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The design of multifunctional nanostructured materials is the key to the development of smart wearable devices. For instance, nanostructures endowed with both piezoelectric and photocatalytic activities could well be the workhorse for solar-light-driven self-cleaning wearable sensors. In this work, a simple strategy for the assembly of a flexible, semitransparent piezophotocatalytic system is demonstrated by leveraging rational wet chemistry synthesis of ZnO-based nanosheets/nanoflowers (NSs/NFs) under basic pH conditions onto flexible ITO/PET supports. A KMnO4 pretreatment before the ZnO synthesis (seeded ZnO) allows for the control of the density, size, and orientation of the NSs/NFs systems compared to the systems produced in the absence of seeding (seedless ZnO). The electrical response of the sensors is extracted at a 1 V bias as a function of bending in the interval between 0 and 90°, being the responsivity toward bending significantly enhanced by the KMnO4 treatment effect. The photocatalytic activity of the sensors is analyzed in aqueous solution (methylene blue, 25 μM) by a solar simulator, resulting in similar values between seedless and seeded ZnO. Upon bending the sensor, the photocatalytic activity of seedless ZnO is almost unaffected, whereas that of seeded ZnO is improved by about 25%. The sensor’s reusability and repeatability are tested in up to three different cycles. These results open up the way toward the seamless integration of bending sensitivity and photocatalysis into a single device.

Stable hydrogen, carbon, nitrogen, oxygen and sulfur (HCNOS) isotope compositions expressed as isotope-delta values are typically reported relative to international standards such as Vienna Standard Mean Ocean Water (VSMOW), Vienna Peedee belemnite (VPDB) or Vienna Cañon Diablo Troilite (VCDT). These international standards are chosen by convention and the calibration methods used to realise them in practice undergo occasional changes. To ensure longevity and reusability of published data, a comprehensive description of (1) analytical procedure, (2) traceability, (3) data processing, and (4) uncertainty evaluation is required. Following earlier International Union of Pure and Applied Chemistry documents on terminology and notations, this paper proposes minimum requirements for publishing HCNOS stable-isotope delta results. Each of the requirements are presented with illustrative examples.

The synthesis of crystals with a high surface-to-volume ratio is essential for innovative, high-performance electronic devices and sensors. The easiest way to achieve this in integrated devices with electronic circuits is through the synthesis of high-aspect-ratio nanowires aligned vertically to the substrate surface. Such surface structuring is widely employed for the fabrication of photoanodes for solar cells, either combined with semiconducting quantum dots or metal halide perovskites. In this review, we focus on wet chemistry recipes for the growth of vertically aligned nanowires and technologies for their surface functionalization with quantum dots, highlighting the procedures that yield the best results in photoconversion efficiencies on rigid and flexible substrates. We also discuss the effectiveness of their implementation. Among the three main materials used for the fabrication of nanowire-quantum dot solar cells, ZnO is the most promising, particularly due to its piezo-phototronic effects. Techniques for functionalizing the surfaces of nanowires with quantum dots still need to be refined to be effective in covering the surface and practical to implement. The best results have been obtained from slow multi-step local drop casting. It is promising that good efficiencies have been achieved with both environmentally toxic lead-containing quantum dots and environmentally friendly zinc selenide.

Glass has been used in widespread applications within several sectors since ancient times and it has been systematically studied under different perspectives. However, its thermodynamic properties and the variety of its compositions, several aspects related to its durability and its alteration mechanisms remain still open to debate. This literature review presents an overview of the most relevant studies on glass corrosion and the interaction between glass and the environment. The review aims to achieve two objectives. On one hand, it aims to highlight how far research on glass corrosion has come by studying model systems created in the laboratory to simulate different alteration conditions and glass compositions. On the other, it seeks to point out what are the critical aspects that still need to be investigated and how the study of ancient, altered glass can add to the results obtained in laboratory models. The review intends also to demonstrate how advanced analytical techniques commonly used to study modern and technical glass can be applied to investigate corrosion marks on ancient samples.

