Search results for: peroxidase mimic activity towards oxidation of pyrogallol
Commenced in January 2007
Frequency: Monthly
Edition: International
Paper Count: 6921

Search results for: peroxidase mimic activity towards oxidation of pyrogallol

6921 Oxidovanadium(IV) and Dioxidovanadium(V) Complexes: Efficient Catalyst for Peroxidase Mimetic Activity and Oxidation

Authors: Mannar R. Maurya, Bithika Sarkar, Fernando Avecilla

Abstract:

Peroxidase activity is possibly successfully used for different industrial processes in medicine, chemical industry, food processing and agriculture. However, they bear some intrinsic drawback associated with denaturation by proteases, their special storage requisite and cost factor also. Now a day’s artificial enzyme mimics are becoming a research interest because of their significant applications over conventional organic enzymes for ease of their preparation, low price and good stability in activity and overcome the drawbacks of natural enzymes e.g serine proteases. At present, a large number of artificial enzymes have been synthesized by assimilating a catalytic center into a variety of schiff base complexes, ligand-anchoring, supramolecular complexes, hematin, porphyrin, nanoparticles to mimic natural enzymes. Although in recent years a several number of vanadium complexes have been reported by a continuing increase in interest in bioinorganic chemistry. To our best of knowledge, the investigation of artificial enzyme mimics of vanadium complexes is very less explored. Recently, our group has reported synthetic vanadium schiff base complexes capable of mimicking peroxidases. Herein, we have synthesized monoidovanadium(IV) and dioxidovanadium(V) complexes of pyrazoleone derivateis ( extensively studied on account of their broad range of pharmacological appication). All these complexes are characterized by various spectroscopic techniques like FT-IR, UV-Visible, NMR (1H, 13C and 51V), Elemental analysis, thermal studies and single crystal analysis. The peroxidase mimic activity has been studied towards oxidation of pyrogallol to purpurogallin with hydrogen peroxide at pH 7 followed by measuring kinetic parameters. The Michaelis-Menten behavior shows an excellent catalytic activity over its natural counterparts, e.g. V-HPO and HRP. The obtained kinetic parameters (Vmax, Kcat) were also compared with peroxidase and haloperoxidase enzymes making it a promising mimic of peroxidase catalyst. Also, the catalytic activity has been studied towards the oxidation of 1-phenylethanol in presence of H2O2 as an oxidant. Various parameters such as amount of catalyst and oxidant, reaction time, reaction temperature and solvent have been taken into consideration to get maximum oxidative products of 1-phenylethanol.

Keywords: oxovanadium(IV)/dioxidovanadium(V) complexes, NMR spectroscopy, Crystal structure, peroxidase mimic activity towards oxidation of pyrogallol, Oxidation of 1-phenylethanol

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6920 Positive effect of Cu2+ and Ca2+ on the Thermostability of Bambara Groundnut Peroxidase A6, and its Catalytic Efficiency Toward the Oxidation of 3,3,5,5 -Tetramethyl Benzidine

Authors: Yves Mann Elate Lea Mbassi, Marie Solange Evehe Bebandoue, Wilfred Fon Mbacham

Abstract:

Improving the catalytic performance of enzymes has been a long-standing theme of analytical biochemistry research. Induction of peroxidase activity by metals is a common reaction in higher plants. We thought that this increase in peroxidase activity may be due, on the one hand, to the stimulation of the gene expression of these enzymes but also to a modification of their chemical reactivity following the binding of some metal ions on their active site. We tested the effect of some metal salts (MgCl₂, MnCl₂, ZnCl₂, CaCl₂ and CuSO₄) on the activity and thermostability of peroxidase A6, a thermostable peroxidase that we discovered and purified in a previous study. The chromogenic substrate used was 3,3′,5,5′-tetramethylbenzidine. Of all the metals tested for their effect on A6, only magnesium and copper had a significant effect on the activity of the enzyme at room temperature. The Mann-Whitney test shows a slight inhibitory effect of activity by the magnesium salt (P = 0.043), while the activity of the enzyme is 5 times higher in the presence of the copper salt (P = 0.002). Moreover, the thermostability of peroxidase A6 is increased when calcium and copper salts are present. The activity in the presence of CaCl₂ is 8 times higher than the residual activity of the enzyme alone after incubation at 80°C for 10 min and 35 times higher in the presence of CuSO4 under the same conditions. In addition, manganese and zinc salts slightly reduce the thermostability of the enzyme. The activity and structural stability of peroxidase A6 can clearly be activated by Cu₂+, which therefore enhance the oxidation of 3,3′,5,5′-tetramethylbenzidine, which was used in this study as a chromogenic substrate. Ca₂+ likely has a more stabilizing function for the catalytic site.

