甲基紫-核酸分子相互作用的紫外-可见光谱及其分析应用

1引言研究了甲基紫与核酸分子相互作用的紫外-可见光谱,在pH7左右,核酸包括小牛胸腺DNA,热变性DNA,酵母RNA能够与甲基紫相互作用,甲基紫最大吸收峰在579nm,随着核酸的加入发生明显的减色效应,减色强度随着核酸浓度加大而增强,据此建立测定核酸的新方法,该方法线性范围宽、简便、快速。2实验部分2．1主要仪器和试剂λ-17紫外-可见分光光度计（美国Pekin－Elmer公司）。核酸溶液：小牛胸腺DNA,酵母RNA（中国科学院上海生物化学研究所）操作液浓度100mg／L;甲基紫溶液：2×10－4‘mol/L水溶液;Tris-HCI缓冲溶液：pH＝7．…     

表面增强红外光谱在生物分析中的应用

表面增强红外光谱可以在单分子水平上原位监测界面吸附分子的振动变化,提供定向和构象的信息,因而备受关注。本文简单介绍了表面增强红外光谱产生、增强机制、基底制备方法、特点,重点评述了表面增强红外光谱在原位解析复杂的生物界面过程和结构变化方面的进展,并展望其发展前景。     

水光谱探针及其在结构分析中的应用

水对化学和生物过程具有重要作用,因此水的结构和性质研究一直备受关注。水的结构易受温度影响,利用温控近红外光谱技术和化学计量学方法,通过提取随温度变化的水光谱信息,不仅可以了解水的结构和性质,还可以将水作为探针,探测溶液或生物体系中分子的定量信息和结构变化。该文总结了利用温控近红外光谱技术研究小分子的结构和蛋白质、温敏聚合物结构转变过程等方面的研究工作,并利用随温度变化的水光谱信息,对化学结构及其变化过程中水的作用及作用机理进行了分析。     

苯并咪唑类化合物的结构与光谱特性研究

为研究苯并眯唑类化合物的结构与光谱特性,设计、合成了不同结构的系列苯并眯唑类化合物,测定了其最大吸收波长(隺max)(320.5～396.0 am)和荧光发射波长(雃)(387.0～497.0 nm),求得了荧光量子产率(～0.69)和Stokes Shift位移值(～9 636.5).研究发现其分子结构与上述光谱特性有密切关系.     

香豆素酰胺类化合物的合成及光谱特性

用(取代)香豆素-3-甲酰氯(Ⅰa～Ⅰc)和取代2-氨基苯并噻唑(Ⅱa～Ⅱd)作用合成了12种新的目标化合物(Ⅲa～Ⅲl),用HRMS、IR、1H NMR对化合物结构进行了表征,确定了化合物的结构,并对其紫外吸收光谱和荧光光谱进行了分析。研究发现:在紫外光谱中,新化合物(Ⅲa～Ⅲl)和原料化合物(Ⅰa～Ⅰc)相比,因共轭链的增长而使其最大吸收波长(λmax)红移;12种化合物表现出比原料化合物(Ⅰa～Ⅰc)较强的荧光性能。     

表面增强拉曼光谱在DNA检测中的应用

表面增强拉曼光谱(Surface Enhanced Raman Spectroscopy,SERS)由于具有光谱分辨率高、信息量大,不受水的干扰,灵敏度高等优点,在生命科学等研究领域得到了广泛应用。近几年来,SERS技术在DNA分析领域中得到迅速的发展,成为国内外研究的热点。本文主要对SERS进行了介绍,并对应用于DNA检测的一些最新SERS技术进行较为全面的综述,展望了SERS技术的应用前景。     

新的N-苯并噻唑基香豆素酰胺类化合物的合成及光谱特性

用具有光学活性和生物学活性的2类化合物(取代)香豆素-3-甲酰氯和2-氨基苯并噻唑作用合成了4种新的兼具香豆素骨架和苯并噻唑基的化合物(3a-3d),用HRMS,IR和1H NMR对化合物结构进行了表征,确定了化合物的结构,并对其紫外吸收光谱和荧光光谱与分子结构的关系进行了讨论.研究发现:在紫外光谱中,新化合物(3a-3d)和2种原料化合物相比,因共轭链的增长而使其最大吸收波长(λmax)红移;4种化合物表现出比原料化合物较强的荧光性能,其中3c的荧光强度最大.文中给出了稀溶液中紫外光谱和荧光光谱相关的一些信息.     

