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Raman spectroscopy, a versatile and nondestructive technique, was employed to develop a methodology for gallium oxide (Ga 2 O 3 ) phase detection and identification. This methodology combines experimental results with a comprehensive literature survey. The established Raman approach offers a powerful tool for nondestructively assessing phase purity and detecting secondary phases in Ga 2 O 3 thin films. X-ray diffraction was used for comparison, highlighting the complementary information that these techniques may provide for Ga 2 O 3 characterization. Few case studies are included to demonstrate the usefulness of the proposed spectroscopic approach, namely the impact of deposition conditions such as metal-organic vapor-phase epitaxy and pulsed electron deposition (PED), and extrinsic elements provided during growth (Sn in the case of PED) on Ga 2 O 3 polymorphism. In conclusion, it is shown that Raman spectroscopy offers a quick, reliable, and nondestructive high-resolution approach for Ga 2 O 3 thin film characterization, especially concerning phase detection and crystalline quality., Competing Interests: Declaration of Conflicting InterestsThe authors declared no potential conflicts of interest with respect to the research, authorship, and/or publication of this article.

Purpose: Carbon ion therapy treatments can be monitored non-invasively with in-beam Positron Emission Tomography (PET). At CNAO the INSIDE in-beam PET scanner has been used in a clinical trial (NCT03662373) to monitor cancer treatments with proton and carbon therapy. In this work we present the analysis results of carbon therapy data, acquired during the first phase of the clinical trial, analyzing data of nine patients treated at CNAO for various malignant tumors in the head-and-neck region., Materials and Methods: The patient group contained two patients requiring replanning, and seven patients without replanning, based on established protocols. For each patient the PET images acquired along the course of treatment were compared with a reference, applying two analysis methods: the beam-eye-view (BEV) method and the γ-index analysis. Time trends in several parameters were investigated, as well as the agreement with control CTs, if available., Results: Regarding the BEV-method, the average sigma value σ was 3.7 mm of range difference distributions for patients without changes (sensitivity of the INSIDE detector). The 3D-information obtained from the BEV analysis was partly in agreement with what was observed in the control CT. The data quality and quantity was insufficient for a definite interpretation of the time trends., Conclusion: We analyzed carbon therapy data acquired with the INSIDE in-beam PET detector using two analysis methods. The data allowed to evaluate sensitivity of the INSIDE detector for carbon therapy and to make several recommendations for the future., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier Ltd.)

Objective. Particle therapy treatments are currently limited by uncertainties of the delivered dose. Verification techniques like Prompt-Gamma-Timing-based Stopping Power Estimation (PGT-SPE) may allow for reduction of safety margins in treatment planning. Approach. From Prompt-Gamma-Timing measurements, we reconstruct the spatiotemporal distribution of prompt gamma emissions, which is linked to the average motion of the primary particles. The stopping power is determined by fitting a model of the average particle motion. Here, we compare a previously published implementation of the particle motion model with an alternative formulation and present two formulations to automatically select the hyperparameters of our procedure. The performance was assessed using Monte-Carlo simulations of proton beams (60 MeV-219 MeV) impinging on a homogeneous PMMA phantom. Main results. The range was successfully determined within a standard deviation of 3 mm for proton beam energies from 70 MeV to 219 MeV. Stopping power estimates showed errors below 5% for beam energies above 160 MeV. At lower energies, the estimation performance degraded to unsatisfactory levels due to the short range of the protons. The new motion model improved the estimation performance by up to 5% for beam energies from 100 MeV to 150 MeV with mean errors ranging from 6% to 18%. The automated hyperparameter optimization matched the average error of previously reported manual selections, while significantly reducing the outliers. Significance. The data-driven hyperparameter optimization allowed for a reproducible and fast evaluation of our method. The updated motion model and evaluation at new beam energies bring us closer to applying PGT-SPE in more complex scenarios. Direct comparison of stopping power estimates between treatment planning and measurements during irradiation would offer a more direct verification than other secondary-particle-based techniques., (Creative Commons Attribution license.)

Fibrous erionite is the only zeolite classified as Group 1 carcinogen by the International Agency for Research on Cancer (IARC). Carcinogenesis induced by erionite is thought to involve several factors as biopersistence, the iron role and cation exchange processes. To better understand these mechanisms, a detailed investigation at the micro scale was performed, collecting elemental information on iron and cation release and their distribution in biological systems by synchrotron micro-X-ray fluorescence mapping (SR-micro-XRF) and synchrotron micro-X-ray absorption spectroscopy (SR-micro-XANES) at the TwinMic beamline (Elettra synchrotron) and at the ID21 beamline of the European Synchrotron Radiation Facility (ESRF). By microscopy and chemical mapping, highly detailed maps of the chemical and morphological interaction of biological systems with fibres could be produced. In detail, THP-1 cell line derived macrophages, used as in vitro model, were analysed during erionite-Na phagocytosis at different time intervals, after single dose exposure. For comparison, cellular fluorescent probes were also used to evaluate the intracellular free sodium and calcium concentrations. Synchrotron analyses visualised the spatial distribution of both fibre and mineral particle associated metals during the phagocytosis, describing the mechanism of internalisation of erionite-Na and its accessory mineral phases. The intracellular distribution of metals and other cations was mapped to evaluate metal release, speciation changes and/or cation exchange during phagocytosis. The fluorescent probes complemented microchemical data clarifying, and confirming, the cation distribution observed in the SR-micro-XRF maps. The significant cytoplasmic calcium decrease, and the concomitant sodium increase, after the fibre phagocytosis seemed due to activation of plasma membrane cations exchangers triggered by the internalisation while, surprisingly, the ion-exchange capacity of erionite-Na could play a minor role in the disruption of the two cations intracellular homeostasis. These results help to elucidate the role of cations in the toxicity of erionite-treated THP-1 macrophages and add knowledge to its carcinogenicity process., Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests:Alessandro Gualtieri reports financial support was provided by Italian Ministry of University and Research. If there are other authors, they declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Inc. All rights reserved.)