Forty-two samples of feed, saliva, urines, and faeces collected from a cattle farm were investigated with the aim to evaluate the occurrence of glyphosate in faeces, urine and saliva. Glyphosate in the feed was also quantified to understand how it was assimilated by mammals. All cows excreted glyphosate in their faeces at concentrations between 57 and 983 ng g

At the beginning of the COVID-19 outbreak (end 2019 - 2020), therapeutic treatments based on approved drugs have been the fastest approaches to combat the new coronavirus pandemic. Nowadays several vaccines are available. However, the worldwide vaccination program is going to take a long time and its success will depend on the vaccine public's acceptance. Therefore, outside of vaccination, the repurposing of existing antiviral, anti-inflammatory and other types of drugs, have been considered an alternative medical strategy for the COVI-19 infection. Due to the broad clinical potential of the drugs, but also to their possible side effects, analytical methods are needed to monitor the drug concentrations in biological fluids and pharmaceutical products. This review deals with analytical methods developed in the period 2015 - July 2021 to detect potential drugs that, according to a literature survey, have been taken into consideration for the treatment of COVID-19. The drugs considered here have been selected on the basis of the number of articles published in the period January 2020-July 2021, using the combination of the keywords: COVID-19 and drugs or SARS-CoV-2 and drugs. A section is also devoted to monoclonal antibodies. Over the period considered, the analytical methods have been employed in a variety of real samples, such as body fluids (plasma, blood and urine), pharmaceutical products, environmental matrices and food.

Planar chiral ferrocenes are well-known compounds that have attracted interest for application in synthesis, catalysis, material science, and medicinal chemistry for several decades. In spite of the fact that asymmetric synthesis procedures for obtaining enantiomerically enriched ferrocenes are available, sometimes, the accessible enantiomeric excess of the chiral products is unsatisfactory. In such cases and for resolution of racemic planar chiral ferrocenes, enantioselective high-performance liquid chromatography (HPLC) on polysaccharide-based chiral stationary phases (CSPs) has been used in quite a few literature articles. However, although moderate/high enantioselectivities have been obtained for planar chiral ferrocenes bearing polar substituents, the enantioseparation of derivatives containing halogens, or exclusively alkyl groups, remains rather challenging. In this study, the enantioseparation of ten planar chiral 1,2- and 1,3-disubstituted ferrocenes was explored by using five polysaccharide-based CSPs under multimodal elution conditions. Baseline enantioseparations were achieved for nine analytes with separation factors (alfa) ranging from 1.20 to 2.92. The presence of pai-extended systems in the analyte structure was shown to impact affinity of the most retained enantiomer toward amylose-based selectors, observing retention times higher than 80 min with methanol-containing mobile phases (MPs). Electrostatic potential (V) analysis and molecular dynamics (MD) simulations were used in order to study interaction modes at the molecular level.

Metal oxides are ideal for the fabrication of gas sensors: they are sensitive to many gases while allowing the device to be simple, tiny, and inexpensive. Nonetheless, their lack of selectivity remains a limitation. In order to achieve good selectivity in applications with many possible interfering gases, the sensors are inserted into an electronic nose that combines the signals from nonselective sensors and analyzes them with multivariate statistical algorithms in order to obtain selectivity. This review analyzes the scientific articles published in the last decade regarding electronic noses based on metal oxide nanowires. After a general introduction, Section 2 discusses the issues related to poor intrinsic selectivity. Section 3 briefly reviews the main algorithms that have hitherto been used and the results they can provide. Section 4 classifies the recent literature into fundamental research, agrifood, health, security. In Section 5, the literature is analyzed regarding the metal oxides, the surface decoration nanoparticles, the features that differentiate the sensors in a given array, the application for which the device was developed, the algorithm used, and the type of information obtained. Section 6 concludes by discussing the present state and points out the requirements for their use in real-world applications.

