Commensurate Nb2Zr5O15: Accessible Within the Field Nb2Zr x O2x+5 After All.

Doped niobium zirconium oxides are applied in field-effect transistors and as special-purpose coatings. Whereas their material properties are sufficiently known, their crystal structures remain widely uncharacterized. Herein, we report on the comparably mild sol-gel synthesis of Nb2Zr5O15 and the elucidation of its commensurately modulated structure via neutron diffraction. We describe the structure using the most appropriate superspace as well as the convenient supercell approach. It is part of an α-PbO2-homeotypic field with the formula Nb2Zr x O2x+5, which has previously been reported only for x≥5.1, and is closely related to the structure of Hf3Ta2O11. The results, supported by X-ray diffraction and additional synthesis experiments, are contextualized within the existing literature. Via the sol-gel route, metastable Nb-Zr-O compounds and their heavier congeners are accessible that shed light on possible structures of these commercially utilized materials.

Preparation of amorphous indomethacin nanoparticles by aqueous wet bead milling and in situ measurement of their increased saturation solubility.

The aim of this study was to prepare amorphous indomethacin nanoparticles in aqueous media and to determine in situ their increased saturation solubility and dissolution rate. Drug nanosuspensions with a Z-average of ∼300 nm were prepared by wet media milling and afterwards freeze-dried. The drug solid state was analyzed by DSC, XRD and FTIR before and after the milling process. Milling of amorphous indomethacin with polyvinylpyrrolidone (PVP) as stabilizer resulted in an amorphous nanosuspension which could not be redispersed in the nanosize range after freeze-drying. The combination of PVP and poloxamer 407 resulted in crystalline nanoparticles: poloxamer 407, a polymer with high molecular weight, competed with PVP for surface coverage, and hindered the interaction between PVP and indomethacin. This indicated the importance of sufficient drug-PVP interactions on the drug particle surface for amorphous state stabilization. Redispersable amorphous indomethacin nanoparticles were obtained by combining the anti-recrystallization effect of PVP with the particle size stabilization provided by sodium dodecyl sulfate. Solubility studies were performed in situ. The solubility of crystalline micronized indomethacin of 6.7 ±â€¯1.3 µg/mL was increased up to 17.3 ±â€¯2.8 µg/mL by its amorphization, with a factor of increase of 2.6. Indomethacin amorphization increased its dissolution rate by a factor of 30. Indomethacin nanocrystals resulted in an increased solubility of 2.6 times, with a solubility of 17.2 ±â€¯0.4 µg/mL. The highest increase was obtained with amorphous indomethacin nanoparticles with a solubility of 35 ±â€¯1.6 µg/mL and 5.2 times higher than the solubility of the original indomethacin. Amorphous indomethacin nanoparticles resulted in the highest dissolution rate, which increased from 0.003 µg/(mL s) to 2.328 µg/(mL s). The synergistic effect obtained by the combination of nanosize and amorphous solid state was demonstrated.

A Molecular Approach to Manganese Nitride Acting as a High Performance Electrocatalyst in the Oxygen Evolution Reaction.

The scalable synthesis of phase-pure crystalline manganese nitride (Mn3 N2 ) from a molecular precursor is reported. It acts as a superiorly active and durable electrocatalyst in the oxygen evolution reaction (OER) from water under alkaline conditions. While electrophoretically deposited Mn3 N2 on fluorine tin oxide (FTO) requires an overpotential of 390 mV, the latter is substantially decreased to merely 270 mV on nickel foam (NF) at a current density of 10 mA cm-2 with a durability of weeks. The high performance of this material is due to the rapid transformation of manganese sites at the surface of Mn3 N2 into an amorphous active MnOx overlayer under operation conditions intimately connected with metallic Mn3 N2 , which increases the charge transfer from the active catalyst surface to the electrode substrates and thus outperforms the electrocatalytic activity in comparison to solely MnOx -based OER catalysts.

Influence of Drug Brittleness, Nanomilling Time, and Freeze-Drying on the Crystallinity of Poorly Water-Soluble Drugs and Its Implications for Solubility Enhancement.

The aim of this study was to assess whether wet bead milling of dexamethasone and tacrolimus suspensions leads to a lower degree of crystallinity of nanocrystals, and if the degree of crystallinity affects the drug solubility, in addition to particle size. Powder X-ray diffraction (XRD) was used to determine the degree of crystallinity of the particles, which decreased during milling until reaching a plateau: the particles had ∼79% degree of crystallinity after 5 h milling. Different milling times were required for the two drugs in order to reach their plateaux, 2 h for dexamethasone and 3 h for tacrolimus. These results could be explained with the brittleness of the drugs. Dexamethasone was more brittle than tacrolimus, with an apparent elastic modulus of 16 GPa compared to ∼12 GPa of tacrolimus. Freeze-drying the nanosuspensions resulted in a reduction in the degree of crystallinity to ∼35% for dexamethasone and to ∼45% for tacrolimus in comparison to non-freeze-dried particles. Solubility studies were performed with a Sirius® inForm based on in situ UV/VIS spectroscopy. The reduced degree of crystallinity of nanocrystals after milling was responsible, in addition to the nanoparticle size, for the solubility increase. Indeed, while the smallest particle size (394 nm for dexamethasone and 240 nm for tacrolimus) did not always result in the highest increase in solubility (factor of 1.04 for dexamethasone and 1.3 with tacrolimus), the smallest degree of crystallinity was always characteristic of the maximum solubility obtained (factor of 1.15 for dexamethasone and 1.7 for tacrolimus).

Complementing Graphenes: 1D Interplanar Charge Transport in Polymeric Graphitic Carbon Nitrides.

Charge transport in polymeric graphitic carbon nitrides is shown to proceed via diffusive hopping of electron and hole polarons with reasonably high mobilities >10(-5) cm(2) V(-1) s(-1). The power-law behavior of the ultrafast luminescence decay exhibits that the predominant transport direction is perpendicular to the graphitic polymer sheets, thus complementing 2D materials like graphene.

Metal-free photocatalytic graphitic carbon nitride on p-type chalcopyrite as a composite photocathode for light-induced hydrogen evolution.

Recently, it has been shown that an abundant material, polymeric carbon nitride, can produce hydrogen from water under visible-light irradiation in the presence of a sacrificial donor. We present herein the preparation and characterization of graphitic carbon nitride (g-C(3)N(4)) films on p-type semiconducting CuGaSe(2) chalcopyrite thin-film substrates by thermal condensation of a dicyandiamide precursor under inert-gas conditions. Structural and surface morphological studies of the carbon nitride films suggest a high porosity of g-C(3)N(4) thin films consisting of a network of nanocrystallites. Photoelectrochemical investigations show light-induced hydrogen evolution upon cathodic polarization for a wide range of proton concentrations in the aqueous electrolyte. Additionally, synchrotron radiation-based photoelectron spectroscopy has been applied to study the surface/near-surface chemical composition of the utilized g-C(3)N(4) film photocathodes. For the first time, it has been shown that g-C(3)N(4) films coated on p-type CuGaSe(2) thin films can be successfully applied as new photoelectrochemical composite photocathodes for light-induced hydrogen evolution.