9-[(4,5-二硫十六烷基)-1,3-二硫环戊烯-2-亚基]-10(9H)-蒽酮的合成及光电性质研究

一种新的具有D-π-A体系的有机分子9-[(4,5-二硫十六烷基)-1,3-二硫环戊烯-2-亚基]-10(9H)-蒽酮(d)被合成.通过1HNMR,13CNMR,IR,TOFMS进行了表征,确定了其结构.利用电化学装置对该体系进行了光电流响应测试,产生的光电流相对稳定、可逆,说明该体系具有明显的光电转换性质.运用Gaussian03量子化学程序包,采用B3LYP密度泛函(DFT)的方法,在6-31G(d)水平上优化了其基态几何结构,得到的几何参数与实验结果基本吻合.研究结果表明,体系中存在着分子内的电荷转移.     

Synthesis,Crystal Structure and Prosperities of 10-（4,5-Dibenzylthio- 1,3-dithiol-2-ylidene）anthracen-9（10H）-one

The title compound 10-（4,5-dibenzylthio-1,3-dithiol-2-ylidene）anthracen-9（10H）- one （C31H22OS4） has been synthesized, and its crystal structure was prepared by crystallization from CH2Cl2-MeOH. The crystal belongs to the triclinic system, space group Pi with a = 10.9758（3）, b = 11.4241（4）, c = 11.7460（2）A^°, α = 62.379（2）, β = 81.227（3）, γ = 80.321（2）°, Mr = 538.73, V = 1281.69（7） A^°^3, Z = 2, Dc = 1.396 g/cm^3, F（000） = 560,μ = 0.395 mm^-1, the final R = 0.0291 and wR = 0.0739. The molecular structure is severely distorted from planarity. The central ring of anthraquinone moiety adopts a boat conformation, while the two outer benzene rings are tilted in the opposite direction to form a dihedral angle of 23.65°. The photocurrent generation was measured and an anodic photocurrent response was obtained. The electronic spectrum was studied by using TDDFr method on the basis of optimized geometries with B3LYP method. The obtained results are in good agreement with the experimental values.     

微波辐射相转移催化下水相合成α，α′-双亚苄基环烷酮

芳醛与环戊酮或环己酮在碳酸钠水溶液中，用微波辐射-相转移催化法合成α，α′-双亚苄基环烷酮。反应在0．5～7min内完成，产率高达80％～99％，后处理极为简便，是一种环境友好的绿色合成．     

巴比妥酸葡萄糖基取代衍生物电子光谱和二阶非线性光学性质的理论研究

应用量子化学AM1半经验方法分别对巴比妥酸及硫代巴比妥酸的葡萄糖基系列取代衍生物B_1-5和T_1-5进行几何优化。基于优化后的稳定构型，利用INDO/CI方法计算其电子光谱。同时，根据完全态求和(SOS)公式计算其二阶非线性光学系数。结果显示，当葡萄糖基单元数增加时，无论是巴比妥酸衍生物还是硫代巴比妥酸衍生物，|β_μ| 均增大，尤其是硫代巴比妥酸衍生物增大更为显著，表明此种非共轭取代基同样可以改善材料的非线性光学性质。此外，随葡萄糖基链增长时，光谱的变化并不十分显著，且由于所有吸收带均在紫外光区内，因此推测所有体系均有望成为具有高度透明性的非线性光学侯选材料。     

四硫富瓦烯衍生物在有机光电功能材料方面的研究进展

四硫富瓦烯(TTF)及其衍生物不仅是分子导体的有效构筑模块之一, 而且在材料化学的诸多领域显示了广阔的应用前景. 本工作综述了近几年TTF及其衍生物在非线性光学、分子光电器件、光伏器件及光致变色方面的最新研究进展.     