This research aimed to characterise pigments used to decorate a polychrome earthenware bas-relief of the 15th century entitled “Madonna with Child, Saint Catherine of Siena, and a Carthusian Prior”, attributed to Giovanni Antonio Amadeo (Pavia, 1447–Milan, 1522) and owned by the Sforzesco Castle Museum of Milan. The artwork underwent a cleaning procedure whose aims were the removal of the dark coating that obscured its surface and restoration work that could bring back its original features. Before the cleaning, six microsamples were collected and analysed using optical microscopy (OM), scanning electron microscopy coupled with energy-dispersive X-ray spectroscopy (SEM-EDXS), and Fourier-transform infrared microspectroscopy in ATR mode (ATR-FTIR), providing the restorers with decisive information on the materials underlying the coating. After the cleaning, the terracotta appeared vibrantly coloured, mainly with bright red, blue, green, black, and white tones. Then, some in situ, non-destructive, spectroscopic measurements were performed by a portable Raman spectrometer on some of the areas that could not otherwise have been sampled. The analyses revealed the presence of natural pigments, including lead white, azurite, yellow ochre, carbon black, calcite, cinnabar, and gypsum. For Madonna’s mantle, cobalt and Prussian blue were employed. Furthermore, the presence of barium sulphate was widely evidenced on the bas-relief. Albeit cobalt blue is of synthetic origin, its presence is compatible with the 15th-century palette, whereas Prussian blue and barium sulphate could be imputed to a previous restoration. Finally, the use of true gold for the background of the earthenware attests to the artwork’s importance and value.

Fish plays a key role in a healthy and balanced Italian diet, but it is also subject to the bioaccumulation of different contaminants depending on the geographical or anthropogenic context from which it is derived. In recent years, the European Food Safety Authority (EFSA) has been focusing its attention on consumer toxicological risk, considering emerging contaminants such as perfluoroalkyl substances (PFASs) and potentially toxic elements (PTEs). Regarding fish, anchovies are among the five small pelagic main commercial species in the European Union and the top five fresh species consumed by households in Italy. Considering the lack of data on PFASs and PTEs in this species, our aim was to investigate the mentioned contaminants in salted and canned anchovies collected over 10 months from different fishing areas, even those far apart, to verify possible variations in bioaccumulation and to consider the risk for the consumer. According to our results, the assessed risk was very reassuring also for large consumers. The only concern, related to Ni acute toxicity, also dependent on the different consumers’ sensitivity, was related to only one sample.

Bucchero is a well-known class of Etruscan ceramics, characterized by being entirely black both on the surface and in the body. In the present investigation, a representative set of bucchero sherds from the excavations of the Etruscan town of Tarquinia (Viterbo, Italy) was analyzed through flame atomic absorption spectroscopy (FAAS), Fourier-transform infrared spectroscopy (FTIR) and near-infrared (NIR) reflection spectroscopy. Both elemental and mineralogical composition data were treated with methods of multivariate analysis. It was thus possible to discriminate between local and imported production, to estimate the firing temperature and to verify the origin of the grey-black color in this peculiar ceramic class. Furthermore, a virtual reconstruction of a bucchero vase starting from fragments was also attempted on the basis of chemical analysis data.

The cleaning of textile artefacts and in particular historical tapestries is generally carried out using standard methods. Different cleaning procedures, including a new method based on a hydro-aspiration mechanism, recently developed by restorers with the aim of improving the efficiency of the cleaning system, were applied to a historical tapestry belonging to the lower edge of one of the tapestries of the “Ulysses Stories” series exhibited at the Quirinale Palace (Rome). The tapestry was made of wool and silk and has precious decorations made of metal yarns, which are particularly fragile. The new cleaning system was compared with the traditional methods commonly used by restorers for tapestry cleaning. For this purpose, the quantity and chemical composition of the particles removed and collected on quartz fibre filters by applying the different cleaning systems, were estimated by means of analytical techniques, such as IC (Ion Chromatography) for the quantification of the ionic species collected into the rinsing water, the TOT (Thermal Optical Transmittance) method for the quantification of the carbonaceous particles and SEM-EDX (Scanning Electron Microscopy coupled to Energy Dispersive X-ray Spectroscopy) for yarn morphological characterization and elemental analysis of the deposited particles. The objective of this study is to identify the correct cleaning method to apply to the polymaterial tapestry and, in particular, to the gilded silver and gold metallic yarns, whose conservation state requires the preservation of the “self-protection” patina necessary for the future exhibition inside the Quirinale Palace. The new hydro-aspiration method was found to be more efficient in removing dirt and preserving the structure of the metallic threads being in this way less invasive in detaching the fragile surface patina and at the same time more effective in removing dirt.

