Recent advances in azo dye degrading enzyme research

Azo dyes, which are characterized by one or more azo bonds, are a predominant class of colorants used in tattooing, cosmetics, foods, and consumer products. These dyes are mainly metabolized by bacteria to colorless aromatic amines, some of which are carcinogenic, by azoreductases that catalyze a NAD(P)H-dependent reduction. The resulting amines are further degraded aerobically by bacteria. Some bacteria have the ability to degrade azo dyes both aerobically and anaerobically. Plant-degrading white rot fungi can break down azo dyes by utilizing a number of oxidases and peroxidases as well. In yeast, a ferric reductase system participates in the extracellular reduction of azo dyes. Recently, two types of azoreductases have been discovered in bacteria. The first class of azoreductases is monomeric flavin-free enzymes containing a putative NAD(P)H binding motif at their N-termini; the second class is polymeric flavin dependent enzymes which are studied more extensively. Azoreductases from bacteria represent novel families of enzymes with little similarity to other reductases. Dissociation and reconstitution of the flavin dependent azoreductases demonstrate that the non-covalent bound flavin prosthetic group is required for the enzymatic functions. In this review, structures and carcinogenicity of azo colorants, protein structure, enzymatic function, and substrate specificity, as well as application of the azo dyes and azoreductases will be discussed.     

表面增强拉曼光谱在偶氮染料检测中的研究进展

简述了偶氮染料的检测现状,对偶氮染料研究中表面增强拉曼光谱检测方法进行了综述。介绍了表面增强拉曼光谱用金属溶胶、金属电极、金属薄膜3种增强基底在偶氮染料检测中的方向,并对其在偶氮染料检测中的研究前景进行了展望。表面增强拉曼光谱法是一种新型光谱分析技术,具有操作简单、快速、灵敏度高等优势,为偶氮染料的检测开辟了新道路。     

Analogs of styryl dyes and the simplest AZO dyes from 2-dimethylaminothiophene

The condensation of 2-dimethylaminothiophene with the appropriate derivatives of quaternary benzothiazole salts has give the vinylene-homologous series of dyes with the structure (I). By coupling with benzenediazonium salts, the simplest azo dyes of structure (III) have been synthesized. The influence on the absorption spectra of the replacement of a dimethylaniline nucleus in polymethine and azo dyes by a 2-dimethylaminothiophene nucleus has been investigated.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 923–925, July, 1973.     

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.     

A Novel Kinetic Approach for Photocatalytic Degradation of Azo Dye with CdS and Ag/CdS Nanoparticles Fixed on a Cement Bed in a Continuous‐Flow Photoreactor

Azo dyes are one of the synthetic dyes that have been used in many textile industries. Azo dye and their intermediate products are toxic, carcinogenic, and mutagenic to aquatic life. Removal of azo dyes is one of the main challenges before releasing the wastes discharged by textile industries. Photocatalytic degradation of azo dyes by nanoparticles is one of the environment‐friendly methods used for the removal of dyes from textile effluents. Therefore, this study focused on degradation of azo dye, Direct Red 264. Photocatalytic degradation of DR 264 azo dye was investigated using CdS and Ag/CdS nanoparticles immobilized on a cement bed in a continuous‐flow photoreactor under UV‐C exposure. The effect of the parameters of type and mass of catalyst, temperature, flow rate, dye concentration, and light intensity were evaluated for azo dye removal. Under optimal conditions, photocatalytic degradation of DR 264 azo dye using Ag/CdS nanoparticles immobilized on a cement bed in a continuous‐flow photoreactor obtained an efficiency of 99.99%. A developed kinetic model was proposed based on the intrinsic elementary reactions. The proposed model is in a good agreement with the Langmuir–Hinshelwood (L–H) equation. The pseudo–steady‐state approximation has considered for the concentration of hydroxyl radicals associated with the L–H model under certain conditions and explains consistently the dependence of the apparent kinetic parameter, k_obs (the reaction rate constant), and K_R (the adsorption equilibrium constant) with the light intensity. Based on the model, k_obs for Ag/CdS was greater than the CdS nanoparticles.     

Decolorization of Some Azo Dyes by Immobilized <Emphasis Type="Italic">Geotrichum</Emphasis> sp. Biomass in Fluidized Bed Bioreactor

Geotrichum sp. strain, which is able to decolorize azo dyes enzymatically, was used in this study for decolorization of synthetics solutions contaminated by toxic azo dyes orange G, trypan blue, azorubine, and methyl red. The biomass of Geotrichum sp. was immobilized in calcium alginate and polyacrylamide gels and used for the decolorization of tested azo dyes in fluidized bed bioreactor. The highest specific decolorization rate was obtained when the fungal biomass was entrapped in calcium alginate beads. Immobilized biomass in calcium alginate continuously decolorized azo dyes after eight repeated batch decolorization experiments without significant loss of activity whereas polyacrylamide immobilized biomass retained only 10% of its activity after 4 days of incubation. The effects of some physicochemical parameters such as temperature, pH, and dyes concentration on decolorization performance of isolated fungal strain were also investigated.     

