静电和疏水效应对TGEV主蛋白酶二聚体稳定性的影响

从TGEV 3CL蛋白酶二聚体结构出发,研究了TGEV 3CL蛋白酶二聚体单体之间的静电和疏水相互作用.蛋白质的静电相互作用通过有限差分方法求解Poisson-Boltzmann方程得到,疏水相互作用通过分析溶剂可及性表面模型得到.考察了不同pH值对TGEV 3CL蛋白酶二聚体静电和疏水相互作用的影响,在pH值为5.5～8.5时,二聚体静电相互作用能、静电去溶剂化能和疏水自由能都较小,表明在该条件下静电和疏水相互作用有利于二聚体的稳定存在,这符合实验结晶所需条件.pH值对静电去溶剂化能的影响大于疏水自由能,表明静电作用是造成强酸或强碱条件下二聚体不能稳定存在的主要原因.     

Ag+、Hf2+与Tl3+对Belousov-Zhabotinskii反应影响的初步研究

本文初步研究TAg＋、Hg’十与T13十对以Mh‘十为催化剂的B－Z反应的影响，观察这些Br’去除离子存在下的极投环行为，并对其机理进行初步研讨．按照FKN机理同，B－Z反应是受Br一控制的．1979年N。SZtiCZills将适量的Ag十加入B·Z反应系统，澳离子选择电极上振荡虽被抑制了，但拍电极上却出现频率更高的振荡问．由于Ag十与Bt一生成了AgBr沉淀，使系统的［Br则降至其临界值以下，因此，Noszticzius认为不可能是Br控制的，FKN机理不再适用．1981年K5rs。等人报导了能与Br一形成稳定配合物的Hg‘十与T户十对B－Z反应的影响［3］…     

苯基荧光酮荧光分光光度法测定痕量锗的研究

锗具有增血、抗炎症、抗衰老等多种医疗功能 ,因此 ,越来越受到人们的关注。荧光光度法测定微量锗已有报道[1～ 4] 。用苯基荧光酮荧光度法测定锗未见报道。本文利用苯基荧光酮与锗在醋酸 醋酸钠缓冲溶液中络合物形成速度快的优势 ,使其先在缓冲溶液中显色 ,然后在 0 .3ｍｏｌ ＬＨＣｌ介质中测定其荧光强度 ,用于粉煤灰中痕量锗的测定 ,得到满意结果。1　实验部分1 1　仪器与试剂ＲＦ - 5 4 0荧光分光光度计 (日本岛津 )。锗标准溶液 ( 1ｇ Ｌ) :称取 0 .1 0 0 0ｇ纯锗粉于 5 0ｍｌ小烧杯中 ,加入 5ｍｌＮａＯＨ ,再加入几滴 30 %Ｈ2 Ｏ2…     

水杨基荧光酮—过氧化氢催化动力学光度法测定痕量锇（Ⅳ）

在碱性介质中，痕量锇（Ⅳ）对水杨基荧光酮（ＳＡＦ）与过氧化氢的氧化还原反应有显著的催化作用。本文以此为基础，提出用分光光度催化动力学测定痕量锇（Ⅳ）的新方法。本法未加掩蔽剂时的线性范围是０．０８－０．８０μｇ／Ｌ，加入掩蔽剂后的线性范围是０．０８－０．８０μｇ／Ｌ，检出限为０．０８μｇ／Ｌ。本法用于实际样品中Ｏｓ（Ⅳ）的测定，结果良好，本实验还测定了此催伦反应的活化能和反应级数。     

Structures of E. coli peptide deformylase bound to formate: insight into the preference for Fe2+ over Zn2+ as the active site metal

E. coli peptide deformylase (PDF) catalyzes the deformylation of nascent polypeptides generated during protein synthesis. While PDF was originally thought to be a zinc enzyme, subsequent studies revealed that the active site metal is iron. In an attempt to understand this unusual metal preference, high-resolution structures of Fe-, Co-, and Zn-PDF were determined in complex with its deformylation product, formate. In all three structures, the formate ion binds the metal and forms hydrogen-bonding interactions with the backbone nitrogen of Leu91, the amide side chain of Gln50, and the carboxylate side chain of Glu133. One key difference, however, is how the formate binds the metal. In Fe-PDF and Co-PDF, formate binds in a bidentate fashion, while in Zn-PDF, it binds in a monodentate fashion. Importantly, these structural results provide the first clues into the origins of PDF's metal-dependent activity differences. On the basis of these structures, we propose that the basis for the higher activity of Fe-PDF stems from the better ability of iron to bind and activate the tetrahedral transition state required for cleavage of the N-terminal formyl group.     

