Dye aggregation in solution: study of C.I. direct red I

The variation of the average number of molecular aggregation for C.I. Direct Red I has been studied in aqueous solutions as a function of the dye concentration, temperature and solution pH. The objective of this paper is to evaluate the optimal conditions and dye structure in the dyeing process. Electrochemical and VIS spectrophotometrical methods have been used to calculate molecular aggregation. The electrochemical calculation uses the reduction process of the dye, and previous calculations by other authors have been reported at a given pH and varying the solution concentration. Molecular aggregation also depends on pH, and an understanding of the reduction mechanism at several pH values is therefore necessary.     

A new nitrite ionic liquid (IL-ONO) as a nitrosonium source for the efficient diazotization of aniline derivatives and in-situ synthesis of azo dyes

A new task-specific nitrite containing ionic liquid derived from the O-nitrosation of N-methyl-N-hydroxybutylimidazolinium chloride was synthesized and used as a source of nitrosonium ion to affect the efficient diazotization of arylamines. The diazonium salts thus obtained were coupled, using standard experimental procedures, to a range of tertiary anilines, phenols and naphthols to afford the requisite azo dyes in good yield. The diazotization and subsequent azo-coupling generated the related azo dyes at 0-5 °C in short reaction times with a simple experimental procedure.     

Surface modification and characterization of carbon spheres by grafting polyelectrolyte brushes

Modified carbon spheres (CSPBs) were obtained by grafting poly(diallyl dimethyl ammonium chloride) (p-DMDAAC) on the surface of carbon spheres (CSs). It can be viewed as a kind of cation spherical polyelectrolyte brushes (CSPBs), which consist of carbon spheres as core and polyelectrolytes as shell. The method of synthesizing carbon spheres was hydrothermal reaction. Before the polyelectrolyte brushes were grafted, azo initiator [4,4′-Azobis(4-cyanovaleric acyl chloride)] was attached to the carbon spheres'' surface through hydroxyl groups. CSPBs were characterized by scanning electron microscope (SEM), Fourier transform infrared spectroscopy (FTIR), gel permeation chromatography (GPC), conductivity meter, and system zeta potential. The results showed that compared with carbon spheres, the conductivity and zeta potential on CSPBs increased from 9.98 to 49.24 μS/cm and 11.6 to 42.5 mV, respectively, after the polyelectrolyte brushes were grafted. The colloidal stability in water was enhanced, and at the same time, the average diameter of the CSPBs was found to be 173 nm, and the average molecular weight and grafted density of the grafted polyelectrolyte brushes were 780,138 g/mol and 4.026 × 10⁹/nm^2, respectively.     

Biocalalyst effects of immobilized anthraquinone on the anaerobic reduction of azo dyes by the salt-tolerant bacteria

The accelerating effect of dissolved redox mediators has been studied in details in the bio-decolorization processes, but there are little literatures about the non-dissolved redox mediators. Here we describe the accelerating effect of anthraquinone as a redox mediator in the bio-decolorization. Decolorization of azo dyes was carried out experimentally using the salt-tolerant bacteria under immobilized anthraquinone and high salt conditions. Anthraquinone as a redox mediator was able to increase the decolorization rate of azo dyes, and was immobilized by entrapment in calcium alginate (CA), Polyvinyl alcohol (PVA)-H(3)BO(3) and agar, respectively. The effects of various operating conditions such as anthraquinone bead number, dissolved oxygen, temperature and pH on microbial decolorization were investigated experimentally. The reusability of the anthraquinone immobilization beads was evaluated with repeated-batch decolorization experiments. After four repeated experiments, the decolorization rate of CA immobilized anthraquinone retained over 90% of their original value. The experiments explored a great improvement of the redox mediator application and the new bio-treatment concept.     

Electrochemical degradation of azo dye C.I. Reactive Red 195 by anodic oxidation on Ti/SnO2-Sb/PbO2 electrodes

This study investigated the electrochemical degradation of C.I. Reactive Red 195 (RR195) in aqueous solution on a Ti/SnO₂-Sb/PbO₂ electrode. The influence of operating variables on the mineralization efficiency was studied as a function of the current density, the initial pH, the initial concentration of the dye and the addition of NaCl. The efficiency of RR195 mineralization decreased with increased initial concentration, from 100 mg L⁻¹ to 400 mg L⁻¹. The current density had both a positive and a negative effect on degradation rates, and no significant effect of initial pH on RR195 mineralization was observed. Measurement of absorbance was used to discriminate the effect of NaCl in the electro-oxidation process. We found that the decolouring efficiency increased whereas the mineralization efficiency decreased with the increasing concentration of NaCl. The intermediates formed during the degradation were detected by gas chromatography-mass spectrometry, and the major aromatic intermediates identified were 1-(3,6,8-trihydroxy-1-naphthyl)urea, nitrobenzene, benzo-1,4-quinone, (3,6,8-trihydroxy-1-naphthyl)carbamic acid and phthalic acid. Quantitative measurement of organic and inorganic ions was done by ion chromatography. On the basis of the reaction products identified, a possible degradation pathway for the anodic oxidation of RR195 in aqueous solution is proposed.     

