硬脂酸二茂铁酯L—B膜修饰SnO2电极的阻抗研究

测定了二茂铁衍生物——硬脂酸二茂铁酯L-B膜修饰SnO_2电极在Fe(CN)_6~(3-/4-)溶液中的阻抗性能,用单纯形法求出了等效电路中的元件参数值,计算了电极反应速度常数K_s。从分析SnO_2电极修饰不同层的硬脂酸二茂铁酯L-B膜的界面阻抗和电极反应的动力学性能,表明与在固相中研究的硬脂酸二茂铁酯L-B膜的阻抗性能明显不同,在Fe(CN)_6~(3-/4-)溶液中表现了电活性分子修饰电极的界面阻抗行为,进一步证实了修饰在SnO_2电极上的硬脂酸二茂铁酯L-B膜在Fe(CN)_6~(3-/4-)的氧化还原电极反应过程中,起电荷传递的中介作用。     

硬脂酸二茂铁酯L—B膜的电化学性能研究

本文研究二茂铁衍生物——硬脂酸二茂铁酯(FcOCOC_(17)H_(35))L-B膜技术修饰SnO_2电极的循环伏安性能.实验结果用电极表面吸附(修饰)分子的表面活度理论进行计算机拟合和此较,实验数据与理论符合较好.进一步求得修饰分子的标准电极电势和修饰量。结果表明硬脂酸二茂铁酯L-B膜电化学性能稳定,可逆性较好,可以作为快速电荷转移的修饰电极材料。     

染料电极的光电转换效应研究

应用一种简便的旋转涂布方法,制备了卟啉/SnO_2,酞菁/SnO_2以及卟啉/酞菁/SnO_2单层和双层电极,在双层电极研究中发现,卟啉和酞菁层的涂布次序对形成的双层电极是否出现叠加现象有很大影响。对所出现的现象进行了初步的讨论。     

金属酞菁及其取代衍生物的结构与光电性能研究进展

由于取代方式的不同,使得金属酞菁衍生物数目庞大,结构各异。晶体结构的不同,造成配合物光电性能等多种性质的改变。酞菁类光敏材料研究方法有溶剂调节法,相转移法、溶胶-凝胶法、气相沉积法和真空热蒸发等,这些技术调变了酞菁衍生物的光电导性能,在光动力疗法等领域意义重大。酞菁类气敏材料对某些气体具有选择性高、响应灵敏等特点,可用于气体传感器的制作。建议进一步探讨取代金属酞菁衍生物的光敏、气敏机理,以便在分子层次上优化设计分子的结构,改善材料性能,拓宽应用范围。     

两亲胆固醇壳聚糖碳酸酯的合成及其单分子膜的形成与性能研究

本文从壳聚糖结构特点出发,利用甲磺酸保护壳聚糖氨基,在羟基上引入胆固醇合成两亲性胆固醇壳聚糖碳酸酯(ACCC),利用FT-IR和~(13)C-NMR方法证明碳酸酯基的生成。采用Langmuir膜技术跟踪探究不同取代度ACCC的单分子膜在空气/水界面上的形成过程及膜性能,由表面压-单分子层表观面积(π-A)等温曲线得知,从气相到固相变化过程中两亲壳聚糖衍生物单分子经历从分散到集中,在空气/水界面上逐渐形成单分子膜,单分子膜稳定性和强度取决于胆固醇取代度的变化。取代度分别是2.6和3.9的ACCC的膜平均极限面积(A*)达到346.76和652.65cm~2,相应塌陷压值分别等于46.13和47.48mN/m,表明这两种胆固醇壳聚糖碳酸酯Langmuir膜具有良好的性能和稳定性。通过Langmuir-Blogett技术将单分子膜转移制备多层膜修饰的ITO电极。     

