Synthesis, Crystal Structure and Bioactivities of 1-（4-Chlorophenyl）-3- [ 5-（pyrid-4-yl）- 1,3,4-thiadiazol-2-yl] urea

The title compound 1-(4-chlorophenyl)-3-[5-(pyrid-4-yl)-1,3,4-thiadiazol-2-yl]urea (C14H10ClN5OS, Mr = 331.79) has been synthesized by the reaction of 2-amino-5-(pyrid-4-yl)- 1,3,4-thiadiazole with 4-chlorobenzoyl azide, and its crystal structure was determined by single-crystal X-ray diffraction. The crystal belongs to triclinic system, space group P with a = 5.8550(8), b = 7.5668(10), c = 16.416(2) , α = 78.364(2), β = 81.204(2), γ = 84.749(2)°, V = 702.58(16) 3, Z = 2, Dc = 1.568 g/cm3, μ = 0.429 mm-1, F(000) = 340, the final R = 0.0442 and wR = 0.1092 for 2001 observed reflections (I > 2σ(I)). X-ray diffraction analysis reveals that the title molecule is nearly planar. In the crystal structure, the molecules are linked by strong intermolecular N-H…N hydrogen bonds together with weak nonclassical intermolecular (C-H…Y, Y = N, O and Cl) hydrogen bonds and stacked through π-π interactions. The preliminary bioassay shows that the title compound exhibits good fungicidal activities against Rhizoctonia solani, Botrytis cinerea and Dothiorella gregaria.     

(Me2NH2)[(Ph3Sn)3(MoO4)2], ein Triorganozinnmolybdat mit Schichtstruktur

(Me₂NH₂)[(Ph₃Sn)₃(MoO₄)₂], a Triorganotin Molybdate with Layer Structure The reaction of [(Ph₃Sn)₂MoO₄] with (Me₂NH₂)Cl in an acetonitrile/water mixture leads to the formation of (Me₂NH₂)[(Ph₃Sn)₃(MoO₄)₂] ( 1 ). ( 1 ) crystallizes in the space group Pca2₁ with a = 1967.0(4), b = 1353.1(2) and c = 2176.6(5) pm. In the crystal structure of 1 Ph₃SnO₂ bipyramides and MoO₄ tetrahedra are linked by corner sharing to give a layer structure. Additionally the layers are connected by O···H···N hydrogen bridges between MoO₄ groups and [Me₂NH₂]⁺ ions to give a 3D network structure.     

Redox and Conformational Equilibria and Dynamics of Cytochrome c at High Electric Fields

Cytochrome c (Cyt‐c) adsorbed in the electrical double layer of the Ag electrode/electrolyte interface has been studied by stationary and time‐resolved surface‐enhanced resonance Raman spectroscopy to analyse the effect of strong electric fields on structure and reaction equilibria and dynamics of the protein. In the potential range between +0.1 and ?0.55 V (versus saturated calomel electrode), the adsorbed Cyt‐c forms a potential‐dependent reversible equilibrium between the native state B1 and a conformational state B2. The redox potentials of the bis‐histidine‐coordinated six‐coordinated low‐spin and five‐coordinated high‐spin substates of B2 were determined to be ?0.425 and ?0.385 V, respectively, whereas the additional six‐coordinated aquo‐histidine‐coordinated high‐spin substate was found to be redox‐inactive. The redox potential for the conformational state B1 was found to be the same as in solution in agreement with the structural identity of the adsorbed B1 and the native Cyt‐c. For all three redox‐active species, the formal heterogeneous electron transfer rate constants are small and of the same order of magnitude (3–13 s^?1), which implies that the rate‐limiting step is largely independent of the redox‐site structure. These findings, as well as the slow and potential‐dependent transitions between the various conformational (sub‐)states, can be rationalized in terms of an electric field‐induced increase of the activation energy for proton‐transfer steps linked to protein structural reorganisation. Further increasing the electric field strength by shifting the electrode potential above +0.1 V leads to irreversible structural changes that are attributed to an unfolding of the polypeptide chain.     

