偶氮染料结构、光稳定性和光化学降解机理研究

本文介绍了偶氮染料分子构型、聚集态及其晶体结构的量子化学与实验研究情况, 综述了偶氮染料光稳定性的结构效应和光化学降解机理及其激光闪光光解与时间分辨共振Ram an 光谱近代实验技术的研究进展。     

表面增强拉曼光谱研究吸附态的变化

测量了吡啶分子在电化学处理的银表面和亚甲基蓝分子在硝酸刻蚀银表面的表面增强拉曼光谱（ＳＥＲＳ）．对ＳＥＲＳ谱线的分析结果表明，吡啶分子在较低的表面吸附分子密度时倾向于平躺方式；而在较高的表面分子密度时，则倾向于向垂直吸附态转化．亚甲基蓝分子在较低浓度时主要是平躺吸附，随Ｃｌ－浓度的增加，亚甲基蓝从“平躺”吸附态转向“站立”吸附态．     

1H,13C NMR spectral data for α-, β-, and γ-lewisites and identification ofcis,trans, trans-γ-lewisite as a new isomer

The¹H and¹³C NMR spectral parameters of α-, β-, and y-lewisites1–5 were obtained and a new isomer,cis,trans,trans-γ-lewisite5, was isolated and identified on the basis of chemical shifts, relative intensities of the signals, and the intra-chain (³ J _hh ,³ J _ch ) and interchain (³ J _casch ) coupling constants. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1833–1835, October, 1993.     

CoMo／Al_2O_3和CoMo／TiO_2－Al_2O_3加氢脱硫催化剂的研

研究了ＣｏＭｏ／Ａｌ２Ｏ３和ＣｏＭｏ／ＴｉＯ２－Ａｌ２Ｏ３催化剂的加氢脱硫性能，并用ＬＲＳ，ＸＲＤ和ＴＰＳ等方法表征其表面相结构和硫化行为．结果表明，以ＴｉＯ２－Ａｌ２Ｏ３为担体的Ｍｏ和ＣｏＭｏ催化剂的活性均比相应的Ａｌ２Ｏ３为担体的高；少量Ｃｏ，Ｎｉ助剂的引入可显著提高ＭｏＯ３在担体上的分散度和改进催化剂的活性；Ｃｏ助剂还有降低Ｍｏ物种硫化温度的作用．     

聚丙撑碳酸酯的辐射效应

研究了室温条件下聚丙撑碳酸酯(PPC)在钴-60和电子加速器辐照过程中的响应行为。结果表明,聚丙撑碳酸酯是一种辐射裂解型聚合物,其分子量随着辐射剂量的增加而减小。1mm厚PPC片材在室温和N2气保护条件下,其裂解G值为Gs,γ-ray=10.81;Gs,EB=4.9。不同的裂解G值表明,O2气在聚丙撑碳酸酯的辐射裂解过程中有重要影响。红外光谱研究表明,辐射后聚丙撑碳酸酯在3474cm-1处的峰宽峰高增加,表明其裂解后端—OH基增加。由于裂解作用,辐射后聚丙撑碳酸酯的抗张强度和断裂伸长率均下降。在通常的辐射消毒剂量范围内(25~50kGy),PPC的保留抗张强度大于23MPa,断裂伸长率大于4%,裂解后试样的力学性能依然能够满足实际应用需要,因此PPC可以经受辐射消毒。     

