Effect of Interfacial SiOx Defects on the Functional Properties of Si-Transition Metal Oxide Photoanodes for Water Splitting.

The transfer of photogenerated charges through interfaces in heterojunction photoanodes is a key process that controls the efficiency of solar water splitting. Considering Co3O4/SiOx/Si photoanodes prepared by physical vapor deposition as a representative case study, it is shown that defects normally present in the native SiOx layer dramatically affect the onset of the photocurrent. Electron paramagnetic resonance indicates that the signal of defects located in dangling bonds of trivalent Si atoms at the Si/SiOx interface vanishes upon vacuum annealing at 850 °C. Correspondingly, the photovoltage of the photoanode increases to ≈500 mV. Similar results are obtained for NiO/SiOx/Si photoanodes. Photoelectrochemical analysis and impedance spectroscopy (in solution and in the solid state) indicate how the defect annealing modifies the Co3O4/SiOx/Si junction. This work shows that defect annealing at the solid-solid interface in composite photoanodes strongly improves the efficiency of charge transfer through interfaces, which is the basis for effective solar-to-chemical energy conversion.

Clinical and Socio-demographic Variables Associated with the Outcome of Vocational Rehabilitation Programs: A Community-Based Italian Study.

This study aims to identify clinical and socio-demographic variables associated with the outcome of vocational rehabilitation programs (VRPs). All users of an Italian Community Mental Health Centre (CMHC) included in VRPs delivered according to the model of Supported Employment in years 2011-2016 were retrospectively enrolled. Fifty users who ended the program with employment were compared with fifty users who dropped out, with respect to clinical and socio-demographic variables. VRPs lasting less than 6 months and oriented toward the competitive labor market had a higher probability of employment. Among users who successfully ended the VRP, the median of health interventions significantly decreased after employment. In the same group of users, less non-health interventions strictly linked to the VRP were required, when compared with users who dropped out. We conclude that employment is associated with improvement of users' clinical conditions and reduced workload for the CMHC.

Polarization dependence of second harmonic generation from plasmonic nanoprism arrays.

The second order nonlinear optical response of gold nanoprisms arrays is investigated by means of second harmonic generation (SHG) experiments and simulations. The polarization dependence of the nonlinear response exhibits a 6-fold symmetry, attributed to the local field enhancement through the excitation of the surface plasmon resonances in bow-tie nanoantennas forming the arrays. Experiments show that for polarization of the input light producing excitation of the plasmonic resonances in the bow-tie nanoantennas, the SHG signal is enhanced; this despite the fact that the linear absorption spectrum is not dependent on polarization. The results are confirmed by electrodynamic simulations which demonstrate that SHG is also determined by the local field distribution in the nanoarrays. Moreover, the maximum of SHG intensity is observed at slightly off-resonance excitation, as implemented in the experiments, showing a close relation between the polarization dependence and the structure of the material, additionally revealing the importance of the presence of non-normal electric field components as under focused beam and oblique illumination.

Real-time cellular impedance monitoring and imaging of biological barriers in a dual-flow membrane bioreactor.

The generation of physiologically relevant in-vitro models of biological barriers can play a key role in understanding human diseases and in the development of more predictive methods for assessing toxicity and drug or nutrient absorption. Here, we present an advanced cell culture system able to mimic the dynamic environment of biological barriers while monitoring cell behaviour through real-time impedance measurements and imaging. It consists of a fluidic device with an apical and a basal flow compartment separated by a semi-permeable membrane. The main features of the device are the integration of sensing through transepithelial electrical impedance (TEEI) measurements and transparent windows for optical monitoring within a dual flow system. Caco-2 cells were cultured in the TEEI bioreactor under both flow and static conditions. Although no differences in the expression of peripheral actin and occludin were visible, the cells in dynamic conditions developed higher impedance values at low frequencies, indicative of a higher paracellular electrical impedance with respect to the static cultures. TEEI measurements at high frequency also enabled monitoring monolayer formation, which can be correlated with the observation of an RC behaviour in the impedance spectra. In particular, the cells subject to flow showed accelerated barrier formation and increased vitality with respect to the static controls, again highlighting the importance of dynamic conditions for epithelial cells.