Introduction: Direct transport from the scene of injury to a trauma centre reduces saves lives. In Ontario, paramedics use the field trauma triage standard (FTTS) to determine if a patient meets trauma bypass criteria. Recent studies have questioned the efficacy of the FTTS in identifying severely injured patients. The objective of this study was to determine the predictive performance of the FTTS on the need for trauma center care in patients who were transported to a trauma center., Methods: This was a single-center health records study of patients transported by ambulance directly to a level 1 trauma center. Hospital based trauma center need and injury severity score-based need were defined. Bivariate associations with one or more FTTS criteria were tested using the Wilcoxon two-sample test for continuous variables, and the Chi-square or Fisher's exact test for categorical indicators. The sensitivity and specificity of each category of the FTTS were calculated., Results: There were 1427 patients included in the study, with 76% men, mean age of 40, and 76% had a blunt mechanism. The overall sensitivity and specificity of the FTTS was 90.9% and 20.8% for hospital-based need and 91.6% and 20.3 for injury severity need. The most sensitive variable for hospital-based need was physiologic criteria (53.7). Mechanism of injury was the most sensitive criteria for injury severity need (54.8). Physiological criteria had the highest association with hospital-based and injury severity need (adjusted odds ratios 7.5 [95% CI 5.8-9.8] and 5.1 [95% CI 3.9-6.7])., Conclusions: The FTTS has fair performance in identifying the need for hospital-based and injury severity need. Systolic blood pressure less than 90 mmHg, Glasgow Coma Scale (motor) less than 6, and falls greater than 6 m were most predictive of trauma center need. Improving prehospital trauma triage is critical to ensure timely transport to a trauma centre., (© 2024. The Author(s), under exclusive licence to the Canadian Association of Emergency Physicians (CAEP)/ Association Canadienne de Médecine d'Urgence (ACMU).)

Goal: In-beam Positron Emission Tomography (PET) is a technique for in-vivo non-invasive treatment monitoring for proton therapy. To detect anatomical changes in patients with PET, various analysis methods exist, but their clinical interpretation is problematic. The goal of this work is to investigate whether the gamma-index analysis, widely used for dose comparisons, is an appropriate tool for comparing in-beam PET distributions. Focusing on a head-and-neck patient, we investigate whether the gamma-index map and the passing rate are sensitive to progressive anatomical changes., Methods/materials: We simulated a treatment course of a proton therapy patient using FLUKA Monte Carlo simulations. Gradual emptying of the sinonasal cavity was modeled through a series of artificially modified CT scans. The in-beam PET activity distributions from three fields were evaluated, simulating a planar dual head geometry. We applied the 3D-gamma evaluation method to compare the PET images with a reference image without changes. Various tolerance criteria and parameters were tested, and results were compared to the CT-scans., Results: Based on 210 MC simulations we identified appropriate parameters for the gamma-index analysis. Tolerance values of 3 mm/3% and 2 mm/2% were suited for comparison of simulated in-beam PET distributions. The gamma passing rate decreased with increasing volume change for all fields., Conclusion: The gamma-index analysis was found to be a useful tool for comparing simulated in-beam PET images, sensitive to sinonasal cavity emptying. Monitoring the gamma passing rate behavior over the treatment course is useful to detect anatomical changes occurring during the treatment course., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Associazione Italiana di Fisica Medica e Sanitaria. Published by Elsevier Ltd. All rights reserved.)

Interfacial regions play a key role in determining the overall power conversion efficiency of thin film solar cells. However, the nanoscale investigation of thin film interfaces using conventional analytical tools is challenging due to a lack of required sensitivity and spatial resolution. Here, we surmount these obstacles using tip-enhanced Raman spectroscopy (TERS) and apply it to investigate the absorber (Sb 2 Se 3 ) and buffer (CdS) layers interface in a Sb 2 Se 3 -based thin film solar cell. Hyperspectral TERS imaging with 10 nm spatial resolution reveals that the investigated interface between the absorber and buffer layers is far from uniform, as TERS analysis detects an intermixing of chemical compounds instead of a sharp demarcation between the CdS and Sb 2 Se 3 layers. Intriguingly, this interface, comprising both Sb 2 Se 3 and CdS compounds, exhibits an unexpectedly large thickness of 295 ± 70 nm attributable to the roughness of the Sb 2 Se 3 layer. Furthermore, TERS measurements provide compelling evidence of CdS penetration into the Sb 2 Se 3 layer, likely resulting from unwanted reactions on the absorber surface during chemical bath deposition. Notably, the coexistence of ZnO, which serves as the uppermost conducting layer, and CdS within the Sb 2 Se 3 -rich region has been experimentally confirmed for the first time. This study underscores TERS as a promising nanoscale technique to investigate thin film inorganic solar cell interfaces, offering novel insights into intricate interface structures and compound intermixing.

Objective. This study addresses a fundamental limitation of in-beam positron emission tomography (IB-PET) in proton therapy: the lack of direct anatomical representation in the images it produces. We aim to overcome this shortcoming by pioneering the application of deep learning techniques to create synthetic control CT images (sCT) from combining IB-PET and planning CT scan data. Approach. We conducted simulations involving six patients who underwent irradiation with proton beams. Leveraging the architecture of a visual transformer (ViT) neural network, we developed a model to generate sCT images of these patients using the planning CT scans and the inter-fractional simulated PET activity maps during irradiation. To evaluate the model's performance, a comparison was conducted between the sCT images produced by the ViT model and the authentic control CT images-serving as the benchmark. Main results. The structural similarity index was computed at a mean value across all patients of 0.91, while the mean absolute error measured 22 Hounsfield Units (HU). Root mean squared error and peak signal-to-noise ratio values were 56 HU and 30 dB, respectively. The Dice similarity coefficient exhibited a value of 0.98. These values are comparable to or exceed those found in the literature. More than 70% of the synthetic morphological changes were found to be geometrically compatible with the ones reported in the real control CT scan. Significance. Our study presents an innovative approach to surface the hidden anatomical information of IB-PET in proton therapy. Our ViT-based model successfully generates sCT images from inter-fractional PET data and planning CT scans. Our model's performance stands on par with existing models relying on input from cone beam CT or magnetic resonance imaging, which contain more anatomical information than activity maps., (Creative Commons Attribution license.)

