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Silica-based electrodes which permanently include a graphite/Au nanoparticles composite were tested for non-enzymatic detection of glucose and fructose. The composite material showed an effective electrocatalytic activity, to achieve the oxidation of the two analytes at quite low potential values and with good linearity. Reduced surface passivation was observed even in presence of organic species normally constituting real samples. Electrochemical responses were systematically recorded in cyclic voltammetry and differential pulse voltammetry by analysing 99 solutions containing glucose and fructose at different concentration values. The analysed samples consisted both in glucose and fructose aqueous solutions at pH 12 and in solutions of synthetic musts of red grapes, to test the feasibility of the approach in a real frame. Multivariate exploratory analyses of the electrochemical signals were performed using the Principal Component Analysis (PCA). This gave evidence of the effectiveness of the chemometric approach to study the electrochemical sensor responses. Thanks to PCA, it was possible to highlight the different contributions of glucose and fructose to the voltammetric signal, allowing their selective determination., This research received funding from the University of Cadiz through the 'Contratos Puente 2015' postdoctoral program and from the University of Modena and Reggio Emilia (Italy) through FAR 2014.

The common thread of the PhD project is the development of strategies, based, primarily, on dynamic electroanalytical techniques, for investigating and characterizing different types of substrates of historic/artistic interest. The use of electrochemical apparatuses and approaches was done, where possible, in the least invasive way, to characterize metal-based materials; from the other side to propose new systems and approaches to study materials, which can suffer from contact with liquid electrolytes. The research on copper natural patinas was applied, in a first part, to relatively easy systems composed by primary patina, essentially made of cuprite. Here, ancient coins were studied by the voltammetry of immobilized particles (VIMP) technique simply by pressing a graphite pencil on their surface, thus resulting in an essentially non-destructive sampling, useful characteristic for the study of cultural heritage materials. The new approach developed has revealed the existence of different corrosion patterns which are sensitive to the composition of the base metal, in particular to the presence of Zn. Voltammetric data suggests the possibility of establishing a chronological ordering of the coins and hence to add this multiple scan strategy to the existing electrochemical dating methods. A further step in the research activity was was to investigate copper-based materials in a more complex corrosion status (presence of primary cuprite together with brochantite). The goal was to study the effect of alternative, to classical and poorly environmentally safe, corrosion inhibitors. Specifically, decanoic acid (HC10) and its sodium salt (NaC10) have been considered here, as potential eco-friendly inhibitors. In a first part of the research activity, the interactions between Cu2+ and HC10 in water and 50% (v/v) E/W mixture was elucidated by a detailed analysis of the voltammetric responses. The results obtained proved useful to clarify some aspects of the mechanisms which could be involved when the corroded roof claddings are treated with the inhibitors and the stability of the coatings when the samples are immersed in synthetic acid rain. A second section of the study aimed at comparing the protective effects of HC10, NaC10 and the poorly environmentally safe benzotriazole (BTA) on bare copper and roof cladding samples. A third section of the study examines in detail the reactivity of the top layer and cross section of the roof cladding samples untreated and treated with HC10 and BTA. This study has been performed by using SECM to get information on the reactivity with high spatial resolution. The ability of the inhibitors to prevent further corrosion of the various layers of patina was assessed in aqueous media containing NO3-, SO42- and Cl-, which are characterized by different complexing ability towards copper ions. The research activity continued in the direction of investigating innovative strategies based on the use of microcapillary (MC) techniques. In particular, MCs filled with conductive hydrogels have been developed with the objective of applying it to study materials that suffer the contact with liquid solutions and metallic objects. Here, the properties of agarose hydrogel as medium to perform voltammetric measurements, using the electroactive redox probes and a Pt microdisk electrode were examined. The hydrogel containing the redox probe and various electrolytes are employed for MC contact measurements above platinum and gold substrates. To demonstrate the suitability of the above microprobe for more practical applications, proof-of-concept measurements were performed to characterize micro areas of metallic silver deposited on to the surface of a pencil graphite line deposited on a paper material. With the purpose to tailor the electrode surface or the content of MCs with more selective compounds, condconducting polymers, presenting intrinsic chiral activity, have been studied.

Since graphene was exfoliated in 2004, two-dimensional (2D) materials have received great attention due to their physical and chemical properties associated with their nanosized thickness and the correlated quantum size effect. 2D planes allow the confinement of charge carriers, heat, and photons, leading to the remarkable electronic and optical properties of these materials. The Faraday Discussion "Chemistry of 2-dimensional materials: beyond graphene" has been an incredible showcase for a variety of highly interesting contributions in the field. This conference comprised a large number of aspects of the topic: from their synthesis and the study of their optical and physical properties to their numerous applications. These concluding remarks aim to capture the recent developments in 2D materials chemistry and physics that were presented and debated during this Faraday Discussion, and more generally in the research field in recent years. Particular attention will be paid to aspects like the synthesis of the materials, their toxicity and biodegradation, and some of their major applications in catalysis, as well as Li-ion batteries, water filtration and sensing. In addition we aim to highlight future challenges that still need to be addressed.

