Synthesis and characterization of 1,3,4-oxadiazole derivatives containing alkoxy chains with different lengths

The synthesis, optical properties, electrochemical properties, electronic structures and applications in electroluminescent device of three series of 1,3,4-oxadiazole derivatives, 1,4-bis[(4-methylphenyl)-1,3,4-oxadiazolyl]phenylene (OXD₁), 5,5′-di-(4-methyl)-2,2′-p-(2,5-bisalkoxyphenylene)-bis-1,3,4-oxadiazole (OXD_2–n) and 1,4-bis[(4-alkoxyphenyl)-1,3,4-oxadiazolyl]phenylene (OXD_3–n) are reported. The molecular structures of the oxadiazole compounds were confirmed by FT-IR, ¹H NMR spectroscopy and elemental analysis. The optical and electrochemical properties of the compounds were investigated by UV–vis absorption and photoluminescence spectroscopy as well as cyclic voltammetry. The results show that introduction of two alkoxy groups whose electron-donating ability is stronger than that of methyl groups increases the electron density of the conjugated segment of OXD_2–n (with side-on alkoxy substituents) and OXD_3–n (with end-on alkoxy substituents), and thus leads to the absorption maximum bathochromic-shift compared to that of OXD₁. The HOMO and LUMO energy levels of the compounds studied are in the range of −2.78 to −2.89 and −5.75 to −6.20 eV. Calculations on the representative compounds by the Dmol³ package of MS Modeling 3.0 revealed that the increase of energy levels in both OXD_2–n and OXD_3–n was due to the change of the frontier molecular orbital distribution in the central benzene ring. The light-emitting devices have been fabricated using blends of MEH-PPV and these compounds as emissive layers, among which, maximum brightness up to 11810 cd m⁻² (8.5 V) has been observed, which is 40 times brighter than that with MEH-PPV. The result of the devices suggested that oxadiazole derivatives studied function well as electron-transporting materials and can be used in LEDs, and thus to enhance the efficiency of LEDs.     

Ab initio study on the kinetics and mechanisms of the formation of Agn (n = 2–6) clusters

The CCSD(T)/11e-RECP//MP2/11e-RECP method was used to explore the potential energy surfaces (PESs) of the formation of Ag_n (n = 2–6) clusters. Two kinds of reaction mechanisms were revealed in the formation of Ag_n clusters, the association mechanism for the formation of Ag₂, Ag₅, and Ag₆ clusters and the association–isomerization mechanism for the formation of Ag₃ and Ag₄ clusters. Based on the canonical transition state theory, the calculated rate constants of the formation of Ag_n clusters displayed an odd–even effect: the rate constants of formation of Ag_n clusters with odd number were larger than those with even number. The rate constant of formation of Ag₄ was the lowest, whereas that of Ag₅ was the highest among Ag_n (n = 2–6) clusters. The formation of Ag₄ was the most difficult step in the aggregation process of the silver clusters. The formation of Ag₄ may be related with the critical point in the silver aggregation process.     

金属基底上吡咯光电化学聚合的研究

近年来,国内外对聚吡咯已进行广泛的研究,主要内容包括:电化学聚合,机理与结构表征,电化学氧化还原性质,聚吡咯的化学修饰。最近报导了半导体上吡咯的光电化学聚合。我们在低于吡咯电聚合电位下观察到聚吡咯的Raman讯号。本文研究在中性溶液中金属基底上吡咯的光电化学聚合,以及光源波长、强度和介质等因素的影响。     

The Synthesis of Gracillin and Dioscin：TWO Typical Representatives of Spirostanol Glycosides

Two spirostanol saponins(gracillin and dioscin)which have the typical sugar moieties were synthesized facilely by a general approach.     

Synthesis and crystal structure of an imidazolate-bridged dicopper tris(2-aminoethyl)amine complex

The [Cu(tren)(Im)Cu(tren)](ClO4)3·MeCN complex [tren=tris(2-aminoethyl)amine; Im=imidazolate anion] has been synthesized and characterized spectrally. The X-ray crystal structure analysis reveals that the imidazolate anion serves as a bridge to form a noncentrosymmetric dimeric structure in the complex. The co-ordination geometry about each copper(II) ion is a distorted trigonal bipyramid with three primary amine groups of the tren ligand forming the equatorial plane. The tertiary amine group and the imidazolate anion are in the axial positions. This revised version was published online in June 2006 with corrections to the Cover Date.     

