Novel zwitterionic oxorhenium(V) complexes: synthesis, characterization and crystal structure of [ReOX2(Hdhp)(PPh3)] (X = Cl, Br; H2dhp = 2,3-dihydroxypyridine)

Dois novos complexos zwitteriônicos de oxorrênio(V), [ReOCl2(Hdhp)(PPh3)] (1) e [ReOBr2(Hdhp)(PPh3)] (2) (H2dhp = 2,3-dihidroxipiridina), foram sintetizados e caracterizados por espectroscopia de absorção no infravermelho, ressonância magnética nuclear de ¹H e 31P, análise elementar e determinação da estrutura cristalina e molecular por difração de raios X em monocristais. Os complexos apresentam geometria de coordenação octaédrica bastante distorcida, com os dois ligantes haletos arranjados em posições cis equatoriais, o ligante trifenilfosfina em posição trans a um dos haletos e o ligante Hdhp- coordenado de forma bidentada através de seus átomos de oxigênio, sendo um em posição trans ao ligante oxo e o outro em posição trans com relação ao outro haleto. Este ligante tem seu átomo de nitrogênio protonado. Os compostos 1 e 2 apresentam empacotamento cristalino bastante diferente, influenciado em ambos os casos por ligações de hidrogênio intermoleculares dos tipos N-H...X (X = Cl, Br) e N-H...O.Two novel zwitterionic oxorhenium(V) complexes, [ReOCl2(Hdhp)(PPh3)] (1) and [ReOBr2(Hdhp)(PPh3)] (2) (H2dhp = 2,3-dihydroxypyridine), were synthesized and characterized by infrared spectroscopy, ¹H and 31P nuclear magnetic resonance, elemental analysis and crystal and molecular structure determination by X-ray diffraction on single crystals. Both complexes show distorted octahedral coordination geometry, with the halide ligands arranged in equatorial cis positions, the triphenylphosphine ligand in a trans position to one of the halides and the Hdhp- ligand coordinated in a bidentate form through its oxygen atoms, one in trans position to the oxo-ligand and the other in trans position to the second halide. The nitrogen atom of this ligand is protonated. Compounds 1 and 2 show quite different crystal packing, both influenced by hydrogen bonds of the types N-H...X (X = Cl, Br) and N-H...O

Plant Diversity Surpasses Plant Functional Groups and Plant Productivity as Driver of Soil Biota in the Long Term

One of the most significant consequences of contemporary global change is the rapid decline of biodiversity in many ecosystems. Knowledge of the consequences of biodiversity loss in terrestrial ecosystems is largely restricted to single ecosystem functions. Impacts of key plant functional groups on soil biota are considered to be more important than those of plant diversity; however, current knowledge mainly relies on short-term experiments.We studied changes in the impacts of plant diversity and presence of key functional groups on soil biota by investigating the performance of soil microorganisms and soil fauna two, four and six years after the establishment of model grasslands. The results indicate that temporal changes of plant community effects depend on the trophic affiliation of soil animals: plant diversity effects on decomposers only occurred after six years, changed little in herbivores, but occurred in predators after two years. The results suggest that plant diversity, in terms of species and functional group richness, is the most important plant community property affecting soil biota, exceeding the relevance of plant above- and belowground productivity and the presence of key plant functional groups, i.e. grasses and legumes, with the relevance of the latter decreasing in time.Plant diversity effects on biota are not only due to the presence of key plant functional groups or plant productivity highlighting the importance of diverse and high-quality plant derived resources, and supporting the validity of the singular hypothesis for soil biota. Our results demonstrate that in the long term plant diversity essentially drives the performance of soil biota questioning the paradigm that belowground communities are not affected by plant diversity and reinforcing the importance of biodiversity for ecosystem functioning

Os polimorfos de carbonato de cálcio: uma síntese fácil de aragonita The polymorphs of calcium carbonate: an easy synthesis of aragonite

<abstract language="eng">Aragonite is a metastable polymorph of calcium carbonate. The calcareous exoskeletons of some organisms like corals or molluscs consist essentially of aragonite. The questions of how, and why these organisms prefer the thermodynamically unstable aragonite for the construction of their hard shells are discussed. The importance of the biomineralization process for the development of new materials is outlined. In the experimental part, a very simple synthesis of polycrystalline aragonite is performed, using carbonated mineral water available at the market. The synthesized aragonite is easily identified by its infrared spectrum

