Phenylthiolate as a sigma- and pi-donor ligand: synthesis of a 3-D organometallic coordination polymer [K2Fe(SPh)(4)](n)

The synthesis and crystal structure of the first mixed-metal organometallic polymer network containing phenylthiolato ligands, [K2Fe(SPh)(4)](n), are investigated. The simple phenyl-thiolate acts as a sigma- and pi-donor ligand to give a 3-D potassium iron coordination polymer with both metal-carbon and metal-sulfur coordination interactions.

Novel polyoxometalate-templated, 3-D supramolecular networks based on lanthanide dimers: Synthesis, structure, and fluorescent properties of [Ln(2)(DNBA)(4)(DMF)(8)][Mo6O19] (DNBA=3,5-dinitrobenzoate)

The spherical Lindquist type polyoxometalate, Mo6O192-, has been used as a noncoordinating anionic template for the construction of novel three-dimensional lanthanide-aromatic monocarboxylate dimer supramolecular networks [Ln(2)(DNBA)(4)(DMF)(8)][Mo6O19] (Ln = La 1, Ce 2, and Eu 3, DNBA = 3,5-dinitrobenzoate, DMF = dimethylformamide). The title compounds are characterized by elemental analyses, IR, and single-crystal X-ray diffractions. X-ray diffraction experiments reveal that two Ln(III) ions are bridged by four 3,5-dinitrobenzoate anions as asymmetrically bridging ligands, leading to dimeric cores, [Ln(2)(DNBA)(4)(DMF)(8)](2+); [Ln(2)(DNBA)(4)(DMF)(8)](2+) groups are joined together by pi-pi stacking interactions between the aromatic groups to form a two-dimensional grid-like network; the 2-D supramolecular layers are further extended into 3-D supramolecular networks with 1-D box-like channels by hydrogen-bonding interactions, in which hexamolybdate polyanions reside. The compounds represent the first examples of 3-D carboxylate-bridged lanthanide dimer supramolecular "host" networks formed by pi-pi stacking and hydrogen-bonding interactions encapsulating noncoordinating "guest" polyoxoanion species. The fluorescent activity of compound 3 is reported.

Aggregation behavior of amphiphilic D-pi-A molecules bearing recognition group

Aggregation behavior of two amphiphilic D-pi -A molecules bearing barbituric acid as both recogniton group and electron-drawing substituent, 5-(4-dodecyl oxybenzylidene)-(1H, 3H)-2,4,6-pyrimidine trione (PB12) and 5-(4-N,N-didodecyl aminobenzylidene)-(1H,3H)-2,4,6-pyrimidine trione (AB(12)) was studied by UV-visible, fluorescence, and surface voltaic spectroscopies (SPS). The experimental results indicate that PB12 tends to form J-aggregate and AB(12) tends to form H-aggregate under increasing concentration. An intramolecular twisted charge transfer (TICT) emission around 500 nm is observed when J-aggregate is formed between PB12 molecules, and an excimer emission around 600 nm is observed when H-aggregate is formed between AB(12) molecules.

环丙烷衍生物在D_2O离子体系中的H/D���换反应

在Ｄ_２Ｏ化学反应气条件下研究了环丙烷衍生物的Ｈ／Ｄ交换反应特性。发现了三种新的 产物离子［Ｍ＋１］~＋、［Ｍ＋２］~＋和［Ｍ＋３］~＋．应用碰撞诱导碎裂（ＣＩＤ）技术研究了这些离子的碎裂反应 特性。实验结果表明三种新的产物离子是由反应物与试剂离子之间发生Ｈ／Ｄ交换反应生成的。并 获得了环丙烷衍生物结构中活泼氢位置及其数量的信息。

电喷雾串联质谱法鉴定桔梗皂苷D

改进了桔梗皂苷D���提取、分离及鉴定方法 .首次利用大孔树脂脱糖脱色及薄层硅胶作色谱系介质 ,并首次利用电喷雾质谱对目标化合物进行跟踪分析 ,使高纯度的目标化合物的分离和鉴定工作得以简化

Electrochemical and spectroscopic study of vitamin D-2 by in situ thin layer CD spectroelectrochemistry

The electrooxidation of vitamin D-2 (VD2) was studied by cyclic voltammetry and in situ circular dichroic (CD) spectroelectrochemistry for the first time, The mechanism of electrooxidation and some useful kinetic and adsorption parameters were obtained. The results showed that the oxidation of VD2 in ethanol solution is an irreversible diffusion controlled process following a weak adsorption of the electroinactive product at a glassy carbon electrode, which blocks the electrochemical reaction. The electrooxidation occurs mainly at the triene moieties of the VD2 molecule. The CD spectroelectrochemical data were treated by the double logarithm method together with nonlinear regression, from which the formal potential E-0 = 1.08 V, alphan = 0.245, the standard electrochemical rate constant k(0) = 4.30( +/- 0.58) x 10(-4) cm s(-1) and the adsorption constant beta = 1.77(+/- 0.25) were obtained. (C) 2001 Elsevier Science B.V. All rights reserved.

