M.A. Rauf

Radiation induced degradation of dyes - an overview.

Synthetic dyes are a major part of our life. Products ranging from clothes to leather accessories to furniture all depend on extensive use of organic dyes. An unfortunate side effect of extensive use of these chemicals is that huge amounts of these potentially carcinogenic compounds enter our water supplies. Various advanced oxidation processes (AOPs) including the use of high-energy radiation have been developed to degrade these compounds. In this review, dye decoloration and degradation as a result of its exposure to high energy radiation such as gamma radiation and pulsed electron beam are discussed in detail. The role of various transient species such as H, OH and e(aq)(-) are taken into account as reported by various researchers. Literature citations in this area show that e(aq)(-) is very effective in decolorization but is less active in the further degradation of the products formed. The degradation of the dyes is initiated exclusively by OH attack on electron-rich sites of the dye molecules. Additionally, various parameters that affect the efficiency of radiation induced degradation of dyes, such as effect of radiation dose, oxygen, pH, hydrogen peroxide, added ions and dye classes are also reviewed and summarized. Lastly, pilot plant application of radiation for wastewater treatment is briefly discussed.

Determination of optimum operating conditions of carmine decoloration by UV/H2O2 using response surface methodology.

In this study, the photolytic decoloration of carmine (C.I. Natural Red 4) via UV radiation in the presence of H2O2 was optimized using response surface methodology (RSM). According to analysis of variance (ANOVA) results, the proposed model can be used to navigate the design space. It was found that the response of carmine degradation is very sensitive to the independent factors of carmine concentration, H2O2 concentration, pH and reaction time. The proposed model for D-optimal design fitted very well with the experimental data with R2 and R(adj)2 correlation coefficients of 0.998 and 0.997, respectively.

Photolytic decolorization of Rose Bengal by UV/H2O2 and data optimization using response surface method

Rose Bengal (C.I. name is Acid Red 94) was irradiated with UV light in the presence of hydrogen peroxide. The photoinduced decolorization of the dye was monitored spectrophotometrically. The apparent rate of decolorization was calculated from the observed absorption data and was found to be pseudo first order. A systematic study of the effect of dye concentration and H(2)O(2) concentration on the kinetics of dye decolorization was also carried out. Dye decolorization increased with increasing H(2)O(2) concentration and decreasing dye concentration. The maximum dye decolorization was determined as 90% with 0.005 mM dye at optimum 0.042 M H(2)O(2) and pH 6.6. Additionally, the effect on decolorization of this dye in the presence of some additives (ions) was also investigated. It was seen that sulphite caused a maximum effect on % decolorization of the dye solution. A plausible explanation involving the probable radical initiated mechanism was given to explain the dye decolorization. The experimental data was also optimized using the response surface methodology (RSM). According to ANOVA results, the proposed model can be used to navigate the design space. It was found that the response of Rose Bengal degradation is very sensitive to the independent factors of dye concentration, H(2)O(2) concentration, pH and reaction time. The proposed model for D-optimal design fitted very well with the experimental data with R(2) and R(adj)(2) correlation coefficients of 0.85 and 0.80, respectively.

Solvatochromic behavior on the absorption and fluorescence spectra of Rose Bengal dye in various solvents

The absorption and fluorescence spectra of Rose Bengal dye were studied in various solvents. It was found that solvent effects on the absorption wavelength are consistent with the solvatochromic model of Kamlet, Abboud and Taft. The solvent polarizability value pi* was found to have a linear relationship with the absorption wavelength of the dye in various solvents. Additionally, the normalized transition energy value (E(T)(N)) showed some scattering when plotted versus Deltanu(af). Density functional calculations were used to assign the absorption in the region 540-570 nm to a pi-pi* transition between the HOMO and LUMO of the anion. Experimental ground state and excited state dipole moments were calculated by using the solvatochromatic shifts of absorption and fluorescence spectra as a function of the dielectric constant (epsilon) and refractive index (n). The dipole moment for Rose Bengal was found to be 1.72 Debye in the ground state, whereas this value was 2.33 Debye in the excited state.

Solvent effect on the spectral properties of Neutral Red

BackgroundThe study was aimed at investigating the effect of various solvents on the absorption spectra of Neutral Red, a dye belonging to the quinone-imine class of dyes. The solvents chosen for the study were water, ethanol, acetonitrile, acetone, propan-1-ol, chloroform, nitrobenzene, ethyleneglycol, acetic acid, DMSO and DMF.ResultsThe results have shown that the absorption maxima of dyes are dependent on solvent polarity. In non-hydrogen-bond donating solvents, solvation of dye molecules probably occurs via dipole-dipole interactions, whereas in hydrogen-bond donating solvents the phenomenon is more hydrogen bonding in nature. To estimate the contribution of the different variables on the wave number of the Neutral Red dye, regression analyses using the ECW model were compared with the π* scale model. This showed that the unified scale for estimating the solvent effect on the absorption of the Neutral Red dye is more adopted and more applicable than the π* scale model.ConclusionAbsorption maxima of dyes are dependent on solvent polarity. Solvation of dye molecules probably occurs via dipole-dipole interactions in non-hydrogen-bond donating solvents, whereas in hydrogen-bond donating solvents the phenomenon is more hydrogen bonding in nature. The unified scale for estimating the solvent effect on the absorption of Neutral Red dye is more adopted and more applicable than the π* scale model. This may be due to complications from both π-π* charge transfer interactions and incomplete complexation of the solute; these effects are averaged out in the derived β and π parameters and thus limit their applicability.