Influence of chromophoric electron-withdrawing groups on photoinduced deformation of azo polymer colloids

This study investigated the influence of chromophoric electron-withdrawing groups on photoinduced deformation behavior of colloidal spheres of three azo polymers. The colloidal spheres were prepared by using the epoxy-based azo polymers (BP-AZ-CA, BP-AZ-CN, and BP-AZ-NT) through gradual hydrophobic aggregation of the polymers in THF-H₂O media. The colloidal spheres were controlled to have similar average sizes by adjusting both the polymer concentrations in the initial THF solutions and water-adding rates in the preparation processes. The colloids were characterized by dynamic light scattering (DLS), transmission electron microscopy (TEM), and scanning electron microscopy (SEM). The colloid deformation was investigated by irradiating the colloidal spheres in solid state with a linearly polarized Ar⁺ laser beam (488 nm, 130 mW/cm²). For comparison, the colloids were also studied by irradiation with a polarized diode solid state laser beam (532 nm, 130 mW/cm²). Upon the light irradiation, all the colloidal spheres were elongated along the polarization direction of the laser beams. The electron-withdrawing groups showed significant influence on the colloid deformation behavior related with the response to the light irradiation. The colloid deformation was more efficiently induced by irradiation with the laser beams having the intermediate wavelengths between the λ_max and the absorption band tails of the azo chromophores. When the hydrophilic carboxylic group was used as the electron-withdrawing groups, more significant deformation was induced under the same light irradiation condition, which could be attributed to the higher hydrophilicity of the polymer. Above observations can lead to a better understanding of the photoinduced deformation mechanism of azo polymer colloids.     

Photodegradation of orange I in the heterogeneous iron oxide-oxalate complex system under UVA irradiation

To understand the photodegradation of azo dyes in natural aquatic environment, a novel photo-Fenton-like system, the heterogeneous iron oxide-oxalate complex system was set up with the existence of iron oxides and oxalate. Five iron oxides, including gamma-FeOOH, IO-250, IO-320, IO-420 and IO-520, were prepared and their adsorption capacity was investigated in the dark. The results showed that the saturated adsorption amount (gamma(max)) was ranked the order of IO-250 > IO-320 > gamma-FeOOH > IO-420 > IO-520 and the adsorption equilibrium constant (Ka) followed the order of IO-250 > IO-520 > gamma-FeOOH > IO-420 > IO-320. The effect of initial pH value, the initial concentrations of oxalate and orange I on the photodegradation of orange I were also investigated in different iron oxide-oxalate systems. The results showed that the photodegradation of orange I under UVA irradiation could be enhanced greatly in the presence of oxalate. And the optimal oxalate concentrations (C(ox)0) for gamma-FeOOH, IO-250, IO-320, IO-420 and IO-520 were 1.8, 1.6, 3.5, 3.0 and 0.8 mM, respectively. The photodegradation of orange I in the presence of optimal C(ox)0 was ranked as the order of gamma-FeOOH > IO-250 > IO-320 > IO-420 > IO-520. The optimal range of initial pH was at about 3-4. The first-order kinetic constant for the degradation of orange I decreased with the increase in the initial concentration of orange I. Furthermore, the variation of pH, the concentrations of Fe3+ and Fe2+ during the photoreaction were also strongly dependent on the C(ox)0 and iron oxides.     

二向色性染料偏振膜的研究

偏振片在液晶显示技术中占据着很重要的位置,改善偏振片的偏振性能是液晶显示技术中的关键问题。二向色性有机染料因具有优良的耐湿热性能,被用作液晶显示偏光材料的研究日渐活跃,现在普遍研究的有偶氮染料偏振片和聚环染料偏振片。     

Laccase-membrane reactors for decolorization of an acid azo dye in aqueous phase: Process optimization

In the present investigation, performance of various laccase-membrane reactor configurations including direct enzyme contact, enzyme impregnated, immobilized enzyme and a reactor system based on laccase immobilization in chitosan membranes for decolorization of azo dye (acid black 10 BX) were examined using laccase enzyme purified from white rot fungi Pleurotus ostreatus 1804. A five-step laccase purification procedure was employed, which improved the enzymatic activity by 8.27 folds. Laccase was confirmed by comparing with the standard marker using SDS-PAGE electrophoresis, which showed molecular weight of 63 kDa. Experimental data showed that laccase has great potential for color removal without addition of external redox mediators. Various process parameters viz. aqueous phase of pH 6.0, enzyme concentration of 1.75 U/ml, dye concentration of 20 mg/L, temperature of 30 °C and reaction time of 120 min were optimized to achieve maximum decolorization efficiencies. Moreover, different laccase-membrane reactor configurations were tested to determine the efficacy of repeated application of laccase on dye decolorization process. Among the different reactor configurations employed, laccase encapsulated in chitosan membrane showed advantages such as short-term contact period and reusability of enzyme for a number of cycles.     

Photocatalytic Degradation of Two Commercial Reactive Dyes in Aqueous Phase Using Nanophotocatalysts

This study involves the photocatalytic degradation of Reactive Black 5 (RB5) and Reactive Orange 4 (RO4) dyes, employing heterogeneous photocatalytic process. Photocatalytic activity of different semiconductors such as titanium dioxide (TiO₂) and zinc oxide (ZnO) has been investigated. An attempt has been made to study the effect of process parameters through amount of catalyst, concentration of dye, and pH on photocatalytic degradation of RB5 and RO4. The experiments were carried out by varying pH (3–11), amount of catalyst (0.25–1.5 g/L), and initial concentration of dye (10–100 mg/L). The optimum catalyst dose was found to be 1.25 and 1 g/L for RB5 and RO4, respectively. In the case of RB5, maximum rate of decolorization was observed in acidic medium at pH 4, whereas the decolorization of RO4 reached maximum in basic region at pH 11. The performance of photocatalytic system employing ZnO/UV light was observed to be better than TiO₂/UV system. The complete decolorization of RB5 was observed after 7 min with ZnO, whereas with TiO₂, only 75% dye degraded in 7 min. In the case of RO4, 92 and 62% decolorization was noticed in the same duration.