North-Eastern Italy and in particular Veneto Region, stands out as a major centre of agriculture and viticulture which has rapidly expanded in the last decade with high productivity indexes. In this context, assessing atmospheric pollution caused by crop spraying with pesticides in rural areas and their transport to high-altitude remote sites is crucial to provide a basis for understanding possible impacts on the environment and population health. We aim to improve existing methods with a highly sensitive technique by using high pressure anion exchange chromatography coupled to a triple quadrupole mass spectrometer. Thus, a total of fourteen polar pesticides were determined in aerosol samples collected from August to December 2021 at Roncade (Venetian plain) and Col Margherita Observatory (Dolomites). The observatory was chosen as the background site as it is representative of the surrounding alpine region. Some samples revealed a substantial amount of cyanuric acid mainly at Roncade (mean concentration of 10 ± 10 ng m

Honey is a natural sweetener constituted by numerous macro- and micronutrients. Carbohydrates are the most representative, with glucose and fructose being the most abundant. Minor honey components like volatile organic compounds (VOCs), minerals, vitamins, amino acids are able to confer honey-specific properties and are useful to characterize and differentiate between honey varieties according to the botanical origin. The present work describes the chemical characterization of honeys of different botanical origin (multifloral, acacia, apple–dandelion, rhododendron, honeydew, and chestnut) produced and collected by beekeepers in the Trentino Alto-Adige region (Italy). Melissopalynological analysis was conducted to verify the botanical origin of samples and determine the frequency of different pollen families. The carbohydrate composition (fourteen sugars) and the profile of VOCs were evaluated permitting to investigate the relationship between pollen composition and the chemical profile of honey. Statistical analysis, particularly partial least squares discriminant analysis (PLS-DA), demonstrates the importance of classifying honey botanical origin on the basis of effective pollen composition, which directly influences honey’s biochemistry, in order to correctly define properties and value of honeys.

Personalized or precision medicine is an emerging approach to the treatment and prevention of disease, which takes into account the individual variability of genes, environment and lifestyles of each person. High Resolution Mass Spectrometry (HRMS) coupled with Ultra High Performance Liquid Chromatography (UHPLC) plays a fundamental role in characterizing and quantifying proteins and metabolites involved in the disease. The proteomic and metabolomic approaches allow the global identification, not guided by a priori hypothesis, of thousands of proteins and hundreds of metabolites present in a biological fluid and the evaluation of how these can vary in the presence of a specific disease compared to a non-pathological condition, allowing to characterize and discriminate between different study groups. In the first part PhD project has been studied the proteomic profile of autoinflammatory diseases to understand the molecular mechanisms underlying genetic diseases. Here, we analyzed the proteomic signature of unstimulated and stimulated monocytes of patients with FMF, TRAPS and MKD, describing the dysregulated intracellular pathways associated with each condition for the identification of possible biomarkers and possible novel therapeutic targets. The objective of the second part of the project is to build, optimize and share spectral MSMS with Accurate Mass Retention Time (AMRT) database libraries, using different metabolic standards (MSMLS, IROA Technologies), involved in key biological processes, to develop robust identification and quantitative methods because the compound identification process being often challenging and requiring a high degree of confidence.

Cystic fibrosis (CF) is a genetic disease caused by mutations in the cystic fibrosis transmembrane conductance regulator (CFTR) gene, encoding an anion channel expressed on the epithelial cells of a variety of tissues. The deletion of phenylalanine in position 508 (F508del) is the most frequent CF-causing mutation, causing impaired trafficking and activity of the mutant channel. Today, two classes of drugs are available to treat CF: potentiators (molecules that increase the mutant CFTR function on the cell surface) and correctors (molecules that improve the processing and the delivery of mutant CFTR to the cell surface). It has been demonstrated that the combination of molecules exploiting different mechanisms of action is needed to achieve a therapeutically relevant rescue of CFTR. The aim of this project is to apply mass spectrometry (MS)-based omics techniques to understand what is associated to CFTR rescue and thus finding new potential targets for CF pharmacological treatment. Several strategies were applied for the functional rescue of CFTR at the plasma membrane (both pharmacological and genetic rescue). Proteomic and lipidomic profilings of F508del-CFTR expressing cells were performed after the application of these rescue strategies. The proteomic experiments were performed following the SWATH label-free quantification workflow, after the optimization of the panhuman ion library for CF research. Together with these experiments, Localisation of Organelle Proteins by Isotope Tagging after Differential ultraCentrifugation (LOPIT-DC) workflow was also applied to detect proteins that change their subcellular localization after the treatment with the most used corrector available for CF therapy (VX-809). Several candidate targets were found to be involved in F508del-CFTR rescue. Compounds aiming at the inhibition of these putative targets were tested on both immortalized and primary cells. Further validation studies are needed to confirm these results.

In this study, the abundance and the distribution of small microplastics (

Graphical abstract Corticosteroids as budesonide can be effective in reducing topic inflammation processes in different organs. Therapeutic use of budesonide in respiratory diseases, like asthma, chronic obstructive pulmonary disease, and allergic rhinitis is well known. However, the pulmonary distribution of budesonide is not well understood, mainly due to the difficulties in tracing the molecule in lung samples without the addition of a label. In this paper, we present a matrix-assisted laser desorption/ionization mass spectrometry imaging protocol that can be used to visualize the pulmonary distribution of budesonide administered to a surfactant-depleted adult rabbit. Considering that budesonide is not easily ionized by MALDI, we developed an on-tissue derivatization method with Girard’s reagent P followed by ferulic acid deposition as MALDI matrix. Interestingly, this sample preparation protocol results as a very effective strategy to raise the sensitivity towards not only budesonide but also other corticosteroids, allowing us to track its distribution and quantify the drug inside lung samples. Supplementary Information The online version contains supplementary material available at 10.1007/s00216-021-03393-6.