Solvothermal Synthesis and Characterization of the New Iron Thioantimonates(III) [Fe(C6H18N4)]FeSbS4 and [Fe(C4H13N3)2]Fe2Sb4S10 Containing FeII and FeIII and Protein‐Analogous [2FeIII‐2S]2+ Clusters

The two new compounds [Fe(tren)]FeSbS₄ ( 1 ) (tren = tris(2‐aminoethyl)amine) and [Fe(dien)₂]Fe₂Sb₄S₁₀ ( 2 ) (dien = diethylendiamine) were prepared under solvothermal conditions and represent the first thioantimonates(III) with iron cations integrated into the anionic network. In both compounds Fe³⁺ is part of a [2Fe^III‐2S] cluster which is often found in ferredoxines. In addition, Fe²⁺ ions are present which are surrounded by the organic ligands. In ( 1 ) the Fe²⁺ ion is also part of the thioantimonate(III) network whereas in ( 2 ) the Fe²⁺ ion is isolated. In both compounds the primary SbS₃ units are interconnected into one‐dimensional chains. The mixed‐valent character of [Fe(tren)]FeSbS₄ was unambiguously determined with Mössbauer spectroscopy. Both compounds exhibit paramagnetic behaviour and for ( 1 ) a deviation from linearity is observed due to a strong zero‐field splitting. Both compounds decompose in one single step.     

Synthetic and structural carboxylate chemistry of neurotoxic aluminum in relevance to human diseases

The contact of Al(III) with biological components in human physiology has increased significantly over the years, due to a number of factors, prominent among which stands the rapid acidification of the environment and the concomitant introduction of that abundant metal ion in human biological fluids. As a result, pathophysiological aberrations in humans have arisen due to Al(III) (neuro)toxicity. Among the efforts targeting the elucidation of the factors responsible for Al(III) toxicity is the exploration of the requisite Al(III)-carboxylate chemistry in aqueous media, and its relevance to soluble, potentially bioavailable species capable of exerting toxic effects. A detailed synthetic, structural, and spectroscopic account of the Al(III)-carboxylate complexes, purported to exist as components in aqueous Al(III)-carboxylic acid speciation, is presented. The structures described are classified as mononuclear, dinuclear, trinuclear, tetranuclear, and polynuclear species, arising from various aqueous and non-aqueous Al(III)-carboxylate ligand reactions. Moreover, the solution chemistry and kinetic behavior of the so far reported complexes is given, with the specific aim of comparing their solid state and solution chemical and structural properties. In this sense, a comprehensive picture on the Al(III) speciation, in the presence of various physiological or biologically relevant carboxylate ligands, appears to emerge, which is expected to contribute to the understanding of Al(III) (neuro)toxicity and its consequence(s) in a multitude of human diseases. Carboxylate containing low and high molecular mass components stand prominent in their chemical preference to react with Al(III) in biological fluids. In this context, factors considered to influence the aqueous low molecular mass Al(III)-carboxylate chemistry, thus affecting the solubility and possibly the bioavailability of the resulting species, are discussed as potential research links to the ultimate manifestation of Al(III) toxicity at the cellular level.     

新型杂多配合物K3H2[GeW8Mo3VO40]·4H2O的合成与晶体结构

用分步酸化、分步加料法合成出新型杂多配合物K3H2[GeW8Mo3VO40]·4H2O,并用X射线单晶衍射法测定其晶体结构,该晶体属单斜晶系,C2空间群,a＝1.894 4(4)nm,b＝3.292 0(7)nm,c＝1.249 4(2)nm,β＝90.25(3)°,V＝7.792(4)nm3,Z＝6.最终偏差因子R＝0.063.RW＝0.067.     

