The Aeolian cultural heritage preserves hundreds of testimonies of the past that have passed through six millennia of history. Among these, the Archeological Park of the Aeolian Islands with the Museum Luigi Bernabo Brea (Italy) preserves a valuable set of artworks, which are related to a little-known 'popular' figurative heritage. It is an assemblage of small glass foils decorated using the technique of reverse painting, datable to between the end of the 17(th) century and the end of the 18(th) century, and actually under investigation by historians. Here, an X-ray fluorescence (XRF) spectroscopy study (performed with portable equipment) is combined with a multivariate approach that allows us to define the best way to process the data to detect compositional differences and similarities among the glass supports. The Principal Component Analysis (PCA) and Hierarchical Cluster Analysis (HCA) were applied both on normalized spectra and on normalized peak areas in order to establish the chemometric approach with the highest grouping ability. Results showed that the analysis of the normalized area provides the most reliable grouping based on the different elemental compositions, without problems coming from the background or peak-shape distortions. The obtained results can be used by researchers involved in the analysis of XRF data as a guideline to perform chemometrics. Furthermore, regarding the reverse glass, they can be divided into different typologies based on composition differences, providing a further discrimination criterion for historians involved in the study of the collection to determine the provenance and dating of the items.

Surface-Enhanced Raman Scattering (SERS) can obtain the spectroscopic response of specific analytes. In controlled conditions, it is a powerful quantitative technique. However, often the sample and its SERS spectrum are complex. Pharmaceutical compounds in human biofluids with strong interfering signals from proteins and other biomolecules are a typical example. Among the techniques for drug dosage, SERS was reported to detect low drug concentrations, with analytical capability comparable to that of the assessed High-Performance Liquid Chromatography. Here, for the first time, we report the use of SERS for Therapeutic Drug Monitoring of the Anti-Epileptic Drug Perampanel (PER) in human saliva. We used inert substrates decorated with gold NPs deposited via Pulsed Laser Deposition as SERS sensors. We show that it is possible to detect PER in saliva via SERS after an optimized treatment of the saliva sample. Using a phase separation process, it is possible to extract all the diluted PER in saliva from the saliva phase to a chloroform phase. This allows us to detect PER in the saliva at initial concentrations of the order of 10(-7) M, thus approaching those of clinical interest.

Choosing renewable energy from wind, solar, hydro, and biomass sources plays an essential role in reducing emissions and moving the global energy transition forward, as also requested by the European Community. Many national and international projects have been funded and now research activities PNRR-funded are starting to develop materials, components and equipment for the conversion and accumulation, the interoperability of sources, the flexibility and the integration of energy systems. In this direction, various groups belonging to the Institute for Chemical and Physical Processes (IPCF), have based their research activity on both an experimental [1-8] and theoretical [9-10] approach in: synthesis and functionalization of nanostructured materials for electrodes and sensitizers realization of dye-sensitized solar cells development of innovative materials, processes and technologies for the production of hydrogen improvement of reliability, efficiency, flexibility and resilience of the national energy system through a multi-scale computational modeling approach development of machine-learning algorithms and of networks for the construction of smart grids for energy management.

Arsenic is a well-known contaminant present in different environmental compartments and in human organs and tissues. Inorganic As(III) represents one of the most dangerous arsenic forms. Its toxicity is attributed to its great affinity with the thiol groups of proteins. Considering the simultaneous presence in all environmental compartments of other common functional groups, we here present a study aimed at evaluating their contribution to the As(III) complexation. As(III) interactions with four (from di-to hexa-) carboxylic acids, five (from mono-to penta-) amines, and four amino acids were evaluated via experimental methods and, in simplified systems, also by quantum-mechanical calculations. Data were analyzed also with respect to those previously reported for mixed thiol-carboxylic ligands to evaluate the contribution of each functional group (-SH,-COOH, and-NH) toward the As(III) complexation. Formation constants of As(III) complex species were experimentally determined, and data were analyzed for each class of ligand. An empirical relationship was reported, taking into account the contribution of each functional group to the complexation process and allowing for a rough estimate of the stability of species in systems where As(III) and thiol, carboxylic, or amino groups are involved. Quantum-mechanical calculations allowed for the evaluation and the characterization of the main chelation reactions of As(III). The potential competitive effects of the investigated groups were evaluated using cysteine, a prototypical species possessing all the functional groups under investigation. Results confirm the higher binding capabilities of the thiol group under different circumstances, but also indicate the concrete possibility of the simultaneous binding of As(III) by the thiol and the carboxylic groups.

