Dušan Ž. Mijin

Synthesis of N‐Substituted 4,6‐Dimethyl‐3‐cyano‐2‐pyridones Under Microwave Irradiation

Abstract N‐substituted 4,6‐dimethyl‐3‐cyano‐2‐pyridones have been prepared from acetylacetone, N‐substituted cyanoacetamide, and pyperidine as catalyst under microwave irradiation without solvent. The rapid and simple method produced pure products in high yields.

Immobilization of lipase from Candida rugosa on Sepabeads®: the effect of lipase oxidation by periodates

The objective of this paper was the investigation of a suitable Sepabeads® support and method for immobilization of lipase from Candida rugosa. Three different supports were used, two with amino groups, (Sepabeads® EC-EA and Sepabeads® EC-HA), differing in spacer length (two and six carbons, respectively) and one with epoxy group (Sepabeads® EC-EP). Lipase immobilization was carried out by two conventional methods (via epoxy groups and via glutaraldehyde), and with periodate method for modification of lipase. The results of activity assays showed that lipase retained 94.8% or 87.6% of activity after immobilization via epoxy groups or with periodate method, respectively, while glutaraldehyde method was inferior with only 12.7% of retention. The immobilization of lipase, previously modified by periodate oxidation, via amino groups has proven to be more efficient than direct immobilization of lipase via epoxy groups. In such a way immobilized enzyme exhibited higher activity at high reaction temperatures and higher thermal stability.

Spectroscopic and quantum chemical investigations of substituent effects on the azo-hydrazone tautomerism and acid–base properties of arylazo pyridone dyes

A series of 5-(4-substituted arylazo)-6-hydroxy-4-methyl-3-cyano-2-pyridone dyes was synthesized and the structure of the dyes was confirmed by UV-Vis, FT-IR, (1)H NMR and (13)C NMR spectroscopic techniques. The azo-hydrazone tautomeric equilibrium was found to depend on the substituents as well as on the acidity and basicity of the media. Ionization constant, pKa, of the dyes was determined by UV-Vis spectroscopy and correlated with the Hammett substituent constants, σp and σI. The interpretation of the effect of different substituent in phenyl ring of arylazo pyridone dyes on their spectroscopic and structural properties was based on quantum chemical calculations performed by the density functional theory (DFT/M06-2X) method. The DFT calculations confirmed the existence of two forms in water solution: hydrazone form in acidic and neutral media and anionic form in basic media. The different contribution of azo and hydrazone canonical forms of anionic form is observed for dyes with electron-donating and dyes with electron-withdrawing groups. The dependence of absorption spectra and determined pKa values to the substituent type seems to be mostly due to azo/hydrazone canonical structure ratio in their anionic form.

Nanocrystalline CeO2-δ as effective adsorbent of azo dyes.

Ultrafine CeO2-δ nanopowder, prepared by a simple and cost-effective self-propagating room temperature synthesis method (SPRT), showed high adsorption capability for removal of different azo dyes. Batch type of adsorption experiments with fixed initial pH value were conducted for the removal of Reactive Orange 16 (RO16), Methyl Orange (MO), and Mordant Blue 9 (MB9). The equilibrium adsorption data were evaluated using Freundlich and Langmuir isotherm models. The Langmuir model slightly better describes isotherm data for RO16 and MO, whereas the Freundlich model was found to best fit the isotherm data for MB9 over the whole concentration range. The maximum adsorption capacities, determined from isotherm data for MO, MB9, and RO16 were 113, 101, and 91 mg g(-1) respectively. The adsorption process follows the pseudo-second-order kinetic model indicating the coexistence of chemisorption and physisorption. The mechanism of azo dye adsorption is also discussed.

Synthesis, structure and solvatochromic properties of some novel 5-arylazo-6-hydroxy-4-phenyl-3-cyano-2-pyridone dyes

BackgroundA series of some novel arylazo pyridone dyes was synthesized from the corresponding diazonium salt and 6-hydroxy-4-phenyl-3-cyano-2-pyridone using a classical reaction for the synthesis of the azo compounds.ResultsThe structure of the dyes was confirmed by UV-vis, FT-IR, 1H NMR and 13C NMR spectroscopic techniques and elemental analysis. The solvatochromic behavior of the dyes was evaluated with respect to their visible absorption properties in various solvents.ConclusionsThe azo-hydrazone tautomeric equilibration was found to depend on the substituents as well as on the solvent. The geometry data of the investigated dyes were obtained using DFT quantum-chemical calculations. The obtained calculational results are in very good agreement with the experimental data.

