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Lipase-catalyzed organic reactions have been widely practiced in the past three decades. Especially interesting are insoluble/immobilized forms due to providing a possibility of facile use and recyclability, thus reducing process costs, and making the procedure more environmentally friendly. Carbon-based supports have been extensively exploited for this purpose, because of neutral and biodegradable nature and thermal and chemical stability. Their high specific surface area, characteristic surface morphology and lower mass transfer resistances play a vital role in the performance of the attached enzyme. This review paper presents an overview of the main aspects of lipase immobilized on multi-walled carbon nanotubes (MWCNTs). Moreover, different immobilization strategies to achieve a biocatalyst with improved performances are discussed. Furthermore, as lipases are considered to have high commercial worth for synthesis of valuable organic molecules, the second part of the paper is dedicated to the overview of the most important industrial sectors in which these nanobiocatalysts have been used. In specific, applications in biodiesel production, flavour ester synthesis and racemization are summarize

Adsorption of anthraquinone dye Acid Blue 111 by alumina-iron oxide doped particles prepared by sol-gel method from aqueous solutions was studied. The adsorbent morphology was revealed by FESEM and the crystallographic phase is analyzed by the XRD technique. The effect of adsorbate and adsorbent concentrations, pH value, type of adsorbent and thermodynamic parameters on dye removal by adsorption was studied. The change of dye concentration during the adsorbtion was followed using the UV-Visible spectrophotometer. The change of the adsorbent surface before and after dye removal was observed using the Fourier Transformation-infrared spectroscopy (FT-IR). The adsorption kinetics is in accordance with the pseudo-second-order kinetics model. The Langmuir and Freundlich adsorption isotherm models were used to describe the adsorption process. The thermodynamic study of dye adsorption proves the process is spontaneous with exothermic nature.

In recent decades an increase usage of chemicals in many ways of modern life is evident. So, the possibility of its intake into organisms, human and animals poisoning and health damage, is nowadays on a high level, especially when it comes to disaster situations caused by using toxic chemicals in terrorist attacks or for military purposes. If we look ahead, the risk of pesticide contamination of the water and soil, as one of the most important resources for surviving, is always present. The wide spectra of pesticide negative effects on the environment initiate the increasing number of investigations of efficient pesticide removal methods, especially from water. The aim of this study was to investigate the efficiency of direct electrochemical oxidation as a method for in-situ degradation of pesticides in the aquatic environment, depending on the concentration of pesticides, present electrolytes, applied current and the pH value of the medium. As a model molecule, the neonicotinoid pesticide thiamethoxam was used. Kinetics of thiamethoxam degradation in aqueous solution was followed by UV/Vis spectrometry.

Nicosulfuron, a sulfonylurea herbicide, was subjected to different Fenton reactions at pH of a nicosulfuron aqueous solution (pH 5). Usually, the optimal pH for the Fenton reaction is between 3 and 4, but the addition of acids is not environmentally acceptable. This is the reason why the reactions were performed at a higher pH value than usual. So, classical Fenton and Fenton-like reactions were applied as well as photo-Fenton and photo-Fenton-like reactions. In addition, microwave Fenton and Fenton-like reactions were used in nicosulfuron degradation. Influences of Fe2+ and Fe3+ concentrations, as well as hydrogen peroxide concentrations, were studied. The Fenton reaction was much faster and more efficient than the Fenton-like reaction, while the photo- Fenton reaction proceeded much faster and more efficiently than the Fenton reaction. The microwave-Fenton and microwave-Fenton-like reactions proceeded with increased efficiency in comparison to the Fenton and Fenton-like reactions. The phytotoxicity and acute toxicity of the reaction products of nicosulfuron oxidation by the photo-Fenton reaction were analyzed. The toxicity testing of nicosulfuron treatment by photo-Fenton process showed a decrease in phytotoxicity, while the acute toxicity tests showed that the samples after treatment had lower toxicity. [Project of the Serbian Ministry of Education, Science and Technological Development, Grant no. 172013, Grant no. 172007 and Grant no. III 46008]

