Induced circular dichroism and structural assignment of the cyclodextrin inclusion complexes of bicyclic azoalkanes

The stoichiometries and binding constants of the host-guest complexes between the bicyclic azoalkanes 1-6 and alpha-, beta-, and gamma-cyclodextrins (CDs) and the induced circular dichroism (ICD) of the complexes were analyzed. Assisted by proximity relationships obtained from 2D ROESY NMR spectra, the signs and intensities of the ICD spectra are interpreted in terms of the solution structures (co-conformations) of the CD complexes. The ICD assignments are based on the orientation-intensity ICD rules of Harata and Kodaka, which relate the ICD signs and intensities to the relative orientation of the electric dipole transition moment of the n,pi azo chromophore to the CD axis. The influence of the size of the guest and the host is discussed and the effect of introducing an additional chromophore (either a phenyl or a second azo group) on the ICD spectra is demonstrated.     

Fast atom bombardment mass spectra of involatile monophosphonated and mixed sulphonated/monophosphonated azo dyestuffs

Fast atom bombardment mass spectra of a range of involatile monophosphonated and mixed sulphonated/monophosphonated azo dyestuffs are presented. Good spectra are obtained and the fragmentations are discussed with special reference to the ions formed by cleavage of the azo linkage. The negative ion spectra are shown to be superior in terms of signal to background and structural information to those obtained in the positive ion mode. The results are compared with those obtained from sulphonated azo dyestuffs.     

A spectral approach to determine location and orientation of azo dyes within surfactant aggregates

The UV–vis absorption properties of azo dyes are known to exhibit a variation with the polarity and acidity of the dye environment. The spectral properties of a series of anionic azo dyes were characterized to further probe the interaction of these dyes with two types of surfactant aggregates: (1) the spherical micelles formed in aqueous solution by alkyltrimethylammonium bromide (C_nTAB) surfactants with n = 10–16 and (2) the unilamellar vesicles spontaneously formed in water from binary mixtures of the oppositely-charged double-tailed surfactants cationic didodecyldimethylammonium bromide (DDAB) and anionic sodium dioctylsulfosuccinate (Aerosol OT or AOT). The observed dye spectra reflect the solvatochromic behavior of the dyes and suggest the location and orientation of the dye within the surfactant aggregates. Deconvolution of the overall spectra into sums of Gaussian curves more readily displays any contributions of tautomeric forms of the azo dyes resulting from intramolecular hydrogen bonding. The rich variation in UV/vis absorption properties of these anionic azo dyes supports their use as sensitive tools to explore the nanostructures of surfactant aggregates.     

三种偶氮化合物的荧光光谱研究

近年来 ,一些重要的有机染料探针在生物大分子光度分析、荧光分析和共振光散射分析方面得到了日益广泛地应用[1,2 ] ,深入研究这些有机染料的结构和光谱特性 ,探讨这些有机染料与生物大分子之间的作用 ,对于筛选性能优良的分子光谱探针 ,设计更加灵敏简便的分子光谱检测器件 ,是现代分析化学十分重要的课题。本文测定了偶氮胂Ⅱ (Ａｒｓｅｎａｚｏ)、铬黑Ｔ(ＥｒｉｏｃｈｒｏｍｅｂｌａｃｋＴ)、铬蓝黑 (ＥｒｉｏｃｈｒｏｍｅｂｌｕｅｂｌａｃｋＲ)等 3种化合物的荧光光谱 ,并用量子化学半经验方法ＡＭ1和ＰＭ3对3种化合物分子进行包括构型…     

Studies of nucleosides and nucleotides—LXI : Purine cyclonucleosides 23 synthesis of sulfoxides of adenine s-cyclonucleosides

8,2′ - Anhydro - 8 - mercapto - 9 - β - d - arabinofuranosyladenine, 8,3′ - anhydro - 8 - mercapto - 9 - β - d - xylofuranosyladenine and 8,5′ - 8 - mercaptoadenosine were oxidized either with N-bromosuccinimide, t-butyl hypochlorite or performic acid to their 8-sulfoxides. Configuration of sulfoxides were determined to be S in former two cases. In the case of 8,5′-cyclonucleoside, both S- and R-compounds were obtained. UV, NMR and CD spectra of these sulfoxides were recorded.     

