Synthesis and Visible Spectral Behaviour of Some New N‐Bridgehead Heterocyclic Cyanine Dyes Incorporating Pyrazolo (4,5‐b) Indolizine (Benzoindolizine)

The new unsymmetrical N‐bridgehead, apo (zeromethine), mono‐methine, dimethine, meso substituted tetramethine and styryl cyanine dyes incorporating pyrazolo (4,5‐b) indolizine (benzoindolizine) nuclei were prepared. Structural confirmation was carried out by elemental analyses, IR, H‐NMR, mass spectra and ¹³C‐NMR with the aid of carbon DEPT spectral data. The visible absorption spectra for the newly synthesized cyanines were examined in 95% ethanol.     

Aggregation effects on evaporation and the air/water interface of dodecyltrimethylammonium hydroxide solutions

 The system dodecyltrimethylammonium hydroxide (DTAOH)–water was studied by surface tension, ion-selective electrodes and evaporation in an electrobalance. Results confirmed earlier conclusions about a stepwise aggregation mechanism in DTAOH solutions. The aggregation process started at a total concentration C _T=(2.51±0.10)×10^-4 mol dm^-3) which probably corresponds to the formation of dimers. At C _T= (1.300±0.041)×10^-3 mol dm^-3 there was a change in the surface and evaporation behavior, corresponding to the formation of small, fully ionized aggregates which grew with increasing concentration. At C _T= (1.108±0.010)×10^-2 mol dm^-3 the formation of true micelles with hydroxide counterions in the Stern layer did not change significantly the evaporation and adsorption behavior. This means that between this concentration and C _T=(3.02±0.28)× M28.8n10^-2 mol dm^-3, the changes in structure were gradual. At the latter concentration there was a sudden change in the monolayer state at the air/water interface, with a strong surfactant desorption, and a major change in evaporation behavior. The changes are compatible with the formation of few, large aggregates reducing the total concentration of kinetically independent solute units, which in turn increased the activity of the solvent. This phenomenon is in agreement with literature information. The reduction in the evaporation rate of water was mainly due to the reduction of the water activity, caused by colligative effects. The reduction of the effective area available for evaporation had only a slight effect in water evaporation. Received: 9 January 1997 Accepted: 19 October 1997     

多种维生素的高效液相色谱分离及应用

在ＳｐｈｅｒｉｓｏｒｂＣ１８柱上，采用含Ｌｉ２ＳＯ４－己烷磺酸钠－三乙胺的水溶液作流动相，同时分离测定四种水溶性维生素：Ｂ１、Ｂ２、Ｂ６及烟酰胺。四种化合物的回收率在９９．２％～９９．９％之间，ＲＳＤ为０．１６％～０．４９％（ｎ＝５）。方法应用于常见的复合维生素药物制剂的含量测定，结果满意。     

用三乙胺盐酸盐对酚醛环氧树脂开环合成水溶性感光高分子的研究

用三乙胺盐酸盐与酚醛环氧树脂开环反应合成了一种水溶性聚合物，研究了相转移催化剂、反应时间、反应温度、开环顺序等条件对反应程度的影响。研究了开环反应中丙烯酸及三乙胺盐酸盐与酚醛环氧树脂的比例对产物的水溶性及感兴性能的影响。     

Host-guest antenna materials

The focus of this review is on host-guest composites with photonic antenna properties. The material generally consists of cylindrical zeolite L crystals the channels of which are filled with dye molecules. The synthesis is based on the fact that molecules can diffuse into individual channels. This means that, under the appropriate conditions, they can also leave the zeolite by the same way. In some cases, however, it is desirable to block their way out by adding a closure molecule. Functionalization of the closure molecules allows tuning of, for example, wettability, refractive index, and chemical reactivity. The supramolecular organization of the dyes inside the channels is a first stage of organization. It allows light harvesting within a certain volume of a dye-loaded nanocrystalline zeolite and radiationless transport to both ends of the cylinder or from the ends to the center. The second stage of organization is the coupling to an external acceptor or donor stopcock fluorophore at the ends of the channels, which can trap or inject electronic excitation energy. The third stage of organization is the coupling to an external device through a stopcock molecule. The wide-ranging tunability of these highly organized materials offers fascinating new possibilities for exploring excitation-energy-transfer phenomena, and challenges for developing new photonic devices.     