Objective . The performance of silicon detectors with moderate internal gain, named low-gain avalanche diodes (LGADs), was studied to investigate their capability to discriminate and count single beam particles at high fluxes, in view of future applications for beam characterization and on-line beam monitoring in proton therapy. Approach . Dedicated LGAD detectors with an active thickness of 55 μ m and segmented in 2 mm 2 strips were characterized at two Italian proton-therapy facilities, CNAO in Pavia and the Proton Therapy Center of Trento, with proton beams provided by a synchrotron and a cyclotron, respectively. Signals from single beam particles were discriminated against a threshold and counted. The number of proton pulses for fixed energies and different particle fluxes was compared with the charge collected by a compact ionization chamber, to infer the input particle rates. Main results . The counting inefficiency due to the overlap of nearby signals was less than 1% up to particle rates in one strip of 1 MHz, corresponding to a mean fluence rate on the strip of about 5 × 10 7 p/(cm 2 ·s). Count-loss correction algorithms based on the logic combination of signals from two neighboring strips allow to extend the maximum counting rate by one order of magnitude. The same algorithms give additional information on the fine time structure of the beam. Significance . The direct counting of the number of beam protons with segmented silicon detectors allows to overcome some limitations of gas detectors typically employed for beam characterization and beam monitoring in particle therapy, providing faster response times, higher sensitivity, and independence of the counts from the particle energy., (Creative Commons Attribution license.)

Although all six asbestos minerals (the layer silicate chrysotile and five chain silicate species actinolite asbestos, amosite, anthophyllite asbestos, crocidolite and tremolite asbestos) are classified as carcinogenic, chrysotile is still mined and used in many countries worldwide. Other countries, like Italy, impose zero tolerance for all asbestos species, but conflicting views repress the development of globally uniform treaties controlling international trade of asbestos-containing materials. Hence, countries with more severe legislations against the use of these hazardous materials lack of an international safety net against importation of non-compliant products. This research reports the first discovery of commercial magnesite raw materials contaminated with white asbestos (chrysotile). X-ray powder diffraction and thermogravimetric/thermodifferential measurements showed the presence of serpentine group minerals in both the semi-processed (powder) and quarried material. The univocal identification of chrysotile in the powders was confirmed by its peculiar Raman bands of the OH stretching vibrations between 3500 and 3800 cm -1 , with an intense peak at ∼3695 cm -1 and a weak contribution at ∼3647 cm -1 . Transmission electron microscope showed that chrysotile forms fibres up to a few microns long and up to 80 nm thick with a nanotube structure characterized by inner channels as large as 30-40 nm. Fibres size analysis obtained by scanning electron microscopy indicates mean length and diameter of 5.95 and 0.109 μm with medians of 2.62 and 0.096 μm, respectively; some among the fibres analysed exhibit the so-called "Stanton size" (i.e., asbestos fibres longer than 8 μm and thinner than 0.25 μm that are strongly carcinogenic). Quantitative analysis showed a chrysotile content around 0.01 wt% not allowed by current regulations in Italy and many other countries. More generally, our findings demonstrate that without shared policies aimed at regulating asbestos circulation on the global market, "asbestos-free" national policies will inevitably fail., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper. The authors wish to state that the commercial samples analysed in this study were provided by Italian suppliers and end-users and considered representative of batches present in the manufacture sites in Italy during the autumn period of the year 2021. Evidence of asbestos contamination from this work is intended only for the analysed samples and, in the absence of further experimental data, should be regarded as accidental. Under no circumstances should the results of this study be generalized in space and time and considered valid for other commercial magnesite samples., (Copyright © 2023 Elsevier B.V. All rights reserved.)

Background: The beam energy is one of the most significant parameters in particle therapy since it is directly correlated to the particles' penetration depth inside the patient. Nowadays, the range accuracy is guaranteed by offline routine quality control checks mainly performed with water phantoms, 2D detectors with PMMA wedges, or multi-layer ionization chambers. The latter feature low sensitivity, slow collection time, and response dependent on external parameters, which represent limiting factors for the quality controls of beams delivered with fast energy switching modalities, as foreseen in future treatments. In this context, a device based on solid-state detectors technology, able to perform a direct and absolute beam energy measurement, is proposed as a viable alternative for quality assurance measurements and beam commissioning, paving the way for online range monitoring and treatment verification., Purpose: This work follows the proof of concept of an energy monitoring system for clinical proton beams, based on Ultra Fast Silicon Detectors (featuring tenths of ps time resolution in 50 μm active thickness, and single particle detection capability) and time-of-flight techniques. An upgrade of such a system is presented here, together with the description of a dedicated self-calibration method, proving that this second prototype is able to assess the mean particles energy of a monoenergetic beam without any constraint on the beam temporal structure, neither any a priori knowledge of the beam energy for the calibration of the system., Methods: A new detector geometry, consisting of sensors segmented in strips, has been designed and implemented in order to enhance the statistics of coincident protons, thus improving the accuracy of the measured time differences. The prototype was tested on the cyclotron proton beam of the Trento Protontherapy Center (TPC). In addition, a dedicated self-calibration method, exploiting the measurement of monoenergetic beams crossing the two telescope sensors for different flight distances, was introduced to remove the systematic uncertainties independently from any external reference., Results: The novel calibration strategy was applied to the experimental data collected at TPC (Trento) and CNAO (Pavia). Deviations between measured and reference beam energies in the order of a few hundreds of keV with a maximum uncertainty of 0.5 MeV were found, in compliance with the clinically required water range accuracy of 1 mm., Conclusions: The presented version of the telescope system, minimally perturbative of the beam, relies on a few seconds of acquisition time to achieve the required clinical accuracy and therefore represents a feasible solution for beam commission, quality assurance checks, and online beam energy monitoring., (© 2023 The Authors. Medical Physics published by Wiley Periodicals LLC on behalf of American Association of Physicists in Medicine.)

Copper-doped antimony selenide (Cu-doped Sb 2 Se 3 ) thin films were deposited as absorber layers in photovoltaic solar cells using the low-temperature pulsed electron deposition (LT-PED) technique, starting from Sb 2 Se 3 targets where part of the Sb was replaced with Cu. From a crystalline point of view, the best results were achieved for thin films with about Sb 1.75 Cu 0.25 Se 3 composition. In order to compare the results with those previously obtained on undoped thin films, Cu-doped Sb 2 Se 3 films were deposited both on Mo- and Fluorine-doped Tin Oxide (FTO) substrates, which have different influences on the film crystallization and grain orientation. From the current-voltage analysis it was determined that the introduction of Cu in the Sb 2 Se 3 absorber enhanced the open circuit voltage (V OC ) up to remarkable values higher than 500 mV, while the free carrier density became two orders of magnitude higher than in pure Sb 2 Se 3 -based solar cells.