修饰的薄膜CdSe电极／Fe（CN）6^4—溶液界面的电荷转移

本文研究了硬脂酸二茂铁酯L-B膜修饰的薄膜Cdse电极的光诱发界面多相电荷转移过程。通过测量异相电荷转移反应速度常数K_(et),进一步分析了修饰的薄膜CdSe电极光电化学过程的可能反应速度控制步。分析表明界面的电荷转移是反应的速度控制步。薄膜CdSe电极可以通过选择电活性修饰分子和溶液中氧化还原离子来进一步提高和改善其光电化学性能。     

酞菁类盘状液晶材料研究进展

拥有大环π电子高度共轭结构的酞菁（Pc）核，具备自组装的潜在特征，且在可见光区域具有强吸收。经修饰改性的酞菁衍生物被应用于液晶显示、太阳能电池、非线性光学等光电材料中。其中，液晶相行为影响材料性能方面更引人关注。通过修饰酞菁核可以改变液晶相行为，最具有代表性的修饰是酞菁核中心空腔阳离子配位和外围添加取代基团。经修饰改性的酞菁衍生物柱状自组装趋势明显，盘状中间相易形成，共轭层之间电子的传输能力得到增强，具备了作为光电材料的基本性质。该文综述了近十几年来酞菁衍生物盘状液晶材料的研究进展，总结了酞菁核的结构修饰对其液晶性能影响之间的构效关系，最后对酞菁衍生物盘状液晶在高性能材料合成方面存在的缺陷和研究方向进行了展望。     

酞菁类盘状液晶材料研究进展

拥有大环π电子高度共轭结构的酞菁（Pc）核,具备自组装的潜在特征,且在可见光区域具有强吸收。经修饰改性的酞菁衍生物被应用于液晶显示、太阳能电池、非线性光学等光电材料中,其中液晶相行为影响材料性能方面更引人关注。通过修饰酞菁核可以改变液晶相行为,最具有代表性的修饰是酞菁核中心空腔阳离子配位和外围添加取代基团。经修饰改性的酞菁衍生物柱状自组装趋势明显,盘状中间相易形成,共轭层之间电子的传输能力得到增强,具备了作为光电材料基本性质。本文综述了近十几年来酞菁衍生物盘状液晶材料的研究进展,分析总结了酞菁核的结构修饰对其液晶性能影响之间的构效关系,最后进一步对酞菁衍生物盘状液晶在高性能材料合成方面存在缺陷和研究方向进行了展望。     

酞菁类光敏剂的研究进展

酞菁类化合物是典型的近红外染料,依据有机光敏染料分子结构的设计原则,在酞菁母核的外围引入适当的取代基可以合成新型的具有特殊结构、优异光电性能的有机光敏染料。综述了酞菁类光敏染料分子的设计原则,以及具有代表性的取代金属酞菁类光敏染料的分子结构和光伏性能。     

多级结构SnO_2及其碳复合物的制备与电化学性能

针对SnO_2作为锂离子电池负极材料循环性能和导电性差的问题,采用水热法制备了SnO_2/C复合物。研究了多级结构SnO_2的制备工艺并以此为基础制备了SnO_2/C复合物,通过XRD、SEM、TEM等分析方法表征了材料的结构、组成和形貌;采用循环伏安、恒流充放电等电化学方法表征SnO_2和SnO_2/C复合材料的电化学性能。实验结果表明,在200 mA·g~(-1)恒电流密度充放电时,SnO_2/C复合物电极充放电循环50次后比容量为346.1 mAh·g~(-1),远高于SnO_2电极;与此同时,无定形碳的引入使SnO_2/C复合物电极的倍率性能也显著提高。     

CuTsPc分子膜／P—si（11 1）界面的光致电荷转移及其机制研究

本文利用L-B技术,在p-Si(111)基底上铺展了单层厚度只有6的CuTSPc超薄分子膜(简称超分子膜)和具有C_(18)脂链间隙的CuTSPc L-B膜两种膜系,首次观察到了CuTSPc分子膜在这种特定界面中的表面光电压谱。并且发现,当CuTSPc仅为一个单分子层时,这两种膜系的表面光伏效应最强。我们的研究结果表明,只有紧邻半导体基底的一个单分子层厚度的染料分子对光致界面电荷转移起关键作用。最后在实验上证实这种电荷转移是电荷直接注入机制,而非间接注入机制。     