This paper describes the analysis of two near-spherical metallic inclusions partially incorporated within two Roman raw glass slags in order to elucidate the process that induced their formation and to determine whether their presence was related to ancient glass colouring processes. The theory of metallic scraps or powder being used in Roman times for glass-making and colouring purposes is widely accepted by the archaeological scientific community, although the assumption has been mainly based on oral traditions and documented medieval practices of glass processing. The analysis of the two inclusions, carried out by X-ray computed tomography, electrochemical analyses, and scanning electron microscopy, revealed their material composition, corrosion and internal structure. Results indicate that the two metallic bodies originated when, during the melting phase of glass, metal scraps were added to colour the material: the colloidal metal–glass system reached then a supersaturation condition and the latter ultimately induced metal expulsion and agglomeration. According to the authors’ knowledge, these two inclusions represent the first documented and studied finds directly associated with the ancient practise of adding metallic agents to colour glass, and their analysis provides clear insights into the use of metallic waste in the glass colouring process.

In ecology, Volatile Organic Compounds (VOCs) have a high bioactive and signaling potential. VOCs are not only metabolic products, but are also relevant in microbial cross talk and plant interaction. Here, we report the first large-scale VOC study of 13 different species of Mortierella sensu lato (s.l.) isolated from a range of different alpine environments. Proton Transfer Reaction&ndash, Time-of-Flight Mass Spectrometry (PTR&ndash, ToF&ndash, MS) was applied for a rapid, high-throughput and non-invasive VOC fingerprinting of 72 Mortierella s.l. isolates growing under standardized conditions. Overall, we detected 139 mass peaks in the headspaces of all 13 Mortierella s.l. species studied here. Thus, Mortierellas.l. species generally produce a high number of different VOCs. Mortierella species could clearly be discriminated based on their volatilomes, even if only high-concentration mass peaks were considered. The volatilomes were partially phylogenetically conserved. There were no VOCs produced by only one species, but the relative concentrations of VOCs differed between species. From a univariate perspective, we detected mass peaks with distinctively high concentrations in single species. Here, we provide initial evidence that VOCs may provide a competitive advantage and modulate Mortierella s.l. species distribution on a global scale.

POST-PRINT VERSION The sources impacting size-segregated aerosol were studied in Venice (Italy), in the framework of the ECOMOBILITY project (ECOlogical supporting for traffic Management in cOastal areas By using an InteLlIgenT sYstem, Interreg Italy-Croatia). The importance of this work lies in the fact that aerosol can have a different impact on human health, based on the particle size: nanoparticles could be potentially more dangerous with respect to coarse and fine particles; at the same time, they are poorly studied. The aim of this work is to perform an overview of the chemical composition of size-segregated aerosol, for carrying out a size-dependent source apportionment of aerosol in the urban area of Venice. Aerosol was collected with a MOUDI 110 cascade impactor. After the gravimetric analysis, filters were divided in three parts and each piece underwent a different analytical procedure, for the analysis of trace metals, carbonaceous and ionic species. Source apportionment was conducted using two different approaches: i) approximate formulae; ii) Positive Matrix Factorization. Sea spray aerosol was found mainly in the coarse fraction. The fine fraction was dominated by secondary inorganic aerosol and organic aerosol. Primary anthropogenic aerosol increased as particle dimension decreased. For the first time, the contribution of shipping emission was investigated using chemical tracers on different size ranges below 1 µm and reaching nanoparticles (

The diagnosis of severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) infection requires the detection of viral RNA by reverse transcription–polymerase chain reaction (RT-qPCR) performed mainly using nasopharyngeal swabs. However, this procedure requires separate analysis per each individual, performed in advanced centralized laboratory facilities with specialized medical personnel. In this study, an alternative approach termed “solid waste-based surveillance (SWBS)” was explored, in order to investigate SARS-CoV-2 infection in small communities through the indirect sampling of saliva left on waste. Sampling was performed at 20 different sites in Italy during the second peak of COVID-19. Three swabs were positive for SARS-CoV-2 using a published RT-qPCR protocol targeting the non-structural protein 14 region, and the viral load ranged 4.8 × 103–4.0 × 106 genome copies/swab. Amino acid substitutions already reported in SARS-CoV-2 sequences circulating in Italy (A222V and P521S) were detected in two positive samples. These findings confirmed the effectiveness of SWBS for non-invasive and dynamic SARS-CoV-2 surveillance., Graphical abstract Unlabelled Image

Although hazelnuts are mostly consumed after toasting and mixed with other ingredients, for manufactures it is important to have efficient quality control tests on the raw product that they purchase from farmers and suppliers. This study explores the possibility to predict sensory quality of raw hazelnuts, classified according to industrial sensory evaluation, using volatilome analysis through Proton Transfer Reaction Mass Spectrometry (PTR-MS) rapid fingerprinting. Firstly, the link between volatile markers for different visual and sensory defects was investigated. Uncompliant hazelnuts showed higher concentrations for a larger number of volatile organic compounds (VOCs) than compliant samples, including some key hazelnuts odorants like 5-methyl-4-heptanone, 5-propyldihydro-2(3H)-furanone, octanal, 2,4-nonadienal and hexanal. Secondly, by mixing defective and good quality hazelnuts, the method sensitivity in recognizing defects percentage was determined. For about 13% of the detected mass peaks, the method was able to discriminate samples containing 20% of hazelnuts with unacceptable quality from good quality samples. Finally, unsupervised data clustering of VOCs fingerprints obtained with different precursor ions (H3O+, NO+ and O2+) provided a correct classification rate higher than 90% for all ions. The applied methodology is suitable to support sensory quality control programs of raw hazelnuts in confectionary industries.