Synthese de substances macromoleculaires renfermant des motifs monomeres derives de colorants—XVIII: Synthese d'oligoamides colores par structure

Oligoamides with amino end-groups have been reacted with acid chlorides of azo or quinophthalic dyes. Oligoamides with 4-nitro phenyl end-groups have been reduced to oligoamides with aminophenyl end-groups; they have been diazotized and coupled with β naphthol. Due to their low thermal stability, oligoamides containing azo groups cannot be spun; on the other hand, oligoamides with quinophthalic groups can be used as macromolecular dyes for polyamides. Coloured fibres have excellent mechanical properties and the dye cannot be extracted by solvent.     

Synthesis and evaluation of a series of symmetrical hot brand bis azo reactive dyes using 4,4′-methylene-bis-metanilic acid on various fibre

4,4′-Methylene-bis-metanilic acid (A) was synthesized by the reaction between metanilic acid and formaldehyde. The compound (A) was used as a bifunctional middle component in the preparation of several symmetrical hot brand bis azo reactive dyes. The compound (A) was tetrazotized and coupled with various m-nitro anilino cyanurated coupling component to give various hot brand bis azo reactive dyes. The entired compounds have been identified by IR, ¹H NMR spectra and elemental analysis. The dyes were applied on silk, wool and cotton fabrics and their fastness properties were evaluated. All the dyes give good fastness properties. The percentage dye bath exhaustion was also been studied.     

Photochromic properties of thienylpyrrole azo dyes in solution

The photochromic behaviour of thienylpyrrole azo dyes in THF solutions was studied for the first time. The photochromic properties are strongly dependent on the substitution pattern on the dyes. Nitro-substituted thienylpyrrole azo dyes are particularly interesting since they exhibit very fast colouration/decolouration processes. The activation energies of these compounds are among the lowest values reported for heterocyclic azo dyes. These compounds show aggregation phenomena in freshly prepared solutions of THF, which lead to variable photochromic behaviours. Only after 1-5 h the solutions reach equilibrium and then reproducible photochromic behaviour can be observed.     

Enhancement of azo dyes removal efficiency by using LDH/Tris/Pd catalyst: Kinetic studies

LDH/Tris/Pd (CaAl‐layered double hydroxide/tris (hydroxymethyl)aminomethane/palladium) was synthesized and appraised for its catalytic activity towards the degradation of two selected azo dyes. The decolorization of azo dyes, acid red 18 (AR 18) and reactive yellow 15 (RY 15), requires considerably small amounts of synthesized catalyst. Kinetic studies show that the catalytic decolorization of these azo dyes follows the first order kinetic model. The reported method is simple and applicable; in addition, the stable catalyst can efficiently decolorize model azo dyes with good recyclability. Therefore, LDH/Tris/Pd can be accepted as the possible component for the utilization in wastewater treatment.     

Synthesis,characterization, and dyeing performance of some azo thienopyridine and thienopyrimidine dyes based on wool and nylon

A string of novel heterocyclic mono azo dyes were synthesized and their utilization in dyeing different fabrics as wool and nylon were discussed. Thienopyridine azo dyes 4 and 6 were prepared by reaction of chloro acetamidederivative 2 with diamino compounds to yield 3 and 5 , followed by reaction with NaNO₂/HCl and coupling with nucleophilic reagent. One-pot reaction of chloro acetamide 2 with ammonium thiocyanat in solvent ethanol gave the unexpected thienopyrimidine derivative 7 , which contain two active sites, the former is primary amine that was able to form diazonium salt that coupled with N,N-dimethylaniline, resorcinol, and/or self-coupling to afford the azo dyes 8-10 , and the latter is active methylene group that underwent coupling with different diazonium salts to give the azo thienopyrimidine derivative dye 11-15 . The dyeing performance of these azo dyes had been investigated in terms of their dyeing behavior and fastness properties on different fabrics. Results showed that the color strength (K/S) values, as well as, washing, rubbing, and resistance to acid, alkali and light showed high efficiency of these heterocyclic mono azo dyes to dye wool rather than nylon fibers.     

Fullerene‐Catalyzed Reduction of Azo Derivatives in Water under UV Irradiation

Metal‐free fullerene (C₆₀) was found to be an effective catalyst for the reduction of azo groups in basic aqueous solution under UV irradiation in the presence of NaBH₄. Use of NaBH₄ by itself is not sufficient to reduce the azo dyes without the assistance of a metal catalyst such as Pd and Ag. Experimental and theoretical results suggest that C₆₀ catalyzes this reaction by using its vacant orbital to accept the electron in the bonding orbital of azo dyes, which leads to the activation of the N?N bond. UV irradiation increases the ability of C₆₀ to interact with electron‐donor moieties in azo dyes.     

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.     