Photomodulated chiral induction in helical azobenzene oligomers

Appending L-alanine to the terminal positions of a helical azobenzene oligomer produced a P helical bias, which increased with oligomer length. Irradiation gave rise to E-->Z isomerization of the terminal azo linkages, which displaced the stereogenic center of L-Ala from the helix backbone and suppressed chiral induction. Theoretical simulations of the CD spectrum of the P helical conformation are in qualitative agreement with the experimental spectra.     

Xerographic property of azo/TiOPc composites in double-layered photoreceptor

The xerographic property has been studied in the double-layered photoreceptor device where azo/TiOPc composite is used as the charge-generation material (CGM) and p-diethylaminobenzaldehyde--naphthalenylphenylhydrazone (DENPH) or p-dimethylaminobenzaldehyde diphenylhydrazone (DMDPH) is used as the charge-transportation material (CTM) under the exposure of various spectral regions. The results show that the azo/TiOPc composites exhibit high photosensitivity not only in the visible and near-infrared regions, but also in the entire spectral ranges, indicating the co-enhancement effect. The UV–VIS spectra suggest that the absorption spectra of the azo/TiOPc composites are broadened. The composite mechanism is investigated through X-ray diffraction and ESR.     

DFT and ab initio study of structure of dyes derived from 2-hydroxy and 2,4-dihydroxy benzoic acids

We present a detailed analysis of the structural, infrared spectra and visible spectra of a series of azo dyes preparation of salicylic acid and 2,4-dihydroxy benzoic acid derivatives as the coupling component. The preparation of these azo dyes with salicylic acid and 2,4-dihydroxy benzoic acid derivatives (salicylic acid, methyl salicylate, ethyl salicylate, butyl salicylate, methyl 2,4-dihydroxy benzoate, ethyl 2,4-dihydroxy benzoate, salicylaldehyde, salicylamide, 2,4-dihydroxy benzamide, salicylaldoxime) have been investigated theoretically by performing HF and DFT levels of theory using the standard 6-31G* basis set. The optimized geometries and calculated vibrational frequencies are evaluated via comparison with experimental values. The vibrational spectral data obtained from solid phase FT-IR spectra are assigned modes based on the results of the theoretical calculations. The observed spectra are found to be in good agreement with the calculations.     

Spectrophotometric Studies on Some Arylazo Barbituric Acids and Arylazo Pyrimidine in Organic Solvents and in Buffer Solutions

The UV and visible spectra of some arylazo barbituric acids and arylazo pyrimidine in pure and mixed organic solvents of varying polarities have been studied. The different absorption bands displayed in the electronic spectra of these compounds are assigned and the possibility of the existence of these compounds in tautomeric equilibrium as well as in intra‐ and intermolecular H‐bonding were examined. The solute‐solvents molecular complexes liable to exist in polar‐nonpolar mixed solvents are investigated. The structure of the azo compounds were confirmed by ¹H NMR and IR spectroscopy. The ionization processes of the compounds were investigated and the possible ionization constants were determined and discussed in terms of molecular structure of the azo compounds.     

N,2-二芳基二氮亚烯甲酰胺合成的新方法

偶氮化合物可用作非线性光学材料、激光盘信息存贮材料和现代科技中的油溶性染料［１］．传统偶氮化合物的制备有重氮盐偶合和取代肼氧化等许多方法［２～４］,其偶氮基两端一般联有烃基或芳环,而联有羰基的偶氮类化合物用通常方法难以制备．本文首次用Ｎ－溴代丁二酰亚...     