A glassy carbon electrode chemically modified with a carbon black coating is proposed here for the rapid and portable determination of cannabidiol (CBD) in a commercial Cannabis seed oil and in fibre-type Cannabis sativa L. leaves. The mechanism of CBD oxidation was studied in relation to simpler phenyl derivatives bearing the same electroactive group, namely resorcinol and 2-methylresorcinol. These molecules also allowed us to determine the best conditions for the electrochemical detection of CBD, as to the pH value and to the best solvent mixture to use. Carbon black was chosen among nanostructured carbon-based materials owing to its outstanding features as an electrode modifier for analyte detection. The performance of the modified electrode was determined by flow injection analyses of standard solutions of CBD, obtaining a linear correlation between the oxidation current and the analyte concentration; the sensor response is characterised by suitable repeatability and reproducibility. The analysis of commercial products by the standard addition method allowed us to ascertain the accuracy of the sensor for the detection of CBD in real samples.

The interactions of dopamine [2-(3,4-Dihydroxyphenyl)ethylamine, (Dop-)] with methylmercury(II) (CH3Hg+), magnesium(II), calcium(II), and tin(II) were studied in NaCl(aq) at different ionic strengths and temperatures. Different speciation models were obtained, mainly characterized by mononuclear species. Only for Sn2+ we observed the formation of binuclear complexes (M2L2 and M2LOH (charge omitted for simplicity), M = Sn2+, L = Dop−). For CH3Hg+, the speciation model reported the ternary MLCl (M = CH3Hg+) complex. The dependence on the ionic strength of complex formation constants was modeled by using both an extended Debye–Hückel equation that included the Van’t Hoff term for the calculation of enthalpy change values of the formation and the Specific Ion Interaction Theory (SIT). The results highlighted that, in general, the entropy is the driving force of the process. The sequestering ability of dopamine towards the investigated cations was evaluated using the calculation of pL0.5 parameter. The sequestering ability trend resulted to be: Sn2+ &gt, CH3Hg+ &gt, Ca2+ &gt, Mg2+. For example, at I = 0.15 mol dm−3, T = 298.15 K and pH = 7.4, pL0.5 = 3.46, 2.63, 1.15, and 2.27 for Sn2+, CH3Hg+, Ca2+ and Mg2+ (pH = 9.5 for Mg2+), respectively. For the Ca2+/Dop- system, the precipitates collected at the end of the potentiometric titrations were analyzed by thermogravimetry (TGA). The thermogravimetric calculations highlighted the formation of solid with stoichiometry dependent on the different metal:ligand ratios and concentrations of the starting solutions.

Water is essential for humans, animals, and plants; pollutants, usually derived from anthropogenic activities, can have a serious effect on its quality. Heavy metals are significant pollutants and are often highly toxic to living organisms, even at very low concentrations. Among the numerous removal techniques proposed, adsorption onto suitable adsorbent materials is considered to be one of the most promising. The objective of the current study was to determine the effectiveness of halloysite nanotubes (HNT) functionalized with organic amino or thiol groups as adsorbent materials to decontaminate polluted waters, using the removal of Hg2+ ions, one of the most dangerous heavy metals, as the test case. The effects of pH, ionic strength (I), and temperature of the metal ion solution on the adsorption ability and affinity of both materials were evaluated. To this end, adsorption experiments were carried out with no ionic medium and in NaNO3 and NaCl at I = 0.1 mol L−1, in the pH range 3–5 and in the temperature range 283.15–313.15 K. Kinetic and thermodynamic aspects of adsorption were considered by measuring the metal ion concentrations in aqueous solution. Various equations were used to fit experimental data, and the results obtained were explained on the basis of both the adsorbent’s characterization and the Hg2+ speciation under the given experimental conditions. Thiol and amino groups enhanced the adsorption capability of halloysite for Hg2+ ions in the pH range 3–5. The pH, the ionic medium, and the ionic strength of aqueous solution all play an important role in the adsorption process. A physical adsorption mechanism enhanced by ion exchange is proposed for both functionalized materials.

