Bose-Einstein condensation of photons in microcavity plasmas.

Bose-Einstein condensation of a finite number of photons propagating inside a plasma-filled microcavity is investigated. The nonzero chemical potential is provided by the electrons, which induces a finite photon mass and allows condensation to occur. We derive an equation that models the evolution of the photon-mode occupancies, with Compton scattering taken into account as the mechanism of thermalization. The kinetic evolution of the photon spectrum is solved numerically, and we find evidence of condensation down to nanosecond timescales for typical microplasma conditions, n_{e}∼10^{14}-10^{15}cm^{-3}. The critical temperature scales almost linearly with the number of photons, and we find high condensate fractions at microcavity-plasma temperatures, for experimentally achievable cavity lengths (100-500µm) and photon numbers (10^{10}-10^{12}).

Testing Diffusion of Cosmic Rays in the Heliosphere with Proton and Helium Data from AMS.

After six years of continuous observations in space, the Alpha Magnetic Spectrometer experiment has released new data on the temporal evolution of the proton and helium fluxes in cosmic rays. These data revealed that the ratio between proton and helium fluxes at the same value of rigidity R=p/Z (momentum/charge ratio) is not constant at R≲3 GV. In particular, the ratio is found to decrease steadily during the descending phase of Solar Cycle 24 toward the next minimum. We show that such a behavior is a remarkable signature of the ß×λ(R) dependence in the diffusion of cosmic rays in heliosphere, where ß is their adimensional speed and λ(R) is their mean free path, a universal function of rigidity for all nuclei. This dependence is responsible for distinctive charge or mass dependent effects in the time-dependent modulation of low-rigidity particles.

A "Nanopore Lithography" Strategy for Synthesizing Hierarchically Micro/Mesoporous Carbons from ZIF-8/Graphene Oxide Hybrids for Electrochemical Energy Storage.

Porous carbons derived from metal-organic frameworks (MOFs) are promising materials for a number of energy- and environment-related applications, but their almost exclusively microporous texture can be an obstacle to their performance in practical uses. Here, we introduce a novel strategy for the generation of very uniform mesoporosity in a prototypical MOF, namely, zeolitic imidazolate framework-8 (ZIF-8). The process, referred to as "nanopore lithography", makes use of graphene oxide (GO) nanosheets enclosing ZIF-8 particles as masks or templates for the transfer of mesoporous texture to the latter. Upon controlled carbonization and activation, nanopores created in the GO envelope serve as selective entry points for localized etching of carbonized ZIF-8, so that such nanopores are replicated in the MOF-derived carbonaceous structure. The resulting porous carbons are dominated by uniform mesopores ∼3-4 nm in width and possess specific surface areas of ∼1300-1400 m2 g-1. Furthermore, we investigate and discuss the specific experimental conditions that afford the mesopore-templating action of the GO nanosheets. Electrochemical characterization revealed an improved capacitance as well as a faster, more reversible charge/discharge kinetics for the ZIF-8-derived porous carbons obtained through nanopore lithography, relative to those for their counterparts with standard activation (no GO templating), thus indicating the potential practical advantage of the present approach in capacitive energy storage applications.

Electrochemical Exfoliation of Graphite in Aqueous Sodium Halide Electrolytes toward Low Oxygen Content Graphene for Energy and Environmental Applications.