The problem of environmental pollution day by day becomes more worrisome, primarily due to the large amounts of wastewater contaminated with various harmful organic compounds, discharged into the environment untreated or partially clean. Feasibility of use of horseradish peroxidase (Amoracia rusticana) in the synthetic dyes decolorization was approved by many researchers. Among a number of supports used for the immobilization, it was found that natural clay, kaolin has excellent features which are a precondition for obtaining biocatalysts with the excellent performances. For this reason, a horseradish peroxidase was immobilized onto kaolin using glutaraldehyde as a cross-linking agent. Obtained biocatalyst was applied in the decolorization of anthraquinone dye C. I. Acid Violet 109. Under determined optimal conditions (pH 4.0, hydrogen peroxide concentration 0.6 mM, dye concentration 30 mg L-1, temperature 24ºC) around 76 % of dye decolorization was achieved. Reusability study showed that resulting biocatalyst was possible to apply four times in the desired reaction with relatively high decolorization percentage. [Projekat Ministarstva nauke Republike Srbije, br. III-46010 i br. 172013]

This study describes the investigation of degradation products of donepezil (DP) using stability indicating RP-HPLC method for determination of donepezil, which is a centrally acting reversible acetylcholinesterase inhibitor. In order to investigate the stability of drug and formed degradation products, a forced degradation study of drug sample and finished product under different forced degradation conditions has been conducted. Donepezil hydrochloride and donepezil tablets were subjected to stress degradation conditions recommended by International Conference on Harmonization (ICH). Donepezil hydrochloride solutions were subjected to acid and alkali hydrolysis, chemical oxidation and thermal degradation. Significant degradation was observed under alkali hydrolysis and oxidative degradation conditions. Additional degradation products were observed under the conditions of oxidative degradation. The degradation products observed during forced degradation studies were monitored using the high performance liquid chromatography (HPLC) method developed. The parent method was modified in order to obtain LC-MS compatible method which was used to identify the degradation products from forced degradation samples using high resolution mass spectrometry. The mass spectrum provided the precise mass from which derived molecular formula of drug substance and degradation products formed and proved the specificity of the method unambiguously. [Projekat Ministarstva nauke Republike Srbije, br. 172013]

Electrochemical decolorization of the Reactive Orange 16 was studied using dimensionally stable Ti/PtOx anode in the chloride containing solution. Different reaction parameters, agitation speed, applied current, sodium chloride concentration, and dye concentration was varied and optimum electrolysis conditions were suggested. The hypohlorous acid was suggested to be an active species in the electrochemical decolorization. Reaction was also studied using UV-Vis spectrophotometry, high-pressure liquid chromatography (HPLC), and total organic carbon (TOC) and total nitrogen (TN) analyses. [Projekat Ministarstva nauke Republike Srbije, br. ON172013 i br. ON172046]

An isocratic, reversed-phase liquid chromatographic method was applied for the investigation of the degradation products of amlodipine besylate under the stressed conditions in solution. Amlodipine besylate stock solutions were subjected to acid and alkali hydrolysis, chemical oxidation and photodegradation as well as to the electrochemical degradation by cyclic voltammetry in 0.05 mol/L NaHCO3 on gold electrode. The total degradation of amlodipine besylate was achieved in 5 mol/L NaOH at 80°C for 6 h and the compound with molecular formula C15H16NOCl was identified as a main degradation product. Under acidic (5 mol/L HCl at 80°C for 6 h) stress conditions 75.2% of amlodipine besylate degradation was recorded. Oxidative degradation in the solution of 3% H2O2-methanol 80:20 at 80°C for 6 h showed that amlodipine besylate degraded to 80.1%. After 14 days of expose in photostability chamber amlodipine besylate solution showed degradation of 32.2%. In electrochemical degradation after 9 hours of cyclization the beginning of amlodipine oxidation was shifted for 200 mV to more negative potentials, with the degradation of 66.5%. Mass spectrometry analysis confirmed the presence of dehydro amlodipine derivate with molecular formula C20H23N2O5Cl in oxidative and acidic conditions while in electrochemical degradation was detected in traces. [Projekat Ministarsva nauke Republike Srbije, br. 172013]

