TiO2纳米晶电极上半菁衍生物分子设计中空间位阻效应的研究

设计合成了具有不同空间位阻的吡啶盐类和喹啉盐类半菁染料(E)-N-(4—磺酸 根丙基)-4-[2-4（4-N，N-二乙基氨基苯基）乙烯基]吡啶鎓盐（EPS），（E）-N-(4- 磺酸根丁基）-4-[2-(4-N,N-二乙氨基苯基）乙烯基]吡啶鎓盐（EPS4）和（E） -N-（4-磺酸根丁基）-4-[2-（4-N，N-二乙基氨基苯基）喹啉鎓盐（EQS4），研究了它们 的光物理性质，并将它们用作TiO2纳米晶电极的光敏化剂引入光电化学电池中。 研究发现:对于吡啶类半菁染料而言，无论是以三个亚甲基或是以四个亚甲基来连接 吸附基团RSO3^-和发色团时，单个的EPS和EPS4分子的光电响应行为一致．但是由于 以三个亚甲基来连接时，与EPS4相比，染料EPS的空间位阻相对较小，有利于其在 多孔膜上的吸附，最终结果是染料EPS对TiO2纳米晶电极的敏化作用好于EPS4．以喹啉 环为受电子基团的染料EQS4与同样含有四个亚甲基的以吡啶环为受电 子基团的EPS4相比，单个EQS4分子的光电响应行为虽然好于EPS4分子，但由于 EQS4分子间的空间位阻较大，影响了它在多孔电极上的吸附，致使其敏化的太阳能 电池的总光电转换效率有所下降．     

纳米晶TiO2电极上半菁衍生物光敏染料

合成了具有不同共轭链长度的吡啶盐类及喹啉盐类半菁染料(E)-N-(4-磺酸丁基)-4-[2-(4-N, N-二甲基氨基苯基)乙烯基]吡啶鎓盐(P1)、(E)-N-(4-磺酸丁基)-4-[2-(4-N, N-二甲基氨基苯基)丁二烯基]吡啶鎓盐(P2)、(E)-N-(4-磺酸丁基)-4-[2-(4-N, N-二甲基氨基苯基)乙烯基]喹啉鎓盐(Q1)以及(E)-N-(4-磺酸丁基)-4-[2-(4-N, N-二甲基氨基苯基)丁二烯基]喹啉鎓盐(Q2).研究了它们的光物理性质，并将它们用作TiO2纳米晶电极的光敏化剂引入光电化学电池.与含有乙烯基共轭桥的染料P1和Q1相比，含有丁二烯基共轭桥的染料P2和Q2在甲醇和氯仿中的最大吸收均发生一定程度的红移，而且吸收光谱变宽.这两类染料都能很好地吸附于TiO2电极上.在比较了四个染料的吸收光谱、摩尔消光系数以及在TiO2电极表面的吸附量后，发现Q1具有最好的光电转化性质.     

新型半菁染料阳离子和含锌硫代富瓦烯配阴离子的电荷转移复合物光电响应性质的研究

对一种新型半菁发色基团的碘化物--(反式)-N-十八烷基-4-(2-(4-(2-二甲基氨基)苯基)乙烯基)喹啉碘化物和含锌硫代富瓦烯配阴离子形成的电荷转移复合物:二-[(反式)-N-十八烷基-4-(2-(4-(2-二甲基氨基)苯基)乙烯基)喹啉]合硫代富瓦烯锌酸盐的成膜性以及它们的LB膜修饰ITO电极上的光电响应性质进行比较研究,用含锌硫代富瓦烯配阴离子对这种半菁发色团阳离子进行组装后,能够改善其成膜性,使单位面积上的半菁发色团数目增加.同时,含锌硫代富瓦烯配阴离子的强吸电子能力还影响半菁发色团的电荷分布,使之有利于电荷分离,从而提高了光电流的量子产率.在无外界影响时,其光电转化的量子产率达0.9%,是碘化物的1.8倍.     

