The Use of UV-Visible Diffuse Reflectance Spectrophotometry for a Fast, Preliminary Authentication of Gemstones

The identification of gemstones is an important topic in the field of cultural heritage, given their enormous value. Particularly, the most important precious stones, namely diamond, emerald, ruby and sapphire, are frequently subjected to counterfeit by substitution with objects of lesser value with similar appearance, colour or shape. While a gemmologist is able to recognise a counterfeit in most instances, more generally, it is not easy to do this without resorting to instrumental methods. In this work, the use of UV-visible diffuse reflectance spectrophotometry with optic fibres (FORS) is proposed as a fast and easy method for the preliminary identification of gemstones, alternative to the classical methods used by gemmologists or to Raman spectroscopy, which is by far the instrumental method with the best diagnostic potential, but it cannot be used in situations of problematic geometric hindrance. The possibilities and the limitations given by the FORS technique are critically discussed together with the spectral features of the most important gemstones. Finally, the application of chemometric pattern recognition methods is described for the treatment of large sets of spectral data deriving from gemstones identification

Identification of Illicit Conservation Treatments in Fresh Fish by Micro-Raman Spectroscopy and Chemometric Methods

In the field of food control for fresh products, the identification of foods subjected to illicit conservation treatments to extend their shelf life is fundamental. Fresh fish products are particularly subjected to this type of fraud due to their high commercial value and the fact that they often have to be transported over a long distance, keeping their organoleptic characteristics unaltered. Treatments of this type involve, e.g., the bleaching of the meat and/or the momentary abatement of the microbial load, while the degradation process continues. It is therefore important to find rapid methods that allow the identification of illicit treatments. The study presented here was performed on 24 sea bass samples divided into four groups: 12 controls (stored on ice in the fridge for 3 or 24 h), and 12 treated with a Cafodos-like solution for 3 or 24 h. Muscle and skin samples were then characterized using micro-Raman spectroscopy. The data were pre-processed by smoothing and taking the first derivative and then PLS-DA models were built to identify short- and long- term effects on the fish's muscle and skin. All the models provided the perfect classification of the samples both in fitting and cross-validation and an analysis of the bands responsible for the effects was also reported. To the best of the authors' knowledge, this is the first time Raman spectroscopy has been applied for the identification of a Cafodos-like illicit treatment, focusing on both fish muscle and skin evaluation. The procedure could pave the way for a future application directly on the market through the use of a portable device

Non-Invasive Study on the Sinope Gospels

The 6th century Codex Sinopensis or Sinope Gospels (Paris, Biblioth\ue8que nationale de France) is one of the most precious purple codices that survive from the Late Antique period. Together with the Vienna Genesis (Wien, 6sterreichische Nationalbibliothek) and the Rossano Gospels (Rossano Calabro, Museo Diocesano), it has an unusually rich decorative apparatus with scenes representing biblical episodes. It can be, therefore, considered one of the most important preserved artistic productions of the early medieval era. The manuscript has been subjected to a non-invasive diagnostic campaign to evaluate the quality of the colourants used in its decoration, to understand how the parchment was coloured, and to carry out a comparison with the Vienna Genesis and the Rossano Gospels. The techniques used were UV-visible diffuse reflectance spectrophotometry with optical fibres (FORS), X-ray fluorescence spectrometry (XRF), spectrofluorimetry, and optical microscopy. Analyses highlighted the presence of ultramarine blue, which, besides the use of pure gold for the ink and paint, certifies the high value of the manuscript. In addition, this must be seen as one of the earliest examples of its use in paintings. The purple colour of the parchment was identified as orchil, a dye extracted from lichens, similar to the results of analytical investigations carried out on other purple codices, and not the expected Tyrian purple dye

Diagnosis of Imported Dengue and Zika Virus Infections in Italy from November 2015 to November 2022: Laboratory Surveillance Data from a National Reference Laboratory

Dengue (DENV) and Zika (ZIKV) viruses are mosquito-borne human pathogens. In Italy, the presence of the competent vector Aedes albopictus increases the risk of autochthonous transmission, and a national plan for arboviruses prevention, surveillance, and response (PNA 2020–2025) is in place. The results of laboratory diagnosis of both viruses by the National Reference Laboratory for arboviruses (NRLA) from November 2015 to November 2022 are presented. Samples from 655 suspected cases were tested by both molecular and serological assays. Virus and antibody kinetics, cross-reactivity, and diagnostic performance of IgM ELISA systems were analysed. Of 524 cases tested for DENV, 146 were classified as confirmed, 7 as probable, while 371 were excluded. Of 619 cases tested for ZIKV, 44 were classified as confirmed, while 492 were excluded. All cases were imported. Overall, 75.3% (110/146) of DENV and 50% (22/44) of ZIKV cases were confirmed through direct virus detection methods. High percentages of cross reactivity were observed between the two viruses. The median lag time from symptoms onset to sample collection was 7 days for both DENV molecular (range 0–20) and NS1 ELISA (range 0–48) tests, with high percentages of positivity also after 7 days (39% and 67%, respectively). For ZIKV, the median lag time was 5 days (range 0–22), with 16% positivity after 7 days. Diagnostic performance was assessed with negative predictive values ranging from 92% to 95% for the anti-DENV systems, and of 97% for the ZIKV one. Lower positive predictive values were seen in the tested population (DENV: 55% to 91%, ZIKV: 50%). DENV and ZIKV diagnosis by molecular test is the gold standard, but sample collection time is a limitation. Serological tests, including Plaque Reduction Neutralization Test, are thus necessary. Co-circulation and cross-reactivity between the two viruses increase diagnostic difficulty. Continuous evaluation of diagnostic strategies is essential to improve laboratory testing