Flotation reagents can be transformed to industrial waste if they are stored for a long period of time. Also, if synthesis or drying process is not performed under defined conditions in industrial plants, which produce flotation reagents, batch of waste may arise and be stored as a waste. The chemical composition of this waste depends on the phase in which it was created, but typically includes: unreacted alkali hydroxide, solvent - alcohol and trithiocarbonate and oxidation product - dixanthogenate. In this paper a new laboratory procedure for the treatment of such wastes is described. The identification and separation of industrial waste components is also included. From the separated dixantogenate and xanthate a laboratory synthesis of thioncarbamates is given. In addition, a semi-industrial treatment of waste xanthate is presented. Synthesis of N-alkyl and N,N-dialkyl-O-isobutylthioncarbamates were obtained from the filtrate obtained in the first step. As a by-product, sodium thioglycolate was produced. This by-product is transformed to a thioglycolic acid by the addition of an acid. Also, the synthesis of thioncarbamates from dixanthogenates, isolated from industrial waste as a cake, is desribed. Described waste treatment is additionally interesting due to the production of sulphur as another by-product. Laboratory synthesis gave thioncarbamates in yields from 69.7 to 87.7 %, while the semi-industrial process for the selected batches produced thioncarbamates in yields from 74.2 to 80.5 %. Taking into account the importance of the synthesized compounds as selective flotation reagents, a new procedure of their synthesis from industrial waste is characterized by good yields and purity of the obtained compounds, the simplicity of process, low environmental impact and short reaction times of synthesis. [Projekat Ministarstva nauke Republike Srbije, br. III 43007]

Electrocatalytic decolorization of the arylazo pyridone dyes has been investigated in the presence of sodium chloride using DSA Ti/PtOx electrode in the diluted sodium hydroxide. Decolorization can be attributed to the indirect oxidation of the investigated dyes by the electrogenerated hypochlorite formed from the chloride oxidation. Electrochemical decolorization has been investigated for the different sodium hydroxide concentration in the range from 40 mg dm-3 to 4 g dm-3, sodium chloride concentration in the range from 15 to 40 g dm-3, agitation speed in the range from 150 to 500 rpm, currents in the range of 100 to 250 mA, and dye concentration from 5 to 20 mg dm-3. The optimum electrolysis conditions have been suggested. Effect of substituents on the reaction rate has also been studied. [Projekat Ministarstva nauke Republike Srbije, br. OI172013, OI172046]

2-Pyridones are important heterocyclic compounds that are widely used in medical chemistry, and their various derivatives have significant biological and medical applications. In this paper, the synthesis of 2-pyridones as well as 2-pyridone based compounds such as 2-quinolones using microwave assisted organic chemistry is reviewed. The review is divided in three parts. In the first part, microwave synthesis of 2-pyridones according to the type of condensation is discussed. In the second part, microwave assisted synthesis of 2-quionolones is listed. At the end of the review several examples of microwave synthesis of other 2-pyridone based compounds (ring fused N-substituted 2-pyridones) are given. [Projekat Ministarstva nauke Republike Srbije, br. 172013]

Linear free energy relationships (LFER) were applied to the IR, 1H and 13C NMR spectral data of N-(substituted phenyl)-2-cyanoacetamides. A variety of substituents were employed for phenyl substitution and fairly good correlations were obtained using the simple Hammett and the Hammett-Taft dual substituent parameter equations. The correlation results of the substituent induced 13C NMR chemical shifts (SCS) of the C1, C=O and N-H atom indicated different sensitivity with respect to electronic substituent effects. A better correlation of the SCSC=O with a combination of electrophilic and nucleophilic substituent constants indicated a significant contribution of extended resonance interaction (π-delocalization) within the π1-unit. The conformations of the investigated compounds were studied using the DFT B3LYP/6-311G method and, together with the results of 13C NMR and IR spectroscopic studies, a better insight into the influence of such a structure on the transmission of electronic substituent effects was obtained.

