On Transition Structures for Hydride Transfer Step in Enzyme Catalysis. A Comparative Study on Models of Glutathione Reductase Derived from Semiempirical, HF, and DFT Methods

As a model of the chemical reactions that take place in the active site of gluthatione reductase, the nature of the molecular mechanism for the hydride transfer step has been characterized by means of accurate quantum chemical characterizations of transition structures. The calculations have been carried out with analytical gradients at AM1 and PM3 semiempirical procedures, ab initio at HF level with 3-21G, 4-31G, 6-31G, and 6-31G basis sets and BP86 and BLYP as density functional methods. The results of this study suggest that the endo relative orientation on the substrate imposed by the active site is optimal in polarizing the C4-Ht bond and situating the system in the neighborhood of the quadratic region of the transition structure associated to the hydride transfer step on potential energy surface. The endo arrangement of the transition structure results in optimal frontier HOMO orbital interaction between NADH and FAD partners. The geometries of the transition structures and the corresponding transition vectors, that contain the fundamental information relating reactive fluctuation patterns, are model independent and weakly dependent on the level of theory used to determine them. A comparison between simple and complex molecular models shows that there is a minimal set of coordinates describing the essentials of hydride transfer step. The analysis of transition vector components suggests that the primary and secondary kinetic isotope effects can be strongly coupled, and this prompted the calculation of deuterium and tritium primary, secondary, and primary and secondary kinetic isotope effects. The results obtained agree well with experimental data and demonstrate this coupling.     

Reactions of magnesium formate on supports

Thermal decomposition of supported magnesium formate has been studied by gas chro-matography.The reaction paths of decomposition of supported magnesium formate depend on thenature of the supports.For Mg(HCO_2)_2/HZSM-5,the zeolite behaves as a dehydration catalyst togive CO and H_2O at lower temperatures;when the zeolite is modified by phosphorus,the methanationreaction will be partly restrained.In the case of Mg(HCO_2)_2/AC,strong adsorption of CO_2 leadsto the formation of the shoulder peak of CO_2 at higher temperatures,however,CH_4 disappears aftermodified by phosphorus.For Mg(HCO_2)_2/Al_2O_3,the dehydrogenation of HCO_2~- takes place on thesurface of Al_2O_3.The decomposition of Mg(HCO_2)_2 on SiO_2 in hydrogen yields two peaks of COand only one appears after modified by phosphorus.When Mg(HCO_2)_2 decomposes on MgO,the firstpeak of CO_2 arises from the reaction of surface Mg~(2+) with HCO_2~- from dissociated Mg(HCO_2)_2.     

双电层相互重叠时蒙脱胶体表面阴离子的负吸附

本文用Ag-AgCl电极判断平衡,测定双电层处于不同重叠程度下肢体表面阴离子的负吸附量Γ.结果表明,胶体表面双电层相互重叠程度可由两胶体表面间的中点电位φd与外Helmhotz面处的电位φd之比表征;阴离子负吸附随双电层重叠程度和电解质浓度的增加而显著减小.     

改性ZSM—5分子筛在甲苯一段硝化中的应用

对ＮａＺＳＭ－５分子筛进行改性，在其表面引入铁，镁离子，用作硝硫混酸对甲苯一段硝化反应的催化剂，明显提高产物中对硝基甲苯的生成比例，研究了影响反应结果的因素。     

Differential pulse polarographic determination of salicylaldehyde as its Girard-P derivative

A method for the determination of salicylaldehyde (2 × 10^–6–10^–4 M) by differential-pulse polarography, based on the in situ formation of its Girard-P derivative in aqueous solution at pH 2.5, is proposed. The relative standard deviation was 1.5% (ten determinations of 4 × 10^–5 M level). The applicability of this method was checked in synthetic samples containing salicyl alcohol,o-aminophenol, 2-methylphenol, salicylic acid and 4-aminobenzoic acid.     

