含萘酰亚胺基元的水杨醛席夫碱的合成及其溶致变色效应

将N-2-（-2-羟乙氧基）乙基4肼基-1,8-萘酰亚胺与水杨醛缩合得到-种新型席夫碱化合物N-（2-（2-羟乙氧基）乙基）4-（2-羟基苯甲醛腙肼基）-1,8-萘酰亚胺（Ⅰ）,对化合物Ⅰ在不同溶剂中的光谱性质研究发现,其表现出特殊的紫外吸收和荧光双重溶致变色效应,可作为荧光分子探针获得应用．对化合物Ⅰ在不同pH值的乙醇水溶液中的光谱性质进行研究,发现该化合物不仅表现出酸碱变色行为,而且具有质子调控荧光分子开关功能及化学荧光传感器特性,有望在酸碱指示剂、分子开关和化学荧光传感器等方面获得应用．     

Synthesis of some novel heterocyclic dyes derived from pyrazole derivatives

Diazotized aryl amines were coupled with 3-substituted 5-amino pyrazoles to produce a series of novel 3-substituted 5-amino-4-arylazopyrazoles. Also, 3-substituted 5-amino-pyrazoles were diazotized and coupled with different phenols to give the corresponding novel 3-substituted 5-aryl azo pyrazoles. These dyes were characterized by elemental analysis and spectral data, applied to different types of fibres (wool, polyester and a blend of wool/polyester as disperse dyes) and their fastness properties were evaluated.     

Synthesis and dyeing performance of some novel thiazole azo disperse dyes

The synthesis of some novel monoazo disperse dyes derived from 5-acetyl-2-amino-4-methylthiazole using various N-alkyl derivatives of aniline and their dyeing performance as disperse dyes have been assessed on cellulose triacetate fabric. The spectral properties of these dyes were also measured. The dyed fabric show good light fastness, very good rubbing, perspiration, washing fastness and excellent sublimation fastness. These dyes have been found to give bright yellow to maroon color shade with very good depth and levelness on fabric. The dyebath exhaustion and fixation on fabric has been found to be very good.     

Photophysical behavior of a novel 4-aza-indole derivative in different solvents: reverse solvatochromism

Research on Chemical Intermediates - The photophysical properties of a new 4-aza-indole derivative [ethyl...     

Lyotropic liquid-crystalline mesophases and a novel,solid physical form of some water-soluble,reactive dyes

Abstract

A novel, solid physical form has been observed when some water-soluble, reactive dyes are isolated from aqueous solution, as sodium salts, by the addition of sodium chloride. This quasi-crystalline form has a fibrous morphology, is birefringent but is not crystalline. Dyes of this type are known to form lyotropic liquid-crystalline mesophases in water. Preliminary X-ray diffraction investigations, reported here, for the mesophases formed by two such dyes indicate that they have columnar structures of the type first proposed for the lyotropic mesophases of the disodium chromglycate/water system and subsequently for other drug and dye molecules. X-ray and electron diffraction studies of the quasi-crystalline form show that it has a closely related columnar structure. The quasi-crystalline form is postulated to result from the formation and subsequent precipitation of columnar dye aggregates, as sodium chloride is added to the aqueous dye solution.     

Lyotropic liquid-crystalline mesophases and a novel, solid physical form of some water-soluble, reactive dyes

A novel, solid physical form has been observed when some water-soluble, reactive dyes are isolated from aqueous solution, as sodium salts, by the addition of sodium chloride. This quasi-crystalline form has a fibrous morphology, is birefringent but is not crystalline. Dyes of this type are known to form lyotropic liquid-crystalline mesophases in water. Preliminary X-ray diffraction investigations, reported here, for the mesophases formed by two such dyes indicate that they have columnar structures of the type first proposed for the lyotropic mesophases of the disodium chromglycate/water system and subsequently for other drug and dye molecules. X-ray and electron diffraction studies of the quasi-crystalline form show that it has a closely related columnar structure. The quasi-crystalline form is postulated to result from the formation and subsequent precipitation of columnar dye aggregates, as sodium chloride is added to the aqueous dye solution.     

Synthesis,characterization and spectroscopic investigation of a novel phenylhydrazone Schiff base with solvatochromism

A novel Schiff base of 4,5-diazafluorene-9-p-nitrophenylhydrazone (DAFND) has been synthesized and characterized. The crystal structures of DAFND and its analogue 4,5-diazafluorene-9-phenylhydrazone (DAFPD) were determined by single crystal X-ray diffraction method. X-ray analyses reveal that DAFPD comprise of a nonplanar molecule and all atoms of DAFND are essentially coplanar. The color of DAFND changes from brown to blue when heated, so called thermochromism and the spectroscopic properties of the two compounds are investigated by electronic absorption spectra, showing DAFND possess solvatochromism, while DAFPD does not have thermochromic and solvatochromic properties. The λ_max of DAFND within various pure solvents are different ranging from 370 nm in toluene to 614 nm in pyridine. The imaginable mechanisms of thermochromism and solvatochromism are proposed.     