Microfluidic valves based on chemically responsive materials have gained considerable attention in recent years. Herein, a wireless enantio-responsive valve triggered by bipolar electrochemistry combined with chiral recognition is reported. A conducting polymer actuator functionalized with the enantiomers of an inherently chiral oligomer was used as bipolar valve to cover a tube loaded with a dye and immersed in a solution containing chiral analytes. When an electric field is applied, the designed actuator shows a reversible cantilever-type deflection, allowing the release of the dye from the reservoir. The tube can be opened and closed by simply switching the polarity of the system. Qualitative results show the successful release of the colorant, driven by chirality and redox reactions occurring at the bipolar valve. The device works well even in the presence of chemically different chiral analytes in the same solution. These systems open up new possibilities in the field of microfluidics, including also controlled drug delivery applications.

Dermis fibroblasts are very sensitive to penetrating UVA radiation and induce photo-damage. To protect skin cells against this environmental damage, there is an urgent need for effective compounds, specifically targeting UVA-induced mitochondrial injury. This study aimed to analyze the effect of carnosine on the proteome of UVA-irradiated human skin fibroblast, cultured in a three-dimensional (3D) biological system recapitulating dermal compartment as a test system to investigate the altered cellular pathways after 48 h and 7 days of culture with or without carnosine treatment. The obtained results indicate that UVA dysregulates Oxidative Phosphorylation, the Fibrosis Signaling Pathway, Glycolysis I and Nrf2-mediated Oxidative Stress Response. Carnosine exercises provide a protective function against the harmful effects of UVA radiation by activating the Nrf2 pathway with the upregulations of some ROS-detoxifying enzymes such as the glutathione S-transferase (GST) protein family. Additionally, carnosine regulates the activation of the Epithelial Adherens Junction and Wound Healing Signaling Pathway by mediating the activation of structural proteins such as vinculin and zyxin as well as fibronectin 1 and collagen type XVIII alpha 1 chain against UVA-induced changes.

This work is concerned with a multi-analytical identification of the colour palette utilised in the decoration of the cover of an Egyptian sarcophagus dated to the Late Dynastic Period and belonging to a private collection. In this study, six different points were analysed with a portable Raman spectrometer; then, in these same points, six micro-fragments were taken from the sarcophagus for laboratory analysis performed by scanning electron microscopy coupled with energy dispersive X-ray spectroscopy (SEM-EDXS), attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR) and visible induced luminescence imaging (VIL). Raman spectra collected in situ showed the characteristic bands of calcite, red ochre and black carbon. SEM-EDXS analyses highlighted the presence of a copper-based pigment in the light blue, blue and black fragments; then, the ATR-FTIR spectrum of the light blue sample only displayed the peculiar bands of Egyptian blue. The latter result was confirmed by VIL analysis, which successfully identified the same pigment in blue-black fragments as well, leading to the possible authentication of the finding. Moreover, the presence of calcite, red ochre, green earth and some organic material was assessed by FTIR spectroscopy, confirming some of the results of in situ Raman analyses. Regarding organic materials, whose investigation is still ongoing, some hypotheses were made on the basis of their FTIR spectra.

Pesticides play a key-role in the development of the agrifood sector allowing controlling pest growth and, thus, improving the production rates. Pesticides chemical stability is responsible of their persistency in environmental matrices leading to bioaccumulation in animal tissues and hazardous several effects on living organisms. The studies regarding long-term effects of pesticides exposure and their toxicity are still limited to few studies focusing on over-exposed populations, but no extensive dataset is currently available. Pesticides biomonitoring relies mainly on chromatographic techniques coupled with mass spectrometry, whose large-scale application is often limited by feasibility constraints (costs, time, etc.). On the contrary, chemical sensors allow rapid, in-situ screening. Several sensors were designed for the detection of pesticides in environmental matrices, but their application in biological fluids needs to be further explored. Aiming at contributing to the implementation of pesticides biomonitoring methods, we mapped the main gaps between screening and chromatographic methods. Our overview focuses on the recent advances (2016-2021) in analytical methods for the determination of commercial pesticides in human biological fluids and provides guidelines for their application.