广义二维相关光谱及其在分析领域中的应用

广义二维相关光谱(generalized two-dimensional correlation spectroscopy)的理论提出至今, 得到了国际学术界的极大关注, 其分析方法已经在分析领域中被广泛应用. 文中在叙说广义二维相关光谱的数学处理过程及其谱图的物理意义的同时, 列举了在化学分析和分子生物学等领域中的有机溶剂成分分析、生物分子在不同pH中的特性分析和蛋白结构分析等应用实例, 并详细地对广义二维相关光谱理论和分析方法进行了评述.     

甲基紫与苋菜红相互作用的双波长共振光散射比率光谱研究及其分析应用

应用双波长共振光散射比率法(DW-RLS)研究了甲基紫与苋菜红之间的相互作用.在pH 1.24的乙酸钠-HCl缓冲溶液中,甲基紫和苋菜红本身的共振光散射(RLS)信号均很弱,但是当它们相互作用形成缔合物时,导致RLS信号明显增强并出现新的RLS光谱,适当浓度的Triton X-100存在使结合反应敏化,缔合物最大散射峰位于528 nm,RLS信号强度与苋菜红的浓度呈线性关系.通过测量528 nm处的RLS强度或两个波长处RLS强度比值(I417/I343),可对苋菜红进行定量检测.当溶液中甲基紫的浓度为1.54×10-5 mol/L时,RLS法测定苋菜红的线性范围和检出限分别为0.05～0.50 μg/mL和0.02 μg/mL,而DW-RLS法的线性范围和检出限分别为0.01～0.60 μg/mL和1 ng/mL,与RLS法相比较,DW-RLS法受酸度、离子强度等环境条件影响较小,并且有更宽的线性范围和更低的检出限.     

镜面反射红外光谱在聚合物分析中的应用

简要介绍了镜面反射红外光谱的基本原理以及它在聚合物结构分析中的应用。镜面反射红外光谱在聚合物的表面结构表征中发挥了重要的作用，可以弥补常规透射红外光谱的不足，是一种很有实用价值的红外分析方法。     

Polarographic determination of phenothiazine and N-substituted compounds

Summary Phenothiazine was nitrated and the structure of the compound formed was elucidated by U.V., I.R., N.M.R. and mass spectroscopy techniques. It has been proved that two nitro-groups were fixed on the ring. The d.c. and a.c. polarographic reductions showed that the two nitro-groups were reduced into aminogroups. The reduction proceeds in two waves, with a total of 12 electrons. N-substituted phenothiazine compounds were also investigated using the same technique.

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Polarographische Bestimmung von Phenothiazin und seinen N-substituierten Derivaten

Zusammenfassung Phenothiazin wurde nitriert und die Struktur der gebildeten Verbindung mit Hilfe der IR-, UV-, KMR- und Massenspektrometrie untersucht. Es ergab sich, daß zwei Nitrogruppen am Ring gebunden waren. Durch Gleich- und Wechselstrompolarographie wurden die Nitrogruppen zu Aminogruppen reduziert, wobei sich zwei Wellen (insgesamt 12 Elektronen) ergaben. Mit denselben Methoden wurden auch N-substituierte Derivate untersucht.

Lecture presented at Euroanalysis I Conference, 28. 8.–1. 9. 1972 in Heidelberg, Germany.     

Spectral and photochemical properties of bifunctional compounds and their complexes

Quantum yields of the step-by-step photocyclization of diphenylamine (DPA) derivatives Ph₂N−(CH₂)n−NPh₂,n=3–6, 9, to the corresponding α,ω-di(carbazolyl)alkanes were measured. Atn>3, the presence of the second DPA group had no effect on the cyclization of the first DPA group; however, cyclization of the second DPA group was retarded after cyclization of the first DPA group. The effect was explained by quenching of the excited DPA group by the carbazole group newly formed in the semi-cyclic compound. For disubstituted propane (n=3), the mutual influence of the two groups at both stages of the reaction was found. For Part 1, see Ref. 1. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1510–1515, August, 1999.     

Synthesis and properties of phenothiazine derivatives. I. Synthesis and properties of bisoxytriazenes containing the phenothiazine fragment

3, 7-Bis(1-phenyl-3-hydroxytriazenyl)phenothiazine has been synthesized from phenothiazine. This compound decomposes to phenyl radicals, nitrogen and 3, 7-bisnitrosophenothiazine under the influence of nitroso compounds and oxidizing agents (PbO₂, Ag₂O). The reaction of bishydroxytriazenylphenothiazene with 2, 4, 6-tribromonitrosobenzene has been studied by EPR spectroscopy.N. P. Ogarev Mordov State University, Saransk 430000. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1284–1287, September, 1996. Original article submitted March 21, 1996.     

