Reduced graphene oxide-ZnO hybrid composites as photocatalysts: The role of nature of the molecular target in catalytic performance

Spurred by controversial literature findings, we enwrapped reduced graphene oxide (rGO) in ZnO hierarchical microstructures (rGO loadings spanning from 0.01 to 2 wt%) using an in situ synthetic procedure. The obtained hybrid composites were carefully characterized, aiming at shining light on the possible role of rGO on the claimed increased performance as photocatalysts. Several characterization tools were exploited to unveil the effect exerted by rGO, including steady state and time resolved photoluminescence, electron microscopies and electrochemical techniques, in order to evaluate the physical, optical and electrical features involved in determining the catalytic degradation of rhodamine B and phenol in water.Several properties of native ZnO structures were found changed upon the rGO enwrapping (including optical absorbance, concentration of native defects in the ZnO matrix and double-layer capacitance), which are all involved in determining the photocatalytic performance of the hybrid composites. The findings discussed in the present work highlight the high complexity of the field of application of graphene-derivatives as supporters of semiconducting metal oxides functionality, which has to be analyzed through a multi-parametric approach.     

Feasibility of glioblastoma tissue response mapping with physiologic BOLD imaging using precise oxygen and carbon dioxide challenge

Magnetic Resonance Materials in Physics, Biology and Medicine - Innovative physiologic MRI development focuses on depiction of heterogenous vascular and metabolic features in glioblastoma. For this...     

Solution‐Processed GaSe Nanoflake‐Based Films for Photoelectrochemical Water Splitting and Photoelectrochemical‐Type Photodetectors

Gallium selenide (GaSe) is a layered compound, which has been exploited in nonlinear optical applications and photodetectors due to its anisotropic structure and pseudodirect optical gap. Theoretical studies predict that its 2D form is a potential photocatalyst for water splitting reactions. Herein, the photoelectrochemical (PEC) characterization of GaSe nanoflakes (single‐/few‐layer flakes), produced via liquid phase exfoliation, for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in both acidic and alkaline media is reported. In 0.5 m H₂SO₄, the GaSe photoelectrodes display the best PEC performance, corresponding to a ratiometric power‐saved metric for HER (Φ_saved,HER) of 0.09% and a ratiometric power‐saved metric for OER (Φ_saved,OER) of 0.25%. When used as PEC‐type photodetectors, GaSe photoelectrodes show a responsivity of ≈0.16 A W^?1 upon 455 nm illumination at a light intensity of 63.5 µW cm^?2 and applied potential of ?0.3 V versus reversible hydrogen electrode (RHE). Stability tests of GaSe photodetectors demonstrated a durable operation over tens of cathodic linear sweep voltammetry scans in 0.5 m H₂SO₄ for HER. In contrast, degradation of photoelectrodes occurred in both alkaline and anodic operation due to the highly oxidizing environment and O₂‐induced (photo)oxidation effects. The results provide new insight into the PEC properties of GaSe nanoflakes for their exploitation in photoelectrocatalysis, PEC‐type photodetectors, and (bio)sensors.     

Size‐Optimized Ultrasmall Porous Silica Nanoparticles Depict Vasculature‐Based Differential Targeting in Triple Negative Breast Cancer

Rapid sequestration and prolonged retention of intravenously injected nanoparticles by the liver and spleen (reticuloendothelial system (RES)) presents a major barrier to effective delivery to the target site and hampers clinical translation of nanomedicine. Inspired by biological macromolecular drugs, synthesis of ultrasmall (diameter ≈12–15 nm) porous silica nanoparticles (UPSNs), capable of prolonged plasma half‐life, attenuated RES sequestration, and accelerated hepatobiliary clearance, is reported. The study further investigates the effect of tumor vascularization on uptake and retention of UPSNs in two mouse models of triple negative breast cancer with distinctly different microenvironments. A semimechanistic mathematical model is developed to gain mechanistic insights into the interactions between the UPSNs and the biological entities of interest, specifically the RES. Despite similar systemic pharmacokinetic profiles, UPSNs demonstrate strikingly different tumor responses in the two models. Histopathology confirms the differences in vasculature and stromal status of the two models, and corresponding differences in the microscopic distribution of UPSNs within the tumors. The studies demonstrate the successful application of multidisciplinary and complementary approaches, based on laboratory experimentation and mathematical modeling, to concurrently design optimized nanomaterials, and investigate their complex biological interactions, in order to drive innovation and translation.     

