具有圆偏振光特性的卟啉衍生物的合成、表征和CD光谱研究

合成了一组不同碳链的胆甾醇酯侧链卟啉配体和金属Zn配合物. 研究了它们的吸收光谱和发射光谱. 将这些卟啉配体以一定浓度掺杂在聚甲基丙烯酸甲酯(PMMA)中制成固体薄膜, 发现由于在卟啉环上引入了手性的胆甾醇酯侧链, 卟啉化合物在soret带和Q带均有较强的CD吸收, 这种现象可能是卟啉环上的四个手性胆甾醇酯侧链与四苯基卟啉环发生偶合作用. 进一步还发现这些卟啉化合物的圆偏振吸收性质与在PMMA中的浓度有关.     

双大环多胺Zn(Ⅱ)配合物及其与DNA作用的溴乙锭荧光探针

以1,4,7,10-四氮杂环十二烷(Cyclen)为原料合成的一种新型双大环多胺配体及其双核Zn2+配合物,其结构用1H NMR、质谱和元素分析等测试技术进行了表征。 以溴乙锭(EB)为探针,用荧光光谱法研究了双环多胺配体及其Zn(Ⅱ)配合物与小牛胸腺DNA的作用,当cComplex 6/cDNA=0.51时,DNA/EB体系的荧光强度降低至原来的47.3%,表明双大环配合物是以嵌入方式与小牛胸腺DNA结合。 化合物对DNA/EB体系的荧光猝灭顺序为：双大环多胺双核Zn(Ⅱ)配合物＞双大环多胺配体＞四氮杂环多胺Zn(Ⅱ)配合物＞四氮杂环多胺。     

二(2-苯并咪唑亚甲基)胺合铜(II)配合物与DNA作用方式的光谱研究

应用紫外、荧光、黏度等方法, 对二(2-苯并咪唑亚甲基)胺合铜(II)配合物与小牛胸腺DNA作用方式进行了研究. 配合物与DNA作用时, 使紫外吸收明显减色, 荧光降低, 黏度降低; Scatchard图表明配合物对溴化乙锭(EB)与DNA的结合为非竞争性抑制. 实验结果表明, 配合物与DNA作用方式可能为静电结合.     

新型β-取代阳离子卟啉光敏剂合成及其与DNA相互作用

在5,10,15,20-四苯基卟啉及其金属配合物的β位引入阳离子型修饰基团溴化吡啶鎓盐, 得到β-[2-(6-吡啶溴化盐)己氧基]萘基-5,10,15,20-四苯基卟啉及其Cu(II), Ni(II), Zn(II)配合物. 通过IR, UV, ¹H NMR, MS以及元素分析对新化合物进行了结构表征. 作为光动力治疗光敏剂与pBR322质粒DNA的相互作用研究表明, 它们对DNA具有良好的光敏切割效果和结合能力, 通过与小牛胸腺DNA相互作用初步研究了它们与DNA的作用模式.     

二(2-苯并咪唑亚甲基)胺合铜(Ⅱ)配合物与DNA作用方式的光谱研究

应用紫外、荧光、黏度等方法，对二(2-苯并咪唑亚甲基)胺合铜(Ⅱ)配合物与小牛胸腺DNA作用方式进行了研究．配合物与DNA作用时，使紫外吸收明显减色，荧光降低，黏度降低；Scatchard图表明配合物对溴化乙锭(EB)与DNA的结合为非竞争性抑制．实验结果表明，配合物与DNA作用方式可能为静电结合。     

不对称大环双核Ni(Ⅱ)配合物的DNA切割性能研究

本文利用模板导向的方式合成了一种含有不对称侧链的大环双核金属Ni(Ⅱ)配合物(大环配体由3-溴甲基-5-甲基水杨醛,乙二胺,N,N-二(氨丙基)-2呋喃甲胺分步合成得到),其结构通过红外光谱、元素分析、X-射线单晶衍射进行了表征。利用紫外光谱、分子荧光和粘度试验对配合物与DNA的相互作用进行了研究,结果表明配合物与CT-DNA的结合常数K=4.8×104mol-1.L荧光淬灭常数Ksv=7.12×103mol-1.L;同时机理研究表明配合物与CT-DNA结合方式为插入模式。     