Encapsulation of three different hydrophobic dyes in functionalized silica particles

This paper describes a method to prepare silica particles able to encapsulate 3 different hydrophobic dyes: Disperse Red, Solvent Red and 2-{4-[4-(Benzyl-ethyl-amino)-phenylazo]-benzenesulfonyl}-ethanol (HESA). Dye doped silica particles were prepared by the sol–gel process in aqueous medium, with a base catalyst, using various concentrations of a “home made” surfactant (named NP₉-Si). The surfactant is the addition byproduct of –OH groups of polyethylene glycol nonylphenyl ether Tergitol^® NP-9 with -NCO groups from (3-isocyanatopropyl) triethoxysilane and was added to increase both the stabilization of the silica particles and the compatibility of the inorganic network versus the dopant (the aromatic dye). It was shown that there is an optimum range of the amount of surfactant which should be added in the sol–gel reaction system. If a higher amount of surfactant is used, it forms probably micelles which entrap the dye and prevent its encapsulation in the formed silica particles. Because the silica particles are designed to encapsulate systems containing aromatic derivatives (aromatic dyes) we used phenyltriethoxy silane and tetraethylorthosilicate as silica precursors. As coupling agent for the silica network we used a bis (trialkoxysilane) derivative—1,2-bis (triethoxy silyl) ethane.     

Synthesis of novel calixarenes having a tweezer-type structure

Monobromide was used as the starting material. The [2+2]photocycloaddition of diolefins directly gave all the calix[4]arene regioisomers having chiral and achiral structures in 20-47% yields. They formed a complex with alkali metal ions and extracted large metal picrates rather than small ones.     

Fungal citridone D having a novel phenylfuropyridine skeleton

Citridone D was isolated from the culture broth of Penicillium sp. FKI-1938 by solvent extraction, silica gel column chromatography and HPLC. The structure of citridone D was elucidated by spectroscopic analysis including NMR analysis. Citridone D was found to have a novel phenylfuropyridine skeleton different from those of other citridones. Citridone D potentiated miconazole activity against Candida albicans.     

Multi-wavelength spectrophotometric determination of the protolytic constants of tetracycline hydrochloride in some nonaqueous-water mixed solvents: a solvatochromism study

Annihilation of the contribution of one chemical component from the original data matrix is a general method in rank annihilation factor analysis (RAFA). However, RAFA is not applicable for studying the protonation equilibria of multiprotic acids but in this study two-rank annihilation factor analysis (TRAFA) was used as an efficient chemometrics algorithm for determination of the protolytic constants (pKa) of tetracycline hydrochloride (TCHC) in some nonaqueous-water mixed solvents such as acetonitrile (AN)-water and methanol (MeOH)-water from the spectral pH-absorbance data. The spectral data was obtained from spectrophotometric acid-base titrations of different solutions of TCHC at (25.0±0.10)°C and an ionic strength of 0.10 M. In TRAFA algorithm the pKa values were obtained with relationship between residual standard deviation (R.S.D.) and hypothetical pKa values. In the case of TCHC, the spectra were divided in two consecutive subdivisions according to their pH range having two pKa and TRAFA was run twice. The validity of the obtained pKa values was checked with well-known chemometrics algorithms such as DATAN, EQUSPEC, SPECFIT/32 and SQUAD. The effects of changing solvent composition on the protolytic constants were explained by linear solvation energy relationships (LSER) utilizing solvatochromic parameters.     

ESR linewidth broadening of a hydrophobic probe in some surfactant solutions

ESR linewidth of tetradecanoyloxy-2,2,6,6-tetramethyl-piperidinyl-l-oxyl was observed in aqueous solutions of hexadecyltrimethylammonium bromide and sodium alkyl (C₁₂ and C₁₄) sulfates at 30 °C. The linewidth increases quadratically with the spin probe concentration to various extents, depending upon micellar properties. The diversity of the linewidth broadening is, however, reduced by plotting the relative linewidth, W/W₀, vs. the average solubilization number, m, where W₀ is the linewidth at the extremely dilute spin probe concentration. All the experimental points fall on a curve regardless of the diverse micellar properties. The broadening is interpreted in terms of a bimolecular and multimolecular collisions between the spin probes exclusively concentrated in micelles in accordance with the Poisson distribution of the spin probe.     