Alveolar macrophages are the first line of defence against detrimental inhaled stimuli. To date, no comparative data have been obtained on the inflammatory response induced by different carcinogenic mineral fibres in the three main macrophage phenotypes: M0 (non-activated), M1 (pro-inflammatory) and M2 (alternatively activated). To gain new insights into the different toxicity mechanisms of carcinogenic mineral fibres, the acute effects of fibrous erionite, crocidolite and chrysotile in the three phenotypes obtained by THP-1 monocyte differentiation were investigated. The three mineral fibres apparently act by different toxicity mechanisms. Crocidolite seems to exert its toxic effects mostly as a result of its biodurability, ROS and cytokine production and DNA damage. Chrysotile, due to its low biodurability, displays toxic effects related to the release of toxic metals and the production of ROS and cytokines. Other mechanisms are involved in explaining the toxicity of biodurable fibrous erionite, which induces lower ROS and toxic metal release but exhibits a cation-exchange capacity able to alter the intracellular homeostasis of important cations. Concerning the differences among the three macrophage phenotypes, similar behaviour in the production of pro-inflammatory mediators was observed. The M2 phenotype, although known as a cell type recruited to mitigate the inflammatory state, in the case of asbestos fibres and erionite, serves to support the process by supplying pro-inflammatory mediators.

We report a detailed characterization of Ge NWs directly grown on glass by a MOVPE system, showing how different growth parameters can affect the final outcome and comparing NWs grown on a monocrystalline Ge(111) substrate with NWs grown on amorphous glass. Our experimental results indicate that the choice of the substrate does not affect any of the relevant morphological, crystallographic or electrical properties of Ge NWs. Lengths are in the 20-30 micrometer range with minimal tapering, while growth rates are very similar to to NWs grown on Ge(111); TEM and Raman characterization show a very good crystallinity of measured nanostructures. We have also analyzed the growth process on glass and we were able to reach a conclusion on the specific growth mechanism for Ge NWs on amorphous substrates. Our findings demonstrate that glass is a valid option as cheap substrate for the mass production of these nanostructures.

We report on the high-pressure solid-state synthesis and the detailed structural characterization of the metastable, CuAu-type CuInS 2 (CA-CIS) phase. Although often present in CIS thin films as unwanted phase, it has been never synthesized in pure form, and its effect on the performance of CIS-based solar cells has been long debated. In this work, pure CA-CIS phase is synthesized in bulk polycrystalline form through a high-pressure-high-temperature solid-state reaction. Single-crystal X-rays diffraction reveals the formation of tetragonal CA-CIS ( a = 3.9324(5), c = 5.4980(7) Å) either in cation-ordered and disordered phase, pointing out the role of the pressure/temperature increase on the Cu/In ordering. The resistivity measurements performed on CA-CIS show low resistivity and a flat trend vs temperature and, in the case of the ordered phase, highlight a bad-metallic behavior, probably due to a high level of doping. These findings clearly rule out the possibility of a beneficial effect of this phase on the CIS-based thin film solar cells.

This paper presents the results of a fully non-invasive photographic and spectroscopic study on a masterpiece by the famous Venetian painter Jacopo Tintoretto (1518-1594): "The Wedding feast at Cana" (1561), located inside the sacristy of the Santa Maria della Salute Basilica in Venice. A restoration campaign was carried out on the painting between 2016 and 2017. Various techniques were chosen to characterize in detail the materials used by the painter, especially pigments: Near Infrared Reflectography (NIR) to identify preparatory sketch and also allowing formulating hypothesis on some pigments; Raman and Fiber Optics Reflectance Spectroscopy (FORS) applied directly to the surface of the object, avoiding sample collection, to identify the pigments palette applied by Tintoretto. Information about binders was also obtained in a totally non-invasive way by using NIR spectroscopy. All analysis points were precisely (±2 mm) registered on a painting virtual map in order to recover them in a future possible conservation project., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2019 Elsevier B.V. All rights reserved.)

One of the challenges in the development of germanium nanowires (Ge NWs) is to increase their length beyond the 10 μm limit without enlarging the NW diameter, i.e. minimizing the tapering. Here we report how it is possible to overcome this hurdle by using isobutyl germane (iBuGe) as a metal organic precursor during MOCVD growth, instead of the commonly used germane. We have grown and characterized by transmission electron microscopy, scanning electron microscopy and Raman various samples and we have analyzed the effect of growth time, precursor flux and growth temperature on the NW length. The use of iBuGe coupled to optimized growth conditions permitted to obtain Ge NWs with lengths up to 30 μm with minimal tapering. To explain why a new precursor has this impact on the morphology of the NWs we consider two possible causes: (i) the role of carbon radicals produced by isobutyl decomposition and (ii) the reduced growth rate of Ge on the sidewalls. On the basis of Raman characterization and temperature-dependence of tapering, we conclude that the reduced tapering is probably due to lower growth rates on the sidewalls.

We report a detailed study on the magnetic properties of the pyroxene series M2M1Si 2 O 6 , with M2  =  Ca and M1  =  Mg, where magnesium and then calcium are progressively substituted by cobalt. For cobalt site occupancy larger than 0.7 at the M1 site, a collinear antiferromagnetic phase is detected for T  <  T N1   =  12 K with a monodimensional character (i.e. M1 site intra-chain order parallel to c axis). Moreover the magnetization easy axis has been estimated to lie roughly along the [1 0 1] direction. Cobalt content  ⩾0.5 at the M2 site (overall content 1.5) determines the formation of a new independent antiferromagnetic order with higher Néel temperature, involving only the M2 site intra-chain interactions. The incoming M2 site order is accompanied by a lowering of the space symmetry which yields to a weakly ferromagnetic resultant due to spin canted distribution of the magnetic moments either along the M1 or M2 chains. Furthermore, metamagnetic transitions are observed for both M1 and M2 site intra-chain orders at relatively low critical magnetic fields, around 2 T, suggesting that this series of pyroxenes can be used as a model system for investigating the fundamental aspects of magnetism in the matter.