Ion track membranes (ITM) are of long-term interest due to the high potential of applications in science and industry. However, the use of the membranes requires a detailed knowledge of (i) their structural parameters, i. e., the density and distribution of the ITM pores, the pore size (radius) and spatial shape, or (ii) the pore filling with other materials (demanding the knowledge of filling efficiency, filler confinement, or filler density). In this work, we studied the nuclear membranes prepared with pores of certain density and size and filled with Au nanoparticles. The analysis was carried out by Ion Transmission Spectroscopy (ITS). ITS is a nondestructive technique to determinate the spatial structure of (sub)micron inhomogeneities (pores, protrusions, etc.) in thin foils from the energy loss of even quasi-monoenergetic alpha particles (e.g., from a thin 241Am source) transmitted through the (empty or filled) pores. The reconstruction of the shape of the pores or pore fillings is performed by simulation of the transmission spectra using the MC code. The nuclear membranes were prepared by the irradiation of a thin polyethylene terephthalate with 157 MeV Xe+26 ions (with the fluence 10(6) cm(-2)) and the subsequent chemical etching in 9 M NaOH water solution at 50 degrees C for 40 min. The pores were filled with the Au nanoparticles (NPs) of a sub-micrometer size using the Pulse Laser Deposition (PLD), and studied by ITS. From the transmission spectra the shape of the pores filled (partially or fully) with Au NPs could be reconstructed. The ITM with pores filled with NPs were also analyzed by scanning electron microscopy (SEM). The results showed good agreement with the MC simulation of the ITS data.

Surface Enhanced Raman Spectroscopy is commonly used as analytical improvement to conventional Raman spectroscopy, able to respond to qualitative diagnostic enquiries, which involve low-concentrated molecular species in complex matrix. In this paper, we described fabrication, characterization and testing of a type of SERS-active substrates realized specifically to detect pigments in work of art. In particular, we detailed the SERS activity of nanostructured noble metal films deposited by pulsed laser ablation onto glass and polishing sheets substrates. The SERS response of the substrates was tested against the presence of some organic dyes in aqueous solutions. Measurements were performed at different pH values, in acidic or basic range, in order to investigate its role in the adsorption mechanism, thus fostering the SERS amplification. In addition, we checked the possible deterioration of the structural properties of the substrates that could occur in presence of alkaline or acidic environment. SERS activity of the substrates was tested against a commonly dye used as a SERS standard (Blue Methylene). Thereafter, substrates have been tested on two organic dyes (Alizarine red-S and Brazilwood), which had proven to be Raman active but present also either a weak Raman scattering cross section and/or a high fluorescence emission. The substrates have proven effective in amplifying Raman scattering of all dyes, quenching troubling fluorescence effects. Furthermore, they have proven to be stable in the pH range between 3 and 11. Furthermore, we carry out of vibrational DFT-calculation of dyes that provide a complete description of the observed SERS spectra.

In this work we report an X-ray fluorescence spectroscopy (XRF) study combined with a multivariate approach allowing to detect compositional differences and similarities among the alloys used in realization of silver collection of San Gennaro items collection. The San Gennaro treasure in Naples (Italy) represents, in fact, one of the most important silver collections in the world. The classification of the collection items is very complex, not only for the large number of objects, but also in consideration that between 1600 and 1700, in Naples, more than 350 laboratories were active, most of them specialized in specific art of work. As a consequence, a given collection object could be composed by various silver pieces that were produced by different laboratories. We applied a multivariate analysis on the XRF measurements data set to find a classification criterion based on the alloy elemental composition. Results showed that the collection items, as a whole or parts of it, can be divided into four large groups characterized by their different Ag/Cu ratio.

