Syntheses and reactions of heterometallic complexes of nickel and copper with tetrathiotungstates. The molecular structures of [Ph(4)P](2)[S2W(mu-S)(2)Ni(S-2)] and W(mu-S)(4)Cu-2(PPh(3))(4)center dot py

Reaction of [Ph(4)P]2WS4 With NiCl2 in methanol solution in the presence of NaOCH3 leads to the formation of [Ph(4)P](2) [S2W(mu-S)(2)Ni(S-2)] (I) A Similar reaction between (NH4)(2)WS4 and NiCl2 under O-2 atmosphere in the presence of Ph(4)PCl or (n)Bu(4)NCl affords [Ph(4)P](2)([(S-2)W(O)(mu-S)(2)]Ni-2] (IIa) and [(n)Bu(4)N](2)([(S-2)W(O)(mu-S)(2)]Ni-2} (IIb) Under argon the same reaction gives [Ph(4)P](2)[Ni(WS4)(2)] (IIIa) and [(n)Bu(4)N](2)[Ni(WS4)(2)] (IIIb). [Ph(4)P](2)[Ni(WOS3)(2)] (IV) and [Ph(4)P](2)[Ni(WO2S2)(2)] (V) can be prepared from the reaction of [Ph(4)P]2WOS3 and [Ph(4)P]2WO2S2 with NiCl2. Treatment of (NH4)(2)WS4 with CuCl in the presence of PPh(3) in boiling pyridine produces W(mu-S)(4)Cu-2(PPh(3))(3) (VI), which can further react with excess PPh(3) to give W(mu-S)(4)Cu-2(PPh(3))(4) . py (VII). Complex I crystallizes in the space group P2(1)/n with the cell parameters: a = 20.049(4), b = 17.010(4), c = 14.311(7) Angstrom; beta = 110.24(3)degrees and Z = 4; R = 0.058 for 4267 independent reflections. The structural study confirms that complex I contains two terminal sulfide ligands, two bridging sulfide ligands, a side-on disulfide ligand, and a planar central W(mu-S)(2)Ni four membered ring. Complex VII crystallizes in the space group C2/c with the cell parameters: a = 26.436(8), b = 20.542(6), c = 19.095(8) Angstrom; beta = 125.00(3)degrees and Z = 4; R = 0.080 for 3802 independent reflections. The structural study reveals a perfect linear arrangement of the three metal atoms Cu-W-Cu.

Synthesis and structure of 1:1 complex of ethylphenyltin dichloride with N-4-methoxyphenyl-2-hydroxynaphthylideneimine

A novel organotin complex, EtPhSnCl(2) . 2HOC(10)H(6)CH = NC6H1OCH3 was synthesized, and its crystal structure was determined by X-ray diffraction method. The crystal is triclinic, belonging to space group, with unit cell parameters a = 1.150 8(5) nm, b = 1. 153 1(5) gm, c = 1. 004 6 (3) nm, alpha = 94. 15 (3)degrees, beta = 115.47 (3)degrees, r = 85. 94 (4)degrees, V = 1199 7(1) nm(3), Z=2, D-c=1.68 g/cm(3), mu=13. 20 cm(-1), F(000)=618 for 4 131 reflections tions. R=0. 047, R(w)=0. 047. The ligand coordinates to tin atom via phenolic oxygen atom. The complex has a distored trigonal bipyramidal structure, the phenolic oxygen atom of the ligand and one of two chlorine atoms occupy the axial position. The distance between noncoodinated nitrogen atom with phenolic oxygen atom is 0. 257 4 nm, which indicates that the intramolecular hydrogen bond of Schiff base ligand is retained in the complex.

钴-4-(5-氯-2-吡啶偶氮)-1,3-二氨基苯-Triton X-100体系的析相富集及痕量钴的光度测定

本文研究了TritonX-100在浊点条件下对钴-4-(5-氯-2-吡啶偶氮)-1,3-二氨基苯(5-Cl-PADAB)络合物的析相条件,在pH4.0～6.0介质中,将胶束溶液加热到92±1℃,保持40min,络合物即被TritonX-100相富集。富集液在575nm测定吸光度,钴含量在0～4μg/5ml范围内服从比尔定律,干扰离子可在TritonX-100析相液中加入H_2SO_4消除。拟定的方法灵敏、简捷,已用于不经分离直接测定人发及自来水中痕量钴。

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.

1-(4-fluorophenyl)-2-{4-phenyl-5-[(1H-1,2,4-triazol-1-yl) methyl]-4H-1,2,4-triazol-3-ylsulfanyl}ethanone

The crystal structure of the title compound, C19H15FN6OS, is stabilized by a weak intermolecular C-(HN)-N-... hydrogen-bond interaction.

Synthesis, crystal structure and biological activities of N '-(4-methoxybenzylidene)-2-(1H-1,2,4-triazol-1-yl) acetohydrazide

The title compound, N'-(4-methoxybenzylidene)-2-(1H-1,2,4-triazol-1-yl)acetohydrazide, was synthesized and its structure was confirmed by means of IR, MS,H-1 NMR and elemental analysis. The single crystal structure of the title compound was determined by X-ray diffraction. The preliminary biological test shows that the synthesized compound has a low antifungal activity.