Raman spectroscopy has been positively evaluated as a tool for the in-line and real-time monitoring of powder blending processes and it has been proved to be effective in the determination of the endpoint of the mixing, showing its potential role as process analytical technology (PAT). The aim of this study is to show advantages and disadvantages of Raman spectroscopy with respect to the most traditional HPLC analysis. The spectroscopic results, obtained directly on raw powders, sampled from a two-axis blender in real case conditions, were compared with the chromatographic data obtained on the same samples. The formulation blend used for the experiment consists of active pharmaceutical ingredient (API, concentrations 6.0% and 0.5%), lactose and magnesium stearate (as excipients). The first step of the monitoring process was selecting the appropriate wavenumber region where the Raman signal of API is maximal and interference from the spectral features of excipients is minimal. Blend profiles were created by plotting the area ratios of the Raman peak of API (A API ) at 1598cm -1 and the Raman bands of excipients (A EXC ), in the spectral range between 1560 and 1630cm -1 , as a function of mixing time: the API content can be considered homogeneous when the time-dependent dispersion of the area ratio is minimized. In order to achieve a representative sampling with Raman spectroscopy, each sample was mapped in a motorized XY stage by a defocused laser beam of a micro-Raman apparatus. Good correlation between the two techniques has been found only for the composition at 6.0% (w/w). However, standard deviation analysis, applied to both HPLC and Raman data, showed that Raman results are more substantial than HPLC ones, since Raman spectroscopy enables generating data rich blend profiles. In addition, the relative standard deviation calculated from a single map (30 points) turned out to be representative of the degree of homogeneity for that blend time., (Copyright © 2017 Elsevier B.V. All rights reserved.)

This work is a part of a large scientific project aimed at highlighting the potential of portable Raman equipment in characterizing jewelry materials preserved in museums, carried out in collaboration with gemologists and archeologists. In detail, we report the results of a measurement campaign performed for the study of gems and jewels preserved in the well-known Medagliere section at the Paolo Orsi Regional Museum of Siracusa (Sicily). The studied materials consist of exquisite examples of engraved loose gems and really rare examples of Hellenistic-Roman jewels, mainly coming from relevant Sicilian archaeological sites. Portable Raman measurements have been carried out using two instruments equipped with different excitation wavelengths. The obtained results have allowed for a complete characterization of the studied gemological materials, also suggesting sometimes misclassification for some valuable objects and gems., (© The Author(s) 2016.)

Ultra-fine particles have recently been included among the risk factors for the development of endothelium inflammation and atherosclerosis, and cobalt (CoNPs) and titanium oxide nanoparticles (TiNPs) have attracted attention because of their wide range of applications. We investigated their toxicity profiles in two primary endothelial cell lines derived from human aorta (HAECs) and human umbilical vein (HUVECs) by comparing cell viability, oxidative stress, the expression of adhesion molecules and the release of chemokines during NP exposure. Both NPs were very rapidly internalised, and significantly increased adhesion molecule (ICAM-1, VCAM-1, E-selectin) mRNA and protein levels and the release of monocyte chemoattractant protein-1 (MCP-1) and interleukin 8 (IL-8). However, unlike the TiNPs, the CoNPs also induced time- and concentration-dependent metabolic impairment and oxidative stress without any evident signs of cell death or the induction of apoptosis. There were differences between the HAECs and HUVECs in terms of the extent of oxidative stress-related enzyme and vascular adhesion molecule expression, ROS production, and pro-inflammatory cytokine release despite the similar rate of NP internalisation, thus indicating endothelium heterogeneity in response to exogenous stimuli. Our data indicate that NPs can induce endothelial inflammatory responses via various pathways not involving only oxidative stress., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

Background: In light of recent developments in nanotechnologies, interest is growing to better comprehend the interaction of nanoparticles with body tissues, in particular within the cardiovascular system. Attention has recently focused on the link between environmental pollution and cardiovascular diseases. Nanoparticles <50 nm in size are known to pass the alveolar-pulmonary barrier, enter into bloodstream and induce inflammation, but the direct pathogenic mechanisms still need to be evaluated. We thus focused our attention on titanium dioxide (TiO₂) nanoparticles, the most diffuse nanomaterial in polluted environments and one generally considered inert for the human body., Methods: We conducted functional studies on isolated adult rat cardiomyocytes exposed acutely in vitro to TiO₂ and on healthy rats administered a single dose of 2 mg/Kg TiO₂ NPs via the trachea. Transmission electron microscopy was used to verify the actual presence of TiO₂ nanoparticles within cardiac tissue, toxicological assays were used to assess lipid peroxidation and DNA tissue damage, and an in silico method was used to model the effect on action potential., Results: Ventricular myocytes exposed in vitro to TiO₂ had significantly reduced action potential duration, impairment of sarcomere shortening and decreased stability of resting membrane potential. In vivo, a single intra-tracheal administration of saline solution containing TiO₂ nanoparticles increased cardiac conduction velocity and tissue excitability, resulting in an enhanced propensity for inducible arrhythmias. Computational modeling of ventricular action potential indicated that a membrane leakage could account for the nanoparticle-induced effects measured on real cardiomyocytes., Conclusions: Acute exposure to TiO₂ nanoparticles acutely alters cardiac excitability and increases the likelihood of arrhythmic events.

Unlabelled: Self-cleaning photocatalytic coatings for biocalcarenite stones, based on TiO2 nanoparticles obtained by sol-gel processes at different pH values and also adding gold particles, have been investigated. The selected test material is a biocalcarenite named "pietra di Lecce" (Lecce stone), outcropping in Southern Italy. Scanning electron microscopy with energy-dispersive X-ray spectroscopy, transmission electron microscopy, X-ray diffraction, and Raman investigations were carried out to characterize the TiO2 nanoparticles and coatings. Nanocrystalline anatase and, to a lesser extent, brookite phases are obtained. Photocatalytic activity of the TiO2 sols and of the coatings on "pietra di Lecce" was assessed under ultraviolet irradiation, monitoring methyl orange (MeO) dye degradation as a function of time. To evaluate the harmlessness of the treatment, colorimetric tests and water absorption by capillarity were performed. The results show good photodegradation rates for titania nanosols, particularly when putting in Au particles, whereas a satisfactory chromatic compatibility between the sol and the surface of the calcarenite is found only without Au addition., Highlights: Sols of nanocrystalline titania at different pH values and with Au particles were prepared and characterized. Satisfactory photodegradation of MeO by the sols in solution and on calcarenite-coated surfaces is obtained. The addition of Au particles improves the photodegradation activity but gives poor chromatic results on "pietra di Lecce."

