A Concerted Electrochemical and Theoretical Investigation of the Ag/TiO2 nano-heterojunction

Suitably designed nano-heterojunctions are able to enhance synergistic functionalities of different materials yielding to \u201cbrave new systems\u201d with innovative and sometimes unexpected physicochemical properties [1]. However, the complete understanding of these devices has to be deeply studied. In this work, a concerted theoretical and electrochemical investigation is proposed to gain insights into a metal-semiconductor interface, namely that created by the silver/anatase hybrid nanocomposite, a promising material for advanced sensing applications [2]. In particular, it provided the first photorenewable and anti-fouling sensor device, enhancing the analytical limits in terms of accuracy, sensitivity, detection limits, and photoactivity [3]. Furthermore, the hybrid material is proven to be extremely robust against aging, showing complete regeneration, also after one-year storage. The electrochemical/electroanalytical virtues of the Ag/TiO2 junction were evaluated in terms of current densities and reproducibility, providing their explanation at the atomic-scale level and demonstrating how and why the final device can act as silver-cation positive electrode [4]. Moreover, Cyclic Voltammetry and Electrochemical Impedance Spectroscopy were used in combination with periodic plane-wave DFT calculations, giving comparable qualitative but also quantitative results. In particular, we theoretically estimated the overall amount of electron transfer toward the semiconductor side of the interface at equilibrium and suitably designed electrochemical experiments, which strictly agree with the theoretical charge transfer estimates. Moreover, photoelectrochemical measurements and theoretical predictions show the unique permanent charge separation occurring in the device [4]. [1] A.V. Emeline, V.N. Kuznetsov, V.K. Ryabchuk, N. Serpone, Environ. Sci. Pollut. Res., 2012, 19, 3666\u20133675. [2] G. Soliveri, V. Pifferi, G. Panzarasa, S. Ardizzone, G. Cappelletti, D. Meroni, K. Sparnacci, L. Falciola, Analyst, 2015, 140, 1486\u20131494. [3] V. Pifferi, G. Soliveri, G. Panzarasa, G. Cappelletti, D. Meroni, L. Falciola, Anal. Bioanal. Chem., 2016, 408, 7339\u20137349. [4] G. Di Liberto, V. Pifferi, L. Lo Presti, M. Ceotto, L. Falciola, J. Phys. Chem. Lett., 2017, 8, 5372\u20135377

TrkB signaling directs the incorporation of newly generated periglomerular cells in the adult olfactory bulb.

In the adult rodent brain, the olfactory bulb (OB) is continuously supplied with new neurons which survival critically depends on their successful integration into pre-existing networks. Yet, the extracellular signals that determine the selection which neurons will be ultimately incorporated into these circuits are largely unknown. Here, we show that immature neurons express the catalytic form of the brain-derived neurotrophic factor receptor TrkB [full-length TrkB (TrkB-FL)] only after their arrival in the OB, at the time when inte-gration commences. To unravel the role of TrkB signaling in newborn neurons, we conditionally ablated TrkB-FL in mice via Cre expression in adult neural stem and progenitor cells. TrkB-deficient neurons displayed a marked impairment in dendritic arborization and spine growth. By selectively manipulating the signaling pathways initiated by TrkB in vivo, we identified the transducers Shc/PI3K to be required for dendritic growth, whereas the activation of phospholipase C-was found to be responsible for spine formation. Further-more, long-term genetic fate mapping revealed that TrkB deletion severely compromised the survival of new dopaminergic neurons, leading to a substantial reduction in the overall number of adult-generated periglomerular cells (PGCs), but not of granule cells (GCs). Surprisingly, this loss of dopaminergic PGCs was mirrored by a corresponding increase in the number of calretinin PGCs, suggesting that distinct subsets of adult-born PGCs may respond differentially to common extracellular signals. Thus, our results identify TrkB signaling to be essential for balancing the incorporation of defined classes of adult-born PGCs and not GCs, reflecting their different mode of integration in the OB. \ua9 2013 the authors

A Concerted Investigation For Metal/Semiconductor Nanointerface : Interlayer Charge Transfer At Ag/TiO2