Keywords: peroxidase activity, copper ions, calcium ions, thermostability

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6919 Optimization of Pyrogallol Based Manganese / Ferroin Catalyzed Nonlinear Chemical Systems and Interaction with Monomeric and Polymeric Entities

Authors: Ghulam Mustafa Peerzada, Shagufta Rashid, Nadeem Bashir

Abstract:

These the influence of initial reagent concentrations on the Belousov-Zhabotinsky (BZ) system with Mn2+/Mn3+ as redox catalyst, inorganic bromate as oxidant and pyrogallol as organic substrate was studied. The reactions were monitored by potentiometery in oxidation reduction potential (ORP) mode. The aforesaid reagents were mixed with varying concentrations to evolve the optimal concentrations at which the reaction system exhibited better oscillations. The various oscillatory parameters such as induction period (tin), time period (tp), frequency (v), amplitude (A) and number of oscillations (n) were derived and the dependence of concentration of the reacting species on these oscillatory parameters was interpreted on the basis of the Field-Koros-Noyes mechanism. Ferroin based BZ system with pyrogallol as organic substrate was optimized under CSTR condition at temperature of 30±0.1oC Effect of molecules like monomer and polymer as additives to the system was checked and their interaction with the system was also studied. It has been observed that the monomer affects the time period, while the polymer has its effect on the amplitude of oscillations because of monomer’s interaction with the bromine and polymer’s with that of the Ferroin.

Keywords: Belousov Zhabotinsky reaction, oscillatory parameters, polymer, pyrogallol

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6918 High Catalytic Activity and Stability of Ginger Peroxidase Immobilized on Amino Functionalized Silica Coated Titanium Dioxide Nanocomposite: A Promising Tool for Bioremediation

Authors: Misha Ali, Qayyum Husain, Nida Alam, Masood Ahmad

Abstract:

Improving the activity and stability of the enzyme is an important aspect in bioremediation processes. Immobilization of enzyme is an efficient approach to amend the properties of biocatalyst required during wastewater treatment. The present study was done to immobilize partially purified ginger peroxidase on amino functionalized silica coated titanium dioxide nanocomposite. Interestingly there was an enhancement in enzyme activity after immobilization on nanosupport which was evident from effectiveness factor (η) value of 1.76. Immobilized enzyme was characterized by transmission electron microscopy, scanning electron microscopy and Fourier transform infrared spectroscopy. Immobilized peroxidase exhibited higher activity in a broad range of pH and temperature as compared to free enzyme. Also, the thermostability of peroxidase was strikingly improved upon immobilization. After six repeated uses, the immobilized peroxidase retained around 62% of its dye decolorization activity. There was a 4 fold increase in Vmax of immobilized peroxidase as compared to free enzyme. Circular dichroism spectroscopy demonstrated conformational changes in the secondary structure of enzyme, a possible reason for the enhanced enzyme activity after immobilization. Immobilized peroxidase was highly efficient in the removal of acid yellow 42 dye in a stirred batch process. Our study shows that this bio-remediating system has remarkable potential for treatment of aromatic pollutants present in wastewater.

Keywords: acid yellow 42, decolorization, ginger peroxidase, immobilization

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6917 Optimization of Process Parameters for Peroxidase Production by Ensifer Species

Authors: Ayodeji O. Falade, Leonard V. Mabinya, Uchechukwu U. Nwodo, Anthony I. Okoh

Abstract:

Given the high utility of peroxidase in several industrial processes, the search for novel microorganisms with enhanced peroxidase production capacity is of keen interest. This study investigated the process conditions for optimum peroxidase production by Ensifer sp, new ligninolytic proteobacteria with peroxidase production potential. Also, some agricultural residues were valorized for peroxidase production under solid state fermentation. Peroxidase production was optimum at an initial medium pH 7, incubation temperature of 30 °C and agitation speed of 100 rpm using alkali lignin fermentation medium supplemented with guaiacol as the most effective inducer and ammonium sulphate as the best inorganic nitrogen. Optimum peroxidase production by Ensifer sp. was attained at 48 h with specific productivity of 12.76 ± 1.09 U mg⁻¹. Interestingly, probable laccase production was observed with optimum specific productivity of 12.76 ± 0.45 U mg⁻¹ at 72 h. The highest peroxidase yield was observed with sawdust as solid substrate under solid state fermentation. In conclusion, Ensifer sp. possesses the capacity for enhanced peroxidase production that can be exploited for various biotechnological applications.