Multiple myeloma (MM) is a malignant disease based on differentiated plasma cells (PCs) in the bone marrow (BM). Flow cytometry and fluorescence microscopy, used to identify a large combination of clusters of differentiation (CDs), are applied for MM immunophenotyping. However, due to the heterogeneous MM immunophenotypes, more antibody panels are necessary for a preliminary diagnosis and for the monitoring of minimal residual disease (MRD). In this study, we evaluated the use of phage clones as probes for the identification of several PCs immunophenotypes from MM patients. First, A 9-mer M13-pVIII phage display library was screened against an MM.1 cells line to identify peptides that selectively recognize MM.1 cells. Then, the most representative phage clones, with amino acid sequences of foreign peptides closer to the consensus, were labelled with isothiocyanate of fluorescein (FITC) and were used to obtain a fluorescent signal on cells in ex-vivo samples by fluorescence microscopy. Selected phage clones were able to discriminate different MM immunophenotypes from patients related to CD45, CD38, CD56, and CD138. Our results highlight the possibility of using a phage-fluorescence probe for the simultaneous examination of the presence/absence of CDs associated with disease usually detected by combination of anti-CD antibodies. The design of a multi-phage imaging panel could represent a highly sensitive approach for the rapid detection of immunophenotype subtypes and the subsequent characterization of patient disease status.

Trusted methods for identifying different Multiple Myeloma (MM) cells and their biological diversity due to their immunophenotypic variety are often little detailed and difficult to find in literature. In this work, we show that micro-Raman spectroscopy can be used to highlight if there is a certain degree of distinction or correlation between the MM subtype plasmacells in relation to the cluster of differentiation (CD45 +/CD38+/CD138-) and (CD45-/CD38+/CD138+). After taking samples from the bone marrow of patients with Multiple Myeloma, the PCs were sorted by flow cytometry, selecting the most common CD of the disease, i.e. CD 45, CD38 and CD138. Some spectral differences are observed comparing the Raman spectra of the two set of samples investigated. To better define in which spectral regions there are greater differences and, therefore, to which biological contributions the changes refers, we also explored the principal component analysis (PCA) of the collected Raman data. The spectral variations between the different sorted cells have been highlighted by plotting loading vectors PC1 and PC2, which shows a net differentiation between the two set of cells. Ultimately, the differences shown by PCA have been associated with the spectral variations observed and explained in terms of changes of proteins and lipid contributions. Thus, the differentiation of Multiple Myeloma subtype plasma cells by confocal micro-Raman spectroscopy can be proposed as a diagnostic tool in the speeding up of cell identification, assessing the intracellular biochemical changes that take place in cancer cells. (c) 2021 Published by Elsevier B.V.

A thorough investigation on the acid-base properties of carnosine, and its potential interactions with the two essential metal cations Ca2+ and Mg2+, is here reported. The thermodynamic parameters of protonation and complexes formation are identified at different values of ionic strength and temperature, based on experiments employing potentiometric, spectrophotometric and H-1 NMR spectroscopic techniques. The involvement of the diverse functional groups in the protonation steps and complex formation equilibria with Ca2+ and Mg2+ are also investigated by means of Density Functional Theory and state-of-the-art ab initio molecular dynamics (AIMD) approaches, respectively. Among other things, AIMD simulations elucidate, for the first time, the complexation mechanisms of Ca2+ and Mg2+ to carnosine by explicitly treating, at the quantum level, the role of the water solvation. Since the biochemical behaviour of carnosine is ruled by the subtle interactions it establishes with metal cations such as Ca2+ and Mg2+, this study provides unprecedented fundamental insights into the mechanisms of action of this dipeptide and, hence, paves the way towards the development of potential therapeutic applications of carnosine.