Spectral and luminescent properties of compounds based on indoline spiropyran and salicylideneimine

Spectral and luminescent properties of two photobifunctional compounds (PBC) were studied, whose molecule includes spirocyclic naphthopyran or naphthoxazine and hydroxyazomethine fragments bound together by different ways, in comparison with model compounds. Temperature and solvent dependences of the luminescence spectrum for PBC 1 and the absence of such dependences for PBC 2 were found. Selective excitation of PBC 1 with enol or cis-keto form of the azomethine fragment leads to the same luminescence spectrum at 293 K.     

Separation and identification of phenothiazine compounds by thin-layer chromatography

The chromatographic behavior of phenothiazine derivatives is studied by thin-layer chromatography with the use of Sorbfil silica gel plates in a binary benzene-methanol mixture of solvents. An empirical equation describing the dependence of the retention value (mobility R _f ) of the substance on the physicochemical properties of the eluent is proposed. The effect of interactions of different types on the value of their chromatographic retention is estimated; the relation of the obtained coefficients of equations for the substances under study is analyzed. The obtained empirical dependences are used to calculate the R _f values. The discrepancy between the calculated and experimental data is below 0.07.     

Potentiometric study of reaction between tetrabutylammonium periodate and phenothiazine in chloroform; application to the analysis of phenothiazine derivatives

The reaction between tetrabutylammonium periodate and phenothiazine in the presence of the strong acids in chloroform was studied by potentiometry and the reaction pathways were determined. The oxidimetric titration conditions of phenothiazine derivatives using a standardized chloroform solution of tetrabutylammonium periodate were optimized and a potentiometric detection of end points was utilized. The relative standard deviation for the determination of 5 mg phenothiazines was obtained about 1-1.5%. The method was applied for the determination of phenothiazines in various pharmaceutical preparations after extraction into chloroform.     

Spectral properties of some metal complexes derived from uracil-thiouracil and citrazinic acid compounds

The reaction of FeCl(3) with uracil (H(2)L(1)), citrazinic acid (H(2)L(6)), 5-(phenylazo)citrazinic acid (H(2)L(7)), 5-(m-hydroxyphenylazo)citrazinic acid (H(2)L(8)) and 5-(m-nitrophenylazo)citrazinic acid (H(2)L(9)) leads to the formation of complexes with the empirical formula Fe(HL)(3).nH(2)O (n=1-3). All of the prepared complexes have octahedral complexation geometry where the azo group is not the reactive site for complexation. Thiouracil (H(2)L(2)) and the 5-(substituted phenylazo)thiouracil (H(2)L(3)-H(2)L(5)) ligands are bidentates on complexation with Co(II), Ni(II) and Cu(II). The complexes have been characterized by elemental analyses, IR, electronic spectra, magnetic susceptibility, DTA, electron spin resonance (copper complexes) and M?ssbauer spectra (iron complexes). The coordination bond lengths between the metal ion and the active centers for complexation were calculated.     

Potentiometric titration of phenothiazine compounds in chloroform and its use in pharmaceutical analysis

The potentiometric titration of some phenothiazine drugs in chloroform is described. A standard solution of bromine in chloroform was used as titrant and the end-points were detected with a small platinum indicator electrode, and an Ag/AgCl electrode in 0.01M Et(4)NCl in chloroform as reference. A fast redox reaction occurs during the titrations and the phenothiazine ring is oxidized to the phenothiazonium free radical (P(+)). The low dielectric constant of the medium favours the formation of (P(+)Br(-)) ion-pairs or (P(+)Br(-)(3)) ion-pairs on further addition of bromine, which has no influence on the position of the first end-point. The method was used for the determination of promethazine, chlorpromazine, trifluoperazine and thioridazine in pharmaceutical preparations after extraction into chloroform. The relative standard deviation for the determination of 5 mg of all these phenothazines was about 1%.     

Spectral and photochemical properties of bifunctional compounds and their charge-transfer complexes. Derivatives of diphenylamine

Spectral properties of diphenylamine (DPA) derivatives Ph₂N-(CH₂) _n -NPh₂ (n = 1, 3, 5, and 9) and their charge-transfer complexes with CBr₄ have been studied. The interaction of two Ph₂N groups results in hypsochromic shifts of absorption bands and changes in their intensities in spectra of diamines whenn = 1 and 3 compared to the spectra ofN-alkyl-substituted derivatives of DPA. The spectrum of the diamine complex whenn = 1 is shifted hypsochromically, while those of the other diamine complexes are shifted bathochromically relative to the spectrum of theN-methyldiphenylamine complex. The positions of absorption maxima in the spectra correlates with the values of redox potentials of amines. Irradiation at the charge-transfer band ( 365 nm) of complexes between diamines and CBr₄ results in the formation of dyes, which absorb at 550 to 700 nm and presumably have di- and triphenylmethane structures.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1725–1730, September, 1995.This work was financially supported by the Russian Foundation for Basic Research (Project No. 93-03-08673).