Interplay between magnetic anisotropies in CoAu and Co films and antidot arrays: effects on the spin configuration and hysteretic behavior.

We studied (i) a set of three Co : Au continuous films, grown by sputtering co-deposition (∼80 nm thick) with concentration ratios of 2 : 1, 1 : 1 and 1 : 0 (i.e., a pure Co film was also included), and (ii) a corresponding set of antidot arrays, produced by nanosphere lithography with the same hexagonal pattern (nominal lattice periodicity ∼520 nm). The samples were investigated by atomic and magnetic force microscopy and SQUID magnetometry. A twofold aim was fulfilled: to gain information on the magnetism of the CoAu compound (saturation magnetization, effective in-plane and out-of-plane anisotropy, exchange stiffness constant and magnetostrictive behavior) and to compare the magnetic behavior of the continuous and patterned samples. The continuous films exhibited a variety of hysteretic behaviours and magnetic configurations, ruled by the interplay between different magnetic anisotropy terms (magnetocrystalline, magnetoelastic and shape). The Co1Au1 film was anisotropic in the plane, whereas Co2Au1 and Co were isotropic and had an out-of-plane magnetization component; stripe domains were observed in Co2Au1, resulting in a transcritical hysteresis loop. A key role in determining these properties was ascribed to the magnetoelastic anisotropy term. Unlike the continuous films, the antidot arrays showed a similar hysteretic behavior and important similarities in the spin configuration were pointed out, despite the different compositions. We argue, also based on micromagnetic simulations, that this occurred because the nanopatterning enabled a local modification of the shape anisotropy, thus smoothing out the differences observed in the continuous films.

Indicators of Complex Care During the Consultation-Liaison Psychiatry Activity at the Transplant Center of the Policlinico Hospital, Modena.

OBJECTIVE: The objective of this study was to identify possible biopsychosocial predictors of organizational complexity in patients referred to the consultant psychiatrist for assessment before liver transplantation. METHODS: This was a case-control study. All psychiatric consultations performed before and after liver transplantation from January 1, 2008 to December 31, 2013 were included. Complexity was operationalized as "undergoing two or more psychiatric consultations". Controls were defined as patients who were assessed only once by the consultant. Cases were represented by patients who underwent two or more consultations. Statistical analysis was performed with STATA 13.1, using logistic regressions. RESULTS: In this study, 515 consultations were requested for 309 patients potentially eligible for liver transplantation. Controls were 209 (67.6%); cases were 100 (32.4%). Positive psychiatric history (odds ratio [OR] = 2.44; 95% confidence interval [CI], 1.43-4.16), viral or toxic (alcohol- or drug-related) liver disease (OR = 1.93; 95% CI, 1.09-3.42), use of psychotropic medications at the baseline (OR = 2.15; 95% CI, 1.14-4.07), and female gender (OR = 1.77; 95% CI, 1.01-3.11) were significantly associated with an increased probability of being cases. CONCLUSIONS: Positive psychiatric history, viral or toxic liver disease, use of psychotropic medications at the index referral, and female gender are possible biopsychosocial predictors of complexity in patients eligible for liver transplantation.

Occupational health physicians and the impact of the Great Recession on the health of workers: a qualitative study.