手性荧光衍生化反相高效液相法分离肾上腺素对映体

 以R (- ) /S (+) 4 (N ,N dimethylaminosulfonyl) 7 (3 iso thiocyanatopyrrolidino) 2 ,1,3 benzoxadiazole(DBD PyNCS)为手性荧光衍生化试剂 ,用反相高效液相法 (RP HPLC)对 DL 肾上腺素对映体进行分离。衍生化反应是在含有 7%吡啶的溶剂中 ,6 5℃温度条件下反应 35min ,生成具有荧光特性的肾上腺素非对映体衍生物(λex=4 6 0nm ,λem=5 5 0nm)。生成的非对映体衍生物在流动相为乙腈 水 (体积比为 2 8∶72 ) ,流速为 1 0mL/min时 ,在DiamonsilTMC18柱 (15 0mm× 4 6mmi d ,5 μm)上分离度可达 2 6。     

9-（4，5-二硫甲基-1，3-二硫杂环戊烯-2甲叉基）蒽-10（9H）-酮的合成及量子化学计算

设计合成了一种新的具有D-π-A结构的有机分子，9-（4，5-二硫甲基-1，3- 二硫杂环戊烯-2-甲叉基）蒽-10（9H）-酮（C_(19)H_(14)OS_4）。以~1H NMR， FTIR，元素分析和UV-vis进行了表征。运用Gaussian 98量子化学程序包，采用 B3LYP密度泛函（DFT）的方法，在6-31G（d）水平上对分子的几何构型进行了优化 ，在优化的基础上用TDDFT的方法计算了化合物的电了防染印花谱，计算值与实验 值基本吻合，用TDHF的方法计算了它的二阶非线性光学系数，与蒽醌相比，其第一 超给化率β较大，为12.03 * 10~(-30)esu。     

Fe3O4/N-异丙烯酰胺(PNIPAM)纳米颗粒的合成

A magnetic and thermosensitive poly(N-isopropylacrylamide)(PNIPAM) nanoparticles were prepared by the following procedure. The core-shell composite microparticles were synthesized by precipitating polymerization with Fe₃O₄ being entrapped with SiO₂ as core and cross-linked PNIPAM as shell. Then， the SiO₂ core was etched by hydrofluoric acid and magnetic thermosensitive Fe₃O₄/PNIPAM particles were formed. It has also been shown that the Fe₃O₄/PNIPAM nanoparticles are featured by lower critical solution temperature (LCST) at 33.0 ℃ while the temperature varies from 28.0 ℃ to 36.0 ℃. The composite magnetic thermosensitive particles were characterized by XRD， SEM， TEM and FTIR. The synthetic mechanism is also discussed.     

Theoretical Studies on Electronic Spectra and Second-order Nonlinear Optical Properties of Glucosyl Substituted Barbituric Acid Derivatives

AMI semi-empirical method was used to optimize the barbituric acid derivatives substituted with glucosyl B1-5 （series B）, and the thiobarbituric acid derivatives substituted with glucosyl T1-5 （series T）. Based on the optimized structures, INDO/CI method was adopted to calculate the electronic spectra. Meanwhile, the second-order nonlinear optical （NLO） coefficients βμ were calculated with the sum-over-state （SOS） formula. The results show that when the number of glucosyl units was increased, ｜βμ｜ values of the barbituric and thiobarbituric acid derivatives were both enhanced, especially for thiobarbituric acid derivatives. It indicates that non-conjugated substituted group could also improve NLO properties of materials when the number of repeated units was increased. Additionally, the absorption bands appearing in UV area are consistent with the proper change of the number of glucosyl units, and consequently it can be concluded that the high transparencies of all systems were scarcely varied.     

细胞色素c在无机复合纳米材料修饰电极上的直接电化学研究

采用超声辅助湿法合成的方法制备了羟基磷灰石与碳纳米管(HAp/MWNT)无机复合纳米材料,并将其修饰到玻碳电极表面上。研究了细胞色素c(Cyt c)在该复合纳米材料修饰电极表面上的电化学行为。实验结果表明,复合修饰材料对细胞色素c有很好的催化作用,其氧化还原峰峰差(ΔEp)为78 mV,式电位为15mV。在6.0×10-7-5.0×10-5mol/L浓度范围内,Cyt c的峰电流与其浓度呈良好的线性关系,其检测下限为3.0×10-7mol/L。关键词:细胞色素c;羟基磷灰石;碳纳米管;HAp/MWNT复合材料