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Guisado-Barrios G Li Y Slawin AM Richens DT Gass IA Murray PR Yellowlees LJ Brechin EK 《Dalton transactions (Cambridge, England : 2003)》2008,(4):551-558
Reaction of MnCl(2).4H(2)O with H(3)L (H(3)L = tris(6-hydroxymethyl-2-pyridylmethyl)amine) in methanol gives hepta-coordinated [Mn(H(3)L)]Cl(2) involving attachment of Mn(II) to all four nitrogens and three hydroxymethyl arms. Reaction of H(3)L with Fe(ClO(4))(2).6H(2)O in CH(3)CN in the presence of NaO(2)CC(6)H(5) in an attempt to make [Fe(III)OH(H(3)L)(O(2)CC(6)H(5))](ClO(4)), a putative model for soybean lipoxygenase-1, instead gave rise to the linear triiron(III) complex [Fe(3)L(2)](ClO(4))(3) with all three hydroxymethyl arms deprotonated and forming three alkoxide bridges between each Fe(III) centre. The central Fe(III) is hexa-coordinated to only the alkoxide bridges and flanked by two hepta-coordinated iron(III) centres analogous to the Mn(ii) complex. [Fe(3)L(2)](ClO(4))(3) exhibits two reversible 1e(-) reductions to mixed-valence [Fe(3)L(2)](2+) and [Fe(3)L(2)](+) forms. Structure data and magnetochemistry on [Fe(3)L(2)](ClO(4))(3) reveals the tightest Fe-O-Fe angle (87.4 degrees ) and shortest Fe...Fe distance (2.834 A) yet found for any weakly antiferromagnetically-coupled high spin alkoxide-bridged di- or triiron(iii) system and challenges current theories involved in correlating the extent/nature of magnetic interactions in such systems based on Fe-O(bridge) distances and Fe-O-Fe angles. The central hexa-alkoxide coordinated Fe(III) is novel and shows a remarkable resistance towards reduction to Fe(II). 相似文献
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Julian R. Osman Joe A. Crayston Allin Pratt David T. Richens 《Journal of Sol-Gel Science and Technology》2008,46(2):126-132
Mixed IrO2–TiO2 oxides were prepared by the sol–gel method by adding an aqueous solution of an iridium(III) acetate precursor [Ir3O(OAc)6 (HOAc)3]OAc, to titanium tetraethoxide in ethanol. By using an acetylacetonate modifier to stabilize the hydrolysed titanium alkoxide
and by omitting a catalyst, gels were produced in all cases. Transmission electron microscopy and EDX analysis confirmed the
high dispersion of iridium in the dried gel material on the nanometre scale. The images also show spherical cage features
up to 20 nm in diameter. High mass losses of the gels in the TGA scans suggested low degrees of hydrolysis of the acetate
precursor, but calcination gave a crystalline, mixed oxide (TixIr1–xO2) solid solution. The precursor is also soluble in ethanol, which provides a slightly modified route to similar materials. 相似文献
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While performing biomolecular interaction analysis (BIA), scientistsoften use surface plasmon resonance (SPR) to measure rate constantsof the associated reactions. A mathematical model of a BIAcoreTM,a common SPR device, consists of a convection-diffusion equationin a channel with a reacting surface at the channel ceiling.Asymptotic and singular perturbation techniques are used toanalyse the concentration of the reacting species in two cases:when the reaction occurs much more slowly than diffusion, andwhen the reaction occurs on the same time-scale as diffusion.Linear and nonlinear integral equations result from the analysis;explicit and asymptotic solutions are constructed for physicallyrealizable cases. These expressions provide a direct way toestimate the rate constants from raw data. 相似文献
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以二硫化碳和金属钠为基础物质合成了四硫富瓦烯(TTF)锌的配合物(TTF)Zn(NBu4)2。利用该化合物与苯甲酰氯反应得到的稳定化合物C17H10O2S5在甲醇钠溶液中与2,3-二溴丙醇反应成功合成出目标化合物(一种新配体),其化学组成为C6H6OS5。利用IR谱、^1HNMR谱及元素分析对此化合物进行了表征。 相似文献
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对-叔丁基杯[8]芳烃键合硅胶制备及其毛细管电色谱性能研究 总被引:1,自引:0,他引:1
以γ-(环氧丙氧)丙基键合硅胶为前体,于硅胶表面键合环氧基,在催化剂存在下以杯芳烃钠盐开环制备杯芳烃键合硅胶固定相.该方法反应条件温和,适用性强.将这个新方法首次用于制备对-叔丁基杯[8]芳烃电色谱键合固定相(C8BS),采用加压电色谱初步评价其电色谱性能.研究结果表明,C8BS电渗流(Electrosmoticflow,EOF)较小,但通过控制键合反应及使用压力辅助电色谱可部分弥补上述不足.该固定相的EOF受流动相pH影响小(pH=3-8),同时大环配体屏蔽效应能有效地克服硅羟基引起的碱性化合物拖尾现象,这对电色谱分离具有重要意义.通过分步封尾研究EOF的来源发现,杯芳烃酚羟基对EOF有弱的贡献,这与报道的杯芳烃涂层具有径向电渗流调控能力相一致. 相似文献
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