Keywords: catalase-peroxidase, enzyme production, peroxidase, polymerase chain reaction, proteobacteria

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6916 Bienzymatic Nanocomposites Biosensors Complexed with Gold Nanoparticles, Polyaniline, Recombinant MN Peroxidase from Corn, and Glucose Oxidase to Measure Glucose

Authors: Anahita Izadyar

Abstract:

Using a recombinant enzyme derived from corn and a simple modification, we are fabricating a facile, fast, and cost-beneficial novel biosensor to measure glucose. We are applying Plant Produced Mn Peroxidase (PPMP), glucose oxidase (GOx), polyaniline (PANI) as conductive polymer and gold nanoparticles (AuNPs) on Au electrode using electrochemical response to detect glucose. We applied the entrapment method of enzyme composition, which is generally used to immobilize conductive polymer and facilitate electron transfer from the enzyme oxidation-reduction center to the sample solution. In this work, the oxidation of glucose on the modified gold electrode was quantified with Linear Sweep Voltammetry(LSV). We expect that the modified biosensor has the potential for monitoring various biofluids.

Keywords: plant-produced manganese peroxidase, enzyme-based biosensors, glucose, modified gold nanoparticles electrode, polyaniline

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6915 Isolation of Soil Thiobacterii and Determination of Their Bio-Oxidation Activity

Authors: A. Kistaubayeva, I. Savitskaya, D. Ibrayeva, M. Abdulzhanova, N. Voronova

Abstract:

36 strains of sulfur-oxidizing bacteria were isolated in Southern Kazakhstan soda-saline soils and identified. Screening of strains according bio-oxidation (destruction thiosulfate to sulfate) and enzymatic (Thiosulfate dehydrogenises and thiosulfate reductase) activity was conducted. There were selected modes of aeration and culture conditions (pH, temperature), which provide optimum harvest cells. These strains can be used in bio-melioration technology.

Keywords: elemental sulfur, oxidation activity, Тhiobacilli, fertilizers, heterotrophic S-oxidizers

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6914 Effect of Cadmium on Oxidative Enzymes Activity in Persian Clover (Trifolium resupinatum L.)

Authors: Homayun Ghasemi, Mojtaba Yousefirad, Mozhgan Farzamisepehr

Abstract:

Heavy metals are among soil pollutant resources that in case of accumulation in the soil and absorption by the plant, enter into the food chain and poison the plants or the people who consume those plants. This research was performed in order to examine the role of cadmium as a heavy metal in the activity of catalase and peroxidase as well as protein concentration in Trifolium resupinatum L. based on a randomized block design with three repetitions. The used treatments included consumption of Cd (NO3)2 at four levels, namely, 0, 100, 200, and 300 ppm. The plants under study were treated for 10 days. The results of the study showed that catalase activity decreased by the increase of cadmium. Moreover, peroxidase activity increased by an increase inthe consumption of cadmium. The analysis of protein level showed that plantlet protein decreased in high cadmium concentrations. The findings also demonstrated that cadmium concentration in roots was higher than in shoots.

Keywords: catalase, heavy metal, peroxidase, protein

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6913 Effects of Garlic (Allium sativum) Juice on Semen Oxidation in Male Rats

Authors: Jamshid Ghiasi Ghalehkandi, Naser Maheri Sis, Yahya Ebrahimnezhad, Shahin Hassanpour

Abstract:

The objective of present study was to examine the effects of fresh garlic juice on semen malondialdehyde (MDA), superoxide dismutase (SOD), glutathione peroxidase (GPx) and total antioxidant status (TAS) in male rats. Fifty-four male rats (230-250 g) were allocated into 3 treatment groups (each include 3 groups and 6 replicate). Group 1 served as water control. In group 2, rats were gavaged with 60 mg/kg garlic juice. In group 3, rats were offered 120 mg/kg garlic juice. Animals received treatments orally and ad libitum access to chow pellets and fresh water. After 4 weeks, animals were killed, testes were taken out and semen samples were used to determine MDA, SOD, GPx and TAS activity. According to the results, garlic juice (120 mg/kg) significantly declined semen MDA activity compared to control group (P<0.05). These results suggest that presumably garlic juice protects semen oxidation in rat testes.