Organotin Complexes of Alizarin and Purpurin

Five novel organotin complexes with the anthraquinone dyes alizarin (1,2-dihydroxyanthraquinone) and purpurin (1,2,4-trihydroxyanthraquinone) were synthesized and characterized by elemental analyses, FTIR and NMR spectroscopy ((1)H, (13)C and (119)Sn). The crystal and Molecular structures Of four complexes were determined by X-ray diffraction on single crystals: [Bu(2)Sn(aliz)(H(2)O)]center dot C(2)H(5)OH (A1 center dot EtO H), [Bu(2)Sn(aliz)(dmso)](2) (A3), [(Bu(2)Sn)(3)O(Hpurp)(2)] (P1) and [Bu(2)Sn(Hpurp)(dmso)](2) (P2), where H(2)aliz = alizarin and H(3)purp = purpurin. The coordination mode of the ligands is identical to that found in their Al/Ca complexes, where they act as dianionic tridentate ligands forming five and six-membered fused chelate rings. The coordination to the tin atoms occurs exclusively via the 1,2- phenolate oxygen and the adjacent quinoid oxygen atoms. The complexes A1, A3 and P1 are dimers with hepta-coordinated tin atoms in form of a slightly distorted pentagonal bipyramid. The trinuclear complex P2 contains two pentacoordinated and one heptacoordinated tin atoms

Crystal structures and thermal behavior of alkaline earth tricyanomethanides

The alkaline earth tricyanomethanides Mg(tcm)(2) center dot 2H(2)O, Ca(tcm)(2), Sr(tcm)(2) - H2O and Ba(tcm)(2) center dot 2H(2)O were prepared from aqueous solutions of the respective chlorides and silver tricyanomethanide. Their IR spectra and thermal behavior are described. The crystal structures of Ca(tcm)(2) and Ba(tcm)(2) center dot 2H(2)O were determined by single crystal X-ray diffraction. The structure of Ca(tcm)(2) is of the type found for several transition metal tricyanomethanides [1], containing two independent interpenetrating networks. Ba(tcm)(2) center dot 2H(2)O has a unique crystal structure corresponding to a three-dimensional coordination polymer with nine fold coordinated Ba atoms connected by water molecules and tricyanomethanide anions

The C. elegans DSB-2 Protein Reveals a Regulatory Network that Controls Competence for Meiotic DSB Formation and Promotes Crossover Assurance

For most organisms, chromosome segregation during meiosis relies on deliberate induction of DNA double-strand breaks (DSBs) and repair of a subset of these DSBs as inter-homolog crossovers (COs). However, timing and levels of DSB formation must be tightly controlled to avoid jeopardizing genome integrity. Here we identify the DSB-2 protein, which is required for efficient DSB formation during C. elegans meiosis but is dispensable for later steps of meiotic recombination. DSB-2 localizes to chromatin during the time of DSB formation, and its disappearance coincides with a decline in RAD-51 foci marking early recombination intermediates and precedes appearance of COSA-1 foci marking CO-designated sites. These and other data suggest that DSB-2 and its paralog DSB-1 promote competence for DSB formation. Further, immunofluorescence analyses of wild-type gonads and various meiotic mutants reveal that association of DSB-2 with chromatin is coordinated with multiple distinct aspects of the meiotic program, including the phosphorylation state of nuclear envelope protein SUN-1 and dependence on RAD-50 to load the RAD-51 recombinase at DSB sites. Moreover, association of DSB-2 with chromatin is prolonged in mutants impaired for either DSB formation or formation of downstream CO intermediates. These and other data suggest that association of DSB-2 with chromatin is an indicator of competence for DSB formation, and that cells respond to a deficit of CO-competent recombination intermediates by prolonging the DSB-competent state. In the context of this model, we propose that formation of sufficient CO-competent intermediates engages a negative feedback response that leads to cessation of DSB formation as part of a major coordinated transition in meiotic prophase progression. The proposed negative feedback regulation of DSB formation simultaneously (1) ensures that sufficient DSBs are made to guarantee CO formation and (2) prevents excessive DSB levels that could have deleterious effects