Although many H-bonded systems have been extensively investigated by means of infrared (IR) spectroscopy, the vibrational response to externally applied electric fields of polar liquids remains poorly investigated. However, local electric fields along with quantum-mechanical interactions rule the behavior of H-bonded samples at the molecular level. Among the many H-bonded systems, liquid methanol holds a key place in that it exhibits a very simple H-bond network where, on average, each molecule acts as a single H-bond donor and, at the same time, as a single H-bond acceptor. Here we report on the IR spectra emerging from a series of state-of-the-art ab initio molecular dynamics simulations of bulk liquid methanol under the action of static and homogeneous electric fields. In addition, the same analysis is here conducted in the absence of the external field and for different temperatures. Although some electric-field-induced effects resemble the response of other polar liquids (such as the global contraction of the IR spectrum upon field exposure), it turns out that, distinctly from water, the "electrofreezing" phenomenon is unlikely to happen in liquid methanol. Finally, we provide atomistic analyses magnifying the completely different nature of electric-field- and temperature-induced effects on bulk liquid methanol and on its vibrational response.

A dye sensitized sensitized solar cell composed of a TiO photoanode sensitized with Y123 dye, Co(II)/Co(III) based electrolyte and a nanostructured gold counter electrode (CE) is presented. Gold nanostructured thin films were deposited on fluorine-doped tin oxide (FTO) glass to supersede the catalytic activity of platinum towards iodine-free redox mediators in dye-sensitized solar cells (DSSCs). As a reference, platinum and gold CEs were prepared by deposition and thermal decomposition of HPtCl and HAuCl, respectively. DSSCs equipped with PLA CEs exhibited comparable performance to the device s with the conventional Pt CEs under the same test conditions.

We have tested thin nano roughened Au films produced by pulsed laser deposition for quantitative SERS sensing of the anti-epileptic drug Perampanel within the range of concentrations of therapeutic interest (3 × 10 M-3 × 10 M). We propose a model to elucidate the dependence of the SERS intensity as a function of analyte concentration and contact time between the Au surface and the solution.

Laser synthesis emerges as a suitable technique to produce ligand-free nanoparticles, alloys and functionalized nanomaterials for catalysis, imaging, biomedicine, energy and environmental applications. In the last decade, laser ablation and nanoparticle generation in liquids has proven to be a unique and efficient technique to generate, excite, fragment and conjugate a large variety of nanostructures in a scalable and clean way. In this work, we give an overview on the fundamentals of pulsed laser synthesis of nanocolloids and new information about its scalability towards selected applications. Biomedicine, catalysis and sensing are the application areas mainly discussed in this review, highlighting advantages of laser-synthesized nanoparticles for these types of applications and, once partially resolved, the limitations to the technique for large-scale applications.

We studied the interaction of 5-aza[5]helicene and 5-aza[6]helicene with gold nanostructured substrates by SERS spectroscopy and DFT calculations. By comparing Raman and SERS experiments we observe significant changes for the normal modes involving nitrogen. This behavior, together with further evidence coming from SERS experiments carried out on the quaternary salts of the same azahelicenes, clearly highlight the direct interaction of nitrogen with the gold surface. DFT calculations on azahelicene models interacting with Au gold clusters reveal the charge transfer between azahelicene and gold. The information obtained from this study is useful in the field of sensor applications, where knowledge of the molecular mechanisms of interaction is fundamental for an appropriate design of the device.

Intense static electric fields can strongly perturb chemical bonds and induce frequency shifts of the molecular vibrations in the so-called vibrational Stark effect. Based on a density functional theory (DFT) approach, here, we report a detailed investigation of the influence of oriented external electric fields (OEEFs) on the dipole moment and infrared (IR) spectrum of the nonpolar centrosymmetric indigo molecule. When an OEEF as intense as ~0.1 V Å-1 is applied, several modifications in the IR spectrum are observed. Besides the notable frequency shift of some modes, we observe the onset of new bands?forbidden by the selection rules in the zero-field case. Such a neat field-induced modification of the vibrational selection rules, and the subsequent variations of the peaks' intensities in the IR spectrum, paves the way toward the design of smart tools employing centrosymmetric molecules as proxies for mapping local electric fields. In fact, here, we show that the ratio between the IR and the Raman intensities of selected modes is proportional to the square of the local field. This indicator can be used to quantitatively measure local fields, not only in condensed matter systems under standard conditions but also in field-emitting-tip apparatus.