Graphene and graphene-based materials have shown great promise in many technological applications, but their large-scale production and processing by simple and cost-effective means still constitute significant issues in the path of their widespread implementation. Here, we investigate a straightforward method for the preparation of a ready-to-use and low oxygen content graphene material that is based on electrochemical (anodic) delamination of graphite in aqueous medium with sodium halides as the electrolyte. Contrary to previous conflicting reports on the ability of halide anions to act as efficient exfoliating electrolytes in electrochemical graphene exfoliation, we show that proper choice of both graphite electrode (e.g., graphite foil) and sodium halide concentration readily leads to the generation of large quantities of single-/few-layer graphene nanosheets possessing a degree of oxidation (O/C ratio down to ∼0.06) lower than that typical of anodically exfoliated graphenes obtained with commonly used electrolytes. The halide anions are thought to play a role in mitigating the oxidation of the graphene lattice during exfoliation, which is also discussed and rationalized. The as-exfoliated graphene materials exhibited a three-dimensional morphology that was suitable for their practical use without the need to resort to any kind of postproduction processing. When tested as dye adsorbents, they outperformed many previously reported graphene-based materials (e.g., they adsorbed ∼920 mg g-1 for methyl orange) and were useful sorbents for oils and nonpolar organic solvents. Supercapacitor cells assembled directly from the as-exfoliated products delivered energy and power density values (up to 15.3 Wh kg-1 and 3220 W kg-1, respectively) competitive with those of many other graphene-based devices but with the additional advantage of extreme simplicity of preparation.

In vitro cytotoxicity evaluation of resveratrol-loaded nanoparticles: Focus on the challenges of in vitro methodologies.

Assessment of toxic effects is mandatory before market placement of pharmaceutical and cosmetic products. Nanotoxicology is an emerging regulatory concern and still a challenging field. Topical application of resveratrol (RSV) has been extensively studied owing to its multi-mechanistic skin anti-aging effects. Nanoencapsulation has been suggested as a promising solution to overcome RSV stability issues. In this work RSV-loaded solid lipid nanoparticles (SLN) and nanostructured lipid carriers (NLC) were prepared using a homogenization/sonication technique. Cytotoxicity assays were conducted with an immortalized cell line of human keratinocytes (HaCaT). For a comprehensive cytotoxicity characterization MTT and Alamar Blue® reduction assays (assessment of metabolic activity), Neutral red uptake (evaluation of lysosomal integrity), and Trypan blue (assessment of membrane integrity) were used. The results obtained with the different assays were not always concordant, as put in evidence by an adequate statistical analysis. Experimental parameters such as washing steps were found to be critical. The study is of interest because it draws attention to the importance of careful selected experimental conditions of in vitro nanotoxicological tests. Experimental protocols should be adapted taking into account nano-related features such as interference with the dyes and light dispersion/absorption properties.

Effect of cobalt loading on the solid state properties and ethyl acetate oxidation performance of cobalt-cerium mixed oxides.

Cobalt-cerium mixed oxides were prepared by the wet impregnation method and evaluated for volatile organic compounds (VOCs) abatement, using ethyl acetate (EtAc) as model molecule. The impact of Co content on the physicochemical characteristics of catalysts and EtAc conversion was investigated. The materials were characterized by various techniques, including N2 adsorption at -196°C, scanning electron microscopy (SEM), X-ray diffraction (XRD), H2-temperature programmed reduction (H2-TPR) and X-ray photoelectron spectroscopy (XPS) to reveal the structure-activity relationship. The obtained results showed the superiority of mixed oxides compared to bare CeO2 and Co3O4, demonstrating a synergistic effect. The optimum oxidation performance was achieved with the sample containing 20wt.% Co (Co/Ce atomic ratio of ca. 0.75), in which complete conversion of EtAc was attained at 260°C. In contrast, temperatures above 300°C were required to achieve 100% conversion over the single oxides. Notably, a strong relationship between both the: (i) relative population, and (ii) facile reduction of lattice oxygen with the ethyl acetate oxidation activity was found, highlighting the key role of loosely bound oxygen species on VOCs oxidation. A synergistic Co-Ce interaction can be accounted for the enhanced reducibility of mixed oxides, linked with the increased mobility of lattice oxygen.

Highly efficient and reusable CNT supported iron(ii) catalyst for microwave assisted alcohol oxidation.

The highly efficient eco-friendly synthesis of ketones (yields over 99%) from secondary alcohols is achieved by combination of [FeCl2{η(3)-HC(pz)3}] (pz = pyrazol-1-yl) supported on functionalized multi-walled carbon nanotubes and microwave irradiation, in a solvent-free medium. The carbon homoscorpionate iron(ii) complex is the first one of this class to be used as catalyst for the oxidation of alcohols.

