Reactive Electrophilic OI- Species Evidenced in High-Performance Iridium Oxohydroxide Water Oxidation Electrocatalysts.

Although quasi-amorphous iridium oxohydroxides have been identified repeatedly as superior electrocatalysts for the oxygen evolution reaction (OER), an exact description of the performance-relevant species has remained a challenge. In this context, we report the characterization of hydrothermally prepared iridium(III/IV) oxohydroxides that exhibit exceptional OER performances. Holes in the O 2p states of the iridium(III/IV) oxohydroxides result in reactive OI- species, which are identified by characteristic near-edge X-ray absorption fine structure (NEXAFS) features. A prototypical titration reaction with CO as a probe molecule shows that these OI- species are highly susceptible to nucleophilic attack at room temperature. Similarly to the preactivated oxygen involved in the biological OER in photosystem II, the electrophilic OI- species evidenced in the iridium(III/IV) oxohydroxides are suggested to be precursors to species involved in the O-O bond formation during the electrocatalytic OER. The CO titration also highlights a link between the OER performance and the surface/subsurface mobility of the OI- species. Thus, the superior electrocatalytic properties of the iridium (III/IV) oxohydroxides are explained by their ability to accommodate preactivated electrophilic OI- species that can migrate within the lattice.

High-Performance Supported Iridium Oxohydroxide Water Oxidation Electrocatalysts.

The synthesis of a highly active and yet stable electrocatalyst for the anodic oxygen evolution reaction (OER) remains a major challenge for acidic water splitting on an industrial scale. To address this challenge, we obtained an outstanding high-performance OER catalyst by loading Ir on conductive antimony-doped tin oxide (ATO)-nanoparticles by a microwave (MW)-assisted hydrothermal route. The obtained Ir phase was identified by using XRD as amorphous (XRD-amorphous), highly hydrated IrIII/IV oxohydroxide. To identify chemical and structural features responsible for the high activity and exceptional stability under acidic OER conditions with loadings as low as 20 µgIr cm-2 , we used stepwise thermal treatment to gradually alter the XRD-amorphous Ir phase by dehydroxylation and crystallization of IrO2 . This resulted in dramatic depletion of OER performance, indicating that the outstanding electrocatalytic properties of the MW-produced IrIII/IV oxohydroxide are prominently linked to the nature of the produced Ir phase. This finding is in contrast with the often reported stable but poor OER performance of crystalline IrO2 -based compounds produced through more classical calcination routes. Our investigation demonstrates the immense potential of Ir oxohydroxide-based OER electrocatalysts for stable high-current water electrolysis under acidic conditions.

The non-aqueous fluorolytic sol-gel synthesis of nanoscaled metal fluorides.

This review article focuses on the mechanism of the non-aqueous fluorolytic sol gel-synthesis of nanoscopic metal fluorides and hydroxide fluorides. Based on MAS-NMR, XRD, WAXS and SAXS investigations in combination with computational calculations, it is shown that a stepwise replacement of alkoxide by F-ions takes place resulting in the formation of a large variety of metal alkoxide fluoride clusters, some of them being isolated and structurally characterised. It is shown that these nanoscopic metal fluorides obtained via this new synthesis approach exhibit distinctly different properties compared with their classically prepared homologues. Thus, extremely strong solid Lewis acids are available which give access to new catalytic reactions with sometimes unexpectedly high conversion degrees and selectivity. Even more interestingly, metal hydroxide fluorides can be obtained via this synthesis route that are not accessible via any other approach for which the hydroxide to fluoride ratios can be adjusted over a wide range. Optically fully transparent sols obtained in this way can be used for the first time to manufacture antireflective coatings, corundum ceramics with drastically improved properties as well as novel metal fluoride based organic-inorganic composites. The properties of these new fluoride based materials are presented and discussed in context with the above mentioned new fields of application.

Direct imaging of octahedral distortion in a complex molybdenum vanadium mixed oxide.