Keywords: garlic juice, chromium chloride, semen, rat

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6912 Enhanced Peroxidase Production by Raoultella Species

Authors: Ayodeji O. Falade, Leonard V. Mabinya, Uchechukwu U. Nwodo, Anthony I. Okoh

Abstract:

Given the high-utility of peroxidase, its production in large amount is of utmost importance. Over the years, actinomycetes have been the major peroxidase-producing bacteria. Consequently, other classes of bacteria with peroxidase production potentials are underexplored. This study, therefore, sought to enhance peroxidase production by a Raoultella species, a new ligninolytic proteobacteria strain, by determining the optimum culture conditions (initial pH, incubation temperature and agitation speed) for peroxidase production under submerged fermentation using the classical process of one variable at a time and supplementing the fermentation medium with some lignin model and inorganic nitrogen compounds. Subsequently, the time-course assay was carried out under optimized conditions. Then, some agricultural residues were valorized for peroxidase production under solid state fermentation. Peroxidase production was optimal at initial pH 5, incubation temperature of 35 °C and agitation speed of 150 rpm with guaiacol and ammonium chloride as the best inducer and nitrogen supplement respectively. Peroxidase production by the Raoultella species was optimal at 72 h with specific productivity of 16.48 ± 0.89 U mg⁻¹. A simultaneous production of a non-peroxide dependent extracellular enzyme which suggests probable laccase production was observed with specific productivity of 13.63 ± 0.45 U mg⁻¹ while sawdust gave the best peroxidase yield under solid state fermentation. In conclusion, peroxidase production by the Raoultella species was increased by 3.40-fold.

Keywords: enzyme production, ligninolytic bacteria, peroxidase, proteobacteria

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6911 Alumina Supported Cu-Mn-Cr Catalysts for CO and VOCs oxidation

Authors: Krasimir Ivanov, Elitsa Kolentsova, Dimitar Dimitrov, Petya Petrova, Tatyana Tabakova

Abstract:

This work studies the effect of chemical composition on the activity and selectivity of γ–alumina supported CuO/ MnO2/Cr2O3 catalysts toward deep oxidation of CO, dimethyl ether (DME) and methanol. The catalysts were prepared by impregnation of the support with an aqueous solution of copper nitrate, manganese nitrate and CrO3 under different conditions. Thermal, XRD and TPR analysis were performed. The catalytic measurements of single compounds oxidation were carried out on continuous flow equipment with a four-channel isothermal stainless steel reactor. Flow-line equipment with an adiabatic reactor for simultaneous oxidation of all compounds under the conditions that mimic closely the industrial ones was used. The reactant and product gases were analyzed by means of on-line gas chromatographs. On the basis of XRD analysis it can be concluded that the active component of the mixed Cu-Mn-Cr/γ–alumina catalysts consists of at least six compounds – CuO, Cr2O3, MnO2, Cu1.5Mn1.5O4, Cu1.5Cr1.5O4 and CuCr2O4, depending on the Cu/Mn/Cr molar ratio. Chemical composition strongly influences catalytic properties, this influence being quite variable with regards to the different processes. The rate of CO oxidation rapidly decrease with increasing of chromium content in the active component while for the DME was observed the reverse trend. It was concluded that the best compromise are the catalysts with Cu/(Mn + Cr) molar ratio 1:5 and Mn/Cr molar ratio from 1:3 to 1:4.

Keywords: Cu-Mn-Cr oxide catalysts, volatile organic compounds, deep oxidation, dimethyl ether (DME)

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6910 Oxidation of Alcohols Types Using Nano-Graphene Oxide (NGO) as Heterogeneous Catalyst

Authors: Ali Gharib, Leila Vojdanifard, Nader Noroozi Pesyan, Mina Roshani

Abstract:

We describe an efficient method for oxidation of alcohols to related aldehydes and ketones by hydrogen peroxide as oxidizing agent, under reflux conditions. Nano-graphene oxide (NGO) as a heterogeneous catalyst was used and had their activity compared with other various catalysts. This catalyst was found to be an excellent catalyst for oxidation of alcohols. The effects of various parameters, including catalyst type, nature of the substituent in the alcohols and temperature, on the yield of the carboxylic acids were studied. Nano-graphene oxide was synthesized by the oxidation of graphite powders. This nanocatalyst was found to be highly efficient in this reaction and products were obtained in good to excellent yields. The recovered nano-catalyst was successfully reused for several runs without significant loss in its catalytic activity.