During the last decades, Raman spectroscopy has grown to an established analytical technique in archaeometry, art analysis and conservation science. Mobile Raman instruments were designed to be used for in situ characterisation and identification of inorganic and organic materials in art and archaeometry. This research paper aims to point out several aspects that need to be considered when selecting a mobile Raman spectrometer for in situ archaeometrical studies. We describe an approach to evaluate these parameters and apply this to a dual laser portable Raman spectrometer. Twofold characterisation of mobile Raman instrumentation for art analysis: (i) investigation of spectroscopic characteristics such as (amongst others) spectral resolution, spectral window, signal to noise ratio and limit of detection; (ii) evaluation of specific properties that are useful for mobile studies in archaeometry. These include options for easy positioning and focussing, the ability to reduce laser power on the surface of the art object and the working distance between the probehead and the artefact. Finally, the research was completed with field tests by studying the pigments of a mediaeval wall painting., (Copyright © 2013 Elsevier B.V. All rights reserved.)

Three bronze samples created by CNR-ISMN (National Research Council-Institute of Nanostructured Materials) to be similar to Punic and Roman coins found in Tharros (OR, Sardinia, Italy) were studied to identify the corrosion products on their surfaces and to evaluate the reliability of the reproduction process. Micro-Raman spectroscopy was chosen to investigate the corroded surfaces because it is a non-destructive technique, it has high spatial resolution, and it gives the opportunity to discriminate between polymorphs and to correlate colour and chemical composition. A significant amount of green copper hydroxychlorides (Cu(2)(OH)(3)Cl) was detected on all the coins. Their discrimination by Raman spectroscopy was challenging because the literature on the topic is currently confusing. Thus, it was necessary to determine the characteristic peaks of atacamite, clinoatacamite, and the recently discovered anatacamite by acquiring Raman spectra of comparable natural mineral samples. Clinoatacamite, with different degrees of order in its structure, was the major component identified on the three coins. The most widespread corrosion product, besides hydroxychlorides, was the red copper oxide cuprite (Cu(2)O). Other corrosion products of the elements of the alloy (laurionite, plumbonacrite, zinc carbonate) and those resulting from burial in the soil (anatase, calcite, hematite) were also found. This study shows that identification of corrosion products, including discrimination of copper hydroxychlorides, could be accomplished by micro-Raman on valuable objects, for example archaeological findings or works of art, avoiding any damage because of extraction of samples or the use of a destructive analytical technique.

Being nondestructive and requiring short measurement times, a low amount of material, and no sample preparation, Raman spectroscopy is used for routine investigation in the study of gemstone inclusions and treatments and for the characterization of mounted gems. In this work, a review of the use of laboratory Raman and micro-Raman spectrometers and of portable Raman systems in the gemology field is given, focusing on gem identification and on the evaluation of the composition, provenance, and genesis of gems. Many examples are shown of the use of Raman spectroscopy as a tool for the identification of imitations, synthetic gems, and enhancement treatments in natural gemstones. Some recent developments are described, with particular attention being given to the semiprecious stone jade and to two important organic materials used in jewelry, i.e., pearls and corals.

Raman spectroscopy represents a new way to obtain detailed comprehensive information on heavy-mineral assemblages. In this work are presented several examples from major Alpine (Po River) and Himalayan (Ganga and Brahmaputra Rivers) fluvio-deltaic sands. Our attention was focused on the chemical properties of garnet, which is a widespread mineral in orogenic sediments, easy to be identified, and relatively stable during both equatorial weathering and intrastratal dissolution. Garnet grains were studied in different samples representative of various depositional environments (fluvial bar, fluvial levee, shoreface, beach berm, eolian dune), in order to investigate specifically the hydraulic behaviour of grains with different density in different hydrodynamic conditions. Raman spectra and semi-quantitative analysis of Raman shifts allowed us to rapidly determine the distribution of garnet types in each sample in order to obtain chemical composition, to calculate the density of each garnet, and finally to infer their respective provenance. This manuscript presents one possible application of the "MIRAGEM" method described by Bersani et al. in this volume. References, data sets and details on the analytical routine are widely explained in the above mentioned work.

Green colored samples on wall paintings and green powder from a pigment pot found in Pompeii area are investigated by micro-Raman, FT-IR and, for one sample, SEM-EDX. To obtain the green color, green earths and malachite were used, together with mixture of Egyptian blue and yellow ochre. The mineralogical identification of the green earths has been attempted through the comparison of the vibrational features, discriminating between celadonite and glauconite spectra. Traces of a modern synthetic pigment containing copper phthalocyanine were found in a fresco fragment.

Fluid inclusions in the quartz crystals present in gold-rich veins from central Honduras have been studied by means of micro-thermometry and micro-Raman spectroscopy in order to provide information on the physico-chemical conditions and chemical composition of the mineralizing fluids. The use of a confocal micro-Raman apparatus allowed to obtain information on the fluid composition, in particular on the gas phase, minimizing the contributions of the host matrix to the Raman signal. The samples studied were collected from an area (Lepaguare mining district, Northern-Central Honduras) rich in ore deposits due to the Cenozoic magmatic activity, where the gold and sulphide mineralization is connected with a system of quartz veins (few decimetres thick) occurring in low-grade metamorphic rocks and produced by hydrothermal fluids. The quartz crystals present in the gold-rich veins often contain fluid inclusions. Four types of fluid inclusions have been observed, but their assemblage in the same clusters and fracture systems, as well as their comparable salinity and homogenization data, suggest that they have the same origin. Micro-thermometry and Raman spectroscopy provide a composition of the mineralizing fluids attributable to the system H(2)O-NaCl-KCl-CO(2)-CH(4), with temperature and pressure intervals of 210-413 degrees C and 1050-3850 bar, respectively. These data agree with an epigenetic origin of the gold deposit (depth < 6 km) related to granitoid or granodiorite intrusions associated to orogenic environments.