卟啉类L—B膜分子间相互作用的光谱研究

以无取代的meso-四-(4-N)-吡啶基卟啉及其过渡族金属(主要Cu~(2+)、Zn~(2+))络合物制备L-B膜,以近紫外-可见吸收光谱和荧光光谱为手段,研究叶啉类分子在氯仿溶液中,L-B膜状态下以及固态状态下的相互作用。探讨分子聚集体的存在对光谱性质的影响。 为了研究叶咻类分子间的相互作用及其对光谱性质的影响,我们首先分析了叶啉在CHCl_3溶液中及固态状态下的近紫外-可见吸收光谱和荧光光谱。并将其与叶啉类分子的L-B膜作比较。结果表明,卟啉类的Soret吸收带带宽及峰位置在三种状态下均不相同,L-B膜的情况介于溶液中的和固体下的情况之间,说明了在L-B膜中,卟啉分子存在着某种形式的聚集体,且在这种聚集体中分子间的相互作用程度比固体弱,可以认为L-B膜上的分子呈准晶体状态。     

Effects of hydrophobic chain length on temperature dependence of monolayer behavior of ester-type tartaric geminis

Ester-type tartaric gemini amphiphiles bearing two carboxyl groups and two hydrophobic alkanoyl groups were prepared from L-tartaric acid, and the pressure-area (π-A) isotherms for a series of symmetric tartaric gemini amphiphiles were measured by the conventional film-balance technique. The effects of the length of the hydrophobic alkanoyl chains and of the subphase temperature (T(sub)) on the π-A isotherms for these compounds were examined. As the length of the hydrophobic alkyl chain increased, a more tightly packed monolayer was formed at the air-water interface. The melting temperature (T(m)) of the monolayer on the water surface was evaluated from the subphase temperature (T(sub)) dependence of the monolayer static elasticity ε(s), based on a π-A isotherm. A clear relationship between T(m) and hydrophobic carbon number (n) was observed for 2D monolayers of tartaric geminis on water surfaces, as well as for fatty acids and/or 3D solids.     

神府东胜煤CS2萃取物组成分析

采用溶剂萃取、色-质联用和色-红联用结合色谱保留值的定性方法，分析研究了神府东胜煤CS2萃取物的化学成分和结构，鉴定出120多种化合物，并对所鉴定出的单个化合物进行了定量分析，讨论了神府东胜煤CS2萃取物化学成分的结构特征．结果表明：萃取物主要由脂肪烃、芳烃和极性化合物三类成分组成．芳烃含量在萃取物中占绝对优势，且主要为1-4环的烷基取代芳烃．脂肪烃除主要成分正构烷烃外，还有少量的类异戊二烯烃和萜烷，极性化合物所占的比例很小，以含氧化合物为主．     

Photoelectric conversion of perylenetetracarboxylic diimides in Langmuir-Blodgett films

This article reports the photoelectric conversion of 3, 4, 9, 10-perylenete-tracarboxylic diimides (PTCDI) in multilayers of Langmuir-Blodgett (L-B) films using the photoelectrochemistry technique and absorption spectroscopy. The rate of electron transfer caused by five different PTCDI molecules was determined and the results demonstrate the photoelectric conversion properties of PTCDI molecules in L-B films.     