Adsorption of ciprofloxacin on surface-modified carbon materials.

The adsorption capacity of ciprofloxacin (CPX) was determined on three types of carbon-based materials: activated carbon (commercial sample), carbon nanotubes (commercial multi-walled carbon nanotubes) and carbon xerogel (prepared by the resorcinol/formaldehyde approach at pH 6.0). These materials were used as received/prepared and functionalised through oxidation with nitric acid. The oxidised materials were then heat treated under inert atmosphere (N2) at different temperatures (between 350 and 900°C). The obtained samples were characterised by adsorption of N2 at -196 °C, determination of the point of zero charge and by temperature programmed desorption. High adsorption capacities ranging from approximately 60 to 300 mgCPxgC(-1) were obtained (for oxidised carbon xerogel, and oxidised thermally treated activated carbon Norit ROX 8.0, respectively). In general, it was found that the nitric acid treatment of samples has a detrimental effect in adsorption capacity, whereas thermal treatments, especially at 900 °C after oxidation, enhance adsorption performance. This is due to the positive effect of the surface basicity. The kinetic curves obtained were fitted using 1st or 2nd order models, and the Langmuir and Freundlich models were used to describe the equilibrium isotherms obtained. The 2nd order and the Langmuir models, respectively, were shown to present the best fittings.

Reutilization of Cr-Y zeolite obtained by biosorption in the catalytic oxidation of volatile organic compounds.

This work aims at the reutilization of a Cr-loaded NaY zeolite obtained by biorecovery of chromium from water as catalyst in the oxidation of volatile organic compounds (VOC). Cr-NaY catalysts were obtained after biosorption of Cr(VI) using a bacterium, Arthrobacter viscosus, supported on the zeolite. The biosorption experiments were conducted at different pH values in the range 1-4. The catalysts were characterized by several techniques, namely ICP-AES, SEM-EDS, XRD, XPS, Raman, H(2)-TPR and N(2) adsorption. The zeolite obtained at pH 4 has the highest content of chromium, 0.9%, and was selected as the best catalyst for the oxidation of different VOC, namely ethyl acetate, ethanol and toluene. For all VOC tested, the catalyst with chromium showed higher activity and selectivity to CO(2), in comparison with the starting zeolite NaY. The presence of chromium shifted also the reaction pathways. In terms of selectivity to CO(2), the following sequence was observed: ethyl acetate>toluene>ethanol.

Adsorption of phenol on supercritically activated carbon fibres: effect of texture and surface chemistry.

The influence of texture and surface chemistry on the phenol adsorption capacity of activated carbon fibres (ACFs) was studied. ACFs were prepared by carbonization of a phenolic textile fibre under nitrogen flow, followed by activation with H(2)O and CO(2) (under atmospheric pressure and supercritical state). The materials were characterised by N(2) and CO(2) adsorption, and by temperature programmed desorption studies. A strong correlation between the amount of adsorbed phenol and the micropore volume has been observed. The relationship between surface oxygen concentration and amount of physisorbed and chemisorbed phenol was assessed, and it was shown that higher amounts of surface oxygen groups decreased the phenol chemisorption capacity of ACFs.

The northernmost record of Bassanago albescens and comments on the occurrence of Rhynchoconger guppyi (Teleostei: Anguilliformes: Congridae) along the Brazilian coast.

The northernmost occurrence of Bassanago albescens in the western Atlantic Ocean (off the coast of Rio de Janeiro, Brazil) is presented and compared with the available data on this species. Specimens formerly identified as Rhynchoconger guppyi from off the southern Brazilian coast are regarded as B. albescens.

Mixture effects during the oxidation of toluene, ethyl acetate and ethanol over a cryptomelane catalyst.