BACKGROUND: Italy is one of the Eurozone members where the 2008 "Great Recession" struck worst, with a 9% drop in national GDP between 2008 and 2013. The negative effects of the recession on the health of the Italian population were documented on a nation-wide level. However, few local or regional studies are currently available in the scientific literature. OBJECTIVES: To assess the impact on workers' health of the economic recession in the industrial area of Sassuolo (Modena, Northern Italy), and to provide recommendations for targeted interventions. METHODS: Two focus groups were conducted, involving 8 occupational health physicians (OHPs) active in the area. Rough descriptions were analyzed using MAXQDA 11, according to the principles of grounded theory. RESULTS: 261 segments were coded, divided into four areas. The first, "changes in contemporary world", pointed out that the recession may have just made pre-existing problems worse, accelerating reductions in staff and workers' benefits. The second, "social area", highlighted a decrease in vertical social capital and the beginning of new trends in emigration. The third, "work area", covered workers' fear of losing their jobs if they were ill and a reduction in horizontal social capital, namely difficult relations between co-workers. The fourth, "medical area", indicated a general worsening of workers' health in the Sassuolo ceramic district compared to previous years. The OHPs reported an increase in muscular-skeletal complaints, gastritis, tension-type headache, irritable bowel syndrome symptoms, back pain, panic attacks, insomnia, tachycardia, and other medically unexplained symptoms. Anxiety problems seemed to prevail over depressive manifestations. An increase was reported for antidepressants and benzodiazepines consumption. CONCLUSIONS: The local impact of the economic crisis on health was mainly negative, consistent with available national data. Mental health professionals could work together with OHPs, e.g., through Balint Group-like meetings, to develop targeted psychosocial and clinical interventions addressing the medical, psychological and social needs of workers, also involving advocacy and fostering workers' empowerment.

HisTOOLogy: an open-source tool for quantitative analysis of histological sections.

HisTOOLogy is an open-source software for the quantification of digital colour images of histological sections. The simple graphical user interface enables both expert and non-expert users to rapidly extract useful information from stained tissue sections. The software's main feature is a generalizable colour separation algorithm based on k-means clustering which accurately and reproducibly returns the amount of colour per unit area for any stain, thus allowing the quantification of tissue components. Here we describe HisTOOLogy's algorithms and graphical user interface structure, showing how it can be used to separate different dye colours in several classical stains. In addition, to demonstrate how the tool can be employed to obtain quantitative information on biological tissues, the effect of different hepatic tissue decellularization protocols on cell removal and matrix preservation was assessed through image analysis using HisTOOLogy and compared with conventional DNA and total protein content assays. HisTOOLogy's performance was also compared with ImageJ's colour deconvolution plug-in, demonstrating its advantages in terms of ease of use and speed of colour separation.

The nano-epsilon dot method for strain rate viscoelastic characterisation of soft biomaterials by spherical nano-indentation.

Nano-indentation is widely used for probing the micromechanical properties of materials. Based on the indentation of surfaces using probes with a well-defined geometry, the elastic and viscoelastic constants of materials can be determined by relating indenter geometry and measured load and displacement to parameters which represent stress and deformation. Here we describe a method to derive the viscoelastic properties of soft hydrated materials at the micro-scale using constant strain rates and stress-free initial conditions. Using a new self-consistent definition of indentation stress and strain and corresponding unique depth-independent expression for indentation strain rate, the epsilon dot method, which is suitable for bulk compression testing, is transformed to nano-indentation. We demonstrate how two materials can be tested with a displacement controlled commercial nano-indentor using the nano-espilon dot method (nano-ε̇M) to give values of instantaneous and equilibrium elastic moduli and time constants with high precision. As samples are tested in stress-free initial conditions, the nano-ε̇M could be useful for characterising the micro-mechanical behaviour of soft materials such as hydrogels and biological tissues at cell length scales.

Profile analysis of hepatic porcine and murine brain tissue slices obtained with a vibratome.