阳离子烷基糖苷的绿色合成及性能评价

采用先醚化、再季铵化的路线合成了阳离子烷基糖苷,n(环氧氯丙烷)∶n(蒸馏水)∶n(烷基糖苷)∶n(烷基叔胺)为1∶16∶1.5∶0.8,醚化条件为:95～100℃,2～4 h,季铵化条件为:50～80℃,4～6 h。系统研究了阳离子烷基糖苷的抑制性能,对于6%的阳离子烷基糖苷钻井液,岩屑一次回收率达96.35%,相对回收率达92.73%,相对抑制率达91.40%。     

Influence of the Ionization Potential and of the Interfacial Electric Field on Photoinduced Hole Transfer Processes in Langmuir-Blodgett Films

The presence of a monolayer of ω-(2-anthryl)-alkanoic acid on an anthracene or perylene single crystal modifies the kinetics of photosensitized hole injection. An increase in the chain length of the ω-(2-anthryl)-alkanoic acid leads to a decrease in the quantum yield of the sensitized hole current (SHC). This effect becomes more important when the ionization potential of the dye is decreased. This argument supports the hypothesis that electron transfer is assisted by an interaction between the HOMO of the dye and that of the alkyl chain. The permanent electric field existing at the interface between the monolayer of ω-(2-anthryl)-alkanoic acid and the monolayer containing the dye is also expected to influence the free energy gain associated with this electron transfer process. When the dye is diluted by tripalmitine instead of arachidic acid, the change in the electrical potential difference at the interface with the monolayer of ω-(2-anthryl)-alkanoic acid leads to a tenfold decrease in the quantum yield of the SHC.     

Insights into the Optimization of Alkyl Phenol/Alkyl Halide Ratio in Gemini Surfactant Synthesis

¹H NMR and thin layer chromatography (TLC) were applied to analyze the component of two series of synthesized sulfonated Gemini surfactants with different spacer lengths (2, 4, and 6 carbons) and hydrophobic chain lengths (9, 12 carbons). Gemini surfactants were prepared by reacting alkylphenol with alkyl halide followed by sulfonation with chlorosulfonic acid. The influence of the molar ratio of alkyphenol to alkyl halide on the mono‐ to diether ratio was investigated and the results indicated that the molar ratio is a key factor to minimize impurities in the target material, due to the high reactivity of alkyl halide. In addition, the results showed that alkyl halide with a shorter spacer group length required a higher molar ratio of alkyl halide to alkylphenol. To synthesize the intermediate Gemini product with 80 % diether content, the molar ratios were optimized using n(alkylphenol):n(1,6‐dibromohexane) = 1:0.55, n(alkylphenol):n(1,4‐dibromobutane) = 1:0.7, and n(alkylphenol):n(1,2‐dibromoethane) = 1:2.5, respectively.     

四－叔丁基金属酞菁衍生物L－B膜的光电性能研究

四－叔丁基金属酞菁衍生物Ｌ－Ｂ膜的光电性能研究董长征，沈永嘉，蓝闽波，任绳武（华东理工大学精细化工研究所，上海２００２３７）肖绪瑞，林原，贾建光，沈涛（中国科学院感光化学研究所光电化学中心，北京１００１０１）关键词Ｌ－Ｂ膜，开路光电压，短路光电流，金...     

Structural effects of pendant groups on thermal and electrical properties of polyimides

Two series of aromatic polyimides containing various‐sized alkyl side groups were synthesized by thermal imidization of the poly(amic acid)s prepared from the polyaddition of benzophenonetetracarboxylic dianhydride and hexafluoro‐isopropylidene bis(phthalic anhydride) with 4,4′‐methylenedianiline, 4,4′‐methylene‐bis(2,6‐dimethylaniline), 4,4′‐methylene‐bis(2,6‐diethylaniline), and 4,4′‐methylene‐bis(2,6‐diisopropylaniline). The extent to which alkyl substitutes affect the thermal properties of polyimides was examined by differential scanning calorimetry, thermomechanical analyzer, and thermogravimetric analysis techniques. The analytical results demonstrated that the incorporation of alkyl moieties causes a moderate increase in the coefficient of thermal expansion and a slight decrease in thermal stability. Notably, all polymers had a decomposition temperature exceeding 500°C. The glass transition temperature increases markedly when hydrogen atoms at ortho positions on aniline rings are replaced with methyl groups, but decreases with growing alkyl side group size. The dielectric measurements show that the polymer possessing a large alkyl side group would have the lower dielectric value. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4672–4678, 2006