Enhancement of the Magnetic Coupling in Exfoliated CrCl3 Crystals Observed by Low-Temperature Magnetic Force Microscopy and X-ray Magnetic Circular Dichroism

Magnetic crystals formed by 2D layers interacting by weak van der Waals forces are currently a hot research topic. When these crystals are thinned to nanometric size, they can manifest strikingly different magnetic behavior compared to the bulk form. This can be the result of, for example, quantum electronic confinement effects, the presence of defects, or pinning of the crystallographic structure in metastable phases induced by the exfoliation process. In this work, an investigation of the magnetism of micromechanically cleaved CrCl₃ flakes with thickness >10 nm is performed. These flakes are characterized by superconducting quantum interference device magnetometry, surface-sensitive X-ray magnetic circular dichroism, and spatially resolved magnetic force microscopy. The results highlight an enhancement of the CrCl₃ antiferromagnetic interlayer interaction that appears to be independent of the flake size when the thickness is tens of nanometers. The estimated exchange field is 9 kOe, representing an increase of ≈900% compared to the one of the bulk crystals. This effect can be attributed to the pinning of the high-temperature monoclinic structure, as recently suggested by polarized Raman spectroscopy investigations in thin (8–35 nm) CrCl₃ flakes.     

Trends and interactions of physical and bio-geo-chemical features in the Adriatic Sea as derived from satellite observations

Time series of satellite data, generated by the AVHRR (1981-1999), CZCS (1979-1985) and SeaWiFS (1998-2002), have been used to assess trends and interactions of physical and bio-geo-chemical features in the Adriatic Sea. The images were processed to estimate Sea Surface Temperature (SST) and Chlorophyll-like Pigment Concentration (CPC). Long-term composites and climatologies were derived, using fixed geographical grids and projections. The AVHRR data show an apparent warming trend, when plotting the sequence of seasonal cycles (monthly mean SST, averaged over the whole basin) against time, due to a steady rise of summer values. Considering 3 regions (north, central and south), split into east and west sections, the northern Adriatic shows high SST fluctuations (possibly associated with the cycle of winter cooling and summer warming, typical of the relatively shallow sub-basin), while the southern Adriatic exhibits a lower variability (possibly influenced by the periodic water incoming from, and outflowing to the Ionian Sea). During summer, an east-west gradient prevails, while during winter only a general north-south gradient can be found. The SeaWiFS-derived CPC values, distributions and trends appear to be consistent with the historical CZCS record. Persistent differences in the quantitative assessment of CPC for coastal waters is due to the use of improved algorithms, less influenced by the presence of dissolved organics and suspended sediments in the water column, for the processing of SeaWiFS data. Apparent incongruities of the space and time patterns in the SeaWiFS record with respect to the reference climatology, obtained by CZCS more than a decade before, occur chiefly when considering the spring bloom in the southern Adriatic and the summer development of the north Adriatic front. The comparison of the long-term times series of satellite data shows that there is a high correlation between patterns in the thermal field and in the colour field. This suggests that different surface waters, identified by the SST index, are also traced by different ecological features, identified by the CPC index. Both indices also show a high correlation with the classical cyclonic circulation scheme of the Adriatic Sea, proposing once again an intimate relationship between the water dynamics and its bio-geo-chemistry.     

Neuroblastoma cells displacement by magnetic carbon nanotubes

In this paper, as-produced multiwall carbon nanotubes (MWNTs) have been analyzed by scanning electron microscopy and energy dispersive X-ray spectrometry, revealing the presence of Fe, Al, and Zn residuals and impurities. MWNTs have then been dispersed in Pluronic F127 aqueous solution and used to seed neuroblastoma cell lines (HN9.10e and SH-SY5Y) for three days. We found that MWNTs interact with cells and induce, under a permanent constant magnetic field, the cell displacement toward the magnetic source.     

High-yield production of graphene by liquid-phase exfoliation of graphite

Fully exploiting the properties of graphene will require a method for the mass production of this remarkable material. Two main routes are possible: large-scale growth or large-scale exfoliation. Here, we demonstrate graphene dispersions with concentrations up to approximately 0.01 mg ml(-1), produced by dispersion and exfoliation of graphite in organic solvents such as N-methyl-pyrrolidone. This is possible because the energy required to exfoliate graphene is balanced by the solvent-graphene interaction for solvents whose surface energies match that of graphene. We confirm the presence of individual graphene sheets by Raman spectroscopy, transmission electron microscopy and electron diffraction. Our method results in a monolayer yield of approximately 1 wt%, which could potentially be improved to 7-12 wt% with further processing. The absence of defects or oxides is confirmed by X-ray photoelectron, infrared and Raman spectroscopies. We are able to produce semi-transparent conducting films and conducting composites. Solution processing of graphene opens up a range of potential large-area applications, from device and sensor fabrication to liquid-phase chemistry.