Lyotropic liquid crystalline phase behavior of amphiphilic monomers and polymers having a rod-like hydrophobic moiety

Distinct changes in the lyotropic mesophase behaviour of nonionic polyethyleneglycol containing amphiphiles are observed, when rigid, rod-like molecular units are introduced into the hydrophobic part of these amphiphiles, or when the amphiphiles are added as side chains to poly(methylhydrogene siloxane), yielding amphiphilic side chain polymers. Low molar mass amphiphiles with a dominating rigid, rod-like hydrophobic unit form planar-like micelles which aggregate into lamellar mesophases. Compared with their corresponding low molar mass amphiphiles, amphiphilic side chain polymers show a distinct stabilization of mesophases composed of anisometric micelles, i.e. hexagonal H₁-phases (built up by rod shaped micelles), and lamellar L -phases (built up by planarshaped micelles). In addition, several of the polymeric amphiphiles exhibit the formation of a lyotropic nematic N_c-phase regime. Optically isotropic I₁-phases composed of approximately spherical-like micelles are, on the other hand, disfavoured by the polymerfixation. Investigations of monodisperse amphiphilic side chain oligomers reveal a linear relationship between the thermal stability of the individual mesophases and the logarithm of the degree of polymerization. Changes in mesophase behaviour, due to the introduction of rigid, rod-like molecular units into the hydrophobic part of the low molar mass amphiphiles, are ascribed to packing restraints of the amphiphiles in the micelles. Alterations in mesophase behaviour which occur as a consequence of polymerfixation are discussed in terms of changes in micellar kinetics, packing restraints, and changes in the interaction between adjacent hydrophobic layers of neighbouring micelles.     

Micelle structures in aqueous solutions of glucose-based surfactants having an isoprenoid-type hydrophobic chain

Surfactant self-diffusion coefficients have been measured on a binary system of 1-O-beta-3,7-dimethyloctyl-D-maltopyranoside (beta-Mal(2)(Ger))/water and a mixed surfactant system of beta-Mal(2)(Ger)/1-O-beta-3,7-dimethyloctyl-D-glucopyranoside (beta-Glc(Ger))/water at 25 degrees C. For comparison, measurements have also been made on 1-O-beta-decyl-D-maltopyranoside (beta-Mal(2)C(10))/water and beta-Mal(2)C(10)/1-O-beta-decyl-D-glucopyranoside (beta-GlcC(10))/water. The hydrodynamic radius of beta-Mal(2)(Ger) micelles obtained from the micellar diffusion coefficient is around 3 nm and nearly equal to that of beta-GlcC(10) micelles within experimental error. In the mixed surfactant systems, the hydrodynamic radii for both systems increase with increasing X(G) (the mole fraction of beta-Glc(Ger) or beta-GlcC(10) in the total mixed solute) above X(G) congruent with 0.4 when the total surfactant concentration is kept constant at 2 wt%. The R(H) of beta-Glc(Ger)/Mal(2)(Ger) micelles increases more rapidly than beta-GlcC(10)/beta-Mal(2)C(10) micelles, and then phase separation occurs at X(G) congruent with 0.65. On the other hand, the R(H) of beta-GlcC(10)/beta-Mal(2)C(10) micelles continues to increase until the phase separation occurs at X(G) congruent with 0.92. Measurements have also been performed as a function of total surfactant concentration at constant X(G) (=0.6). The CMC of the beta-Glc(Ger)/Mal(2)(Ger) system is larger than that of the beta-GlcC(10)/beta-Mal(2)C(10) system as expected from the results of the pure surfactant systems published previously. The R(H) increases with increasing total surfactant concentration for both systems. At higher concentrations, the R(H) of beta-Glc(Ger)/Mal(2)(Ger) micelles increases more rapidly than beta-GlcC(10)/beta-Mal(2)C(10) micelles. These results can be explained by the fact that the geranyl and decyl chains have the same volume but different chain lengths.     