Background In preterm infants, InSurE (Intubation-Surfactant-Extubation) and LISA (less invasive surfactant administration) techniques allow for exogenous surfactant administration while reducing lung injury associated with mechanical ventilation. We compared the acute pulmonary response and lung deposition of surfactant by LISA and InSurE in surfactant-depleted adult rabbits. Methods Twenty-six spontaneously breathing surfactant-depleted adult rabbits (6-7 weeks old) with moderate RDS and managed with nasal continuous positive airway pressure were randomized to 3 groups: (1) 200 mg/kg of surfactant by InSurE; (2) 200 mg/kg of surfactant by LISA; (3) no surfactant treatment (Control). Gas exchange and lung mechanics were monitored for 180 min. After that, surfactant lung deposition and distribution were evaluated monitoring disaturated-phosphatidylcholine (DSPC) and surfactant protein C (SP-C), respectively. Results No signs of recovery were found in the untreated animals. After InSurE, oxygenation improved more rapidly compared to LISA. However, at 180' LISA and InSurE showed comparable outcomes in terms of gas exchange, ventilation parameters, and lung mechanics. Neither DSPC in the alveolar pool nor SP-C signal distributions in a frontal lung section were significantly different between InSurE and LISA groups. Conclusions In an acute setting, LISA demonstrated efficacy and surfactant lung delivery similar to that of InSurE in surfactant-depleted adult rabbits. Impact Although LISA technique is gaining popularity, there are still several questions to address. This is the first study comparing LISA and InSurE in terms of gas exchange, ventilation parameters, and lung mechanics as well as surfactant deposition and distribution. In our animal study, three hours post-treatment, LISA method seems to be as effective as InSurE and showed similar surfactant lung delivery. Our findings provide some clarifications on a fair comparison between LISA and InSurE techniques, particularly in terms of surfactant delivery. They should reassure some of the concerns raised by the clinical community on LISA adoption in neonatal units.

International audience; We present a thorough evaluation of the water soluble fraction of the trace element composition (Ca, Sr, Mg, Na, K, Li, B, Rb, U, Ni, Co, As, Cs, Cd, Mo, Se, Eu, Ba, V, Ge, Ga, Cr, Cr, P, Ti, Mn, Zr, Ce, Zn, Fe, Gd, Y, Pb, Bi, Yb, Al, Nb, Er, Nd, Dy, Sm, Ho, Th, La, Lu, Tm, Pr, Tb, Fe, In, Tl) and their fluxes in the annual snowpack and the firn of the Hansbreen (a tidewater glacier terminating in the Hornsund fjord, southwest Spitsbergen). The trace element samples were obtained from a 3 m deep snow pit dug at the plateau of the glacier (450 m a.s.l.), and from a 2 m deep firn core collected from the bottom of the snow pit. The comparison of elemental fluxes and enrichment factors allowed us to constrain specific summer and wintertime deposition patterns of water soluble trace elements in the southern part of the Svalbard archipelago. Our results suggest that the chemical composition of the Hansbreen (and likely other glaciers where the summit is close to the equilibrium line) is mainly affected by summertime deposition of trace elements from local sources and some volatile elements, which may be transported into the Arctic when polar vortex is weak. The melting of the annual snowpack seems to have a minor influence on the overall chemical signature of the glacier ice.

Nearly all ice core archives from the Arctic and middle latitudes (such as the Alps), apart from some very high elevation sites in Greenland and the North Pacific, are strongly influenced by melting processes. The increases in the average Arctic temperature has enhanced surface snow melting even of higher elevation ice caps, especially on the Svalbard Archipelago. The increase of the frequency and altitude of winter “rain on snow” events as well as the increase of the length of the melting season have had a direct impact on the chemical composition of the seasonal and permanent snow layers due to different migration processes of water-soluble species, such as inorganic ions. This re-allocation along the snowpack of ionic species could significantly modify the original chemical signal present in the annual snow. This paper aims to give a picture of the evolution of the seasonal snow strata with a daily time resolution to better understand: a) the processes that can influence deposition b) the distribution of ions in annual snow c) the impact of the presence of liquid water on chemical re-distribution within the annual snow pack. Specifically, the chemical composition of the first 100 cm of seasonal snow on the Austre Broggerbreen Glacier (Spitsbergen, Svalbard Islands, Norway) was monitored daily from the 27th of March to the 31st of May 2015. The experimental period covered almost the entire Arctic spring until the melting season. This unique dataset gives us a daily picture of the snow pack composition, and helps us to understand the behaviour of cations (K+, Ca2+, Na+, Mg2+) and anions (Br−, I−, SO42−, NO3−, Cl−, MSA) in the Svalbard snow pack. We demonstrate that biologically related depositions occur only at the end of the snow season and that rain and melting events have different impacts on the snowpack chemistry.

The impact of climate change in the European Alps has been roughly twice the global average, dramatically reducing permafrost extent and thickening of its active layer. Therefore, the study of the abiotic factors (i.e. chemical/physical parameters) affecting the microbial diversity inhabiting Alpine permafrost appears to be of dramatic relevance. Within the European Alps, the Stelvio area exhibits these effects in a particularly evident way, with important consequences on microbial ecosystems. Therefore, microbial communities inhabiting a permafrost core collected in the Scorluzzo active rock glacier (Stelvio Pass, Italian Central Alps) were investigated along a depth gradient (410 to 524 cm from the surface). The taxonomic structures of bacterial and fungal communities were investigated via a next-generation sequencing (NGS) approach (Illumina MiSeq), targeting the bacterial V3-V4 regions of 16S rDNA and the fungal ITS2 region. Abiotic soil factors (grain size, electrical conductivity, ice/water content, pH, Loss-on-Ignition - LOI, total and organic carbon, nitrogen and phosphorous) were analysed. Richness and Shannon-H diversity indices were correlated to abiotic factors. Bacterial diversity was significantly (p