This study is aimed at characterizing soft tissue slices using a vibratome. In particular, the effect of two sectioning parameters (i.e., step size and sectioning speed) on resultant slice thickness was investigated for fresh porcine liver as well as for paraformaldehyde-fixed (PFA-fixed) and fresh murine brain. A simple framework for embedding, sectioning and imaging the slices was established to derive their thickness, which was evaluated through a purposely developed graphical user interface. Sectioning speed and step size had little effect on the thickness of fresh liver slices. Conversely, the thickness of PFA-fixed murine brain slices was found to be dependent on the step size, but not on the sectioning speed. In view of these results, fresh brain tissue was sliced varying the step size only, which was found to have a significant effect on resultant slice thickness. Although precision-cut slices (i.e., with regular thickness) were obtained for all the tissues, slice accuracy (defined as the match between the nominal step size chosen and the actual slice thickness obtained) was found to increase with tissue stiffness from fresh liver to PFA-fixed brain. This quantitative investigation can be very helpful for establishing the most suitable slicing setup for a given tissue.

Viscoelastic characterisation of pig liver in unconfined compression.

Understanding and modelling liver biomechanics represents a significant challenge due to the complex nature of this organ. Unfortunately, there is no consensus on liver viscoelastic properties, and results are strongly dependent on sample type and status, adopted testing method, and testing conditions. Standard force-triggered tests (e.g. step response or dynamic mechanical tests) necessitate an initial contact between sample and testing apparatus, which may result in significant pre-stress to very soft and highly hydrated samples. In a previous study we proposed the epsilon dot method (ε̇M): a testing and analysis framework to address the drawbacks of standard mechanical tests. Focusing on ex-vivo unconfined bulk compressive tests, here we use both the ε̇M and dynamic mechanical analysis (DMA) to derive liver viscoelastic parameters in the region of small strains or the linear viscoelastic region (LVR). As liver samples were visibly deteriorated at the end of frequency sweep tests, a modified approach was adopted to reduce DMA testing times. This approach, termed step-reconstructed DMA (SRDMA), is based on dynamic measurements around specific frequencies and then reconstruction of liver behaviour in the entire frequency range of interest. The instantaneous elastic modulus obtained from SRDMA tests (2.65 ± 0.30 kPa) was significantly higher than that obtained with the ε̇M (2.04 ± 0.01 kPa). We show that the overestimation of stiffness is due to data acquisition in a local rather than an absolute LVR, highlighting the importance of using a rapid and zero pre-stress approach to characterise very soft and highly hydrated biological tissues.

Mechanostructure and composition of highly reproducible decellularized liver matrices.

Despite the increasing number of papers on decellularized scaffolds, there is little consensus on the optimum method of decellularizing biological tissue such that the micro-architecture and protein content of the matrix are conserved as far as possible. Focusing on the liver, the aim of this study was therefore to develop a method for the production of well-characterized and reproducible matrices that best preserves the structure and composition of the native extra cellular matrix (ECM). Given the importance of matrix stiffness in regulating cell response, the mechanical properties of the decellularized tissue were also considered. The testing and analysis framework is based on the characterization of decellularized and untreated samples in the same reproducible initial state (i.e., the equilibrium swollen state). Decellularized ECM (dECM) were characterized using biochemical, histological, mechanical and structural analyses to identify the best procedure to ensure complete cell removal while preserving most of the native ECM structure and composition. Using this method, sterile decellularized porcine ECM with highly conserved intra-lobular micro-structure and protein content were obtained in a consistent and reproducible manner using the equilibrium swollen state of tissue or matrix as a reference. A significant reduction in the compressive elastic modulus was observed for liver dECM with respect to native tissue, suggesting a re-examination of design parameters for ECM-mimicking scaffolds for engineering tissues in vitro.

Strain rate viscoelastic analysis of soft and highly hydrated biomaterials.