In the field of hybrid materials, suitably designed nanoheterojunctions enhance synergistic functionalities and allow to obtain \u201cbrave new materials\u201d with physicochemical properties that are not simply the addition of the precursors\u2019 ones, but are completely new, different, and sometimes unexpected. For these reasons, the use of them has paved the way toward promising applications in many fields, such as electrocatalysis, photocatalysis, electroanalysis, and environmental chemistry, impacting on the everyday life [1]. However, research on such systems is most often dominated by trial and error procedures, while a deep atomistic understanding of the phenomena inside the junction region driving appropriate design of the final device is missing. Here, a concerted theoretical and electrochemical investigation is proposed to gain insights into the important class of heterojunctions made by metal-semiconductor interfaces. The presented case of study is the silver/anatase hybrid nanocomposite, a very promising material for advanced sensing applications [2]. Considering that in most cases titania semiconductors are useless in electroanalysis and silver is subject to fouling and oxidation/passivation, such broad outcomes were totally unexpected. Specifically, Ag/TiO2 interfase provided the first photorenewable sensor device, pushing the limits in terms of accuracy, sensitivity, detection limits, and photoactivity [3]. Despite the ongoing research, a quantitative and comprehensive understanding of the physics behind this nanocomposite is still missing, thus preventing its full exploitation and the extension of the same paradigm to other systems and devices. In particular, cyclic voltammetry and electrochemical impedance spectroscopy are used in combination with periodic plane-wave DFT calculations, giving comparable qualitative, but also quantitative results. We measure the exceptional electrochemical virtues of the Ag/TiO2 junction in terms of current densities and reproducibility, providing their explanation at the atomic-scale level and demonstrating how and why silver acts as a positive electrode [4]. We theoretically estimate the overall amount of electron transfer toward the semiconductor side of the interface at equilibrium and suitably designed electrochemical experiments strictly agree with the theoretical charge transfer estimates. Moreover, photoelectrochemical measurements and theoretical predictions show the unique permanent charge separation occurring in the device, possible because of the synergy of Ag and TiO2, which exploits in a favorable band alignment, in a smaller electron\u2013hole recombination rate and in a reduced carrier mobility when electrons cross the metal\u2013semiconductor interface. Finally, the hybrid material is proven to be extremely robust against aging, showing complete regeneration, even after one year [4]. [1] A.V. Emeline, V.N. Kuznetsov, V.K. Ryabchuk, N. Serpone, Environ. Sci. Pollut. Res. 19 (2012) 3666\u20133675. [2] G. Soliveri, V. Pifferi, G. Panzarasa, S. Ardizzone, G. Cappelletti, D. Meroni, K. Sparnacci, L. Falciola, Analyst 140 (2015) 1486\u20131494. [3] V. Pifferi, G. Soliveri, G. Panzarasa, G. Cappelletti, D. Meroni, L. Falciola, Anal. Bioanal. Chem. 408 (2016) 7339\u20137349. [4] G. Di Liberto, V. Pifferi, L. Lo Presti, M. Ceotto, and L. Falciola, J. Phys. Chem. Lett. 8 (2017) 5372\u20135377

Expression pattern of Stomatin-domain proteins in the peripheral olfactory system

Recent data show that Stomatin-like protein 3 (STOML3), a member of the stomatin-domain family, is expressed in the olfactory sensory neurons (OSNs) where it modulates both spontaneous and evoked action potential firing. The protein family is constituted by other 4 members (besides STOML3): STOM, STOML1, STOML2 and podocin. Interestingly, STOML3 with STOM and STOML1 are expressed in other peripheral sensory neurons: dorsal root ganglia. In here, they functionally interact and modulate the activity of the mechanosensitive Piezo channels and members of the ASIC family. Therefore, we investigated whether STOM and STOML1 are expressed together with STOML3 in the OSNs and whether they could interact. We found that all three are indeed expressed in ONSs, although STOML1 at very low level. STOM and STOML3 share a similar expression pattern and STOML3 is necessary for STOM to properly localize to OSN cilia. In addition, we extended our investigation to podocin and STOML2, and while the former is not expressed in the olfactory system, the latter showed a peculiar expression pattern in multiple cell types. In summary, we provided a first complete description of stomatin-domain protein family in the olfactory system, highlighting the precise compartmentalization, possible interactions and, finally, their functional implications

Au Nanoparticles Decorated Graphene-Based Hybrid Nanocomposite for As(III) Electroanalytical Detection