3-Cyano-4-ethoxymethyl-6-methyl-2-pyridone is an important precursor in the synthesis of vitamin B6, obtained in the addition reaction between 2-cyanoacetamide and 1-ethoxy-2,4-pentanedione catalyzed by lipase from Candida rugosa (triacylglycerol ester hydrolases, EC 3.1.1.3). This work shows new experimental data and mathematical modeling of lipase catalyzed synthesis of 3-cyano-4-ethoxymethyl-6-methyl-2-pyridone, starting from 1-ethoxy-2,4-pentanedione and 2-cyanoacetamide. Kinetic measurements were done at 50 oC with enzyme concentration of 1.2 % w/v. Experimental results were fitted with two kinetic models: the ordered bi-ter and ping-pong bi-ter model, and the initial rates of the reaction were found to correlate best with a ping-pong bi-ter mechanism with inhibition by 2-cyanoacetamide. Obtained specificity constants indicated that lipase from C. rugosa had higher affinity towards 1-ethoxy-2,4-pentanedione and less bulky substrates. [Projekat Ministarstva nauke Republike Srbije, br. 172013, br. III 46010 and br. 172049]

In the last three or four decades disperse dyes derived from pyridones (in particular azo pyridone dyes) have gained in importance, and are widely used in various fields. These compounds have excellent coloration properties, and are suitable for the dyeing of polyester fabrics. Basic features of these dyes are simplicity of their synthesis by diazotation and azo coupling. They generally have high molar extinction coefficient with medium to high light and wet fastness. The absorption maxima of these dyes show their visible absorption wavelength ranging from yellow to orange, which can be attributed to poorly delocalized electrons in the pyridone ring. However, there are several dyes with deep colors such as red or violet. Pyridone dyes with alkyl and aryl groups in ortho position to azo group show 2-pyridone/2-hydroxypyridine tautomerism, while those containing OH and NHR groups conjugated with the azo group show azo-hydrazone tautomerism. Determining azo-hydrazone tautomerism could be therefore interesting, since the tautomers have different physico-chemical properties and most importantly different coloration. The literature on azo-hydrazone tautomerism, determination of equilibrium position, and investigation of substituent and solvent influence on tautomerism has been summarized in the presented review. The general conclusion is that the equilibrium between two tautomers is influenced by the structure of the compounds and by the solvents used. The tautomeric behavior patterns of the arylazo pyridone dyes in the reviewed literature has been studied using various instrumental techniques, including FT-IR, UV-vis, and NMR spectroscopy. The quantum chemical calculations related to the azo-hydrazon tautomerism have also been included. A large number of pyridone dyes exist in hydrazone form in solid state, while in solvents there is a mixture of tautomers. In addition, the X-ray single-crystal diffraction data analysis of some commercial pyridone dyes has been discussed concluding that they all crystallize in the hydrazone form.

The catalytic abilities of gold electrode were tested for the quantitative determination of amphetamine (A) and 3,4-methylenedioxy-N-methylamphetamine (MDMA) standards by their oxidation using cyclic voltammetry (CV). The value of the oxidative currents of A and MDMA standards at 0.80 V vs. SCE in 0.05 M NaHCO3 at the scan rate of 50 mV/s is linear function of concentration in range of 110.9-258.9 mM and 38.7-229.2 mM, respectively. Square wave voltammetry (SWV) revealed linear increase of current with concentration of MDMA (range 30.9-91.6 mM) and thus quantitative determination of amphetamine derivates. SWV analysis is successfully performed in spiked urine samples as well. A and MDMA in the presence of sucrose and as a content in illegally produced tablets were also analyzed. The voltammetric determination of A and MDMA derivatives using CV and SWV at gold electrode is a rapid, selective and simple procedure and its accuracy was confirmed with reference method, high performance liquid chromatography (HPLC). The spiked urine samples analysis offers additional possibility for the rapid detection of A and MDMA in human urine.