Photochemical Preparation of Highly Water-Soluble Pendant [60]Fullerene-Aminopolymers

Abstract— In order to introduce fullerene cages into an aqueous environment, pendant [60]fullerene-poly(propionylethyle-neimine-co-ethyleneimine) was prepared photochemical-ly. The pendant polymer is highly water soluble, with equivalent aqueous solubilities of the polymer-bound [60]fullerene much higher than the solubility of [60]ful-lerene in toluene. The photochemical reaction between [60]fullerene and secondary amine moieties in the ami-nopolymers likely follows a photoinduced electron transfer-proton transfer mechanism. The pendant polymer structures, which are represented by dehydrogenated di-and tetra-aminofullerene linkages, were characterized by use of proton and 13C NMR, Fourier transform-infrared spectroscopy, gel-permeation chromatography and optical spectroscopic methods.     

Poly（meta-phenylene） Derivative with Rigid Twisted Biphenyl Units in Backbone： Synthesis, Structural Characterization, Photophysical Properties and Electroluminescence

A soluble poly(meta-phenylene)derivative with rigid twisted biphenyl unit was synthesized by the Yamamoto coupling reaction.The polymer is soluble in common organic solvents,and the number-average molecular weight is about 6500.The UV-Vis and quantum chemical calculation indicate that the different conformation segments named "conformers" exist in the polymer backbones;it was also further confirmed by the single crystal X-ray diffraction study of the dimeric model compound.The π-π transition of biphenyl segments of twisted and planar conformations made the polymer exhibit a strong absorption around 256 nm and a weak absorption at about 300 nm.Furthermore,the polymer exhibits a strong UV photoluminescence at 372 nm when the excitation wavelengths are longer than 300 nm.The ultraviolet-emitting electroluminescence(EL)device with the single layer structure shows EL λmax of the derivative at 370 nm.     

电子亲和势法判断负离子聚合单体的活性

提出了利用不同取代基烯类单体的电子亲和势来判断其负离子聚合反应活性的方法.采用密度泛函理论的B3LYP/6-31G(d)方法优化了不同取代基烯类单体几何构型,在B3LYP/6-311++G(3df,2p)水平上计算了其电子亲和势.通过电子亲和势计算值与文献报道实验数据比较,表明本文采用的计算方法是比较可靠的.结合不同取代基烯类单体的电子亲和势的计算结果,通过与Q-e关系及取代基常数σ数据进行比较表明,电子亲和势可以用来判断不同单体负离子聚合反应的活性高低.     

Preparation and characterization of sodium carboxymethylcellulose/poly(N-isopropylacrylamide)/clay semi-IPN nanocomposite hydrogels

A new kind of pH-/temperature-responsive semi-interpenetrating polymer network hydrogels based on linear sodium carboxymethylcellulose (CMC) and poly(N-isopropylacrylamide) (PNIPA) cross-linked by inorganic clay (CMC/PNIPA/Clay hydrogel) was prepared. The temperature- and pH-responsive behaviors, the mechanical properties of these hydrogels were investigated. The CMC/PNIPA/Clay hydrogels exhibited a volume phase transition temperature around 32 °C with no significant deviation from the conventional PNIPA hydrogels. The swelling ratio of the CMC/PNIPA/Clay hydrogels gradually decreased with increasing the contents of clay. The influence of pH value on swelling behaviors showed that there is a maximum swelling ratio at pH 5.9. Moreover, the CMC/PNIPA/Clay hydrogels exhibited excellent mechanical properties with high tensile stress and elongation at break in excess of 1200%.     

Observations on the swelling characteristics of the zwitterionic hydrogel of poly(1-3-sulfopropyl)-2-vinyl-pyridinium-betaine hydrogel

Samples of poly[1-(3-sulfopropyl)-2-vinyl-pyridinium-betaine] (PSPV) have been synthesized to high conversion by free radical polymerization in aqueous solution of the zwitterionic monomer SPV with several concentrations of the crosslinker N,N′-methylene-bis-acrylamide (MBA). The densities of the resultant xerogels increased regularly with the content of MBA. Hydrogels obtained by swelling them in water and aqueous KSCN solution were examined by gravimetric and dimensional analysis. The water contents increased with decreasing content of MBA, the value of 92.7 wt% at the lowest MBA content being higher than that for other zwitterionic hydrogels. Enhanced swelling occurred in 1 M aq. KSCN at each MBA content, the total swelling being 98.1 wt% at the lowest crosslinker content. Swelling increased with increasing temperature. An approximate procedure to formulating swelling equilibrium in term of the volume fraction of water in hydrogel, in conjunction with the van’t Hoff equation, yields a small positive value for the enthalpy of swelling. This is compared with values derived similarly for other hydrogels.