Complex Mo,V-based mixed oxides that crystallize in the orthorhombic M1-type structure are promising candidates for the selective oxidation of small alkanes. The oxygen sublattice of such a complex oxide has been studied by annular bright field scanning transmission electron microscopy. The recorded micrographs directly display the local distortion in the metal oxygen octahedra. From the degree of distortion we are able to draw conclusions on the distribution of oxidation states in the cation columns at different sites. The results are supported by X-ray diffraction and electron paramagnetic resonance measurements that provide integral details about the crystal structure and spin coupling, respectively.

Metal fluoride-based transparent nanocomposites with low refractive indices.

The utilisation of magnesium and aluminium fluoride nanoparticles in the preparation of transparent composites leading to materials with superior properties was investigated. Nanoscopic magnesium and aluminium fluoride has been prepared by the fluorolytic sol-gel route from the alkoxides and was surface modified by the reaction with trifluoroacetic acid or perfluorobutyric acid. IR spectroscopic experiments of the xerogels and crystal structure analysis of a trinuclear [Mg3(µ3F)(µ-TFA)6(OCH3)2(py)](3-) cluster unit indicate that the carboxylate group is bound to the particle surface in a monodentate or bidentate bridging fashion. These particles were successfully incorporated into acrylate polymers with up to 40 wt% content to give fully transparent material. Ellipsometry and m-line measurements of thin films show the reduction of the refractive index of composite films with increasing metal fluoride filler content.

Microglia isolated from patients with glioma gain antitumor activities on poly (I:C) stimulation.

The role of microglia, the brain-resident macrophages, in glioma biology is still a matter of debate. Clinical observations and in vitro studies in the mouse model indicate that microglia and macrophages that infiltrate the brain tumor tissue in high numbers play a tumor-supportive role. Here, we provide evidence that human microglia isolated from brain tumors indeed support tumor cell growth, migration, and invasion. However, after stimulation with the Toll-like receptor 3 agonist poly (I:C), microglia secrete factors that exerted toxic and suppressive effects on different glioblastoma cell lines, as assessed in cytotoxicity, migration, and tumor cell spheroid invasion assays. Remarkably, these effects were tumor-specific because the microglial factors impaired neither growth nor viability of astrocytes and neurons. Culture supernatants of tumor cells inhibited the poly (I:C) induction of this microglial M1-like, oncotoxic profile. Microglia stimulation before coculture with tumor cells circumvented the tumor-mediated suppression, as demonstrated by the ability to kill and phagocytose glioma cells. Our results show, for the first time to our knowledge, that human microglia exert tumor-supporting functions that are overridden by tumor-suppressing activities gained after poly (I:C) stimulation.

Inorganic-organic nanocomposites based on sol-gel derived magnesium fluoride.

Monodispersed magnesium fluoride nanoparticles are utilized for the first time to prepare transparent inorganic-organic nanocomposite materials with improved mechanical properties. The fluorolytic sol-gel synthesis route has been modified for the preparation of monodispersed magnesium fluoride nanoparticles with a size of 2-3 nm. MgF(2) particles are effectively stabilised against agglomeration by phosphonic acids, which strongly bind to the particles and lead to an increased compatibility of the inorganic particles with the organic polymers. This way, highly transparent nanocomposite materials with up to 20 wt% magnesium fluoride in different acrylates are obtained, featuring high dispersion of MgF(2) particles in the polymer matrix and an increased hardness by the factor of 2. The nature of interaction between phosphonic acids and magnesium fluoride is thoroughly investigated by IR and NMR showing a monodentate coordination of phosphonates to the particle's surface.

Alternariol.

IN THE TITLE COMPOUND (SYSTEMATIC NAME: 3,7,9-trihydr-oxy-1-methyl-6H-benzo[c]chromen-6-one), C(14)H(10)O(5), the methyl group is shifted out of the molecular plane due to a steric collision, thus causing a slight twist of the benzene rings. The mol-ecular structure is stabilized by an intra-molecular O-H⋯O hydrogen bond, generating an S(6) ring. In the crystal, mol-ecules are connected by inter-molecular O-H⋯O hydrogen bonds into a three-dimensional network.