Keywords: nano-graphene oxide, oxidation, aldehyde, ketone, catalyst

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6909 Alumina Supported Copper-Manganese-Cobalt Catalysts for CO and VOCs Oxidation

Authors: Elitsa Kolentsova, Dimitar Dimitrov, Vasko Idakiev, Tatyana Tabakova, Krasimir Ivanov

Abstract:

Formaldehyde production by selective oxidation of methanol is an important industrial process. The main by-products in the waste gas are CO and dimethyl ether (DME). The idea of this study is to combine the advantages of both Cu-Mn and Cu-Co catalytic systems by obtaining a new mixed Cu-Mn-Co catalyst with high activity and selectivity at the simultaneous oxidation of CO, methanol, and DME. Two basic Cu-Mn samples with high activity were selected for further investigation: (i) manganese-rich Cu-Mn/γ–Al2O3 catalyst with Cu/Mn molar ratio 1:5 and (ii) copper-rich Cu-Mn/γ-Al2O3 catalyst with Cu/Mn molar ratio 2:1. Manganese in these samples was replaced by cobalt in the whole concentration region, and catalytic properties were determined. The results show a general trend of decreasing the activity toward DME oxidation and increasing the activity toward CO and methanol oxidation with the increase of cobalt up to 60% for both groups of catalyst. This general trend, however, contains specific features, depending on the composition of the catalyst and the nature of the oxidized gas. The catalytic activity of the sample with Cu/(Mn+Co) molar ratio of 2:1 is gradually changed with increasing the cobalt content. The activity of the sample with Cu/(Mn+Co) molar ratio of 1: 5 passes through a maximum at 60% manganese replacement by cobalt, probably due to the formation of highly dispersed Co-based spinel structures (Co3O4 and/or MnCo2O4). In conclusion, the present study demonstrates that the Cu-Mn-Co/γ–alumina supported catalysts have enhanced activity toward CO, methanol and DME oxidation. Cu/(Mn+Co) molar ratio 1:5 and Co/Mn molar ratio 1.5 in the active component can ensure successful oxidation of CO, CH3OH and DME. The active component of the mixed Cu-Mn-Co/γ–alumina catalysts consists of at least six compounds - CuO, Co3O4, MnO2, Cu1.5Mn1.5O4, MnCo2O4 and CuCo2O4, depending on the Cu/Mn/Co molar ratio. Chemical composition strongly influences catalytic properties, this effect being quite variable with regards to the different processes.

Keywords: Cu-Mn-Co catalysts, oxidation, carbon oxide, VOCs

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6908 Comparative Study of Isothermal and Cyclic Oxidation on Titanium Alloys

Authors: Poonam Yadav, Dong Bok Lee

Abstract:

Isothermal oxidation at 800°C for 50h and Cyclic oxidation at 600°C and 800°C for 40h of Pure Ti and Ti64 were performed in a muffle furnace. In Cyclic oxidation, massive scale spallation occurred, and the oxide scale cracks and peels off were observed at high temperature, it represents oxide scale that formed during cyclic oxidation was spalled out owing to stresses due to thermal shock generated during repetitive oxidation and subsequent cooling. The thickness of scale is larger in cyclic oxidation than the isothermal case. This is due to inward diffusion of oxygen through oxide scales and/or pores and cracks in cyclic oxidation.

Keywords: cyclic, diffusion, isothermal, cyclic

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6907 Synthesis and Characterization of Zinc (II) Complex and Its Catalytic Activity on C(SP3)-H Oxidation Reactions

Authors: Yalçın Kılıç, İbrahim Kani

Abstract:

The conversion of hydrocarbons to carbonyl compounds by oxidation reaction is one of the most important reactions in the synthesis of fine chemicals. As a result of the oxidation of hydrocarbons containing aliphatic sp3-CH groups in their structures, aldehydes, ketones or carboxylic acids can be obtained. In this study, OSSO-type 2,2'-[1,4-butanedylbis(thio)]bis-benzoic acid (tsabutH2) ligand and [Zn(µ-tsabut)(phen)]n complex (where phen = 1,10-phenantroline) were synthesized and their structures were characterized by single crystal x-ray diffraction method. The catalytic efficiency of the complex in the catalytic oxidation studies of organic compounds such as cyclohexane, ethylbenzene, diphenylmethane, and p-xylene containing sp3-C-H in its structure was investigated.

