Synthesis and molecular structures of di- and trinuclear molybdenum complexes containing pyridine-2-thiolato (pyS) ligand

Dinuclear complexes [Mo-2(mu-pyS)(2)(CO)(4)(PPh(3))(2)] (1), [Mo-2(mu-pyS)(2)(CO)(5)(PPh(3))] (2) and a trace quality of trinuclear complex [Mo-3(mu-pyS)(2)(mu(3)-pyS)(2)(CO)(6)] (3) were obtained from the reaction of [Mo(CO)(3)(MeCN)(3)] with pyridine-2-thione (pySH) and PPh(3) in THF. The crystal structures of 1.2C(7)H(8) and 3.7 C7H8 have been determined by X-ray diffraction studies. Crystals of 1.2C(7)H(8) are monoclinic, space group C2/c and Z = 4, with a = 18.797(3), b = 11.143(4), c = 28.157(7) Angstrom, beta = 101.23(2)degrees. The structure was refined to R = 0.050 and Rw = 0.057 for 3146 observed reflections, Crystals of 3.7 C7H8 are monoclinic, space group P2(1)/a and Z = 4, with a = 13.912(2), b = 17.161(2), c = 15.577(3) Angstrom, beta = 101.17(1)degrees. The structure was refined to R = 0.046 and Rw = 0.051 for 4357 observed reflections. The molecule of 1 consists of two Mo(CO)(2)(PPh(3)) fragments linked by an Mo-Mo bond (2.974(2)Angstrom) and by two doubly-bridging pyS ligands. The compound 3 contains a bent open geometry of three molybdenum atoms (Mo(1)-Mo(2)-Mo(3) angle 122.99(3)degrees) linked by two Mo-Mo bonds (2.943(1) and 2.950(1) Angstrom) and by two doubly- and two triply-bridging pyS ligands.

Effect of structures of modifiers on electrochemistry of di-mu-oxo dimanganese 2,2'-bipyridine complex

The gold electrodes modified with 2-picolinic acid , nicotinic acid, iso-nicotinic or thiophene were prepared using membrane transfer method, The electrochemistry of di-mu-oxodimanganese 2,2'-bipyridine complex was studied in the acetic acid buffer solution at different modified gold electrodes, It was found that the modifiers which can promote the electrochemical reaction of the complex should be of at least two functional groups, One group can be bound to the electrode surface and the other can form electron transfer pathway between the modifier and the complex through sal; bridge or hydrogen bond, In addition, the mechanism of the electrochemical reaction was discussed.

POLYMERIZATION OF ACRYLONITRILE INITIATED BY DI(2,6-DI-TERT-BUTYL-4-METHYLPHENOXO) SAMARIUM COMPLEX

The polymerization of acrylonitrile initiated by organolanthanide complexes alone is studied for the first time. The effect df polymerization conditions on catalytic activity of the title complex and molecular weight of the polymers produced have been studied.

A BIS(2,6-DI-TERT-BUTYL-4-METHYLPHENOLATO)-SAMARIUM(II) COMPLEX, [SM(OAR)2(THF)3]-THF

The title complex, bis(2,6-di-tert-butyl-4-methyl-phenolato-O)tris(tetrahydrofuran-O)samarium tetrahydrofuran solvate, [Sm(C15H23O)2(C4H8O)3].C4H8O, has distorted trigonal bipyramidal geometry around the Sm(II) atom. The 0(2), 0(3) and 0(4) atoms of the

SYNTHESIS AND MOLECULAR-STRUCTURE OF NBU2[(MEO)3C6H2C(O)N2CHC6H4O]SN FORMED IN THE REACTION OF DI-N-BUTYLTIN(IV) OXIDE WITH 3,4,5-TRIMETHOXY-BENZOYL SALICYLAHYDRAZONE

The title complex was synthesized and characterized by H-1, C-13, Sn-119 NMR and IR spectra. A single crystal X-ray diffraction study confirmed its molecular structure and revealed that 3,4,5-trimethoxy-benzoyl salicylahydrazone was a tridentate and approximately planar ligand. The complex crystallizes in the triclinic space group P1BAR with a = 9.208(3), b = 12.536(2), c = 12.187(4) angstrom, alpha = 113.12(2), beta = 90.58(2), gamma = 81.42(2), V = 1277.5(6) angstrom, Z = 2. The structure was refined to R = 0.033 and R(w) = 0.041 for 3944 observed independent reflections. The tin atom has a distorted trigonal bipyramidal coordination. The Sn-C bond lengths are 2.129(5) and 2.113(5) angstrom (av. 2.121(5) angstrom), the C-Sn-C angle is 123.3(2); the bond length between the tin atom and the chelating nitrogen is 2.173(3) angstrom. Two chain carbon atoms and the chelating nitrogen atom occupy the basal plane. The skeleton of two erect oxygen atoms and the tin atom is bent (O-Sn-O angle = 153.5(1)). In the complex, the ligand exists in the enol-form.

