新型水溶性金属酞菁化合物的合成与表征

以含有咪唑阳离子的邻苯二腈为前驱体,通过环合反应分别合成了四咪唑阳离子取代的锌酞菁和铜酞菁,它们的结构均通过了红外光谱、核磁氢谱、元素分析和紫外-可见吸收光谱的表征.这2种酞菁化合物在水、DMF、DMSO及甲醇中均呈现出良好的溶解性.利用紫外-可见吸收光谱法考察了它们在不同种溶剂中、不同浓度下的聚集行为,并利用循环伏安法和方波伏安法测试了它们的电化学性质.     

香豆素衍生物溶液的光谱和光物理行为

通过对一系列不同取代的香豆素化合物在不同溶剂中的光谱测定,研究了结构和溶剂极性对它们光物理行为的影响.发现了它们的光物理特征与其结构和多种溶剂极性参数间存在的一些关系,为进一步更好的利用这类化合物提供了重要依据.     

22-降-豆甾-22-含氮化合物的合成及抗肿瘤活性

通过结构改造,合成了不同支链的甾体化合物并测定了它们的抗肿瘤细胞增殖活性,探讨了不同支链对抗肿瘤活性的影响。     

1,3-二苯基-4-酰基-5-吡唑酮螯合剂离解常数和两相分配常数的测定

在水-二氧六环混合体系中,用电位滴定法测定了四种新的β－二酮螯合剂在二氧六环不同含量时的离解常数,通过外推,求得它们在纯水中的离解常数。采用两相滴定法,测定了它们在氯仿、苯和正己烷三种有机溶剂与水之间的两相分配常数。     

O-甲基-α-羟基烃基膦酸酯单金属盐的合成

以KF-Al2O3为催化剂,通过亚膦酸二甲酯与各种酮加成反应,生成一系列α-羟基烃基膦酸酯,它们再与不同的碱金属盐作用合成了12个未见文献报道的O-甲基-α-羟基烃基膦酸酯单金属盐。通过^1H NMR,IR和元素分析确证了它们的结构。     

以樟脑酸及咪唑基化合物为配体的锌配合物的合成、晶体结构及荧光性质

以硝酸锌、樟脑酸(H2CAM)和1,2-二咪唑基二甲苯(obix)或4,4′-二咪唑基二甲联苯(bimb)为原料,在水热条件下得到2个结构不同的配位聚合物[Zn(obix)(CAM)]n(1)和[Zn(bimb)(CAM)]n(2)。对它们进行了元素分析、红外光谱和热重等分析,并利用X-射线洐射测定了它们的单晶结构。配合物1中2个锌离子通过2个obix配体桥连成一个24元大环,它再通过CAM配体连接成一维管状结构,而配合物2中锌离子通过两种配体桥连成二维层状结构。结果说明了辅助配体在配合物组装过程中起着非常重要的作用。此外还研究了它们的荧光性质。     

磷与碳、硅、硼、铝形成的二元簇离子的激光产生

在自制的装置上，用高能密度的脉冲激光束在高真空中直接溅射红磷和碳、硅、硼或铝粉的混合物，通过激光等离子体反应，产生了十分丰富的XnPm±（X＝C，Si，B，Al）二元原子簇，记录了它们的飞行时间质谱．对这些簇离子组分的分析发现，它们的成键和结构因其组成元素的不同而有明显的差异，这些差异反映了它们独特的结构化学行为．     

硅桥连双环戊二烯基ⅣB族金属二氯化物的反应

研究了标题化合物[(Me~2Si)~n(C~5H~4)~2MCl~2, n=1,2,3;M=Ti, Zr, Hf]与酚的反应, 水解反应以及与卤素的相互置换反应。结果表明, 由于硅桥的不同它们表现出不同的反应活性。通过这些反应制备了十种新化合物, 用元素分析, 'H NMR 以及质谱鉴定了它们的结构。     

某些冠醚化合物的XPS内壳及其价带谱研究

本文研究某些冠醚化合物的XPS内壳谱、振起伴峰及XPS价带谱。分析了它们的内壳谱特征,指出它们的振起伴峰是由于分子内电荷转移的结果。同时探讨了它们的XPS价带谱中由具有最低结合能峰位所确定的“电离势”与分子中苯环上不同取代基效应间的关系。     

新型吸附剂—球形碳化树脂的研究Ⅵ.

