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Nanocrystalline TiO[sub 2] has been obtained by a sol-gel process by controlling the crystal size through the water/alkoxide ratio. Raman spectra of anatase nanocrystals with average sizes of 9.5–13.4 nm are reported and the correlation between the Raman band shape (peak position and linewidth) of the main feature at 144 cm[sup -1] and the crystals dimension is discussed. While in this system a minor role is played by nonstoichiometry and pressure effects, a model based on the phonon confinement, which takes into account the size distribution as determined by the transmission electron microscopy images, correctly reproduces the Raman band shape change. © 1998 American Institute of Physics. [ABSTRACT FROM AUTHOR]

The crystal chemistry of a natural, gem-quality, blue-grey Zn-rich spinel crystal from Jemaa, Kaduna State, Nigeria, was studied using electron microprobe, single-crystal X-ray diffraction, optical absorption and Raman spectroscopies. The composition of the crystal approaches the gahnite endmember (ZnAl2O4), ∼94 mol.%, with the remainder being dominated by a hercynite component (FeAl2O4). The unit-cell dimension is 8.0850(3) Å and the tetrahedral and octahedral bond distances are determined as T-O 1.9485(6) Å and M-O 1.9137(3) Å . Crystal chemical analysis resulted in the empirical structural formula T(Zn0.94Fe2+0.03Al0.03)M(Al1.96Fe2+0.03Fe3+0.0.1)O4, which shows Zn and Al almost fully ordered in the tetrahedrally and octahedrally coordinated T and M sites, respectively. Raman spectra obtained using the excitation of the blue 473.1 nm line of a Nd:YAG laser display three of the five Raman-active modes predicted for the general oxide spinel group of minerals. These are the Eg mode at 420.6 cm-1 and the T2g modes at 510 cm-1 and 661 cm-1, due to vibrations in the AlO6 octahedra. Optical absorption spectra recorded in the UV/VIS-NIR-MIR range 2000-29000 cm-1 show a dominant absorption band at ∼5000 cm-1 which is caused by spin-allowed electronic d-d transitions in Fe2+ located at the T sites. The blue-grey hue exhibited by the sample is mainly due to spin-forbidden electronic transitions in TFe2+ and to MFe2+ → MFe3+ intervalence charge transfer, and the poor saturation of the colour is due to the small concentration of Fe2+ and Fe3+. [ABSTRACT FROM AUTHOR]

Abstract: Photoinduced dichroism measurements have been performed in hybrid silica-based sol–gel films containing Carbazole units, 2,4,7-trinitro-9-fluorenone (TNF) and Disperse Red 1 (DR1) at different concentrations. The dynamics of the parallel and perpendicular absorbances gives information on the azo-dye orientation under illumination and suggests that the dominant mechanism for the photoinduced anisotropy is the angular redistribution of the DR1 trans-molecules. Recording, storage and erasure, have been demonstrated for writing and reading light at 488nm. [Copyright &y& Elsevier]

Photorefractive gratings have been obtained with 632.8 nm writing beams in organic–inorganic SiO2-based films. The hybrid glass is prepared by a sol–gel technique, starting from organic Si precursors, and contains Disperse Red 1 (DR1), carbazole units and 2,4,7-trinitro-9-fluorenone (TNF). The photorefractive gain, which has been found unexpectedly even without poling field, has been determined through an asymmetric energy exchange by two-beam coupling measurements. The effects of the polarization of the writing beams and of a circularly polarized photoisomerizing radiation during the erasure of the grating have been interpreted in terms of an orientational contribution to the grating formation. [Copyright &y& Elsevier]

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. [Copyright &y& Elsevier]

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.)