Response of coastal marine eco-environment to river fluxes into the sea: A case study of the Huanghe (Yellow) River mouth and adjacent waters

The impact of the Huanghe (Yellow) River outflows on its estuary was investigated with river gauging and shipboard hydrographic observations. The river flux has been decreasing dramatically; the discharges of water and sediment in the 1990s dropped to 27.4% and 31.9% of those in the 1950s, respectively, resulting in frequent and lengthy events of downstream channel dry-up since the 1970s. There were accumulatively 897 zero-flow days during the 1990s in the river course below the Lijin Hydrological Station, 100 km upstream from the river mouth, which is 82.4% of that in 1972. As freshwater input decreases, river-borne nutrients to the estuarine increased significantly. Concentration of dissolved inorganic nitrogen (DIN) in the 1990s was four times of that in 1950s. Changes in amount and content of the riverine inputs have greatly affected the estuarine ecosystem. Over the past several decades, sea surface temperature and salinity in the estuary and its adjacent waters increased and their distribution pattern altered in response to the reduction of freshwater inflow. The distribution of and seasonal succession in nutrient concentrations in the surface layer have also changed with a shift of river outlet and the decrease in riverine nutrient loads. Furthermore, deterioration of estuarine ecosystem by less river input has decreased primary productivity in the deltaic region waters, and in turn depressed the fishery. (C) 2008 Published by Elsevier Ltd.

PCBs and its coupling with eco-environments in Southern Yellow Sea surface sediments

In this paper, the spatial distribution and source of the PCBs in surface sediments of the Southern Yellow Sea (SYS) and influencing factors, such as the sediment characteristics (components, relative proportions and total organic carbon contents), and hydrodynamic conditions were analyzed. PCB concentrations in the surface sediments ranged from 518-5848 pg/g, with average values of 1715 pg/g decreasing sharply compared to last year. In the study area, the PCB pollution level in the middle area was the highest, followed by that of the east coast and the west coast, respectively. Although the PCB level in the coastal areas was lower than that in the middle areas, it was proven in our study that the Yellow Sea obtained PCBs by virtue of river inputs. There was a positive and pertinent correlation between the clay proportion and PCB concentrations, and the increase of the PCB concentrations was directly proportional to the increase of TOC contents, with r = 0.61, but it was contrary to the sediment grain size. Consequently, the factors controlling PCB distribution had direct or indirect relationships with sediment grain size; moreover, the hydrodynamic conditions determined the sediment components and grain size. In conclusion, hydrodynamic conditions of the Yellow Sea were the most important influencing factors effecting the distribution of PCBs in the surface sediments of the SYS. (C) 2007 Elsevier Ltd. All rights reserved.

The antioxidant activity of 2-(4(or 2)-hydroxyl-5-chloride-1,3-benzene-di-sulfanimide)-chitosan

Chitosan (CS) with two different molecular weights was modified by reacting with 4-hydroxyl-5-chloride-1,3-benzene-disulfo-chloride or 2-hydroxyl-5-chloride-1,3-benzene-disulfo-chloride to give new 2-(4(or 2)-hydroxyl-5-chloride-1,3-benzene-di-sulfanimide)-chitosan (2-HCBSAHCS, 2-HCBSALCS, 4-HCBSAHCS, 4-HCBSALCS). The structure of the derivatives was characterized by FT-IR and C-13 NMR spectroscopy. The antioxidant activities of the derivatives were investigated employing various established systems, such as hydroxyl radical ((OH)-O-center dot)/superoxide anion (O-2(radical anion)) scavenging/reducing power and chelating activity. All the derivatives showed stronger scavenging activity on hydroxyl radical than chitosan and ascorbic acid (Vc), and IC50 of 4-HCBSAHCS, 4-HCBSALCS, 2-HCBSAHCS and 2-HCBSALCS was 0.334, 0.302, 0.442, 0.346 mg/mL, respectively. The inhibitory activities of the derivatives toward superoxide radical by the PMS-NADH system were strong. The results showed that the superoxide radical scavenging effect of 2-(4(or 2)-hydroxyl-5-chloride-1,3-benzene-disulfanimide)-chitosan was higher than chitosan. The derivatives had obviously reducing power and slight chelating activity. The data obtained in in vitro models clearly establish the antioxidant potency of 2-(4(or 2)-hydroxyl-5-chloride-1,3-benzene-disulfanimide)-chitosan. (C) 2007 Elsevier Masson SAS. All rights reserved.

Sistema base para avaliação e eco-certificação de atividades rurais.

O Sistema Base para Eco-certificação de Atividades Rurais (Eco-cert.Rural PROCISUR) consiste de um conjunto de planilhas eletrônicas que integram vinte e quatro indicadores do desempenho de uma dada atividade rural, no âmbito de um estabelecimento. Sete aspectos essenciais de avaliação são considerados: i. Uso de Insumos e Recursos, ii. Qualidade Ambiental, iii. Respeito ao Consumidor, iv. Emprego, v. Renda, vi. Saúde e vii. Gestão e Administração. Os indicadores foram construídos em matrizes de ponderação nas quais dados obtidos em campo, de acordo com o conhecimento do produtor/administrador do estabelecimento, são automaticamente transformados em índices de impacto expressos graficamente. Os resultados da avaliação permitem, ao produtor/administrador, averiguar quais práticas de manejo produzem maior impacto no desempenho de sua atividade e, aos tomadores de decisões, gestores e organizações, a definição de políticas e instrumentos para melhoria de desempenho das atividades rurais, bem como a implantação de um sistema de benchmarking para a identificação de empreendimentos com melhor desempenho ambiental e determinação de estudo de caso afinados com os planos de desenvolvimento local sustentável.