Tryptophan and its bioactive metabolites are associated with health conditions such as systemic inflammation, cardiometabolic diseases, and neurodegenerative disorders. There are dynamic interactions among metabolites of tryptophan. The interactions between metabolites, particularly those that are strong and temporally reproducible could be of pathophysiological relevance. Using a targeted metabolomics approach, the concentration levels of tryptophan and 18 of its metabolites across multiple pathways was quantified in 24-hours urine samples at 2 time-points, age 17 years (baseline) and 18 years (follow-up) from 132 (52% female) apparently healthy adolescent participants of the DOrtmund Nutritional and Anthropometric Longitudinally Designed (DONALD) Study. In sex-specific analyses, we applied 2 network approaches, the Gaussian graphical model and Bayesian network to (1) explore the network structure for both time-points, (2) retrieve strongly related metabolites, and (3) determine whether the strongly related metabolites were temporally reproducible. Independent of selected covariates, the 2 network approaches revealed 5 associations that were strong and temporally reproducible. These were novel relationships, between kynurenic acid and indole-3-acetic acid in females and between kynurenic acid and xanthurenic acid in males, as well as known relationships between kynurenine and 3-hydroxykynurenine, and between 3-hydroxykynurenine and 3-hydroxyanthranilic acid in females and between tryptophan and kynurenine in males. Overall, this epidemiological study using network-based approaches shed new light into tryptophan metabolism, particularly the interaction of host and microbial metabolites. The 5 observed relationships suggested the existence of a temporally stable pattern of tryptophan and 6 metabolites in healthy adolescent, which could be further investigated in search of fingerprints of specific physiological states. The metabolites in these relationships may represent a multi-biomarker panel that could be informative for health outcomes.

In this paper the first example of using C-dots (CDs) as sensing nanomaterial for monitoring low concentrations of NO2 in ambient air is reported. In the logic to support a green circular economy, CDs were prepared from a natural low cost precursor consisting in olive solid waste (OSW) by a simple pyrolysis process combined with chemical oxidation. Characterization data showed the formation of spherical CDs with dimensions in the narrow size range from 0.5 to 5 nm and charged with functional groups (COO- (carboxylate), C-O-C (epoxide) and C-OH (hydroxyl) imprinting excellent water colloidal dispersion. The nanomaterial was used to fabricate and test a conductometric gas sensor (CDs-sensor) that was found to exhibit excellent performances in terms of high and selective response to sub-ppm concentration of NO2 at low temperature (150 °C), low limit of detection (LOD) of 50 ppb, good reproducibility and stability over use and aging. To the best of our knowledge, this is the first example reported in the literature of CDs high performances gas sensing material. Results here presented pave the way for a new class of a carbon nanomaterial for gas sensing to be applied in the field of environmental monitoring.

The extraction of grape processing waste (wine pomace) via microwave-hydrodiffusion and gravity (MHG) from three different cultivars grown in Sicily (Syrah, Perricone and Nero d’Avola) rapidly affords aqueous extracts highly concentrated in valued biophenols including flavonoids, anthocyanins and phenolic acids. The method does not employ organic solvent, acid or base and does not require grinding or freeze drying of the wine pomace nor separation of the grape skins from seeds and stem. All the extracts have a pronounced stability as shown by their red-violet color fully retained after storage for more than a year (15 months) in freezer under air. Concentrations of phenolics up to 2000 ppm were detected in the aged extracts of Sicily’s local cultivar Perricone, which also has the highest content of flavonoids. These findings provide a simple and economically viable extraction route to biophenol-rich red extracts that can be used as food colorants as well as to formulate nutraceutical, cosmetic and personal care products starting from an agricultural by-product available in >10 million tonne yearly amount.

A major challenge for breath research is the lack of standardization in sampling and analysis. To address this, a test that utilizes a standardized intervention and a defined study protocol has been proposed to explore disparities in breath research across different analytical platforms and to provide benchmark values for comparison. Specifically, the Peppermint Experiment involves the targeted analysis in exhaled breath of volatile constituents of peppermint oil after ingestion of the encapsulated oil. Data from the Peppermint Experiment performed by proton transfer reaction mass spectrometry (PTR-MS) and selected ion flow tube mass spectrometry (SIFT-MS) are presented and discussed herein, including the product ions associated with the key peppermint volatiles, namely limonene, alpha- and beta-pinene, 1,8-cineole, menthol, menthone and menthofuran. The breath washout profiles of these compounds from 65 individuals were collected, comprising datasets from five PTR-MS and two SIFT-MS instruments. The washout profiles of these volatiles were evaluated by comparing the log-fold change over time of the product ion intensities associated with each volatile. Benchmark values were calculated from the lower 95% confidence interval of the linear time-to-washout regression analysis for all datasets combined. Benchmark washout values from PTR-MS analysis were 353 min for the sum of monoterpenes and 1,8-cineole (identical product ions), 173 min for menthol, 330 min for menthofuran, and 218 min for menthone; from SIFT-MS analysis values were 228 min for the sum of monoterpenes, 281 min for the sum of monoterpenes and 1,8-cineole, and 370 min for menthone plus 1,8-cineole. Large inter- and intra-dataset variations were observed, whereby the latter suggests that biological variability plays a key role in how the compounds are absorbed, metabolized and excreted from the body via breath. This variability seems large compared to the influence of sampling and analytical procedures, but further investigations are recommended to clarify the effects of these factors. Marie Skodowska-Curie Actions Innovative Training Network: Ion-Molecule Processes for Analytical Chemistry Technologies (IMPACT) through the European Commission's HORIZON 2020 Programme [674911]; UK's National Physical Laboratory