Electrochemical sensors integrating hybrid nanostructured platforms are a promising alternative to conventional detection techniques for addressing highly relevant challenges of heavy metal determination in the environment. Hybrid nanocomposites based on graphene derivatives and inorganic nanoparticles (NPs) are ideal candidates as active materials for detecting heavy metals, as they merge the relevant physico-chemical properties of both the components, finally leading to a rapid and sensitive current response. In this work, a hybrid nanocomposite formed of reduced graphene oxide (RGO) sheets, surface functionalized by π-π interactions with 1-pyrene carboxylic acid (PCA), and decorated in situ by Au NPs, was synthesized by using a colloidal route. The hybrid nanocomposite was characterized by cyclic voltammetry and electrochemical impedance spectroscopy with respect to the corresponding single components, both bare and deposited as a layer-by-layer junction onto the electrode. The results demonstrated the high electrochemical activity of the hybrid nanocomposite with respect to the single components, highlighting the crucial role of the nanostructured surface morphology of the electrode and the PCA coupling agent at the NPs-RGO interphase in enhancing the nanocomposite electroactivity. Finally, the Au NP-decorated PCA-RGO sheets were tested by anodic stripping voltammetry of As(III) ion—a particularly relevant analyte among heavy metal ions—in order to assess the sensing ability of the nanocomposite material with respect to its single components. The nanocomposite has been found to present a sensitivity higher than that characterizing the bare components, with LODs complying with the directives established by the U.S. EPA and in line with those reported for state-of-the-art electrochemical sensors based on other Au-graphene nanocomposites

Time-resolved single-photon detection module based on silicon photomultiplier: A novel building block for time-correlated measurement systems

We present the design and preliminary characterization of the first detection module based on Silicon Photomultiplier (SiPM) tailored for single-photon timing applications. The aim of this work is to demonstrate, thanks to the design of a suitable module, the possibility to easily exploit SiPM in many applications as an interesting detector featuring large active area, similarly to photomultipliers tubes, but keeping the advantages of solid state detectors (high quantum efficiency, low cost, compactness, robustness, low bias voltage, and insensitiveness to magnetic field). The module integrates a cooled SiPM with a total photosensitive area of 1 mm2 together with the suitable avalanche signal read-out circuit, the signal conditioning, the biasing electronics, and a Peltier cooler driver for thermal stabilization. It is able to extract the single-photon timing information with resolution better than 100 ps full-width at half maximum. We verified the effective stabilization in response to external thermal perturbations, thus proving the complete insensitivity of the module to environment temperature variations, which represents a fundamental parameter to profitably use the instrument for real-field applications. We also characterized the single-photon timing resolution, the background noise due to both primary dark count generation and afterpulsing, the single-photon detection efficiency, and the instrument response function shape. The proposed module can become a reliable and cost-effective building block for time-correlated single-photon counting instruments in applications requiring high collection capability of isotropic light and detection efficiency (e.g., fluorescence decay measurements or time-domain diffuse optics systems)

Functional expression of TMEM16A in taste bud cells

Key points: Taste transduction occurs in taste buds in the tongue epithelium. The Ca2+-activated Cl– channels TMEM16A and TMEM16B play relevant physiological roles in several sensory systems. Here, we report that TMEM16A, but not TMEM16B, is expressed in the apical part of taste buds. Large Ca2+-activated Cl− currents blocked by Ani-9, a selective inhibitor of TMEM16A, are measured in type I taste cells but not in type II or III taste cells. ATP indirectly activates Ca2+-activated Cl– currents in type I cells through TMEM16A channels. These results indicate that TMEM16A is functional in type I taste cells and contribute to understanding the largely unknown physiological roles of these cells. Abstract: The Ca2+-activated Cl– channels TMEM16A and TMEM16B have relevant roles in many physiological processes including neuronal excitability and regulation of Cl– homeostasis. Here, we examined the presence of Ca2+-activated Cl– channels in taste cells of mouse vallate papillae by using immunohistochemistry and electrophysiological recordings. By using immunohistochemistry we showed that only TMEM16A, and not TMEM16B, was expressed in taste bud cells where it largely co-localized with the inwardly rectifying K+ channel KNCJ1 in the apical part of type I cells. By using whole-cell patch-clamp recordings in isolated cells from taste buds, we measured an average current of −1083 pA at −100 mV in 1.5 μm Ca2+ and symmetrical Cl– in type I cells. Ion substitution experiments and blockage by Ani-9, a specific TMEM16A channel blocker, indicated that Ca2+ activated anionic currents through TMEM16A channels. We did not detect any Ca2+-activated Cl– currents in type II or III taste cells. ATP is released by type II cells in response to various tastants and reaches type I cells where it is hydrolysed by ecto-ATPases. Type I cells also express P2Y purinergic receptors and stimulation of type I cells with extracellular ATP produced large Ca2+-activated Cl− currents blocked by Ani-9, indicating a possible role of TMEM16A in ATP-mediated signalling. These results provide a definitive demonstration that TMEM16A-mediated currents are functional in type I taste cells and provide a foundation for future studies investigating physiological roles for these often-neglected taste cells