含N,N-二(2-苯并咪唑甲基)亚胺单核镍(Ⅱ)配合物与DNA相互作用的研究

用荧光光谱法和紫外-可见吸收光谱法研究了含N,N-二(2-苯并咪唑甲基)亚胺单核镍(Ⅱ)配合物与小牛胸腺DNA(ct-DNA)作用的机理。结果表明,随着ct-DNA浓度的增加,配合物表现较强的荧光增强作用,且在不同的温度下荧光增强常数Ks随温度的升高而降低,表明配合物与ct-DNA的作用机理是静态增强过程。根据双对数方程计算出了不同温度下的结合常数K和结合位点数n。稳态荧光猝灭及溴化乙锭(EB)竞争取代实验研究表明配合物与ct-DNA可能以嵌插方式结合。吸收光谱表明配合物增加了DNA双螺旋结构的稳定性。     

光谱法研究对氨基苯乙酮缩对二甲氨基苯甲酰腙与DNA的相互作用

合成了对氨基苯乙酮缩对二甲氨基苯甲酰腙(AAPABH),采用荧光光谱法和UV-Vis吸收光谱法研究了AAPABH与DNA的相互作用。在pH 7.4Tris-HCl缓冲溶液中,以345 nm激发该化合物发射弱荧光,加入DNA后出现明显的荧光增强现象,表明探针分子与DNA结合形成了稳定配合物,其结合常数为5.48×107L/mol。研究了离子强度对体系荧光强度的影响,结果显示NaCl的加入未引起AAPABH-DNA体系荧光强度明显变化,表明AAPABH和DNA间不存在静电作用;同时DNA对AAPABH吸收光谱的影响表现为减色效应、探针分子与热变性后的DNA作用力明显小于与未变性DNA间的作用力、探针分子与溴化乙锭(EB)竞争结合DNA使得EB-DNA体系荧光猝灭,上述实验结果均表明探针分子主要以嵌插作用方式与DNA作用。     

咔咯及其金属配合物与DNA的作用和抗肿瘤活性

咔咯及其金属配合物与DNA相互作用和它们的抗肿瘤活性研究已成为咔咯大环化学前沿课题之一。本文综述了咔咯及其金属配合物与DNA相互作用和关于这类化合物在抗肿瘤方面的研究进展,系统介绍了咔咯及其金属配合物与DNA结合模式、在氧化剂存在或光照条件下的核酸酶活性、与G-四链体DNA相互作用以及这类化合物抗肿瘤活性。     

光谱法研究[Ce(NO_3)_3(Phen)_2]配合物晶体结构及其与DNA之间的相互作用

对配合物[Ce(NO3)3(Phen)2]的吸收光谱、荧光光谱和拉曼光谱进行了归属,研究了该配合物的晶体结构。同时,用光谱法研究了该配合物与DNA之间的相互作用。研究发现,DNA加入后,配合物的紫外吸收峰和表面增强拉曼峰明显降低,而荧光强度明显增强。配合物对EB与DNA作用有竞争。这些表明配合物与DNA有较强的相互作用,并且主要键合模式是插入作用。测得配合物与DNA的键合常数为1·7×105。     

Metallacarboranes and their interactions: theoretical insights and their applicability

This tutorial review will deal with the study of metallacarboranes and their interactions with other molecules from a theoretical point of view. This contribution is devoted to guide experimental chemists through calculations that some years ago were reserved to theoretical specialists. The widespread availability of fast computers enables nowadays studies of complex compounds (e.g. metallacarboranes) from different perspectives including simulation of NMR, infrared or Raman spectra and calculation of other properties such as atomic charges or inter-/intramolecular interactions. The insights gained on the basis of theoretical calculations are crucial for either finding novel or improving existing applications of metallacarboranes. For example, in the case of enzyme inhibitors, the interactions of the metallacarboranes with the surrounding protein and how the interaction affects the efficiency are difficult problems to study experimentally. The use of theoretical tools can provide a detailed understanding of the physico-chemical basis of the interactions and thus offers a chance to control the overall process.     

二苯基哌嗪磺胺化合物的合成及其抗微生物活性

以乙酰苯胺和4-氯二苯甲酮为起始原料,经多步反应方便而有效地合成了二苯基哌嗪磺胺化合物,所得目标化合物及其中间体的结构经1H NMR、13C NMR、IR、MS谱和元素分析等证实.研究了化合物的体外抗微生物活性,结果表明目标化合物14和16对所测菌株的抗菌活性均优于磺胺.     