A rapid system to obtain molar compositions of minerals belonging to the garnet group by means of Raman spectroscopy is illustrated here. A series of standard garnets, whose composition was determined by means of Wavelength Dispersive System (WDS) electron microprobe measurements, was used to correlate the wavenumbers of the different Raman peaks with chemical composition. A simple software routine was then developed in order to obtain garnet molar composition starting from the Raman spectrum, based on the assumption that in a solid solution belonging to the garnet family the Raman wavenumbers are linear combinations of end member wavenumbers, weighted by their molar fraction. The choice of the Raman bands used for the calculations and their behaviour are also discussed. The method, called MIRAGEM (Micro-Raman Garnets Evaluation Method), was then tested on a second series of garnets with satisfactory results.

Two holy water fonts (dated at the beginning of the XVII century) in the Santa Maria della Steccata Church in Parma (Italy) have recently been restored. Before the intervention, a detailed investigation on their degradation products was carried out to understand the mechanisms of alteration of the materials and to suggest appropriate restoration procedures. The analyses were performed by means of powder X-ray diffraction (XRD), micro-Fourier transform infrared (FTIR) and micro-Raman spectroscopies. Calcite, iron oxides, silicates and sodium chloride (from salted holy water) were found in the red coloured calcarenite. On and under the lead coverings, different lead oxides (mainly massicot), other lead salts (lead basic carbonate, cerussite, plumbonacrite Pb10O(OH)6(CO3)6 and lead-chlorine compounds as laurionite PbOHCl and phosgenite Pb2CO3Cl2) were identified by Raman spectroscopy and XRD. Haematite alpha-Fe2O3, goethite alpha-FeO(OH) and lepidocrocite gamma-FeO(OH) were found on and around the iron hinges. Lead compounds and sodium chloride, through crystallization and solubilization cycles, were responsible for the stone's degradation, whereas the iron corrosion materials on the hinges produced mechanical stress and cracks in the stone. Various suggestions have been given on how to restore these fonts and to remove the causes of damage.

Purpose: Thoracic outlet syndrome includes arterial, venous or neurological symptoms. Frequently difficult to diagnose clinically, confirmatory imaging studies are usually required. The purpose of this study is to review the diagnostic work-up during management of patients with thoracic outlet syndrome and demonstrate the value of angiography in the sitting position., Materials and Methods: Retrospective study of 81 surgical procedures for thoracic outlet syndrome, between 1997 and 2005, in 56 patients aged 17-57 years. Surgery was bilateral in 26 cases, with bilateral surgery in a single setting for 1 patient. All patients presented clinical symptoms confirmed on US, angiography, venogram or EMG. Angiography, from a transfemoral approach, was initially performed in the supine position, without and with dynamic maneuver, and in the sitting position with dynamic maneuver when needed., Results: In 48 patients, supine rest angiography showed stenosis in 6% of cases and supine dynamic angiography showed stenosis in 81% of cases, with severe stenosis in only 35% of cases (stenosis>80% or arterial occlusion). Angiography in the sitting position was performed in 33 patients, showing worsening of stenosis in 91% of cases, with severe stenosis in 87%., Conclusion: Angiography in the sitting position with dynamic maneuver improves the sensitivity for detection of thoraci coutlet syndrome. This procedure may be considered in addition to other imaging modalities routinely used including Doppler US, CT and MRI.

Background: Stroke is the most common cause of permanent disability in Europe and is a major public health problem. A recent significant therapeutic advance is the administration of recombinant tissue plasminogen activator (rtPA) for cerebral infarcts within three hours of symptom onset. French guidelines limit its use to patients in specialized stroke units. There is only one stroke unit in the region of Aquitaine, in Bordeaux, 200 km from Pau and too far to transfer patients within the necessary time. With the collaboration of our colleagues in Bordeaux we decided to assess whether stroke thrombolysis could be feasibly and safely administered in our district general hospital., Design: From September 2004 through August 2005, eligible patients received rtPA treatment in the emergency department. The National Institutes of Health Stroke Scale (NIHSS) was administered at admission, immediately after treatment, and 24 hours later. In January 2006, a prospective follow-up assessed the NIHSS, Modified Rankin Scale (MRS) and Barthel Index Score (BIS) for all subjects still alive and collected data about those who had died., Results: In all, 553 patients were admitted for stroke: 306 had cerebral infarcts and 25 (8.1%) were treated by intravenous thrombolysis. The mean age of the patients who received thrombolysis was 67 years (range: 33-80), and the sex ratio was 4/1 (20 men and 5 women). Mean delay from symptom onset to treatment was 150 min (range 105-180). The median NIHSS score was 13 (range 8-22) at admission, 10 (range 0-22) after treatment, and 7 the next day (range 0-22). Two patients (8%) died during the acute phase. On January 2006, after a median follow-up of 11.6 months (range: 6-16), 18 (72%) patients were still alive: 13 (52%) with good outcomes (MRS, 0-1) and 3 severely disabled and institutionalized (BIS, 0-50)., Conclusion: Our results show that thrombolysis is possible in Pau. The population in our catchment area has a good proportion of stroke patients eligible for thrombolytic treatment. Outcomes and mortality rate are consistent with experience elsewhere. The creation of a stroke unit should help improve prognosis while complying with management guidelines.

Polarization holographic gratings in sp configuration are written at 488 nm in photorefractive organic-inorganic films based on SiO2. The films, prepared by a solgel technique, contain Disperse Red 1, carbazole units, and 2,4,7-trinitro-9-fluorenone. The gratings are characterized by their diffraction efficiency for a 632.8-nm probe. The polarization gratings act as a half-wave plate, and the diffraction efficiency is independent of the polarization direction of the probe.