Reaktionen von MoNCl3 und WNCl3 mit elementarem Fluor. Kristallstrukturen von [MoO2F2(THF)2] und [WF4(NCl)(CH3CN)]

Reactions of MoNCl₃ and WNCl₃ with Elemental Fluorine. Crystal Structures of [MoO₂F₂(THF)₂] and [WF₄(NCl)(CH₃CN)] The nitrido chlorides MoNCl₃ and WNCl₃ as well as WCl₄(NCl) react with elemental fluorine forming the N-chloro imido complexes MoF₄(NCl) and WF₄(NCl), which were characterized by IR spectroscopy. With tetrahydrofurane MoF₄(NCl) reacts to give [MoF₄(NCl)(THF)], which in THF solution slowly converts into [MoO₂F₂(THF)₂]. From WF₄(NCl) with acetonitrile the complex [WF₄(NCl)(CH₃CN)] is obtained. Both donor acceptor complexes were characterized by crystal structure determinations. [MoO₂F₂(THF)₂] : Space group P2₁/n, Z = 4, structure solution with 1823 unique reflections, R = 0.033 for reflections with I > 2σ(I). Lattice dimensions at ?40°C: a = 636.2, b = 1119.5, c = 1625.2 pm; β = 93.92(1)º. The compound has a monomeric molecular structure with the fluorine atoms in trans-position to one another and with the oxygen atoms of the THF molecules in trans to the oxo ligands. [WF₄(NCl)(CH₃CN)] : Space group P2₁/m, Z = 2, structure solution with 1119 unique reflections, R = 0.038 for reflections with I > 2σ(I). Lattice dimensions at 20°C: a = 511.7, b = 714.9, c = 1002.5 pm; β = 102.59(10)º. The compound has a monomeric molecular structure in which the nitrogen atom of the acetonitrile molecule coordinates in trans-position to the N-chloro imido group W?N? Cl. The structural parameters of this group are WN = 172.2 pm, NCl = 161.1 pm, WNCl = 178.6º.     

Application of relaxation periods during electrodialysis of a casein solution: Impact on anion-exchange membrane fouling

Electrodialysis (ED) is a membrane process used on a large scale. However, one of the common problems is fouling of ion-exchange membranes stacked in the cell. The use of pulsed power, consisting in applying a constant current density during a fixed time of application (T_on) followed by a pause duration (T_off), was demonstrated recently as an effective fouling mitigation method for electrodialysis. Up until now, no work has investigated the potential of electrodialysis using pulsed electric field on protein fouling. The aim of the present work was to study the influence of pulsed electric field (PEF) with a low frequency square shaped periodic signal (T_on = 10 s–T_off = 10 s, T_on = 10 s–T_off = 40 s) in comparison with dc current during electrodialysis of a casein solution at different current densities (10, 20 and 30 mA/cm²) on membrane fouling. It appeared from these results that PEF, under certain conditions of pulse, would avoid fouling on anion-exchange membranes. For 10 s–40 s pulsed electric field conditions, no fouling was observed with any density, while for 10 s–10 s PEF conditions, fouling appeared only at current density over 10 mA/cm². dc current, whatever the current density conditions, led to a fouling on the diluate side of the AEM. Furthermore, when fouling occurred, magnitude layer thickness and dry weight increased with the applied current density. The nature of the fouling was identified as 97% protein. The protein fouling would be due to the dissociation of water molecules and/or heat increase at the anion-exchange membrane interface. The relaxation time of the pulse would limit both phenomena on the membrane.     

μs级负充电时不同体积分数去离子水与乙二醇混合液电性能的实验研究

 以去离子水与乙二醇的混合液（体积分数分别为36.5%,48.7%,59.0%及71.2%，以下简称混合液）作为同轴传输线的绝缘介质，进行了μs级高电压负充电条件下的正电极击穿实验，研究了混合液的击穿电压、击穿时间、相对介电常数及电阻率与体积分数的关系。实验结果表明：在充电电压为20kV时，71.2%的混合液比36.5%的混合液的平均击穿电压提高25.1%，平均击穿时间延长10.49%，而相对介电常数减小868%。同时，随着充电时间的缩短，混合液的击穿电压提高。