制备了不同结构的苯乙烯—二乙烯苯大孔共聚物小球,通过磺化、高温裂解和水蒸汽活化得到一系列球形碳化树脂。测定了它们的比表面、表现密度、骨架密度、孔隙率、孔体积及平均孔径。研究了它们对肌酸酐、尿酸和B_(12)的吸附率,以及对苯酚的吸附性能。结果表明,它们对上述四种物质具有良好的吸附性能。     

Polymethine dyes with several conjugated chromophores

Triscyanine dyes with three successively conjugated chromophores were obtained from diquaternary salts of four isomeric dimethylbenzobisthiazoles and two isomeric hexamethylbenzodipyrrolenines. The spectra of the dyes contain three absorption bands, the intensities of which depend on the angles formed by the directions of the interacting chromophores and are determined by the structure of the heteroring. The magnitude of the separation of the frequencies of the two extreme absorption maxima of the triscyanines exceeds the magnitude of the separation of the frequencies of the maxima of the corresponding biscyanine dyes by a factor of √2. A dye with four successively conjugated chromophores was obtained from centrosymmetric hexamethylbenzodipyrrolenine, and its absorption spectrum was examined.     

Absorption maxima study of chromophores of indigoid dyes

Molecular structure of 21 chromophores of indigoid dyes were studied by an ab initio MP2/6–31 + G*/ /HF/6–31 + G* method. Bond lengths and bond angles were affected by π-electron conjugation. The difference between molecular structures of chromophores and indigoid dyes indicated that benzene rings and five-membered rings in indigoid dyes are structurally important. Absorption maxima of chromophores were successfully calculated by the CI-singles-MP2/6–31 + G* theory. Like indigoid dyes, absorption maxima of the chromophores are affected by the positions of the donor and acceptor groups on the trimethine group. Bathochromic shifts of the absorption maxima were observed with the best donor group of (SINGLE BOND)NH among (SINGLE BOND)NH, (SINGLE BOND)O, and (SINGLE BOND)S groups. Appropriate substitution of longer-chain polymethines brought about chromophoric systems having hypsochromic shifts. From these calculations, the absorption maxima of some indigoid dyes could be explained by their chromophores qualitatively. © 1996 John Wiley & Sons, Inc.     

Synthesis and Characterization of Novel Monoazo Naphthalimide Disperse Dyes Containing Carboxylic Acid Group with High Heat Fastness Properties

A group of novel monoazo disperse dyes containing carboxylic acid‐1,8‐naphthalimide group has been synthesized. All intermediates and dyes were purified by recrystalization and the column chromatography method. The purified products were characterized by ¹H NMR, ¹³C NMR, FTIR, DSC, UV‐VIS and Elemental Analysis. Spectrophotometric investigations of the synthesized dyes in different solvents were carried out in order to obtain their absorption maxima, molar extinction coefficients and solvatochromic effects. The absorption maxima of the synthesized dyes in acetone varied (513‐549 nm) and the molar extinction coefficient was (17405‐38939 l/mol cm). By changing the media from chloroform to DMF, the solvatochromism effect for all dyes increased. Dispersion of the synthesized dyes was prepared in water containing dispersing agent and applied to polyester fabrics. The dyed fabrics showed that all of the synthesized dyes were suitable for coloring polyester fibers, producing deep red to bluish red with very good fastness properties.     

The molecular structures and the absorption maxima of the H-chromophores of the indigoid dyes

The molecular structures of the H-chromophore of the indigoid dyes and five other isomers are studied by ab initio MP2/6-31 + G*//HF/6-31 + G* method. The bond angles are affected by the π-electron conjugation. The molecular structures of the H-chromophores and indigoid dyes indicate that the benzene rings and the five-membered rings are structurally important. The absorption maxima of the H-chromophores are successfully calculated by CI-singles-MP2/6-31 + G* theory for the first time and correspond to the HOMO, LUMO transition. All these transitions are the π-π* transitions. Like the indigoid dyes, trans isomers have the bathochromic shifts of the absorption maxima, and the bathochromic shifts are found with the best donor group of ? NH. From these calculations, the absorption maxima of some indigoid dyes can be explained by their H-chromophores qualitatively. © 1995 by John Wiley & Sons, Inc.     