Mechanistic studies of photoinduced degradation of Orange G using LC/MS

Photocatalytic degradation of Orange G dye was carried out with UV light in the presence of TiO2 mixed with 20% chromium oxide as a catalyst. The conditions for maximum dye degradation were optimized in terms of catalyst amount, dye concentration, pH and time. The dye degradation followed pseudo first-order kinetics. LC-MS/MS was used to track the numerous intermediate products formed during the course of dye degradation. Major intermediate products confirmed were substituted phenols, aromatic hydroxyl amine, nitroso hydroxyl aromatic amines and dicarboxyl aromatic compounds. These intermediates along with some minor products were correlated to suggest a possible degradation pathway of Orange G. The dye degradation occurred mainly by three pathways, namely the hydroxylation of the aromatic ring, desulfonation and oxidative cleavage of the azo bond.

Spectroscopic studies of keto–enol tautomeric equilibrium of azo dyes

Azo dyes account for 60–70% of all dyes known to date. Understanding the factors that affect the direction of keto–enol tautomerism in azo dyes through spectral measurements is crucial to their potential applications. This review encompasses the most important spectroscopic studies of different azo dyes categorized by their structures within the last few years (2010–2014). It is concluded that the stability of the keto and enol forms largely arises from the ability to establish intra-molecular and inter-molecular hydrogen bonding, respectively. There are many factors that affect the keto or enol form, for example, polar solvent, high temperature, neutral pH and electron withdrawing substituents favor the keto form through intramolecular hydrogen bonding, whereas, nonpolar solvent, low temperature, high pH and electron donating groups favor the enol form through intermolecular hydrogen bonding. Encapsulation inside nanocaged microheterogenous systems creates a rigid environment that stabilizes the enol form mostly, while in the solid state, most of the tautomeric equilibrium lies in favor of the keto form. Understanding of keto–enol tautomerism in azo dyes helps to probe solvation dynamics, to tune the pKa values in chemical sensing, and to explain proton transfer in the excited state.

Liquid chromatography tandem mass spectrometry analysis of photodegradation of a diazo compound: A mechanistic study

The photolytic degradation of the diazo dye, Amido Black, using UV/H(2)O(2) has been carried out experimentally and parameters for most efficient dye degradation have been determined. The degradation of the dye was followed by UV-Vis spectroscopy, HPLC, and LC-MS and is proposed to be initiated by ()OH radicals formed by the photolysis of H(2)O(2). A detailed study was also carried out using LC-MS and LC-MS/MS to determine the degradation pathway of the dye as well as to identify some of the intermediate products formed. Our results suggest that Amido Black degradation occurs preferentially by ()OH radical attack at the more electron rich diazo functionality of the molecule. Furthermore, evidence is presented that subsequent steps in this diazo dye degradation pathway include radical denitration, radical desulfonation and radical diazotization. This report is one of the very few studies that have proposed possible mechanistic pathways for the degradation pathways of a diazo compound.

Mechanistic study of a diazo dye degradation by Soybean Peroxidase

BackgroundEnzyme based remediation of wastewater is emerging as a novel, efficient and environmentally-friendlier approach. However, studies showing detailed mechanisms of enzyme mediated degradation of organic pollutants are not widely published.ResultsThe present report describes a detailed study on the use of Soybean Peroxidase to efficiently degrade Trypan Blue, a diazo dye. In addition to examining various parameters that can affect the dye degradation ability of the enzyme, such as enzyme and H2O2 concentration, reaction pH and temperature, we carried out a detailed mechanistic study of Trypan Blue degradation. HPLC-DAD and LC-MS/MS studies were carried out to confirm dye degradation and analyze the intermediate metabolites and develop a detailed mechanistic dye degradation pathway.ConclusionWe report that Soybean peroxidase causes Trypan Blue degradation via symmetrical azo bond cleavage and subsequent radical-initiated ring opening of the metabolites. Interestingly, our results also show that no high molecular weight polymers were produced during the peroxidase-H2O2 mediated degradation of the phenolic Trypan Blue.

A hands-on approach to teaching environmental awareness and pollutant remediation to undergraduate chemistry students

Background : One of the unfortunate side effects of the industrial revolution has been the constant assault of the environment with various forms of pollution. Lately, this issue has taken a more critical dimension as prospects of global climate change and irreversible ecosystem damage are becoming a reality. Purpose : College graduates (especially chemists), should therefore not only be aware of these issues but also be taught how chemistry can help reduce environmental pollution. Furthermore, the role and importance of chemistry in sustainable development and solving environmental problems needs to be highlighted. Programme/intervention description : To this effect, we have designed a simple undergraduate experiment that is based on the green chemistry approach of using photolytic oxidation to degrade a model organic pollutant. This approach used UV light and hydrogen peroxide to produce reactive hydroxyl radicals, which subsequently break down and degrade Acridine Orange (model pollutant). The dye degradation was monitored spectrophotometrically and the apparent rate of decolouration was found to be first order. Possible radical initiated mechanisms that may be involved in this remediation experiment have been used to explain the observed dye decolouration. Sample : To test the usefulness of this newly developed experiment, we incorporated it as a module into a second year ‘Professional skills’ chemistry course with an enrollment of six female students. Anonymous survey of the students after the completion of the module was very positive and indicated that objectives of the experiment were satisfactorily achieved. Results : We believe this experiment not only raises students’ awareness about green chemistry and environmental issues, but also teaches them valuable experimental skills such as experimental design, data manipulation and basic kinetics. Survey of students who were taught this unit in a second year course was very positive and supported the usefulness of this unit for chemistry students. Conclusions : In summary, we describe here an undergraduate chemistry experiments that was found to be very effective in teaching students about the hazards of environmental pollution and the role of green chemistry in solving ‘real-life’ problems, as well as chemical kinetics, data acquisition and manipulation.