SYNTHESIS OF CROSS-CONJUGATED （p-PHENYLENE）S-POLY（p- PHENYLENEVINYLENE）S HYBRIDS WITH LOW CONTENT OF STRUCTURAL DEFECTS

The novel shish-kebab-type liquid crystalline cross-conjugated （p-phenylene）s-poly（p-phenylenevinylene）s hybrid was synthesized through Gilch polymerization. Their structures and properties were characterized by NMR, GPC, DSC, X-ray diffraction and polarizing optical microscope （POM）. ^1H-NMR investigation of the polymers indicates that the shish-kebab-structure has a strong ability to suppress the structural defects in the polymers. The polymers are enantiotropic liquid crystals. The melting point （Tm） of the polymers decreases when the length of the alkoxy tails of the mesogenic units increases. The mesophase was identified by X-ray diffraction method. They showed not only a smectic LC phase, but also a strong green fluorescence in chloroform. The maximum absorption band of the ＂kebabs＂ of the two, 5-bis（4＇- alkoxyphenyl）benzene at 280 nm did not appear in absorption spectra of the polymers. The same phenomena were also observed in the fluorescence spectra. These results imply that the polymers have formed a cross-conjugated uniform structure and achieved an extended n-conjugation polymer.     

细菌视紫红质多重突变体结构变化及其中间态的寿命

采用基因定点突变的方法, 构建了细菌视紫红质(Bacteriorhodopsin, BR)的3种突变体蛋白, 即单突变体BRE194Q、三突变体BRI119T/T121S/A126T和四突变体BRI119T/T121S/A126T/E194Q. 测定了突变体和野生型BR在水溶液和聚乙烯醇(PVA)膜中的紫外-可见吸收光谱和拉曼光谱, 采用显微视频录像技术记录了PVA膜中野生型和3个突变体样品的M态寿命. 与野生型BR相比较, 在水溶液中, 单突变体的可见吸收光谱的最大吸收峰发生了轻微红移, 三突变体和四突变体的最大吸收峰则分别发生了11.0和12.0 nm的明显蓝移. 在PVA膜中, 3个突变体BR的可见吸收光谱的最大吸收峰均发生蓝移, 四突变体BR的最大吸收峰为557 nm, 蓝移达15.0 nm. 四突变体BR在水溶液中的共振拉曼光谱不仅表现有与M态特征相关的1567和1573 cm-1谱带, 还有L态特征带1334 cm-1及N态特征带1200, 1328, 1530和1549 cm-1. 在PVA膜中的样品与在水溶液中的比较, 四突变体共振拉曼光谱的1334和1549 cm-1带消失, 同时1187 cm-1带的强度下降. 显微视频录像技术记录的PVA膜中样品的M态寿命表明, 野生型BR的M态寿命最短, 单突变体的M态寿命小于1.0 s, 三突变体的寿命为3.0 s, 四突变体的寿命为2.0 s.     

Synthesis of alkyl-substituted phosphorus phthalocyanines and triazatetrabenzocorroles

New alkyl-substituted phosphorus phthalocyanines and triazatetrabenzocorroles were synthesized. The structures of these complexes were confirmed by ¹H, ¹³C, and ³¹P NMR spectroscopy, mass spectrometry, and electronic absorption spectroscopy. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1403–1407, July, 2007.     

Synthesis, structures, and optical and electrochemical characteristics of novel crown-containing polythiophene systems

The synthesis, structures, and optical and electrochemical characteristics of novel crown-containing styryl mono-and polythiophenes were described. The double bonds were constructed by the Horner-Wadsworth-Emmons method. The Suzuki and Stille cross-coupling reactions were used to create polythiophene chains. Optical measurements revealed intense absorption and fluorescence of crown-containing polythiophenes; the band positions and shapes in their absorption and emission spectra depend on the structure of the polythiophene. The electrochemical characteristics of the compounds obtained were measured. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 932–939, May, 2007.     

SYNTHESIS AND CHARACTERIZATION OF N-（1-NAPHTHYL） SUCCINIMIDE

In this paper a modified two-step procedure for synthesis of N-（1-naphthyl） suecinimide （NaS） was developed, and the molecular structure of NaS was properly characterized by XRD, FT-IR, 1H NMR, DSC, etc. The results show that the melting point of our product is 159 ℃-160.5 ℃, and the characteristic infrared absorption band of carbonyl group splits into two peaks （1705cm^-3/1779cm^-3）, which are found to be quite different from the documented data （rap 147℃ -149℃; IR C=0-1700cm^-3）. Besides, photophysical spectroscopy was found to be powerful to study the molecular structure and crystal morphology of NaS compound.