Measuring the viscoelastic behavior of highly hydrated biological materials is challenging because of their intrinsic softness and labile nature. In these materials, it is difficult to avoid prestress and therefore to establish precise initial stress and strain conditions for lumped parameter estimation using creep or stress-relaxation (SR) tests. We describe a method ( ɛ˙M or epsilon dot method) for deriving the viscoelastic parameters of soft hydrated biomaterials which avoids prestress and can be used to rapidly test degradable samples. Standard mechanical tests are first performed compressing samples using different strain rates. The dataset obtained is then analyzed to mathematically derive the material's viscoelastic parameters. In this work a stable elastomer, polydimethylsiloxane, and a labile hydrogel, gelatin, were first tested using the ɛ˙M, in parallel SR was used to compare lumped parameter estimation. After demonstrating that the elastic parameters are equivalent and that the estimation of short-time constants is more precise using the proposed method, the viscoelastic behavior of porcine liver was investigated using this approach. The results show that the constitutive parameters of hepatic tissue can be quickly quantified without the application of any prestress and before the onset of time-dependent degradation phenomena.

Bone scaffolds with homogeneous and discrete gradient mechanical properties.

Bone TE uses a scaffold either to induce bone formation from surrounding tissue or to act as a carrier or template for implanted bone cells or other agents. We prepared different bone tissue constructs based on collagen, gelatin and hydroxyapatite using genipin as cross-linking agent. The fabricated construct did not present a release neither of collagen neither of genipin over its toxic level in the surrounding aqueous environment. Each scaffold has been mechanically characterized with compression, swelling and creep tests, and their respective viscoelastic mechanical models were derived. Mechanical characterization showed a practically elastic behavior of all samples and that compressive elastic modulus basically increases as content of HA increases, and it is strongly dependent on porosity and water content. Moreover, by considering that gradients in cellular and extracellular architecture as well as in mechanical properties are readily apparent in native tissues, we developed discrete functionally graded scaffolds (discrete FGSs) in order to mimic the graded structure of bone tissue. These new structures were mechanically characterized showing a marked anisotropy as the native bone tissue. Results obtained have shown FGSs could represent valid bone substitutes.

Local-field enhancement effect on the nonlinear optical response of gold-silver nanoplanets.

We report on the nonlinear optical properties of Au-Ag nanoplanets produced by ion implantation and irradiation in silica, experimentally investigated by means of the single beam z-scan technique. The measurements provided experimental evidence of the intense local-field enhancement effect theoretically demonstrated for these plasmonic nanosystems. In particular, this has a dramatic impact on their nonlinear absorption behavior and results in a tunable changeover from reverse saturable absorption to saturable absorption by slightly varying the pump intensity and in the possibility to activate and observe nonlinear phenomena of the electron dynamics otherwise unaccessible in the intensity range that can be employed to study these materials. Finally, for the nanoplanet configuration we found a dramatic decrease of the intensity-dependent absorption coefficient, which could be very promising for obtaining optical gain materials.

Gene expression profile of human colon cancer cells treated with cross-reacting material 197, a diphtheria toxin non-toxic mutant.

Cross-Reacting Material 197 (CRM197) is a diphtheria toxin non-toxic mutant that has shown antitumor activity in mice and humans. It is still unclear whether this anti-tumorigenic effect depends on its strong inflammatory-immunological property, its ability to inhibit heparin-binding epidermal growth factor (HB-EGF), or even its possible weak toxicity. CRM197 is utilized as a specific inhibitor of HB-EGF that competes for the epidermal growth factor receptor (EGFR), overexpressed in colorectal cancer and implicated in its progression. In this study we evaluate the effects of CRM197 on HT-29 human colon cancer cell line behaviour and, for CRM197 recognized ability to inhibit HB-EGF, its possible influence on EGFR activation. In particular, while HT-29 does not show any reduction of viability after CRM197 treatment (MTT modified assay), or changes in cell cycle distribution (flow cytometry), in EGFR localization, phospho-EGFR detected signals (immunohistochemistry) or in morphology (scanning electron microscopy, SEM) they show a change in the gene expression profile by microarray analysis (cDNA microarray SS-H19k8). The overexpression of genes like protein phosphatase 2, catalytic subunit, alpha isozyme (PPP2CA), guanine nucleotide-binding protein G subunit alpha-1(GNAI1) and butyrophilin, subfamily 2, member A1 (BTN2A1) has been confirmed with real-time-qPCR. This is the first study where the CRM197 treatment on HT-29 shows a possible scarce implication of endogenous HB-EGF on EGFR expression and cancer cell development. At the same time, our results show the alteration of a specific and selected number of genes.