Synthesis and. crystal structure of N '-(4-fluorobenzylidene)-2-(1H-1,2,4-triazole-1-yl) acetohydrazide

N'-(4-fluorobenzylidene)-2-(1H-1 2,4-triazole-1-yl) acetohydrazide was synthesized by the reaction of 4-fluorobenzaldehyde with 2-(1H-1 2,4-triazole-1-yl) acetohydrazide. The structure was confirmed via elemental analysis, MS, H-1 NMR, IR, and X-ray diffraction. It crystallized in a monoclinic system with space group P2 (1) a = 0.4905 (1) nm, b = 0.8160 (2) nm, c = 1.4105 (3) nm, beta = 93.33 (3)degrees, Z = 2, V = 0.5636 (2) nm(3), D-c = 1.457 Mg/m(3), mu = 0.112 mm(-1), F(000) = 256, and final R-1 = 0.0685. Several intermolecular hydrogen-bond interactions existed in the crystal structure, facilitating the stabilization of the compound.

反式和顺式-1，2-二氰-（4-乙基苯）乙烯结构的谱学分析

合成了2种新型的可溶性四氮杂卟啉中间体：反式-1，2二氰-（4-乙基苯）乙烯和顺式-1，2-二氰（4-乙基苯）乙烯。通过UV-Vis，FFIR，GC／MS，^1H NMR等方法对这2种化合物的结构进行了表征，给出了它们完整的结构信息。分析比较了顺、反异构体结构上的差异，分析两者的紫外-可见光谱（UV-Vis）、红外光谱（FTIR）和核磁共振光谱（^1H NMR）谱图的差异及其产生原因。

2,4-D对鱼腥藻增殖的效应

本文在实验室批量培养,室外小池大量培养和塑料大棚大面积培养的基础上,研究了植物激素2,4-D刺激鱼腥藻增殖的效应。浓度在0.01—2.00μg/mL范围内都具有刺激鱼腥藻增殖的效果,随着浓度增加,这种效果降低。品质分析结果表明,0.01μg/mL2.4-D可提高蛋白质和叶绿素a的含量;浓度为0.05μg/mL时,二者的含量与对照相差不大;浓度达到0.1μg/mL时,二者的含量降低。本文提出,2,4-D刺激鱼腥藻增殖的应用浓度应在0.05μg/mL以下,以0.01μg/mL效果最佳。

（一）2，4－二甲基戊二烯基烯土氯化物的合成及其对丁二烯的聚合活性（二）酞菁铜衍生物 LB 膜材料的合成及其气敏特性

本文通过元素分析，红外光谱，热失重分析，质谱。X 光电子能谱的测定以及对化合水解产物的分析。确认合成了下列三种新型 2，4－二甲基戊二烯基稀土氯化物。（I）[2,4-(CH_3)_2C_5H_5]LnCl_2·nTHF (2,4-(CH_3)_2C_5H_5 = 2, 4－二甲基戊二烯基；Ln = Pr, Nd, Sm, Gd; n = 3)。（II）[2,4-(CH_3)_2C_5H_5]LnCl_2·nTHF (Ln = Pr, Nd; n = 2, 3)。（III）[2,4-(CH_3)_2C_5H_5]LnCl_2·nTHF (Ln = Nd, Sm; n = 1)。在稀土金属有机化合物中尚未见此类化合物的报导。化合物的质谱分析结果表明，配位的四氢呋喃分子容易从配合物分子中脱落，形成带一个四氢呋喃，甚至不带四氢呋喃的配合物。说明配合物分子中不带四氢呋喃的形式是较稳定的。化合物的 X 光电子能谱结果表明化合物不是混合物。化合物水解产物的定量气相色谱分析进一步证实所合成的化合物为我们所预期的产物。实验结果表明，单体转化率受溶剂影响较大。在以环戊烷为溶剂的聚合反应中，聚合活性较高。而以甲苯为溶剂的聚合反应中，其聚合活性较低。在主催化剂不变的条件下，改变 Al/Nd 摩尔比，单体的转化率有明显的变化。同一 Al/Nd 摩尔比，不同催化剂用量也对单体的转化率有较大的影响。对聚合物的微观结构分析表明，溶剂，铝钕摩尔比催化剂用量对聚丁二烯的顺－1，4 含量均有影响，但影响不大。

1,2,4-三氯苯胁迫对萌发大豆种子中活性氧的影响

以盆栽法研究了不同浓度 1,2 ,4 三氯苯 (TCB)胁迫对萌发大豆种子中活性氧代谢的影响 .结果表明 ,10 0～ 30 0 μg·g-1TCB胁迫初期 (1～ 3天 )促使萌发大豆种子呼吸强度升高及其峰值提前出现 ,超氧阴离子自由基 (O2 - )及过氧化氢 (H2 O2 )的积累显著增加 ,同时伴随丙二醛 (MDA)含量升高 ,显示发生膜脂质过氧化作用 .TCB胁迫 1～ 6天使活性氧清除酶功能紊乱 ,其中过氧化物酶 (POD)活性升高 ,超氧化物岐化酶 (SOD)活性开始上升后转为下降 .在萌发大豆种子受TCB胁迫伤害过程中 ,活性氧代谢失衡造成的膜脂质过氧化将起着重要作用 .

1，2，4－三氯苯在土壤中的降解

在好氧和厌氧两种条件下研究了１，２，４－三氯苯的降解，结果表明，１，２，４－三氯苯的好氧降解和厌氧降解均遵循一级反应动力学在同样水分、温度及初始浓度条件下，１，２，４－三氯苯的好氧降解比厌氧降解迅速，其半衰期分别为１．８９～５．８６和５．０７～１９．０８ｄ土壤中１，２，４－三氯苯的初始浓度对于其降解也有显著影响，在０～１００μｇ·ｇ－１的范围内，浓度增高时，其降解加快，说明污染物浓度对降解的影响；在１０～３０℃范围内，温度增高导致降解过程加快，归因于温度升高对微生物酶活性的激活作用．