Albeit arsenic As(s) is a well-known carcinogenic contaminant, the modalities by which it interacts with living organisms are still elusive. Details pertaining to the binding properties of As(s) by common nucleotides such as AMP, ADP and ATP are indeed mostly unknown. Here we present an investigation, conducted via experimental and quantum-based computational approaches, on the stability of the complexes formed by arsenic with those nucleotides. By means of potentiometric and calorimetric measurements, the relative stability of AMP, ADP and ATP has been evaluated as a function of the pH. It turns out that ATP forms more stable structures with As(s) than ADP which, in turn, better chelates arsenic than AMP. Such a stability sequestration capability of arsenic (ATP > ADP > AMP) has been interpreted on a twofold basis via state-of-the-art ab initio molecular dynamics (AIMD) and metadynamics (MetD) simulations performed on aqueous solutions of As(s) chelated by AMP and ATP. In fact, we demonstrate that ATP offers a larger number of effective binding sites than AMP, thus indicating a higher statistical probability for chelating arsenic. Moreover, an evaluation of the free energy associated with the interactions that As(s) establishes with the nucleotide atoms responsible for the binding quantitatively proves the greater effectiveness of ATP as a chelating agent.

Arsenic is one of the inorganic pollutants typically found in natural waters, and its toxic effects on the human body are currently of great concern. For this reason, the search for detoxifying agents that can be used in a so-called "chelation therapy" is of primary importance. However, to the aim of finding the thermodynamic behavior of efficient chelating agents, extensive speciation studies, capable of reproducing physiological conditions in terms of pH, temperature, and ionic strength, are in order. Here, we report on the acid-base properties of meso-2,3-dimercaptosuccinic acid (DMSA) at different temperatures (i.e., T = 288.15, 298.15, 310.15, and 318.15 K). In particular, its capability to interact with As(III) has been investigated by experimentally evaluating some crucial thermodynamic parameters (Delta H and T Delta S), stability constants, and its speciation model. Additionally, in order to gather information on the microscopic coordination modalities of As(III) with the functional groups of DMSA and, at the same time, to better interpret the experimental results, a series of state-of-the-art ab initio molecular dynamics simulations have been performed. For the sake of completeness, the sequestering capabilities of DMSA-a simple dithiol ligand-toward As(III) are directly compared with those recently emerged from similar analyses reported on monothiol ligands.

Discovery of new markers for the identification and discrimination of cell types is one of the principal objectives in cancer diagnostics. In the last years, many researchers used phage-display technology in vitro and in vivo to obtain random peptide probes able to bind towards cancer targets to be used in diagnostic systems and new targeted drug. In this work, we proposed a Single Drop Biosensor based on phage-labelled probes to detect leukaemia cells in blood from patients affected by chronic lymphocytic leukaemia (CLL). Results show that phage-labelled probes were able to recognize lymphocytes and lymphoblastic cells both in leukemic peripheral blood mononuclear cells and in whole blood from patients affected by CLL. The "proof of concept" proposed, using the phage labelled as bio-probe, could be an alternative way to produce new biosensor for monitoring of chronic pathology.

Sepsis is a systemic inflammatory response ensuing from presence and persistence of microorganisms in the bloodstream. The possibility to identify them at low concentrations may improve the problem of human health and therapeutic outcomes. So, sensitive and rapid diagnostic systems are essential to evaluate bacterial infections during the time, also reducing the cost. In this study, from random M13 phage display libraries, we selected phage clones that specifically bind surface of Staphyloccocus aureus, Pseudomonas aeruginosa and Escherichia coli. Then, commercial magnetic beads were functionalized with phage clones through covalent bond and used as capture and concentrating of pathogens from blood. We found that phage-magnetic beads complex represents a network which enables a cheap, high sensitive and specific detection of the bacteria involved in sepsis by micro-Raman spectroscopy. The enter process required 6 h and has the limit of detection of 10 Colony Forming Units on 7 ml of blood (CFU/7 ml).