敏化染料分子长径比对太阳能电池性能的影响

采用同一系列但分子长径比不同的3种染料:2-氰基-3-[2-[4-{2-[4-N,N-二(4-甲基苯基)氨基苯基]乙烯基}-苯基氨基)-嘧啶-5-取代基]-丙烯酸(MTPA-Pyc)、2-氰基-3-(4-{2-[4-N,N-二(4-甲基苯基)氨基苯基]乙烯基}-苯基)-丙烯酸(MTPAcc)和2-氰基-3-[4-N,N-二(4-甲基苯基)氨基苯基]-丙烯酸(MTPAc),研究了在不同吸附溶剂中3种染料分子在Ti O2上的吸附量和聚集态,探讨了敏化染料分子长径比对染料敏化太阳电池性能的影响.结果表明,MTPAcc具有最合适的分子长径比,其在Ti O2表面的吸附量及应用的光电性能最高;吸附溶剂的极性增大有利于提高染料的吸附量,但也会影响染料分子的聚集态.当以四氢呋喃为吸附溶剂时,MTPAcc在Ti O2表面的吸附量大且不发生聚集,对应的敏化太阳能电池器件在所有结果中表现最好,在490 nm处的单色光光电转化效率(IPCE)极值达到84%,总光电转化效率(η)达到5.72%.     

新型半菁染料阳离子和含锌硫代富瓦烯配阴离子的电荷？…

对一种新型半菁发色基团的碘化物－（反式）－Ｎ－十八烷基－４－（２－二甲基氨基）苯基）乙烯基）喹啉碘化物和含锌硫代富瓦烯配阴离子形成的电荷转移复合物：二－［（反式）－Ｎ－十八烷基－４－（２－（４－（２－二甲基氨基）苯基）乙烯基）喹啉］合硫代富瓦烯锌酸盐的成膜性以及它们的ＬＢ膜修饰ＩＴＯ电极上的光电响应性能进行比较研究，用含锌硫代富瓦烯配阴离子对这种半菁发色团阳离子进行组装后，能够改善其成膜性，使单位     

具有扩展π共轭桥的D-π-A结构的染料LB膜的光电转换性质研究

合成了具有扩展π共轭桥的两亲性D－π－A染料,N－十八烷基－2－[(4-N,N‘-二甲基胺苯基）－1,3－丁二烯基]吡啶盐碘化物（BEP2）,通过Brewster角显微镜观察了BEP2在空气／水界面上的成膜行为,运用Langmuir-Blodgett技术将它转移到ITO（indium-tin-oxide)导电玻璃上,在传统的三电极体系中测定其光电转换性质,研究了氧化还原物质、偏压和光强等因素对它的影响,发现其比母体染料N－十八烷基－2－[(4-N,N‘-二甲基胺苯基）乙烯基]吡啶盐碘化物（EP2）具有更高的光电转移效率。     

半菁类染料敏化太阳能电池的光电化学性能研究

研究了三种不同长度碳链取代的半菁类染料2-[4-(N,N-二羧乙基)氨基]苯乙烯基-1,3,3-三甲基苯并吲哚鎓碘(BIDC1)、2-[4-(N,N-二羧乙基)氨基]苯乙烯基-1-丁基-3,3-二甲基苯并吲哚鎓碘(BIDC2)和2-[4-(N,N-二羧乙基)氨基]苯乙烯基-1-辛基-3,3-二甲基苯并吲哚鎓碘(BIDC3)敏化太阳能电池的光电化学性能。其中BIDC1的敏化效果最好,在100mW/cm2氙灯光源下,开路电压、短路电流、填充因子和转换效率分别是430mV、1.31mA/cm2、0.52、0.29%。研究表明,随着半菁染料碳链取代基的增长,光电转换效率逐渐降低。     