吡啶酮偶氮分散染料光谱性能

吡啶酮分散染料应用性能优异 ,其色谱主要为黄色及橙色 ,尤以黄色为主 [1～ 3]。Cheng和 Peng等 [2 ,3] 对以氨基噻二唑类和苯系芳胺为重氮组分的吡啶酮类染料的可见光谱及互变异构进行了研究 ,Ertan等 [4 ] 研究了以氨基噻唑和氨基苯并噻唑为重氮组分的吡啶酮偶氮染料的可见光谱 ,结果表明上述染料色谱主要仍为黄色。为得到具有更深色谱的吡啶酮类染料 ,我们用不同的重氮组分合成了一系列吡啶酮分散染料 ,研究了其在不同溶剂及不同 p H值下的光谱 ,发现该类染料亦可达到红、甚至蓝色谱 ,其中染料 1 a、1 b及 2 b3个染料结构未见报道。O2 …     

偶氮染料结构、光稳定性和光化学降解机理研究

本文介绍了偶氮染料分子构型、聚集态及其晶体结构的量子化学与实验研究情况, 综述了偶氮染料光稳定性的结构效应和光化学降解机理及其激光闪光光解与时间分辨共振Ram an 光谱近代实验技术的研究进展。     

偶氮染料吸附和光催化氧化动力学

以甲基橙和酸性大红两种偶氮染料为模拟污染有机物,对它们的暗吸附和光催化氧化行为进行研究.实验结果表明,两种偶氮染料的吸附受溶液酸碱度影响很大,酸性（pH=3）条件下,两种染料吸附量都很大,酸性大红吸附量更大；近中性（pH≈6）时两种染料的吸附显著减少；碱性（pH=9）条件下两种染料不发生吸附.光催化反应结果显示,碱性条件或酸性条件下两种染料降解速度都很快.说明在不同酸碱度条件下,光催化反应按不同机理进行.酸性条件下,反应在催化剂表面进行,在碱性介质中,光催化氧化在溶液中进行.提出了一个碱性条件下的动力学方程,经过进一步简化,可以得到表观一级方程,形式上和准一级L-H方程十分相似,但其含义不同.     

Multiwavelength spectrophotometric determination of acidity constants of some azo dyes

A multiwavelength spectrophotometric titration method was applied to study the acidity constants of some azo dyes in water. The UV-vis absorption spectra of azo dye solutions were recorded in the course of their pH-metric titration with a standard base solution. The protolytic equilibrium constants, spectral profiles, concentration diagrams and also the number of components have been calculated. The quantitative effects of the substituents on the acidity of the studied azo dyes were investigated by the linear free energy relationship (LFER) using Hammet sigma constant (sigma) and field and resonance effects of Kamlet and Taft (f and Re, respectively).     

Supramolecular motifs in s-block metal-bound sulfonated monoazo dyes, part 1: structural class controlled by cation type and modulated by sulfonate aryl ring position

The solid-state structures of 43 Li, Na, K, Rb, Mg, Ca and Ba salts of para- and meta-sulfonated azo dyes have been examined and can be categorised into three structural classes. All form alternating organic and inorganic layers, however, the nature of the coordination network that forms these layers differs from class to class. The class of structure formed was found to be primarily governed by metal type, but can also be influenced by the nature and position of the organic substituents. Thus, for the para-sulfonated azo dyes, Mg compounds form solvent-separated ion-pair solids; Ca, Ba and Li compounds form simple coordination networks based on metal-sulfonate bonding; and Na, K and Rb compounds form more complex, higher dimensional coordination networks. Compounds of meta-sulfonated azo dyes follow a similar pattern, but here, Ca species may also form solvent-separated ion-pair solids. Significantly, this first attempt to classify such dyestuffs using the principles of supramolecular chemistry succeeds not only for the simple dyes used here as model compounds, but also for more complex molecules, similar to modern colourants.     

蓝光有机存储染料研究进展

近年来,蓝光有机存储染料作为超高密度存储技术的核心已经日益受到人们的广泛关注,出现了与之相关的大量专利文献报道.本文介绍了卟啉染料、偶氮染料、菁染料、芪类染料和香豆素衍生物染料等蓝光染料的合成及应用,并对蓝光有机存储染料的发展趋势作了展望.     

Silicone nanomicelle dyeing method on polyester fibre: Comparative evaluation of chemical properties,fastness properties,and DFT

Disperse Red 177(9a), Disperse Red 343(9b), Disperse Blue 165(9c), Disperse Blue 165.1(9d), Disperse Blue 366(9e), and Disperse Blue 148(9f) were examined in the solvent. During silicon nanomicelle dyeing, we employed 9(a–f) azo disperse dyes on polyester. On polyester fabric, dye 9(a–f) offers equal washing, light, and rubbing fastness in both the conventional and silicone nanomicelle techniques. The dye can now be transported directly into the fibre core without the use of auxiliary dyes owing to the reduction in the particle size of azo dyes, which is made possible by nanoemulsions superior dispersion. The levelling property of the dispersed dye is enhanced by the dyeing process. When both techniques are applied, the lightfastness properties of all dyes are improved. It provides a very good to outstanding protection factor for textile materials. These 9(a–f) azo disperse dyes have moderate to outstanding photostability, net electrophilicity index, and lightfastness.