observer variability, may open a new way to integrative findings with wide implications for basic pathology, tumour classification schemes and therapeutic strategies.

Il volume edito da Lorenza-Ilia Manfredi e Silvia Festuccia, raccoglie i recenti risultati di un progetto multidisciplinare di ricerca, studio e valorizzazione del sito di Aouam in Marocco. L'obiettivo del progetto bilaterale "Phoenician-Punic Archaeology, Geology, Archaeometry, territorial information systems, mining history" in collaborazione tra ISMA-CNR e l'Universitè Moulay Ismail of Meknes è di definire il contesto storico e tecnologico che caratterizza il ciclo di produzione metallurgica nel medio Atlas.