N-甲基丙烯酰-N′-嘧啶基哌嗪及其聚合物敏化的丙烯腈光聚合

我们曾报道过同一分子中含有给电子生色基团和电子受体基团的一类功能性单体,如甲基丙烯酸-4-N,N-二甲氨基苄酯(DMABMA),N-(4-N′,N′-二甲氨基苯基代丙烯酰胺,N-(4-N′、N′)-二甲氨基苯基代甲基丙烯酰胺(DMAPMA),8-丙烯酰氧喹啉(AQ),N-丙烯酰-N′-苯基哌嗪(APP)的合成、聚合以及单独或与过氧化二酰构成氧化还原体系以引发烯类单体的聚合研究。N-甲基丙烯酰-N′-嘧啶基哌嗪(MPMP)     

2,6-吡啶二亚胺基锰(Ⅲ)配合物的合成、晶体结构及催化性能

由三齿含氮配体2,6-二[1-(2,6-二甲基苯基亚胺)乙基]吡啶(L1)、2,6-二[1-(2,6-二乙基苯基亚胺)乙基]吡啶(L2)和2,6-二[1-(2,4,6-三甲基苯基亚胺)乙基]吡啶(L3)分别与MnCl2·4H2O在乙腈中反应,合成了3个新的具有较大空间位阻的2,6-吡啶二亚胺基氯化锰配合物L1Mn(Ⅱ)...     

N,N'-二乙基喹啉菁染料分子吸附在溴化银溶胶上的表面增强喇曼散射

N,N'-二乙基喹啉菁染料分子吸附在硫敏化过的溴化银溶胶上产生强的表面增强喇曼散射,这种散射实际上是在直晒银上产生的。N,N'-二乙基喹啉菁染料分子吸附在硫敏化过的溴化银溶胶和银溶胶上的喇曼谱基本相似。而未经硫敏化的溴化银溶胶和经硫敏化后再被高硫酸钠氧化的溴化银溶胶中测不到N,N'-二乙基喹啉菁染料的表面增强喇曼信号。本实验进一步表明,表面增强喇曼散射方法可以用于感光机理的研究。     

Dichroism of absorption and polarization of phosphorescence of molecules of the closed form of nitrobenzospirothiopyran

The spectral-polarization characteristics of absorption and phosphorescence of molecules of the initial form of nitro-substituted indolinospirobenzothiopyran were studied in oriented polyethylene films and in solutions with different polarity. An oscillator model of the electron transitions responsible for the formation of absorption and luminescence spectra was suggested. It was established that the principal differences in the spectral and photophysical properties of the compound studied and its oxygen-containing analog are associated with the fact that the electronegativity of the S atom is lower than that of the O atom. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1143–1146, June, 1997.     

Synthesis of phenolic components of Grains of Paradise

Two vanilloids, (5E)-8-(4-hydroxy-3-methoxyphenyl)oct-5-en-4-one (1) and 4-[3-hydroxydecyl]-2-methoxyphenol (2), isolated from the dried seeds of Grains of Paradise (Aframomum melegueta), were synthesized; the latter compound was made as the S-enantiomer and the material derived from the seeds was found to be a 1:1.7 mixture of the R and S isomers. The synthetic route used should allow the preparation of analogs having extended alkyl chains and consequently different lipophilicity, and 3, a homolog of 2, was also prepared.     

非那雄胺合成工艺改进

非那雄胺能抑制5α-还原酶的活性,明显降低二氢睾酮水平,是一种治疗良性前列腺增生的有效药品。该合成工艺以甾烯酮酸为原料,将其与氯化亚砜反应,无须分离即与叔丁胺反应得17β-酰胺化合物,再氧化开环,环合,氢化,脱氢合成了非那雄胺。经元素分析、IR、1HNMR、13CNMR、MS分析表征了其结构。该法无须使用昂贵的2,2-二吡啶二硫化物和剧毒药品苯亚硒酸酐,且以乙酸铵代替氨气,降低了对设备的要求和腐蚀,更适用于工业生产。     