2,4,6-三硝基苯酚改性锆铝复合氧化物固定相分离富勒烯的色谱性能研究

制备了用于分离C60和C70的2，4，6－三硝基苯酚改性锆铝复合氧化物高效液相色谱固定相，考察了流动相中甲苯的含量、柱温及流速对C60和C70分离的影响，同时比较了酸腐蚀前后锆铝复合氧化物基质对分离的影响，结果表明，2，4，6－三硝基苯酚改性酸腐蚀后锆铝复合氧化物填料对富勒烯表现出较强的分离能力，具有作为富勒烯制备分离的潜力。     

Effect of amphiphilic molecules upon chromatic transitions of polydiacetylene vesicles in aqueous solutions

Effect of amphiphilic molecules upon the chromatic transitions of polymerized 10,12-pentacosadiynoic acid (PCDA) vesicles in aqueous solutions was reported. The colorimetric response of polymerized PCDA vesicles for 1-pentanol is higher than that for ethanol due to more hydrophobic property of 1-pentanol. The colorimetric response of polymerized PCDA vesicles for sodium dodecyl sulfate (SDS) and Triton X-100 is lower than that for cetyltrimethylammonium bromide (CTAB). The strong ability of CTAB to induce chromatic transition of the vesicles is related to the positively charged headgroups of CTAB, which favors approach of CTAB to the negatively charged carboxylate groups at the vesicle surface. The insertion of alkyl chain of CTAB into the hydrophobic domain perturbs the conformation of the conjugated polymer backbone and induces color change of polydiacetylene vesicles. For a series of alkylamine hydrochloric salts, the longer the alkyl chain, the stronger the ability of alkylamine to induce chromatic transition of polydiacetylene vesicles.     

Synthesis and magnetic properties of trinuclear nickel(II) complexes bridged by α-benzyldioximato groups

Four new NiII–NiII–NiII homotrinuclear complexes namely [Ni(-BD)2{NiL2}](ClO4)2 [L = 1,10-phenanthroline (phen), 5-nitro-1,10-phenanthroline (5-NO2-phen), 2,2-bipyridyl (bpy) or 4,4-dimethyl-2,2bipyridyl (Me2bpy) and (-BD)– = -benzyldioximato ion] have been prepared and characterized. Based on elemental analyses, i.r. spectra, conductivity measurements, extended -benzyldioximato-bridged systems consisting of three nickel(II) ions in which the central nickel(II) ion has a square-planar environment and the end capped two nickel(II) ions have a distorted octahedral environment are proposed for these structures. The temperature dependence of the magnetic susceptibility for complexes (1) (phen), (2) (5-NO2-phen), (3) (bpy) and (4) (Me2bpy) were measured over the 77–300 K range and the observed data were successfully simulated by an equation based on the spin Hamiltonian operator (H^ = –2JS^1S^2), giving the exchange integral J = –13.31 cm–1 for (1), J = –7.37 cm–1 for (2), J = –8.96 cm–1 for (3) and J = –7.33 cm–1 for (4) These results indicate a weak antiferromagnetic spin exchange interaction between the two terminal nickel(II) io     

L-赖氨酸锌兔体内生物利用度研究

用原子吸收分光光度法和氨基酸自动分析仪法分别测定兔血清锌浓度和血清L-赖氨酸含量．结果表明．L-赖氨酸锌中锌的相对生物利用度明显优于硫酸锌．而其中的L-赖氨酸的相对生物利用度与L-赖氨酸组比较无明显差异．     

铁钼硫原子簇化合物的合成与结构化学 Ⅵ.[MoFe_3S_4]双类立方烷化合物的循环伏安及穆谱研究

我们曾报道双类立方烷簇合物(Et_4N)_4[Mo_2Fe_7S_8(SR)_(12)](R=Ph,1;R=o-tolyl,2;R=m-tolyl,3;R=p-tolyl,4)的结构,磁性质,及化学反应.氧化还原酶的固氮酶,其活性部位的 Mo 和 S 元素,可以发生丰富的氧化还原反应,研究这类铁钼硫簇合物的氧还性质,对了解电子传递情况是极为有用的.