Benzonitriles: Survey of their importance and scaling of their vibrational frequencies

This work provides a short survey of the studies carried out on benzonitrile and its derivatives, with special attention on a spectroscopic point of view. The importance and main applications of these molecules are also briefly indicated. For an accurate assignment of their vibrational spectra, the scaling procedures for the wave numbers are described. For this purpose, the performance of semiempirical, ab initio, and density functional methods, with different basis sets, is determined. A “resume” of the main scaling factors to be used in the calculated wave numbers is shown. The results obtained for several benzene derivatives, and in particular for four benzonitriles, are analyzed. © 2003 Wiley Periodicals, Inc. Int J Quantum Chem 94: 189–204, 2003     

Thermozymes and their applications

Enzymes from thermophilic microorganisms, thermozymes, have unique characteristics such as temperature, chemical, and pH stability. They can be used in several industrial processes, in which they replace mesophilic enzymes or chemicals. Thermozymes are often used when the enzymatic process is compatible with existing (high-temperature) process conditions. The main advantages of performing processes at higher temperatures are reduced risk of microbial contamination, lower viscosity, improved transfer rates, and improved solubility of substrates. However, cofactors, substrates, or products might be unstable or other side reactions may occur. Recent developments show that thermophiles are a good source of novel catalysts that are of great industrial interest. Thermostable polymer-degrading enzymes such as amylases, pullulanases, xylanases, proteases, and cellulases are expected to play an important role in food, chemical, pharmaceutical, paper, pulp, and waste-treatment industries. Considerable research efforts have been made to better understand the stability of thermozymes. There are no major conformational differences with mesophilic enzymes, and a small number of extra salt bridges, hydrophobic interactions, or hydrogen bounds seem to confer the extra degree of stabilization. Currently, overexpression of thermozymes in standard Escherichia coli allows the production of much larger quantities of enzymes, which are easy to purify by heat treatment. With wider availability and lower cost, thermophilic enzymes will see more application in industry.     

Cyclazines and their analogs

The formylation of 2-methyl-6-cyanomethylthiopyridines, 2-methyl-4-cyanomethylthiopyrimidines, or 3-amino-5-methylthiazolopyrimidinium salts gave cyclazine derivatives of new heterocyclic systems with an angular nitrogen atom, which were used for the preparation of polymethine dyes. The relationship of the color and structure of these compounds was studied.For Communication 2, see ref. [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1280–1285, September, 1992.     

Heteroadamantanes and their derivatives

6-Cyano-1,3-diazaadamantan-6-ols and- 9-cyano-3,6-diazahomoadamantan-9-ols, whose reaction with ammonia forms the corresponding 6-cyano-6-amino-1,3-diazaand 9-cyano-9-amino-3,6-diazahomoadamantanes, were prepared by the exchange reaction of 1,3-diazaadamantan-6-ones and 3,6-diazahomoadamantan-9-ones with acetone cyanohydrin. When heated with ammonium carbonate, spirohydantoins were directly obtained from the former compounds and from the initial ketones by Bucherer—Bergs synthesis.See [1] for Communication 15.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 648–652, May, 1992.     

Polymethylenepolynitramines and their derivatives

Hitherto unknownN-fluoro-substituted polymethylenepolynitramines were synthesized by fluorinating the respective polymethylenepolynitramines with elemental fluorine in anhydrous acetonitrile.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2174–2176, December, 1994.     

Aminonitropyridines and their N-oxides

2,6-Diamino-3,5-dinitropyridine 1-oxide has been prepared by mixed acid nitration of 2,6-diaminopyridine, followed by oxidation using hydrogen peroxide in acetic acid. 3,5-Dinitro-2,4,6-triaminopyridine has been prepared by oxidative amination of 2-chloro-3,5-dinitropyridine or 2,6-diamino-3,5-dinitropyridine using potassium permanganate in liquid ammonia, or by “vicarious nucleophilic amination” of 2,6-diarnino-3,5-dinitropyridine using hydroxylamine in aqueous potassium hydroxide. 3,5-Dinitro-2,4,6-triaminopyridine 1-oxide has been prepared by oxidation of 3,5-dinitro-2,4,6-triaminopyridine using hydrogen peroxide in acetic acid, and by “vicarious nucleophilic amination” of 2,6-diamino-3,5-dinitropyridine 1-oxide. Nmr spectroscopy and single crystal X-ray diffraction studies have shown that these compounds have the planar structures and intra- and inter-molecular hydrogen bonding necessary to confer on the materials the high density, the thermal and chemical stability, and the explosive insensitivity required for new insensitive energetic materials.     

Pyrazines and their N-oxides

The N-oxides of 2- and 2,3-substituted pyrazines were synthesized. It was found that the synthesized 2-formylpyrazine N,N-dioxide, in which the aldehyde group is in the hydrated form, undergoes redox transformations leading to deoxidation of one of the ring nitrogens and oxidation of the dihydroxymethyl group to a carboxyl group under the influence of alkaline reagents.See [10] for communication II.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1275–1280, September, 1972.