Die Kernresonanzspektren von N-substituierten 2.6-Dimethylmorpholinen

The NMR spectra of N-substituted 2,6-dimethylmorpholines after separation into cis- and trans-isomers by VPC have been investigated. The spectral parameters (chemical shift and coupling constants) are evaluated by a mathematical analysis. The spectra of the cis-compounds show some special features so far unexplainable. The difference of the chemical shift of the protons in 3-position of the cis-isomers depends strongly on the nature of the N-substituent.     

Synthesis,Characterization and Antifungal Activity of Metal Complexes of 2-(5-((2-Chlorophenyl)Diazenyl)-2-Hydroxybenzylidene) Hydrazinecarbothioamide

Abstract

New metal complexes of Co(II), Cu(II), Ni(II), Zn(II), Mn(II), Fe(III), Ru(III), UO₂(II), and VO(II) with the Schiff base, 2-(5-((2-chlorophenyl)diazenyl)-2-hydroxy- benzylidene) hydrazine-carbothioamide (H₂L) have been prepared and characterized by elemental and thermal analyses, FT-IR, UV–Vis, mass spectra, ¹H-NMR, and ESR as well as conductivity and magnetic moments measurements. The IR spectra showed that the ligand acts as neutral tridentate, neutral bidentate or monobasic tridentate ligand. The geometries of metal complexes were either octahedral or square pyramidal. The ESR spectra of the solid copper(II) complexes indicated an axial symmetry type of a d_(x2-y2) ground state with considerably ionic or covalent environment. The effect of the presence of an azo group on the biological activity of the ligand was investigated. The ligand and its complexes are biologically inactive due to the presence of azo group.

Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the related elements to view the free supplemental file.     

Colour and constitution of azo compounds derived from diaminoazines

Visible absorption spectra have been recorded for azo compounds derived from 2,5-dichlorosulphanilic acid azo-coupled with $\text{N}$,$\text{N}$-diethyl-m-phenylenediamine, and with azine analogues. The effects of the ring-aza substituents as well as cyano on the spectra indicate a surprising difference in sensitivity of the two ring positions meta to the azo group. M.O. calculations show chat the amino group ortho to the azo linkage introduces asymmetry into the HOMO, and this is responsible for the differing effects of substitution.     

偶氮聚电解质的合成及其pH敏感行为和热光性能研究

利用偶氮聚电解质上的羧基和偶氮生色基团的特性,研究了侧链偶氮聚电解质的pH值敏感性和热光性能.采用重氮-偶合反应方法合成了偶氮苯生色分子4-(4′-硝基苯基偶氮)苯酚,将生色分子、环氧氯丙烷和α-甲基丙烯酸通过自由基聚合法,合成了侧链偶氮聚电解质.利用傅里叶红外光谱(FTIR)、紫外-可见光谱(UV-V is)和核磁共振(1H-NMR)等分析手段对所合成的侧链偶氮聚电解质进行了结构表征.采用差示扫描量热分析仪(DSC)对偶氮聚电解质进行了热稳定性表征,其玻璃化转变温度(Tg)为189.8℃,表明具有较高的热稳定性.研究了不同pH值的偶氮聚电解质溶液的紫外-可见光谱,结果表明,偶氮聚电解质对pH值具有高度敏感性.采用衰减全反射(ATR)原理测量聚合物波导薄膜在650 nm和TM偏振下的折射率和热光系数dn/dT,其值为-1.92479×10-4℃-1,是无机材料如硅酸锌玻璃(5.5×10-6℃-1)和硼硅酸盐玻璃(4.1×10-6℃-1)的10倍以上,较有机材料聚苯乙烯(-1.23×10-4℃-1)和PMMA(-1.20×10-4℃-1)大.     

Fast atom bombardment mass spectra of involatile sulphonated azo dyestuffs

Fast atom bombardment mass spectra of a range of involatile mono and disazo sulphonated dyestuffs are presented. Excellent spectra are obtained for dyestuffs containing up to five sulphonate groups. The fragmentations are discussed with special reference to the ions formed by cleavage of the azo linkage. The negative ion spectra are shown to be superior to those obtained in the positive ion mode.     