Novel Heptamethine 3H-Indocyanines and their Spectral Properties

Novel heptamethine 3H-indocyanine dyes are synthesized and embedded into a matrix of silica gel derived from tetraethoxysilicane. The photophysical properties of these near infrared dyes in various solvents and in SiO2 sol gel were investigated. The results show that the dyes containing cyclohexenylene bridge and N-(p-carboxy)benzyl groups have better photostability and longer absorption wavelength than those containing linear heptamethine bridge and/or N-(5-carboxy)pentanyl groups. The absorption maxima of these dyes are in reverse proportion to the polarity of the solvents. The microenvironment of the dyes in SiO2 sol-gel characters medium polarity (between methanol and DMF) according to the absorption maxima.     

Synthesis of thiazole derivatives

5- and 6-Vinyl-2-methylbenzothiazoles were synthesized. Thiacyanine dyes with vinyl groups attached to the heterocyclic residues were obtained from the quaternary salts of the new bases. The main absorption maxima of the dyes were determined.For part XXIII, see [1].     

Free-electron molecular-orbital treatment of chalcone group of dyes

The position and intensity of the absorption bands of a number of chalcone dyes have been calculated on the basis of the free-electron molecular-orbital (FEMO ) theory. The three to four absorption maxima of the chalcones are calculated by assuming the molecule to consist of two parts. The hypothetical cleavage is affected at the site of C?O bond such that first and second part of the molecule contains six and eight π electrons, respectively. Each part is then treated as an independent entity and the absorption maxima obtained by the application of joint and continuity condition of Kuhn are in agreement with the experimental values. The perturbation energy correction due to the substituted functional groups with higher electronegativity than carbon have also been made in the absorption maxima. The oscillator strengths corresponding to the values of the absorption maxima have been obtained as well.     

Condensation of 5-bromo-, 3-bromo-, and 3-iodoacenaphthenequinones with 3-hydroxythionaphthene and its derivatives

The oxidation of 3-bromo-and 3-iodoacenaphthene has given 3-bromo-and 3-iodoacenaphthenequinones. The condensation of 5-bromo-, 3-bromo-, and 3-iodoacenaphthenequinones with 3-hydroxythionaphthene and its derivatives has yielded indigoid dyes, and the main light absorption maxima of these dyes have been determined.     

Condensation of 5-bromo-, 3-bromo-, and 3-iodoacenaphthenequinones with 3-hydroxythionaphthene and its derivatives

The oxidation of 3-bromo-and 3-iodoacenaphthene has given 3-bromo-and 3-iodoacenaphthenequinones. The condensation of 5-bromo-, 3-bromo-, and 3-iodoacenaphthenequinones with 3-hydroxythionaphthene and its derivatives has yielded indigoid dyes, and the main light absorption maxima of these dyes have been determined.     

Spectroscopic studies of a near-infrared absorbing pH sensitive aminodienone-carbocyanine dye system

Synthetic red and near-infrared absorbing dyes may be used as probe molecules in a large number of applications. Dyes exhibiting spectral changes with hydrogen ion concentration are useful as pH probes. Those dyes which have their absorption and fluorescence maxima in the long wavelength region of the visible spectral region are specially valuable because of decreased interference and semiconductor laser applications. In this paper we have evaluated an aminodienone dyes 1 which demostrates pH dependent absorption and fluorescence spectra as well as solvent polarity dependence. In organic solvents the long wavelength absorption band of the dye is in the reduced interference region. The absorption maximum is at 535 nm in neutral or alkaline solutions in methanol. The absorption spectra undergo a strong bathochromic shift in the presence of acids (lambda(max) = 709 nm) with a concomitant change in the fluorescence spectra. This pH sensitive dye was found to be specially especially useful for organic solvents. The analytical utility of this and similar near-infrared absorbing dyes is discussed.