Study of hydration of two cements of different strengths

Main hydration products of two cement pastes, i.e. CSH-gel, portlandite (P) (and specific surface S) were studied by static heating, and by SEM, TEM and XRD, as a function of cement strength (C-33 and C-43) hydration time (th) and subsequent hydration in water vapour.Total change in mass on hydration and air drying, M_o, increased with strength of cement paste and with hydration time. Content of water escaping at 110 to 220°C, defined as water bound with low energy, mainly interlayer and hydrate water, was independent on cement strength but its content increased with (th). Content of chemically bound (zeolitic) water in CSH-gel, escaping at 220-400°C, was slightly dependent on strength and increased with (th). It was possibly derived from the dehydroxylation of CSH-gel and AFm phase. Portlandite water, escaping at 400-500°C, was independent on cement strength and was higher on longer hydration. Large P crystals were formed in the weaker cement paste C-33. Smaller crystals were formed in C-43 but they increased with (th). Carbonate formated on contact with air (calcite, vaterite and aragonite), decomposed in cement at 600-700^oC. It was high in pastes C-33(1 month) and C-43(1 month), i.e. 5.7 and 3.3%, respectively; it was less than 1% after 6 hydration months (low sensitivity to carbonation) in agreement with the XRD study showing carbonates in the air dry paste (1month), and its absence on prolonged hydration (6 months) and on acetone treatment. Water vapour treatment of (6 months) pastes or wetting-drying increased this sensitivity.Nanosized P-crystals, detected by TEM, could contribute to the cement strength; carbonate was observed on the rims of gel clusters.This revised version was published online in November 2005 with corrections to the Cover Date.     

Determination of heats of detonation and influence of components of composite explosives on heats of detonation of high explosives

The heats of detonation of 20 simple high explosives and explosive mixtures were determined by means of an adiabatic detonation calorimeter designed by the authors. The results indicated that the performance of the instrument was reliable and the experimental data were very accurate. For explosive mixtures, there was a linear accumulative relationship between the heats of detonation of the explosive mixture and its components. Accordingly, the heats of detonation of explosive mixtures could be calculated directly from the heats of detonation of simple explosives and the characteristic heats of other components. The experiments showed that the gold or brass shell of the cylindrical charge could be substituted by a thick-walled porcelain shell, which had the advantage of cheapness.

     

Investigation of Kinetics of Solid-Phase Synthesis of Lithium Orthosilicate

The kinetics of the interaction between lithium carbonate and silica with various degrees of dispersion was investigated by TG and DTA methods. It was found that the utilization of pyrogenic silica with a specific surface area of about 300 m²g^-1 instead of aerosil with one of 175 m²g^-1 leads to an increase of the reaction rate between lithium carbonate and silica, which depends on the formation and growth of lithium orthosilicate crystals in the first stage, and is conditioned by the diffusion of lithium and oxygen ions through the lithium orthosilicate layer formed at temperatures above 800 K. This supposition is supported by the kinetic analysis results obtained with the use of the different models. The optimal regime of heating is recommended. This revised version was published online in July 2006 with corrections to the Cover Date.     

小环化合物中饱和碳质子化学位移的计算

小环化合物由于其张力、构型、构象和各向异性效应等原因,环碳上质子化学位移缺乏规律性,难以预测,对此作者曾提出一种近似算法。本文根据303种小环化合物中饱和碳质子的化学位移实验数据,将适于计算这类质子化学位移的公式表述为:     

恶臭嗅辨实验室建设探讨

针对恶臭测试的环境影响问题,提出了解决的实例方案,并对方案的要点及优缺点进行讨论,此方案在实际操作中具有较好的效果。     

结合实际发展电化学科学─—武汉大学电化学研究室工作简介

结合实际发展电化学科学─—武汉大学电化学研究室工作简介查全性,陆君涛（武汉大学化学系电化学研究室,武汉４３００７２）在物理化学的众多分支学科中,电化学长期保持良好的发展势头。除了电化学所研究的体系（溶液、电极／溶液界面等）具有广泛的基础意义外,促使电...