取代基对偶氮类颜料光伏特性的影响

偶氮类材料由于其具有成本低、来源丰富、易于加工以及可以通过接不同性质的取代基得到不同性能的光电导体等优点 ,作为光接受器材料 ,其导电类型、光生电荷及传输过程以及光照后表面电荷的种类在静电复印、激光打印中起着决定性的作用 [1～ 3] .由于取代基会影响偶氮类材料的费米能级 (电子填充水平 ) ,从而影响其导电类型 .如何判断其导电类型以及光照后表面电荷的种类还是一个难题 .本文首次利用 SPS(表面光电压谱 )和 FISPS(场诱导表面光电压谱 )技术对几种具有不同取代基的双偶氮类有机颜料的光伏特性进行了研究 ,发现取代基对它们…     

13C-NMR-spektren stereoisomerer 1,4-dialkylspiro[4.5]decan-derivate

The ¹³C NMR spectra of a series of 7-substituted 1,4-dialkylspiro[4.5]decanes and of suitable reference compounds are assigned and the derived substituent effects upon the chemical shifts are discussed. In particular, consideration of γ and δ-effects allows the differentiation between 1,4-cis- and 1,4-trans-compounds. Furthermore, the (relative) configuration of the chiral spiroatom C-5 is determined.     

Stereospezifische Fragmentierungen in den Massenspektren von Cyclohexandiaminen und Bis(aminomethyl)cyclohexanen. 33. Mitteilung über massenspektrometrische Untersuchungen,,

Stereospecific Fragmentations in the Mass Spectra of Cyclohexanediamines and Bis(aminomethyl)cyclohexanes The mass spectral behaviour, especially loss of NH₃, of the six isomeric cyclohexanediamines 1--3 (cis and trans each, Scheme 1) as well as of the six isomeric bis(aminomethyl)cyclohexanes 4--6 (cis and trans each, Scheme 6) has been investigated. The cis- and trans-compounds of the 1,2-isomers 1 and 4 show very similar spectra, because of the ease of ring cleavage at C(1)–-C(2) and the similar geometrical relations in all ring conformations. The cis- and trans-compounds of both the 1,3- and 1,4-isomers 2, 3, 5 and 6 show striking differences in their mass spectra due to stereospecific elimination of NH₃ from the molecular ion.     

Synthesis and properties of azo dye aligning layers for liquid crystal cells

The synthesis and properties of azo dyes that can be used for photoaligning liquid crystals (LCs) have been investigated. The structures and the synthetic procedure for the azo dyes are presented. The photoaligning of azo dyes takes place purely due to the reorientation of the molecular absorption oscillators perpendicular to the UV light polarization. The qualitative model for the phenomenon in terms of the rotational diffusion of the azo dye molecules in the field of the polarized light is discussed. The order parameters S = -0.4 (80% of the maximum absolute value S_m = -0.5) were measured from the polarized absorption spectra at the wavelength 372 nm. A temperature stable pretilt angle of 5.3° was obtained by a two-step exposure of the azo dye film using normally incident polarized light followed by oblique non-polarized light. The azimuthal anchoring energy of the photoaligned substrate was A_ϕ ≈10^-4 J m^-2, which is the same as the anchoring of the rubbed polyimide (PI) layer. The voltage holding ratio value of a photoaligned LC cell was found to be even higher than for a rubbed PI layer, which enables the applications of azo dyes as aligning layers in active matrix liquid crystal displays. The thermal stability of the photoaligned azo dye layers is sufficiently high, but UV stability has to be improved, e.g. by polymerization. A new LCD aligning technology based on polymerized azo dye layers is envisaged.     

一种光存储用短波长偶氮染料金属螯合物的光谱学与热学特性研究

设计合成一类与短波长(635～650nm)半导体激光器相匹配用于有机光盘的光存储介质的偶氮染料金属螯合物.测定了偶氮染料及其金属螯合物的紫外 可见光吸收光谱,采用分光光度法确定该金属螯合物的结构与组成,计算了它的稳定常数.差热热重分析显示该金属螯合物具有较好的热学性能,有望可作为光记录介质.