In the field of air analysis, highlights within the period covered by this review included a wearable air sampler with an inbuilt GPS sensor which enabled autonomous sampling to be performed at specific sites once the device had been preprogrammed with the requisite location coordinates. A prototype high resolution laser absorption spectroscopic instrument was developed as a potential SI-traceable alternative to ID-CV-ICP-MS for determining mercury concentrations in air and its isotopic composition. Improvements in the capabilities of single-particle aerosol mass spectrometers were noted. New measurements using tools such as LDI-MS and PTR-MS are providing new insights into the composition of carbonaceous particles. A large amount of effort continues to be directed towards multi-element preconcentration methods for water analysis, using either liquid or solid phase extraction to boost the sensitivity of instrumentation. Species-specific preconcentration methods were developed for the determination of mercury or arsenic species and methodologies employed to isolate elements from matrices such as seawater before isotope-ratio determinations. The focus of elemental speciation has shifted towards elemental fractionation with the determination of nano-sized fractions. The advent of ICP-MS/MS instrumentation has made the analysis of non-metallic elements such as F or P possible with improved detection limits. An interesting development of the isotope dilution technique was the use of isotopically labelled cell gasses to investigate the possibility of carrying out isotope dilution analysis of monoisotopic elements such as As or Y. Much effort has been devoted to characterising new and existing matrix-matched reference materials for calibration and quality control in the determination of the elemental and isotopic composition of geological samples. Zircon geochronology is a very active area of research and there is now considerable interest in developing U-Pb dating methods for other accessory minerals and carbonates. The application of in situ techniques such as LA-ICP-MS, SIMS, and LIBS to obtain geochemical information at high spatial resolution is another continuing theme. The ongoing interest in the optimisation of methods for extraction of analytes from soil and plants included developments relating to nanoparticles, estimation of bioavailability and non-chromatographic speciation analysis. The relative maturity of the AAS, AES and AFS techniques means that there have been few reports of major advances in these fields. Many of the developments in ICP-MS have been driven by the increased availability of ICP-MS/MS instrumentation. The importance of sample preparation in LIBS has increasingly been recognised. Proximal analysis - in which chemometric approaches are applied to data obtained by atomic (and molecular) spectroscopy to infer physical or chemical properties of a sample e.g. the pH of a soil - are becoming more common, in particular in relation to field-portable techniques such as LIBS and pXRFS, with increased attention being paid to the opportunities arising from data fusion.

[EN] The application of a multiple-scan strategy to study the structure of the corrosion patina of copper/bronze ancient objects using the voltammetry of immobilized microparticles (VIMP) is described. Upon nanosample attachment to graphite electrodes in contact with aqueous acetate buffer, voltammetric signatures characterizing cuprite with variable degree of crystallinity are recorded by means of successive cathodic scans reflecting the composition of the corrosion patina. The reported methodology, complemented with ion beam-field emission scanning electron microscopy (FIB-FESEM) and high-resolution field emission scanning electron microscopy (HRFESM-EDX), is applied to a set of coins fabricated between 1709 and 1962 revealing different corrosion patterns., Project CTQ2017-85317-C2-1-P, supported with Ministerio de Economia, Industria y Competitividad (MINECO), Fondo Europeo de Desarrollo Regional (ERDF) and Agencia Estatal de Investigacion (AEI), is gratefully acknowledged. The authors wish to thank Mr. Manuel Planes, Dr. Jose Luis Moya and Alicia Nuez Imbernon technical supervisors of the Electron Microscopy Service of the Polytechnical University of Valencia.

Highly sensitive NO2 gas sensors with low detection limit are vital for practical application in air pollution monitoring. Here, the NO2 gas sensing performance of porous ZnO nanosheets and nanoplates were investigated, with different shape and thickness. It was found that ultra-thin ZnO nanoplates had a higher sensitivity than coral-like ZnO nanosheets. The results were attributed to the high specific surface and very small thickness of the ultrathin nanoplates. The nanoplates have indeed a thickness of 15 nm compared to that of the nanosheets which is 100 nm, and a BET surface area of 75 m2/g, while that of the nanosheets is 6 m2/g. The chemosensor based on ultra-thin ZnO nanoplates shows a response (calculated as the ratio between the resistance of the sensor in the presence of the gas and in its absence) of 76 to 0.5 ppm of NO2 at 200 °C, with a theoretical detection limit of 3 parts per trillion and a selectivity higher than 760 towards acetone, ethanol, isopropyl alcohol, triethylamine, SO2 and CO. The specific surface and the small thickness of the ultra-thin nanoplates contribute to its highly improved sensing performance, making it ideal for NO2 gas sensing.

Biosensing platforms are answering the increasing demand for analytical tools for environmental monitoring of small molecules, such as per- and polyfluoroalkyl substances (PFAS). By transferring toxicological findings in bioreceptor design we can develop innovative pathways for biosensor design. Indeed, toxicological studies provide fundamental information about PFAS-biomolecule complexes that can help evaluate the applicability of the latter as bioreceptors. The toolbox of native mass spectrometry (MS) can support this evaluation, as shown by the two case studies reported in this work. The analysis of model proteins’ (i.e. albumin, haemoglobin, cytochrome c and neuroglobin) interactions with well-known PFAS, such as perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS), demonstrated the potential of this native MS screening approach. In the first case study, untreated albumin and delipidated albumin were compared in the presence and absence of PFOA confirming that the delipidation step increases albumin affinity for PFOA without affecting protein stability. In the second case study, the applicability of our methodology to identify potential bioreceptors for PFOS/PFOA was extended to other proteins. Structurally related haemoglobin and neuroglobin revealed a 1 : 1 complex, whereas no binding was observed for cytochrome c. These studies have value as a proof-of-concept for a general application of native MS to identify bioreceptors for toxic compounds.