In the present work, a method is proposed that combines spectrofluorimetry with multivariate analysis (cluster and principal components) to non-invasively investigate natural dyes used, mainly in the form of lakes, in illuminations. First, a consistent number of mock-up samples of red and purple lakes (from brazilwood, madder, kermes, cochineal, lac dye, folium and orcein) were prepared following the recipes reported in ancient treatises, then the experimental conditions for their non-invasive investigation were optimized by benchtop instrumentation and transferred to a portable microprobe suitable for in situ analyses. For all the coloring materials examined, it was thus possible to obtain a satisfactory grouping of samples containing the same dye. The analytical protocol was finally extended to the characterization of dyes in the Crescenzago choir books, illuminated manuscripts dating back to the end of the 15th century.

One of the organ-specific functions of the liver is the excretion of bilirubin into the bile. Membrane transport of bilirubin from the blood to the liver is not only an orphan function, because there is no link to the protein/gene units that perform this function, but also a poorly characterised function. The aim of this study was to investigate the pharmacology of bilirubin uptake in the liver of the female Wistar rat to improve basic knowledge in this neglected area of liver physiology. We treated isolated perfused livers of female rats with repeated single-pass, albumin-free bilirubin boli. We monitored both bilirubin and bilirubin glucuronide in perfusion effluent with a bio-fluorometric assay. We tested the ability of nine molecules known as substrates or inhibitors of sinusoidal membrane transporters to inhibit hepatic uptake of bilirubin. We found that cyanidin 3-glucoside and malvidin 3-glucoside were the only molecules that inhibited bilirubin uptake. These dietary anthocyanins resemble bro-mosulfophthalein (BSP), a substrate of several sinusoidal membrane transporters. The SLCO-specific substrates estradiol-17 beta-glucuronide, pravastatin, and taurocholate inhibited only bilirubin glucuronide uptake. Cya-nidin 3-glucoside and taurocholate acted at physiological concentrations. The SLC22-specific substrates indo-methacin and ketoprofen were inactive. We demonstrated the existence of a bilirubin-glucuronide transporter inhibited by bilirubin, a fact reported only once in the literature. The data suggest that bilirubin and bilirubin glucuronide are transported to the liver via pharmacologically distinct membrane transport pathways. Some dietary anthocyanins may physiologically modulate the uptake of bilirubin into the liver.

Here, we present the results related to a new unique terrestrial ecosystem found in an englacial hypersaline brine found in Northern Victoria Land (Antarctica). Both the geochemistry and microbial (prokaryotic and fungal) diversity revealed an unicity with respect to all the other known Antarctic brines and suggested a probable ancient origin mainly due a progressive cryoconcentration of seawater. The prokaryotic community presented some peculiarities, such as the occurrence of sequences of Patescibacteria (which can thrive in nutrient-limited water environments) or few Spirochaeta, and the presence of archaeal sequences of Methanomicrobia closely related to Methanoculleus, a methanogen commonly detected in marine and estuarine environments. The high percentage (35%) of unassigned fungal taxa suggested the presence of a high degree of undiscovered diversity within a structured fungal community (including both yeast and filamentous life forms) and reinforce the hypothesis of a high degree of biological uniqueness of the habitat under study.

Magnesium has been listed among the 30 critical raw materials by the European Union. In recent years, many green and sustainable alternative Mg2+ sources have been sought to satisfy the EU’s demand and to avoid mineral ore consumption. In this context, saltwork bitterns, the by-products of solar sea salt production, have attracted much attention thanks to their high Mg2+ concentrations (up to 80 g/L) and low Ca2+ and bicarbonate contents (95% (w/w). This work presents a comprehensive experimental effort of reactive precipitation tests with NaOH solutions at stoichiometric and over-stoichiometric concentrations to: (i) assess the technical feasibility of Mg2+ recovery from real bitterns collected in saltworks of the Trapani district (Italy) and, (ii) for the first time, conduct an extensive purity investigation of the precipitated magnesium hydroxide powders as brucite. This experimental investigation demonstrates the possibility of extracting highly valuable compounds from saltwork bittern waste, embracing the water valorization and resource recovery approach.