H/D exchange reaction of cyclopropane derivatives in the ion system of CD3OD

The fragmentation properties of the product ions [M + 1](+), [M + 2](+) and [M + 3](+) formed by ion-molecule reaction of four cyclopropane derivatives with the ion system of CD3OD were investigated by using collision-induced dissocation technique. The experiment results indicated that the product ions were produced via the H/D exchange reaction between reactants and reactive reagent ions of CD3OD. There are two exchangable hydrogen atoms on the ring of compounds 1 and 2, and only one for compound 3 and 4.

环丙烷衍生物在CD_3OD���子体系中的H/D���换反应

研究了环丙烷衍生物在CD3 OD���子体系中的H/D���换反应产物离子 [M +1]+ 、[M +2 ]+ 和[M +3]+ 的碰撞诱导碎裂 (CID)反应特征。实验结果表明这些产物离子是由反应物与试剂离子之间发生H/D���换反应生成的。获得了环丙烷衍生物结构中活泼氢位置及其数量的信息

The channel behavior of gramicidin D in the self-assembled monolayer

It was found for the first time that gramicidin D (GD) molecules can be incorporated into the ODM monolayer which is self-assembled on the surface of the gold electrode and form monovalent cation channels.

Electrochemical study of gramicidin D forming ion-permeable channels in the bilayer lipid membranes

Gramicidin within the lipid bilayer matrix is a well-known channel-forming polypeptide, but the mechanism of the ions across the membrane induced by gramicidin is not well understood. We found that at very low concentration of gramicidin in a bilayer lipid membrane, the channel behavior was controlled by the voltage applied across the membrane. When the voltage is higher than 75 mV, the channel is closing, while lower than 75 mV, the channel is opening. But when the concentration of the gramicidin in the BLMs is high, the channel behavior is changed into voltage-independent. (C) 1998 Elsevier Science Ltd. All rights reserved.

聚(ε-己内酯)/聚(d,l-丙交酯)共混物膜在酶促降解过程中的形态变化

聚（ε┐己内酯）／聚（ｄ，ｌ┐丙交酯）共混物膜在酶促降解过程中的形态变化张杰甘志华＊梁奇志景遐斌（吉林工业大学理学院应用化学系长春）（中国科学院长春应用化学研究所长春１３００２２）关键词聚己酸内酯－聚丙交酯共混物，酶促降解，形态１９９７－１０－３０收…

生物降解ε-己内酯/d,l-丙交酯共聚物的合成与表征

采用一种新型的稀土配位化合物Ｙ（ＣＦ３ＣＯＯ）３／Ａｌ（ｉ－Ｂｕ）３为催化剂，制备了不同组成的ε－己内酯／ｄ，ｌ－丙交酯共聚物，并用ＧＰＣ、ＮＭＲ和ＤＳＣ表征了共聚物的结构．结果表明通过改变初始投料中两种单体的比例，可以调节共聚酯的化学结构，而共聚物的形态则受结构影响很大．

介体型双酶D-氨基酸传感器的制备

用一种全氟代磺酸酯阳离子交换树酯(East-man AQ-55),将D-氨基酸氧化酶(DAAO),辣根过氧化物酶(HRP)以及1,1′-二(α-羟基乙基)二茂铁(BHFc)同时包埋在玻碳电极(GCE)表面,制成双酶D-氨基酸电流式传感器。电极的工作电位为+0.18V(vs.SCE)响应时间小于50s。对于D-丙氨酸来说,测定的最适宜pH为7.8,测定的线性范围为0.05～0.75mmol/L该电极具有良好的重现性,可以连续使用200次。

固体ASm_2I_5的d-f跃迁荧光和反射光谱(A=K,Rb,Cs,T1)

本文系统地研究了化合物ASm_2I_5(A=K,Rb,Cs,T1)固体粉末的荧光光谱和反射光谱.讨论了Sm~(2+)在立方晶体场中的分裂能随着碱金属离子半径的增大而减小和f-d���发能随着A-I(A=Rb,T1)键的共价性增加而明显降低的现象.并从晶场效应和化学键性质两个方面解释了ASm_2I_5(A=K,Rb,Cs)和ASm_2I_5(A=Rb,T1)中的Sm~(2+)荧光光谱分别发生蓝移和红移的现象.