Stability of extreme ultraviolet multilayer coatings to low energy proton bombardment.

In this work we present results of an new experiment related to low energy protons bombardments on nano-structured optical coatings. Multilayer structures protected by different capping layers have been fabricated and exposed to low energy protons (1 keV). The experimental parameters have been selected considering the potential application of the coatings to solar mission instrumentation. Future solar missions will investigate the Sun from very close distances and optical components are constantly exposed to low energy ion particles irradiation. The experiment was repeated fixing the proton flux while varying the total dose accumulated. Results show that physical processes occurred at the uppermost interfaces can strongly damage the structure.

Coupling between magnetic and optical properties of stable Au-Fe solid solution nanoparticles.

Au-Fe nanoparticles constitute one of the simplest prototypes of a multifunctional nanomaterial that can exhibit both magnetic and optical (plasmonic) properties. This solid solution, not feasible in the bulk phase diagram in thermal equilibrium, can be formed as a nanostructure by out-of-equilibrium processes. Here, the novel magnetic, optical and magneto-optical properties of ion-implanted Au-Fe solid solution nanoparticles dispersed in a SiO(2) matrix are investigated and correlated. The surface plasmon resonance of the Au-Fe nanoparticles with almost equicomposition is strongly damped when compared to pure Au and to Au-rich Au-Fe nanoparticles. In all cases, the Au atoms are magnetically polarized, as measured by x-ray magnetic circular dichroism, and ferromagnetically coupled with Fe atoms. Although the chemical stability of Au-Fe nanoparticles is larger than that of Fe nanoparticles, both the magnetic moment per Fe atom and the order temperature are smaller. These results suggest that electronic and magnetic properties are more influenced by the hybridization of the electronic bands in the Au-Fe solid solution than by size effects. On the other hand, the magneto-optical transitions allowed in the vis-nIR spectral regions are very similar. In addition, we also observe, after studying the properties of thermally treated samples, that the Au-Fe alloy is stabilized, not by surface effects, but by the combination of the out-of-equilibrium nature of the ion implantation technique and by changes in the properties due to size effects.

Tunable, directional and wavelength selective plasmonic nanoantenna arrays.

Linear arrays of noble metal nanoparticles, supporting Bragg plasmonic resonances, are proposed as optical nanoantennae. Electrodynamic calculations show that tunable, directional and wavelength selective emission enhancement is obtained throughout the visible and near-infrared spectrum by varying the dielectric environment and the array geometrical parameters, and thus tuning the Bragg modes. Large quantum efficiency enhancements are possible even in the case of poor emitters (1% intrinsic efficiency), spanning wavelengths that are relevant in lighting (lambda approximately equal 400 nm) and telecommunication (lambda approximately equal 1.5 microm) applications. Nanoantenna array angular emission is highly directional and extremely sensitive to the array geometrical parameters and the dielectric environment.

Au and NiO nanocrystals doped into porous sol-gel SiO(2) films and the effect on optical CO detection.

Thin-film composites comprised of NiO and NiO/Au nanoparticles in a porous SiO(2) matrix have been prepared using the sol-gel technique. When at elevated temperatures (200 °C< T<350 °C) and exposed to carbon monoxide, the films undergo reversible changes in optical transmittance at wavelengths in the visible-near IR region. For NiO composite films heated at 330 °C and exposed to 1% CO in air, there is an increase in transmittance which approaches 2-4% over most of the visible range. For NiO/Au composite films the transmittance increase exhibits a wavelength dependence, with a maximum change which is close to 6% at λ≈630 nm and which is close to zero in the Au plasmon resonance range (λ≈550 nm).