Chemometric Tools for 2D-PAGE Data Analysis

Two-Dimensional Polyacrylamide Gel Electrophoresis (2D-PAGE) provides two-dimensional maps where proteins appear separated according to their isoelectric point (pI) and molecular weight (MW). Usually these maps are very complex (i.e., hundreds or thousands of spots can be present in each map), and characterized by a low reproducibility, which hinders the possibility to identify reliable biomarkers unless robust methods are applied. The analysis of different sets of 2D-PAGE maps (e.g., control vs. pathological or control vs. drug-treated samples) to identify candidate biomarkers (proteins under- or over-expressed in different conditions) is usually carried out through image analysis systems providing a so-called spot volume dataset where each sample corresponds to a map described by the optical densities of all the detected spots. The identification of candidate biomarkers can be therefore accomplished by comparing different maps by classical monovariate statistical tests applied spotwise, or by multivariate chemometric tools applied to the entire set of spots present on each map. Here, the most exploited multivariate techniques will be considered, ranging from pattern recognition to classification methods

Two-Dimensional Gel Electrophoresis Image Analysis

Gel-based proteomics is still quite widespread due to its high-resolution power; the experimental approach is based on differential analysis, where groups of samples (e.g., control vs diseased) are compared to identify panels of potential biomarkers. However, the reliability of the result of the differential analysis is deeply influenced by 2D-PAGE maps image analysis procedures. The analysis of 2D-PAGE images consists of several steps, such as image preprocessing, spot detection and quantitation, image warping and alignment, spot matching. Several approaches are present in literature, and classical or last-generation commercial software packages exploit different algorithms for each step of the analysis. Here, the most widespread approaches and a comparison of the different strategies are presented

Plumage coloration and morphometrics of the Little Owl Athene noctua in the Western Palearctic

The Little Owl is a species with a wide range in the Palearctic. Thirteen subspecies have been described based on small coloration or size differences. Recently, genetic studies in the western portion of the European range have shown the presence of some well distinct clades. We examined the variation in structural size and coloration of Western Palearctic birds, with particular attention to the pattern of light and dark pigmentation on the tail, and we checked for the presence of UV reflection through reflectance spectroscopy. We did not find clear-cut differences in size or plumage between the currently accepted subspecies, nor between individuals pertaining to the different genetic clade areas. There is a trend for individuals from the western genetic clade (Iberia, France, England and central Europe) to have longer tarsus with smaller wings, while individuals from the eastern generic clade (Balkans) have an opposite pattern. Italian birds are intermediate. The tail of Balkan birds has a wider dark pigmentation, with reduced light spots. Little owl feathers do not show reflectance in the UV part of the spectrum. We found a very large variation of morphological and color patterns between individuals collected in the same geographical area. Currently, the arrangement of individuals to any Little owls' subspecies on morphological data appears to be a very difficult task

Alla ricerca dei materiali pittorici: le analisi non invasive

The Rosselli Missal has been the object of an interdisciplinary study with non-invasive techniques (FORS, fluorimetry, XRF spectrometry, optical microscopy, eZooMS, IR photography) aiming at the identification of the colourants used for its decoration. The full set of colourants was identified, with a particular focus on the evidences of different hands at work and on the geographic provenance of the colourants themselves. The results highlighted the systematic use of precious pigments such as lapis lazuli, cinnabar, gold and silver, reinforcing the symbolic value of the manuscript. Less valuable but interesting dyes such as brasilwood an d folium, used either pure or in a mixture with pigments in order to obtain a wide range of hues, were also identified. The palettes used by the various artists were considered with relation to the geographic area around Avignon, finding that many of the colourants were at easy disposal of the artists. Information concerning the preparation of the parchment and its animal source was also obtained: calf and goat were used to produce the parchment of the Missal by at least two different working techniques

Role of Lanthanides in the Traceability of the Milk Production Chain

The traceability and authentication of milk were studied using trace and ultratrace elements as chemical markers. Among these variables, the group of lanthanides resulted in being particularly useful for this purpose as a result of their homogeneous distribution inside milk, which showed on the contrary to be intrinsically inhomogeneous from the elemental point of view. Using in this pilot study milk samples from a factory in Piedmont (Italy), we demonstrated that the distribution of lanthanides can be used as a fingerprint to put into relation the soil of the pasture land on which cows graze and the bottled milk produced in the factory. In fact, the distribution is maintained nearly unaltered along the production chain of milk, apart from the passage into the stomachs of the cows. Using the same variables, it was possible to discriminate between milk produced in the factory and milk samples taken from the large-scale retail trade