Populated coastal areas are exposed to emissions from harbour-related activities (ship traffic, loading/unloading, and internal vehicular traffic), posing public health issues and environmental pressures on climate. Due to the strategic geographical position of Italy and the high number of ports along coastlines, an increasing concern about maritime emissions from Italian harbours has been made explicit in the EU and IMO (International Maritime Organization, London, UK) agenda, also supporting the inclusion in a potential Mediterranean emission control area (MedECA). This work reviews the main available outcomes concerning shipping (and harbours’) contributions to local air quality, particularly in terms of concentration of particulate matter (PM) and gaseous pollutants (mainly nitrogen and sulphur oxides), in the main Italian hubs. Maritime emissions from literature and disaggregated emission inventories are discussed. Furthermore, estimated impacts to air quality, obtained with dispersion and receptor modeling approaches, which are the most commonly applied methodologies, are discussed. Results show a certain variability that suggests the necessity of harmonization among methods and input data in order to compare results. The analysis gives a picture of the effects of this pollution source, which could be useful for implementing effective mitigation strategies at a national level.

The toolbox of medicinal chemists includes the 1,4-benzodiazepine scaffold as a “privileged scaffold” in drug discovery. Several biologically active small molecules containing a 1,4-benzodiazepine scaffold have been approved by the FDA for the treatment of various diseases, with most of them being used for their psychotropic effects. The therapeutic potential of 1,4-benzodiazepines has stimulated the interest of synthetic chemists in developing new synthetic strategies to a range of substituted analogues for biological evaluation. A structural variation of the classical benzodiazepine skeleton is observed e.g. in alprazolam, midazolam, and related benzodiazepines, which contain a 1,2,4-triazole or an imidazole ring fused to the benzodiazepine core. Irrespective of the presence of the fused heterocyclic ring, the seven-membered diazepine ring is far from planar, and its shape resembles a twist chair. Then, the unsymmetrical substitution pattern around the seven membered cycle renders these molecules chiral, as they lack any reflection-type symmetry element. However, chirality of this molecules is labile at room temperature, becausea simple ring flipping process converts one enantiomer into the other, and 1,4-benzodiazepines exist as a mixture of rapidly interconverting conformational enantiomers in solution at or near room temperature. Physical separation of the interconverting enantiomers of diazepam and of other related 1,4-benzodiazepin-2-ones can be accomplished by low temperature HPLC on chiral stationary phases (CSPs). If the HPLC column is cooled down to temperatures where the interconversion rate is sufficiently low, compared to the chromatographic separation rate, distinct separated peaks can be observed, provided the CSP is sufficiently enantioselctive. The apparent rate constants for the on-column enantiomerization and the corresponding free energy activation barriers were obtained by simulation of exchange-deformed HPLC profiles using a computer program based on the stochastic model. Here we report on the dynamic HPLC investigations carried out on a set of fused imidazo and triazolo-benzodiazepines (alprazolam, midazolam, triazolam and estazolam) The experimental dynamic chromatograms and the corresponding interconversion barriers reported in this paper show that the third fused heterocyclic ring increase the energy barrier by 2 kcal/mol.

Thesynthesis of Co-based two-dimensional (2D) metal azolate framework nanosheets (MAF-5-CoII NS) is described usinga simple hydrothermal method. The product was isostructural to MAF-5 (Zn). The as-prepared MAF-5-CoII NS exhibited high surface area (1155m2/g), purity, and crystallinity. The MAF-5-CoII NS–modified screen-printed electrode (MAF-5-CoII NS/SPE) was used for nonenzymatic detection of glucose in diluted human blood plasma (BP) samples with phosphate buffer saline (PBS, pH7.4) and NaOH (0.1M, pH13.0) solutions. The MAF-5-CoII NS nanozyme displayed good redox activity in both neutral and alkaline media with the formation of CoII/CoIII redox pair, which induced the catalytic oxidation of glucose. Under the optimized detection potential, the sensor presented a chronoamperometric current response for the oxidation of glucose with two wide concentration ranges in PBS-diluted (62.80 to 180μM and 305 to 8055μM) and NaOH-diluted (58.90 to 117.6μM and 180 to 10,055μM) BP samples, which were within the limit of blood glucose levels of diabetic patients before (4.4–7.2mM) and after (10mM) meals (recommended by the American Diabetes Association). The sensor has a limit of detection of ca. 0.25 and 0.05μM, respectively, and maximum sensitivity of ca. 36.55 and 1361.65mA/cm2/mM, respectively, in PBS- and NaOH-diluted BP samples. The sensor also displayed excellent stability in the neutral and alkaline media due to the existence of hydrophobic linkers (2-ethyl imidazole) in the MAF-5-CoII NS, good repeatability and reproducibility, and interference-free signals. Thus, MAF-5-CoII NS is a promising nanozyme for the development of the disposable type of sensor for glucose detection in human body fluids. [Figure not available: see fulltext.]