Progression of Organic Reactions on Resin Supports Monitored by Single Bead FTIR Microspectroscopy

We report the time courses of five solid-phase reactions obtained using single bead FTIR microspectroscopy. This time-resolved information aided in the determination of the required reaction time, the nature of the solid-phase reaction, and resin property, effectively assisting in the initial phase of our combinatorial chemistry efforts. Our results showed that solid-phase organic reactions proceed faster than generally speculated. In addition, we have shown that reactions on the surface and in the interior of the bead occur at the same rate for reactions studied. The reaction on the TentaGel resin was shown to be not faster than reactions on Wang resin, suggesting that the diffusion of the substrate into polystyrene bead copolymerized with 1% divinylbenzene is not rate-limiting. Finally, the capability of obtaining IR spectra from the partial surface of a single bead demonstrated the femtomolar detection limit of single bead FTIR microspectroscopy.     

Fe_3(CO)_9(μ_3-S)_2的P(SR)Cl_2和P(SR′)_3取代物的合成和结构研究

用P(SR)Cl_2和P(SR′)_3作n-酸配体,分别与Fe_3(CO)_9(μ_3-S)_2进行取代反应,得到6种新的一取代产物Fe_3(CO)_8(μ_3-S)_2L和3种新的二取代产物Fe_3(CO)_7(μ_3-S)_2L_2,并对它们进行了IR、~1H NMR和MS表征,测定了其中一种取代物Fe_3(CO)_8(μ_3-S)_2[P(SC_6H_5)Cl_2]的分子和晶体结构。     

Highly efficient, one-step macrocyclizations assisted by the folding and preorganization of precursor oligomers

Highly efficient, one-step macrocyclizations leading to the formation of macrocyclic hexa(aramides) in high yields (69-82%) are described. The one-step macrocyclizations were facilitated by the preorganization or folding of the backbones of uncyclized precursors in the course of macrocyclization. The preorganization of backbones was achieved by the presence of localized three-centered hydrogen bonds that were adopted in the design of a class of closely related, backbone-rigidified foldamers. The macrocyclization involved reactions between diacid chloride 1 and diamine 2. The crude reaction mixtures and products were conveniently examined by mass spectrometric method (MALDI-TOF). Compared to most traditional one-step macrocyclizations that usually require high dilution conditions and often lead to very low overall yields of the desired products, cyclic hexamers 3 were obtained as the overwhelmingly major product under a variety of reaction conditions, suggesting the generality of this approach.     

A New Application of Carbon Nanotubes Constructing Biosensor

Carbon nanotubes used for constructing biosensor was described for the first time. Single-wall carbon nanotubes (SWNTs) functionalized with carboxylic acid groups were used to immobilize glucose oxidase forming a glucose biosensor. The biosensor response can be determined by amperometric method at a low applied potential (0.40V).     

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］…     

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.