Post-processing of vis, nir, and swir multispectral images of paintings. New discovery on the the drunkenness of noah, painted by andrea sacchi, stored at palazzo chigi (ariccia, rome)

IR Reflectography applied to the identification of hidden details of paintings is extremely useful for authentication purposes and for revealing technical hidden features. Recently, multispectral imaging has replaced traditional imaging techniques thanks to the possibility to select specific spectral ranges bringing out interesting details of the paintings. VIS–NIR–SWIR images of one of the The Drunkenness of Noah versions painted by Andrea Sacchi, acquired with a modified reflex and InGaAs cameras, are presented in this research. Starting from multispectral images we performed post-processing analysis, using visible and infrared false-color images and principal component analysis (PCA) in order to highlight pentimenti and underdrawings. Radiography was performed in some areas to better investigate the inner pictorial layers. This study represents the first published scientific investigation of The Drunkenness of Noah’s artistic production, painted by Andrea Sacchi

Graphene Oxide-Based Hybrids for Chemiresistive VOCs Sensors

INTRODUCTION The sensing of gas molecules is of primary importance for environmental monitoring, control of chemical processes, medical applications, and so on1. In recent years, graphene-based gas sensors have attracted much attention due to enhanced graphene thermo-electric conductivity, surface area and mechanical strength. Thus, different structures have been developed and high sensing performances and room temperature working conditions were achieved1. However, they still suffer from several problems, which could be overcome by covering the graphene surface with metal oxide nanoparticles2. Furthermore, studies regarding the detection of Volatile Organic Compounds (VOCs) are still at the beginning1. Hence, the present work will be aimed at: i) optimizing the synthetic routes of ad hoc composite VOCs sensing materials (based on graphene oxide/SnO2 or ZnO hybrids) and their deep physico-chemical characterizations; ii) engineering the gas sensor device; and iii) evaluating the sensing performances at both high and mild temperatures (also exploiting the UV light) towards gaseous ethanol, acetone and ethylbenzene. EXPERIMENTAL/THEORETICAL STUDY Starting from pure graphite, graphene oxide (GO) powder was synthesized by adopting the Hummer\u2019s modified method2. The synthetic route was deeply investigated by modulating both the starting carbon material (powder or flakes graphite) and the concentration of the H2O2 (i.e. the quenching/oxidizing agent), thus tailoring the final GO surface/structural properties. Once optimized this step, SnO2 or ZnO were grown on its surface by a hydrothermal method, varying the starting salt precursor/GO weight ratio (ZnxGO or SnxGO, x = 4, 8, 16, 32). For comparison, pure SnO2 and ZnO (both commercial and home-made) were also tested. Several physico-chemical techniques have been used to characterize all the as-prepared nanopowders, such as XRPD, BET, Raman, FTIR, XPS, TEM and electrochemical analyses (CV and EIS). Subsequently, a homogeneous layer was deposited by spraying technique onto Pt-Interdigitated Electrodes (IDEs) starting from an ethanol suspension of each sample (2.5 mg mL-1). Then, gaseous ethanol, acetone and ethylbenzene (the more interesting one, being nowadays the less studied VOC) were sensed by using a Linkam Scientific stage, equipped with an electrochemical workstation for the chronoamperometric measurements. RESULTS AND DISCUSSION The effective synthesis of graphene oxide sheets and, subsequently, the growth of metal oxide nanoparticles on its surface were confirmed by exploiting different physico-chemical techniques. As concerns the VOCs sensing analyses, we obtained very promising results (in terms of both response/recovery time and sensibility down to ppb levels) for either pure and hybrid materials at 350\ub0C, and at lower temperatures (150\ub0C to RT, by exploiting UV light) for the graphene-based samples (Figure 1), thanks to the presence of the carbon material.Furthermore, a similar behavior has been noticed towards acetone and ethylbenzene pollutants. CONCLUSION Very promising results have been obtained with graphene oxide-based materials, which reveal to be more performing than the corresponding pure samples. Hence, these powders may represent very potential candidates for the gas sensing of highly toxic VOCs traces, both for environmental and medical diagnosis1 purposes