Spectral study of the aggregation of benzothiazolic cyanine dyes in solutions and polymolecular layers

The formation ofJ-aggregates of three polymethine dyes in solutions and in Langmuir-Blodgett (LB) polylayers was studied. The dyes formJ-aggregates in mixtures of solvents of different polarity: hexane-chloroform and heptane-chloroform taken in various ratios. The formation ofJ-aggregates in LB polylayers depends on the type of matrix and on the matrix: dye ratio.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 96–99, January, 1995.The authors are grateful to Corresponding Member of the Russian Academy of Sciences M. V. Alfimov for valuable remarks and to Dr. A. I. Tolmachev for kindly donating samples of dyes.This work was financially supported by the Russian Foundation for Basic Research (Project No. 94-03-09182).     

Kupplungsreaktionen von Diazoniumbetainen mit 1,6-Methano[10]-annulenderivaten und ihre Cyclisierungsreaktionen zu Heterocyclen

Summary Coupling reactions of the diazoniumbetaines2, 4, 6a, 6b, 6c with derivatives of 1,6-methano[10]annulene1a–c and/or -naphthol7 yield the dyes3a–c, 5a, 5c, 8a–c, 9, 11. The syntheses of different triazine derivatives12a–c, 13a–c, 15, 16, and17a, 17c are described.

Herrn Kollegen Gerhard Schwenker mit den besten Wünschen zum 65. Geburtstag gewidmet     

Regioselective synthesis and biological activity of oxidized chitosan derivatives

Oxidized chitosan derivatives with various degrees of oxidation (DS, 0.1–1.0) were prepared by the treatment of chitosan with CrO₃/aq HClO₄ or by the oxidation of ­3‐O‐ and N‐protected chitosan with 30% aq H₂O₂/Na₂WO₄ followed by 3‐O‐ and N‐deprotection. The oxidized products were then N‐acetylated with Ac₂O in order to improve their water‐solubility. Although the oxidized chitosan derivative of DS 0.28 and the degree of N‐acetylation of chitosan (DA) 38% was insoluble in the pH 3–8 region, that of DS 0.26 and DA 76% was soluble in the neutral pH range. The newly‐prepared acetylated and oxidized chitosan derivatives were found to suppress the chemiluminescence response of inflammatory cells such as canine polymorphonuclear cells (PMNs). Analysis by the surface plasmon resonance method revealed that the bind and release behavior of PMNs to acetylated oxidized chitosan derivatives was similar to that against carboxymethylated chitosan derivatives. The amount of water‐soluble chitosan derivative bound to cytokine IL‐8 was found to be affected by the structural and electronic features of the chitosan substituents in the chitosan chain. Copyright © 2003 John Wiley & Sons, Ltd.     

Capillary electrophoresis determinative and GC-MS confirmatory method for water-soluble organic acids in airborne particulate matter and vehicle emission

Urban fine airborne particulate matter (PM2.5) and vehicle emission samples were studied for water-soluble low-molecular-weight carboxylic acids using CE with indirect UV detection. Further identification of these acids was achieved using GC-MS as their butyl esters (after derivatization with BF3/butanol). Several dicarboxylic acids in the range C2-C10 including straight-chain, branched-chain, cis- and trans-unsaturated, and aromatic acids were confirmed by GC-MS. In addition, aromatic acids such as benzoate, phthalate, terephthalate, isophthalate, and 4-methylphtalate were present in such samples, but some of these were not well resolved by the used CE method. Oxocarboxylic acids (Cn(w) with n > 4) were also identified by GC-MS but not determined by CE due to lack of standards. The rapidity and simplicity of the CE method were clearly demonstrated, and the method was observed to be advantageous for routine monitoring of water-soluble organic acids in airborne PM2.5 and vehicle emission at low microg/L levels.     

Novel Water Soluble Fluorescent Trimethine Indocyanines Containing N-ρ-Carboxybenzyl Group

Indocyanine dyes as fluorescent labeling reagents have been used in bioanalysis1,2. Arylsulfonate indocyanine dyes 1d and 1e developed by Waggoner A. S. et al.3,4 have excellent fluorescent properties combined with good aqueous solubility, are a new generation of fluorescent label compounds for proteins, oligonucleotides and other compounds containing hydroxyl, mercaptol or primary amine groups5. However, photostability of these dyes has been a problem. Z. G. YAO et al.6 reported that p…