Numerous fungicide applications are required to control Erysiphe necator, the causative agent of powdery mildew. This increased demand for cultivars with strong and long-lasting field resistance to diseases and pests. In comparison to the susceptible cultivar ‘Teroldego’, the current study provides information on some promising disease-resistant varieties (mono-locus) carrying one E. necator-resistant locus: BC4 and ‘Kishmish vatkana’, as well as resistant genotypes carrying several E. necator resistant loci (pyramided): ‘Bianca’, F26P92, F13P71, and NY42. A clear picture of the metabolites’ alterations in response to the pathogen is shown by profiling the main and secondary metabolism: primary compounds and lipids; volatile organic compounds and phenolic compounds at 0, 12, and 48 hours after pathogen inoculation. We identified several compounds whose metabolic modulation indicated that resistant plants initiate defense upon pathogen inoculation, which, while similar to the susceptible genotype in some cases, did not imply that the plants were not resistant, but rather that their resistance was modulated at different percentages of metabolite accumulation and with different effect sizes. As a result, we discovered ten up-accumulated metabolites that distinguished resistant from susceptible varieties in response to powdery mildew inoculation, three of which have already been proposed as resistance biomarkers due to their role in activating the plant defense response.

Different Light-Absorbing Snow Impurities (LASI) can deposit on snow- and ice-covered surfaces. These particles are able to decrease snow and ice albedo and trigger positive albedo feedback. The aim of this work was to develop a new method to quantify the carbonaceous fractions that are present in snow and ice samples that contribute significantly to their darkening. Currently, in the literature, there is an absence of a unified and accepted method to perform these studies. To set up the method proposed here, snow samples were collected at two Italian locations, Claviere and Val di Pejo (Northern Italy). The samples were analyzed using two main techniques, Total Organic Carbon analysis (TOC analysis) and Thermal Optical analysis in Transmittance mode (TOT), which enabled the speciation of the carbonaceous fraction into organic (OC), inorganic (IC), and elemental carbon (EC), and further into the soluble and insoluble parts. The results highlighted a correlation between the nature of the sample (i.e., location, age, and exposure of the snow) and the experimental results, giving validity to the method. For example, the abundant presence of terrigenous constituents was reflected in high amounts of insoluble IC. Moreover, due to the trend between insoluble IC and Elemental Carbon (EC), the role of IC in TOT analysis was investigated. Indeed, IC turned out to be an interfering agent, suggesting that the two techniques (TOC analysis and TOT) are complementary and therefore need to be used in parallel when performing these studies. Finally, the results obtained indicate that the newly proposed method is suitable for studying the carbonaceous fractions in snow samples.

POST-PRINT VERSION Microplastics are emerging pollutants of great concern since they are widely distributed in the environment.While the occurrence of microplastics was studied in marine and freshwaters, sediments, soil, and differentclasses of organisms, the atmosphere was somewhat understudied, although it can be the most significanttransport pathway from mid to high latitudes. This work is one of the first studies testing the possible applicationof pyrolysis gas chromatography-mass spectrometry (Py-GC/MS) for detecting polymers in atmospheric aerosol.It explored the possibility of a direct inlet analysis of sampling filters, proposing for the first timethecalculationof an "aerosol organic baseline" for estimating the level of interferences to specific polymer tracers due to theorganic matter content of atmospheric aerosol. The direct inlet analysis was tested for environmental samplesand commercial dust, using the micro-FTIR analytical technique as a reference. Polyethylene (PE), polypropylene(PP), and polystyrene were detected in atmospheric aerosol samples; PE, PP, and Nylon 6 (polyamide 6, PA6)were detected in the commercial dust. The first results obtained on the atmospheric aerosol allow for highlightingthe technique’s potential and drawing insights from the difficulties encountered. Results suggest that thedirect analysis of the sampling filters can be employed as an exploratory technique due to its fast response, evenif further research is needed to obtain a comprehensive polymeric characterisation of atmospheric aerosol.