Influence of process parameters on the photodegradation of synthesized azo pyridone dye in TiO2 water suspension under simulated sunlight

Photocatalytic degradation of synthesized azo pyridone dye (5-(4-sulpho phenylazo)-6-hydroxy-4-methyl-3-cyano-2-pyridone), in aqueous solutions by simulated sunlight in the presence of commercial TiO2, Aeroxide P25, was studied. The reaction kinetics analysis showed that photodegradation exhibits pseudo first-order kinetics according to Langmuir-Hinshelwood model. The effects of various process parameters on the photocatalytic degradation were investigated. The optimal catalyst content and pH were determined. A decrease in the reaction rate was observed upon the increase of the initial dye concentration. Degradation of the dye was enhanced by hydrogen peroxide, but it was inhibited by ethanol. The influence of temperature was studied, and the energy of activation was determined. According to total organic carbon (TOC) analysis, 54% of TOC remained when 100% of the dye was decolorized. Although the intermediates were not determined in this study, the TOC results clearly indicate their presence during the reaction. In addition, photocatalytic degradation of simulated dyehouse effluents, containing tested azo pyridone dye and associated auxiliary chemicals was investigated.

Photocatalytic degradation of azo pyridone dye: Optimization using response surface methodology

Abstract Response surface methodology (RSM) and central composite design have been applied to describe and optimize photocatalytic degradation of azo pyridone dye using TiO2, H2O2, and simulated sun light. The mutual interactions between three independent variables, viz. H2O2 concentration, irradiation time, and TiO2 content were obtained. The results revealed that the most influential variables under selected reaction conditions were irradiation time and TiO2 content. The optimized conditions for the photocatalytic degradation of azo pyridone dye were as follows: H2O2 concentration: 130.5 mg/L, irradiation time: 54.8 min, and TiO2 content: 2.48 g/L. Under these conditions, the maximum decolorization efficiency of 96.43% was achieved. This experimental value was in good agreement with the predicted one, which proved the validity of the model. Operation cost analysis indicated that irradiation time had the major influence on total process cost. The RSM based on the central composite design was shown to be ...

Photochemical Behavior of the Insecticide Methomyl Under Different Conditions

This article describes the photolytic and photocatalytic removal of the insecticide methomyl at low concentration from different types of water, upon UV, visible or natural solar light radiation, in the presence of TiO2 and ZnO, as well as using Fe-ZSM-5 zeolite and AlFe-pillared montmorillonite (photo-Fenton process). The rate of photodecomposition of methomyl was measured using UV spectrometry and HPLC, while its mineralization was investigated by ion chromatography (IC) and total organic carbon (TOC) analysis. The photochemical removal of methomyl is a natural and applicable model for the purification of water.

Decolorization of Anthraquinonic Dyes from Textile Effluent Using Horseradish Peroxidase: Optimization and Kinetic Study

Two anthraquinonic dyes, C.I. Acid Blue 225 and C.I. Acid Violet 109, were used as models to explore the feasibility of using the horseradish peroxidase enzyme (HRP) in the practical decolorization of anthraquinonic dyes in wastewater. The influence of process parameters such as enzyme concentration, hydrogen peroxide concentration, temperature, dye concentration, and pH was examined. The pH and temperature activity profiles were similar for decolorization of both dyes. Under the optimal conditions, 94.7% of C.I. Acid Violet 109 from aqueous solution was decolorized (treatment time 15 min, enzyme concentration 0.15 IU/mL, hydrogen peroxide concentration 0.4 mM, dye concentration 30 mg/L, pH 4, and temperature 24°C) and 89.36% of C.I. Acid Blue 225 (32 min, enzyme concentration 0.15 IU/mL, hydrogen peroxide concentration 0.04 mM, dye concentration 30 mg/L, pH 5, and temperature 24°C). The mechanism of both reactions has been proven to follow the two substrate ping-pong mechanism with substrate inhibition, revealing the formation of a nonproductive or dead-end complex between dye and HRP or between H2O2 and the oxidized form of the enzyme. Both chemical oxygen demand and total organic carbon values showed that there was a reduction in toxicity after the enzymatic treatment. This study verifies the viability of use of horseradish peroxidase for the wastewaters treatment of similar anthraquinonic dyes.

The immobilization of enzyme on Eupergit® supports by covalent attachment.

A selection of the best combination of adequate immobilization support and efficient immobilization method is still a key requirement for successful application of immobilized enzymes on the industrial level. Eupergit) supports exhibit good mechanical and chemical properties and allow establishment of satisfactory hydrodynamic regime in enzyme reactors. This is a good recommendation for their wide application in enzyme immobilization after finding the most favorable immobilization method. Methods for enzyme immobilization that have been previously reported as efficient, considering the obtained activity of immobilized enzyme are presented: direct binding to polymers via their epoxy groups, binding to polymers via a spacer made from ethylene diamine/glutaraldehyde, and coupling the periodate-oxidized sugar moieties of the enzymes to the polymer beads.