A novel viscoelastic system from a cationic surfactant and a hydrophobic counterion

The phase behavior of 2-hydroxy-1-naphthoic acid (2,1-HNC) mixed with cetyltrimethylammonium hydroxide (CTAOH) is reported. This novel system is compared with the published one of 3-hydroxy-2-naphthoic acid (3,2-HNC) mixed with CTAOH. We investigated the phase behavior and properties of the phases in aqueous solutions of 100 mM CTAOH with 2,1-HNC. In both systems a multilamellar vesicle phase is formed when the naphthoate/surfactant ratio (r) reaches unity. When an increasing amount of 2,1-HNC is mixed with a micellar solution of 100 mM CTAOH, an isotropic low-viscous micellar solution, a viscoelastic gel (consisting of rodlike micelles), a turbid region (two-phase region), and a viscoelastic liquid crystalline gel (consisting of multilamellar vesicles, MLV) were formed. The vesicular phase is highly viscoelastic and has a yield stress value. The transition from the micellar to the vesicle phase occurs for CTAOH/2,1-HNC over a two-phase region, where micelles and vesicles coexist. Also it was noticed that 2,1-HNC is dissolved in 100 mM CTAOH until the naphthoate/surfactant ratio reaches approximately 1.5, and the liquid crystalline phases were found to change their color systematically when they were viewed between two crossed polarizers. The vesicles have been characterized by differential interference contrast microscopy, freeze-fracture electron microscopy, and cryo-electron microscopy (cryo-TEM). The vesicles were polydisperse and their diameter ranged from 100 to 1000 nm. The interlamellar spacing between the bilayers was determined with small angle neutron scattering and agrees with the results from different microscopical methods. The complex viscosity rises by six orders of magnitude when rodlike micelles are formed. The complex viscosity decreases again in the turbid region, and then rises approximately six orders of magnitude above the water viscosity. This second rising is due to the formation of the liquid crystalline MLV phase.     

Synthesis of some novel pyrazolo[1,5-a]pyrimidine derivatives and their application as disperse dyes

A series of novel monoazo-disperse dyes containing pyrazolo[1,5-a]pyrimidine structures were synthesized starting with the coupling reaction between ethyl cyanoacetate and 4-hydroxybenzenediazonium chloride, followed by treatment of the resulting hydrazone product with hydrazine hydrate. The pyrazolohydrazone 6 is then treated with either 2,4-pentandione and enaminonitrile or aryl-substituted enaminoketones to give the target pyrazolo[1,5-a]pyrimidine dyes 7 and 15a-d. Structural assignments to the dyes were made using NMR spectroscopic methods. A new high temperature method, using microwave heating, was employed to apply these dyes to polyester fibers. Most of the dyed fabrics tested displayed moderate light fastness and excellent washing fastness properties.     

Synthesis of some novel bis(hetaryl)azo disperse dyes and investigation of their absorption spectra

3‐Amino‐2‐cyano‐4,6‐disubstituted‐thieno{2,3‐b}pyridines and 3‐aminopyridine were diazotized and coupled with 2‐phenylindole, 2‐methylindole, and 1‐methyl‐2‐phenylindole, respectively. These dyes were characterized by UV‐Visible, FT‐IR, ¹H NMR, and mass spectroscopic techniques. Solvent effects on the visible absorption spectra of the dyes were evaluated. The color of the dyes is discussed with respect to the nature of the heterocyclic ring and substituent present therein. In addition, effects of temperature, concentration, as well as acid and base on the visible absorption maxima of the dyes are reported. © 2007 Wiley Periodicals, Inc. Heteroatom Chem 18:622–630, 2007; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20361     

Synthesis of a novel ferrocene derivative having flame-retardant and smoke-suppressant properties

Reaction of ferrocene with chlorendic anhydride (1,4,5,6,7,7-hexachloro-5-norbornene-2,3-dicarboxylic acid anhydride) under Friedel–Crafts reaction conditions affords a new monosubstituted dervative of ferrocene which has significant flameretardant and smoke-suppressant properties when incorporated into poly(vinyl chloride) (PVC). The monocarboxylic acid from the above reaction undergoes smooth methylation with diazomethane to give the corresponding methyl ester. ¹H and ¹³C NMR spectra of these compounds have been compared with those obtained from similar compounds, namely β-ferrocenoylpropanoic acid and its methyl ester. Distant asymmetric centres in the chlorendic anhydride substituent markedly affect the proton spectra of the ferrocene derivative.     

Liquid crystal properties of novel diacetylenes having a pyridine end group

Asymmetrical diacetylenes with a pyridine ring bonded directly to one end of the diacetylene unit and an aryl system containing a flexible alkoxy chain at the opposite end, have been synthesized and show liquid crystalline behaviour. The mesophase behaviour is shown to be dependent on the length of the flexible alkoxy chain. Incorporation of one of these diacetylenes in a polymer 'guest-host' system at a 15 wt% concentration gave a high X⁽²⁾ non-linear optical susceptibility of 4.27 × 10^-9e.s.u.