The catalytic oxidation of two-component VOC mixtures (ethanol, ethyl acetate and toluene) was studied over cryptomelane. Remarkable mixture effects were observed on the activity and the selectivity. Toluene inhibits both ethyl acetate and ethanol oxidation, this effect being more evident in the case of ethyl acetate. For instance, the temperature for 100% conversion is about 210 °C when ethyl acetate is oxidised alone, and 250 °C or higher, when it is oxidised in mixtures with toluene. On the contrary, toluene oxidation is only slightly inhibited by the presence of ethyl acetate, while the presence of ethanol has a promoting effect. Concerning the mixtures of ethyl acetate and ethanol, both compounds have a mutual inhibitory effect, which is more evident in the case of ethyl acetate (the temperature for 100% conversion of ethyl acetate is about 45 °C higher when ethyl acetate is oxidised in mixtures with ethanol, while in the case of ethanol the corresponding increase is only 10 °C).

Human stem cells expressing novel TSP-1 variant have anti-angiogenic effect on brain tumors.

Novel therapeutic agents combined with innovative modes of delivery and non-invasive imaging of drug delivery, pharmacokinetics and efficacy are crucial in developing effective clinical anticancer therapies. In this study, we have created and characterized multiple novel variants of anti-angiogenic protein thrombospondin (aaTSP-1) that comprises unique regions of three type-I-repeats of TSP-1 and used engineered human neural stem cells (hNSC) to provide sustained on-site delivery of secretable aaTSP-1 to tumor-vasculature. We show that hNSC-aaTSP-1 has anti-angiogenic effect on human brain and dermal microvascular endothelial cells co-cultured with established glioma cells and CD133+ glioma-initiating cells. Using human glioma cells and hNSC engineered with different combinations of fluorescent and bioluminescent marker proteins and employing multi-modality imaging techniques, we show that aaTSP-1 targets the vascular-component of gliomas and a single administration of hNSC-aaTSP-1 markedly reduces tumor vessel-density that results in inhibition of tumor-progression and increased survival in mice bearing highly malignant human gliomas. We also show that therapeutic hNSC do not proliferate and remain in an un-differentiated state in the brains of glioma-bearing mice. This study provides a platform for accelerated development of future cell-based therapies for cancer.

Tuning of texture and surface chemistry of carbon xerogels.

The influence of different activation processes on the textural and surface chemical properties of carbon xerogels was studied. Carbon xerogels were prepared by the conventional sol-gel approach using resorcinol and formaldehyde; two different pHs of sol-gel processing led to carbon materials with distinct pore size distributions. The materials were subjected to controlled activation by three different methods: activation by oxygen plasma, activation by HNO(3), and activation by diluted air. Treatments with HNO(3) and diluted air created oxygen groups on the external surface as well as inside the pore channels, whereas plasma is more suitable for introducing oxygen groups selectively on the external surface. Nevertheless, it was shown that samples with wider pores can be oxidized to some extent on the pore interiors by plasma. Significant changes in total surface area by air activation were observed.

Anchoring of a [Mn(salen)Cl] complex onto mesoporous carbon xerogels.

Carbon xerogels were synthesized by the conventional sol-gel approach using formaldehyde and resorcinol. The wet gel was dried by two different procedures followed by carbonization, leading to mesoporous carbon xerogels with considerably different pore size distributions. The materials were subsequently oxidized with air, in order to introduce functional groups on the surface, in particular phenols, anhydrides and carbonyls. The capacity of the carbon xerogels for direct immobilization of metal complexes was tested with a manganese(III) salen complex which possesses an extended ligand pi system and two reactive hydroxyl groups on the aldehyde fragment. The manganese loadings of the various samples indicate that larger amounts of Mn(III) complex were immobilized in the oxidized carbon xerogels when compared with the parent unactivated materials, suggesting that complex immobilization took place preferably by covalent bond between the surface oxygen functional groups and the ligand reactive groups, rather than by pi-pi interactions. The size and shape of the carbon xerogel pores were also shown to play an important role in the final loading of the manganese(III) salen complex.