A molecular MoS₂ edge site mimic for catalytic hydrogen generation

Inorganic solids are an important class of catalysts that often derive their activity from sparse active sites that are structurally distinct from the inactive bulk. Rationally optimizing activity is therefore beholden to the challenges in studying these active sites in molecular detail. Here, we report a molecule that mimics the structure of the proposed triangular active edge site fragments of molybdenum disulfide (MoS(2)), a widely used industrial catalyst that has shown promise as a low-cost alternative to platinum for electrocatalytic hydrogen production. By leveraging the robust coordination environment of a pentapyridyl ligand, we synthesized and structurally characterized a well-defined Mo(IV)-disulfide complex that, upon electrochemical reduction, can catalytically generate hydrogen from acidic organic media as well as from acidic water.     

Diversity of Ophiostomatales species associated with conifer-infesting beetles in the Western Carpathians

Bark beetles (Coleoptera: Curculionidae, Scolytinae) are commonly recognised as important agents of tree mortality in coniferous forests of the Western Carpathians. They, together with weevils, are consistently associated with ophiostomatoid fungi. Information regarding conifer beetle-associated fungi in the Western Carpathians remains incomplete and unreliable, particularly with respect to fir-infesting bark beetles. This study aims to clarify associations between fungi in the genera Graphilbum, Leptographium, Ophiostoma and Sporothrix (Ophiostomatales) and their beetle vectors in Norway spruce (Picea abies), European larch (Larix decidua) and silver fir (Abies alba). Samples associated with 20 bark beetle species and weevils were collected from nine stands in Poland and the Czech Republic. Fungi were isolated from adult beetles and galleries. Isolates were identified based on morphology, DNA sequence comparisons for four gene regions (ITS, LSU, ß-tubulin, TEF 1-α) and phylogenetic analyses. In total, 46 distinct taxa were identified, including 25 known and 21 currently unknown species. Several associations between fungi and subcortical insects were recorded for the first time. In addition, O. borealis and O. quercus were detected from A. alba for the first time. The composition of the fungal communities varied among the studied tree species and to a lesser degree among the beetle species. The spruce-infesting bark beetles were commonly associated with species of Leptographium s. l. and Ophiostoma s. str.; the larch-infesting bark beetles were often associated with Ophiostoma s. str. and Sporothrix, while the fir-infesting bark beetles were commonly associated with Ophiostoma s. str. and Graphilbum. The most commonly encountered fungal associates of the examined insects were (a) Grosmannia cucullata, G. piceiperda, Grosmannia sp. 1, Ophiostoma macroclavatum and O. piceae with the spruce-infesting bark beetles; (b) O. pseudocatenulatum and Sporothrix sp. 1 with the larch-infesting bark beetles; and (c) O. piceae, Ophiostoma sp. 2 and Graphilbum sp. 2 with the fir-infesting bark beetles. The differences in fungal associates among the bark beetle species occurring on P. abies, L. decidua and A. alba could be linked to the different habitats that these beetles occupy.     

Synthesis of a stable compound with fivefold bonding between two chromium(I) centers

Although in principle transition metals can form bonds with six shared electron pairs, only quadruply bonded compounds can be isolated as stable species at room temperature. Here we show that the reduction of {Cr(mu-Cl)Ar'}2 [where Ar' indicates C6H3-2,6(C6H3-2,6-Pri2)2 and Pr indicates isopropyl] with a slight excess of potassium graphite has produced a stable compound with fivefold chromium-chromium (Cr-Cr) bonding. The very air- and moisture-sensitive dark red crystals of Ar'CrCrAr' were isolated with greater than 40% yield. X-ray diffraction revealed a Cr-Cr bond length of 1.8351(4) angstroms (where the number in parentheses indicates the standard deviation) and a planar transbent core geometry. These data, the structure's temperature-independent paramagnetism, and computational studies support the sharing of five electron pairs in five bonding molecular orbitals between two 3d5 chromium(I) ions.     

Hot water extractable C and N in relation to microbiological properties of soils under beech forests

Hot water extraction is sometimes recommended as an easy method to estimate the readily mineralizable fractions of total C (C_t) and total N (N_t) in arable soils. However, the usefulness of this method for forest soils has not been adequately studied. The objectives of this study were to relate the hot water extractable C (C_hw) and N (N_hw) to microbiological and chemical properties of the forest soils under beech (Fagus sylvatica L.) stands and to test the ability of near infrared spectroscopy (NIRS) to predict chemical and microbial properties of these soils. Soils differing in humus type, soil type and soil texture were collected from five locations and five depths. In all soils the amount of C_hw was higher than the microbial biomass C (C_mic) indicating that a considerable part of C_hw was of non-microbial origin. The amount of C_hw in mineral soil correlated significantly (r =–0.30–0.53) with C_mic, basal respiration (BAS) and C_t/N_t ratio but was not related to C_mic/C_t ratio. The amount of N_hw was correlated with C_mic, BAS, C_mic/C_t ratio, and C_t/N_t ratio (r =–0.59–0.78). However, C_t and N_t values showed better relationships (r =–0.42–0.88) with all the parameters, indicating no advantage in using C_hw and N_hw in forest soils. NIRS predicted satisfactorily C_t, N_t, C_hw, N_hw, C_mic, C_mic/C_t ratio and BAS in the mineral soils [the regression coefficients (a) of linear regression (measured against predicted values) ranged from 0.84 to 1.17 and the correlation coefficients (r) ranged from 0.86 to 0.94] indicating the applicability of NIRS to estimate these properties.