The Synthesis of 1,4‐Bis[N‐(4/6‐Substituted Benzothiazole‐2‐yl)‐N′‐Glycosylguanidino]Benzenes

The starting material O‐protected glycosyl isothiocyanate ( 1?3 ) was refluxed with 1,4‐diaminobenzene in CHCl₃ under nitrogen atmosphere to give 1,4‐bis(N‐glycosyl)thioureidobenzene ( 4?6 ). Then 1,4‐bis[N‐(4/6‐substituted benzothiazole‐2‐yl)‐N′‐glycosylguanidino]benzenes ( 8a?8e , 9a?9e , 10a?10e ) were obtained in good yield by reaction of compounds ( 4?6 ) with 2‐amino‐4/6‐benzothizoles ( 7a?7e ) and HgCl₂ in the presence of TEA in DMF. The structures of all 18 new compounds were confirmed by IR, ¹H NMR, LC‐MS and elemental analysis. The bioactivity of anti‐HIV‐1 protease (HIV‐1 PR) and against angiotensin converting enzyme (ACE) have been evaluated.     

反相悬浮聚合法合成超强吸水剂

以两性高分子作悬浮稳定剂，用反相悬浮聚合法合成了聚（丙烯酸盐－丙烯酰胺）类超强吸水剂．研究了交联剂、稳定剂、引发剂等用量、中和程度、单体组成及链转移剂等聚合条件对吸水剂吸水性能的影响．得到了吸蒸馏水１０５０ｍＬ／ｇ及吸０．９％ＮａＣｌ溶液８６ｍＬ／ｇ的超强吸水剂．此外，还比较了含不同反离子的聚丙烯酸类吸水剂的吸水性能     

天线若丹明染料分子内能量与电荷传递的研究

染料三重态在染料激光的应用中起着重要作用，尤其是三重态一Z重态（T－T）吸收常常会造成谐振腔损耗＊．为了减少由基态吸收而造成的话振腔损耗，带有紫外吸收天线分子的三发色团染料已在研究问，2，5·二苯基螨喳（PP0）在紫外区（如308删）有很强的吸收，PPO－rhod．系列染料（见图1）在紫外区的吸收就很强，由PPO到若丹明母体的单线态一单线态（S功能量传递使这类三发色团染料具有较大的荧光量子效率，较小的基态重复吸收耗能卜，司．然而，在610N640nm区域中这些天线若丹明染料的激光输出效率远远小于若丹明Rh630＊，其原因正是…     

电化学聚对苯膜的现场ESR及其性能研究

本文用现场电化学-ESR联合测试的技术, 对电化学聚对萃膜在浓H_2SO_4中的性质进行了研究, 结果表明: 聚对苯膜具有高的电导率和相对低的自旋磁化率, 极化子与偶极化子为主要导电者, 并在一定的电位下相互转化, 自旋粒子有很大的离域性。膜中链与链之间可能存在部分的氧桥结构, 而引起体系结构的某些变化, 使聚对苯膜的电导提高以及掺杂容易进行。掺杂量受电位控制, 浓H_2SO_4中的HSO_4~-嵌入/脱嵌的电化学可逆性很好, 最大掺杂量可相当于每5个苯环单元氧化出一个正电荷, 可望将电化学聚对苯用作稳定的二次电池电极材料。     

Application of preparative high-speed counter-current chromatography for separation of methyl gallate from Acer truncatum Bunge

Preparative separation of methyl gallate in leaves extract of Acer truncatum Bunge was conducted using high-speed counter-current chromatography (HSCCC) with a solvent system composed of ethyl acetate-ethanol-water at volume ratios of 5:1:5 (v/v/v). In a single operation, 57.5 mg of methyl gallate was obtained from 120 mg of the extract. HPLC analyses of the counter-current chromatography (CCC) fraction revealed that the methyl gallate was having over 97% purity. Its structure was identified by 1H NMR and 13C NMR.