Micro-Raman spectroscopy, combined with gas chromatography and ultra-violet fluorescence photography, was used to study some wall paintings in the S. Giovanni Evangelista Abbey in Parma, Italy. The restoration of some painted chapels enabled a comparison between two painters of the 16th century: Parmigianino (Girolamo Francesco Maria Mazzola, 1503-1540) and Michelangelo Anselmi (1492?-1556?). Micro-Raman spectroscopy determined the palette used by the artists, leading to the identification of different white, yellow, red, brown, green, blue and black pigments. Some pigments are evidence of later restorations. Gas chromatography combined with mass spectroscopy revealed the presence of organic binding media and enabled to distinguish between fresco and secco paintings.

Acute epiduritis is an uncommon disease especially in children. We report an unusual case of acute epiduritis in a child, revealed by characteristic clinical signs and Magnetic Resonance Imaging (MRI). Given the absence of identified infectious or tumoral cause, and the ineffectiveness of antimicrobial treatment, a therapeutic test with polyvalent immunoglobulins was implemented. Rapid clinical improvement led to the retrospective diagnosis of probable immunological acute epiduritis.

Objective: This study evaluated the diagnostic accuracy of high-spatial-resolution sonography in the diagnosis of occult fractures of the waist of the scaphoid., Subjects and Methods: Sonography of the scaphoid bone with a 12-MHz transducer was performed in 54 patients with clinically suspected scaphoid fracture and normal findings on initial radiographs, including specific scaphoid images. Three levels of clinical suspicion were considered: high (20%), moderate (30%), and low (50%). Attention was paid to the continuity of the scaphoid cortex and to the surrounding soft tissues (i.e., hemarthrosis or hematoma). Data from early sonograms were then compared with the results of radiography repeated 10-14 days after the initial trauma. In cases of persistent suspicion despite normal findings on follow-up radiographs, the presence of fracture was evaluated on CT (four patients), MR imaging (one patient), or bone scanning (one patient)., Results: Follow-up examinations proved fracture of the scaphoid waist in five patients. In all patients, diagnosis of fracture was suspected on initial sonograms showing cortical disruption associated with soft-tissue abnormalities. There was one false-positive finding and no false-negative results. Using cortical disruption as a diagnostic criterion, we found the sensitivity, specificity, and accuracy of high-resolution sonography for the depiction of scaphoid fracture to be 100%, 98%, and 98%, respectively. Using soft-tissue abnormalities alone as a criterion, we found the sensitivity, specificity, and accuracy of high-resolution sonography to be 100%, 65%, and 68%, respectively. The overall prevalence of occult fracture was 9%, ranging from 3.7% for low suspicion to 27% for high suspicion of fracture., Conclusion: High-resolution sonography is a reliable and accurate method of evaluating occult fractures of the scaphoid waist. Cortical disruption is the diagnostic key. Soft-tissue abnormalities alone lack specificity.

Intramedullary metastases from a non neurogenic cancer are relatively rare, representing approximately 1-2,1% of metastatic sites according to published autopsy reports. Their association with syrinx is extremely rare. Four cases have been described in the last 30 years. We report the case of a 60 year old female with past medical history of Peutz-Jeghers disease, who presented with clinical signs suggestive of medullary lesions of the cervical spine. MR imaging showed tumoral lesions at different levels associated with syrinx. Surgical biopsy confirmed the intramedullary lesions which, by pathology, were found to be of metastatic origin.

We report one case of traumatic rupture of the inferior vena cava. CT was performed during the acute phase and showed retroperitoneal hematoma near the inferior vena cava with extravasation of contrast agent. After stabilization angiography showed pseudo-aneurysmal picture of inferior vena cava.

The authors recall the anatomy of the deep neck spaces and report the case of a 3-year-old girl with a parapharyngeal abscess followed by a pseudo-aneurism of the carotide artery. Ultrasonography, CT scan and angiography findings are described. This case puts in mind of the seriousness of neck abscesses. Each specific anatomical location must be definite for a better therapeutic approach on account of hemorrhagic risks of parapharyngeal abscesses.

The authors report a case of a gastric involvement by a multiple myeloma, suspected on ultrasonography although the gastric endoscopy was normal. The barium examination and the CT scan agreed with the ultrasound hypothesis confirmed by histology.

The sonographic pattern of an intussusception in a 21 months old child is reported. The value and the meaning of this pattern is discussed according clinical and anatomical presentation of intussusception.

The authors describe the different imaging techniques and their interest. They discuss their etiology. The association with stenosis of the coeliac axis incites to think at a hemodynamic theory.

Carcinoid tumors of the rectum are rare and their radiologic visualization is exceptional. In the series we report about an incidental finding during double contrast enema which takes the form of an expanding tumor developing inside the intestinal lumen and showing no signs of malignity. Standard investigation in the follow up of rectal carcinoid tumors showed no hepatic mestastisis, no other foci in the digestive tract and no biologic anomalies. The patient did not complain of carcinoid syndrome. Double contrast enema is the only process enabling the discovery of rectal masses so small with non negligible frequency (2% of our explorations). Whatever the radiologic aspect and localization, fibroscopic and histologic examinations are necessary in order to make an accurate diagnosis of their nature.

The authors describe two personnel observations of ileal carcinoid tumors, demonstrated by double contrast small bowel examination. Confirmation came from operation and histology. Small bowel examination can demonstrate limited carcinoid tumors giving no angiographic traduction.

The authors study a case of nodular lymphoid hyperplasia, extending from the duodenal bulb to the rectum, associated to an agammaglobulinemia; they observe the variations of the roentgenology appearance and the distribution of the elementary pictures; they discuss the meaning of the disease, the association or the evolution to a lymphoid carcinoma.

Fifty seven patients (51 women and 6 men) undergoing cholecystectomy had ultra-sound evaluation on the 3rd, 5th, 7th and 9th post-operative days. In all the cases, the right upper quadrant has been observed correctly with a phased array 3.5 MHg transducer. Eleven of the fifty seven patients (19%) were found to have fluid collection in the gallbladder fossa. The collection has a rounded or an oval configuration, in the proportion of 11 and 55 mm, surrounded by an echogenic area. These fluid collections were of no clinical and biological significance and disappeared in 2 or 4 days time. The authors discuss the relationship between the presence of fluid and the use of drains or different surgical techniques.

Osteolysis of the distal clavicular shaft is an uncommon sequel to trauma. The clinical and radiological aspects are described. The pathogenesis and the early manifestations of osteolysis are discussed.