Keywords: metal complex, OSSO-type ligand, catalysis, oxidation

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6906 Performance of Bimetallic Catalyst in the Oxidation of Volatile Organic Compounds

Authors: Faezeh Aghazadeh

Abstract:

The catalytic activity of Pt/γ-Al₂O₃ and Pt-Fe/γ-Al₂O₃ catalysts was investigated to bring about the complete oxidation of 2-Propanol. Among them, Pt-Fe/γ-Al₂O₃ was found to be the most promising catalyst based on activity. The catalysts were characterized by (XRD), (SEM), (TEM) and ICP-AES techniques. Iron loadings on Pt/γ-Al₂O₃ had a great effect on catalytic activity, and Pt-Fe/γ-Al₂O₃ (1.75 wt% Fe) catalyst at calcination temperature 300°C was observed to be the most active, which might be contributed to the favorable synergetic effects between Pt and Fe, high activity and the well-dispersed bimetallic phase. The combustion of 2-Propanol in the vapor phase was carried out in a conventional flow U-shape glass reactor used in the differential mode at atmospheric pressure. 2-Propanol was analyzed by a gas chromatograph VARIAN 3800 CX equipped with an FID. As observed, better performance and activity were observed for Pt-Fe/Al₂O₃ bimetallic catalyst. These results indicate that the high dispersion on support gives a positive effect on catalytic activity.

Keywords: volatile organic compounds, bimetallic catalyst, catalytic activity, low temperature

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6905 Influence of Synthetic Antioxidant in the Iodine Value and Acid Number of Jatropha Curcas Biodiesel

Authors: Supriyono, Sumardiyono

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Biodiesel is one of the alternative fuels that promising for substituting petrodiesel as energy source which is have advantage on sustainability and eco-friendly. Due to the raw material that tend to decompose during storage, biodiesel also have the same characteristic that tend to decompose and formed higher acid value which is the result of oxidation to double bond on a chain of ester. Decomposition of biodiesel due to oxidation reaction could prevent by introduce a small amount of antioxidant. The origin of raw materials and the process for producing biodiesel will determine the effectiveness of antioxidant. The quality degradation on biodiesel could evaluated by measuring iodine value and acid number of biodiesel. Biodiesel made from High Fatty Acid Jatropha curcas oil equality by using esterification and esterification process will stand on the quality by introduce 90 ppm pyrogallol powder on the biodiesel, which could extend the quality from 2 hours to more than 6 hours in rancimat test evaluation.

Keywords: biodiesel, antioxidant, iodine number, acid value

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6904 Alumina Supported Copper-Manganese Catalysts for Combustion of Exhaust Gases: Effect of Preparation Method

Authors: Krasimir Ivanov, Elitsa Kolentsova, Dimitar Dimitrov

Abstract:

The development of active and stable catalysts without noble metals for low temperature oxidation of exhaust gases remains a significant challenge. The purpose of this study is to determine the influence of the preparation method on the catalytic activity of the supported copper-manganese mixed oxides in terms of VOCs oxidation. The catalysts were prepared by impregnation of γ-Al2O3 with copper and manganese nitrates and acetates and the possibilities for CO, CH3OH and dimethyl ether (DME) oxidation were evaluated using continuous flow equipment with a four-channel isothermal stainless steel reactor. Effect of the support, Cu/Mn mole ratio, heat treatment of the precursor and active component loading were investigated. Highly active alumina supported Cu-Mn catalysts for CO and VOCs oxidation were synthesized. The effect of preparation conditions on the activity behavior of the catalysts was discussed. The synergetic interaction between copper and manganese species increases the activity for complete oxidation over mixed catalysts. Type of support, calcination temperature and active component loading along with catalyst composition are important factors, determining catalytic activity. Cu/Mn molar ratio of 1:5, heat treatment at 450oC and 20 % active component loading are the best compromise for production of active catalyst for simultaneous combustion of CO, CH3OH and DME.

Keywords: copper-manganese catalysts, CO, VOCs oxidation, exhaust gases

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6903 Copper (II) Complex of New Tetradentate Asymmetrical Schiff Base Ligand: Synthesis, Characterization, and Catecholase-Mimetic Activity

Authors: Cahit Demetgul, Sahin Bayraktar, Neslihan Beyazit

Abstract:

Metalloenzymes are enzyme proteins containing metal ions, which are directly bound to the protein or to enzyme-bound nonprotein components. One of the major metalloenzymes that play a key role in oxidation reactions is catechol oxidase, which shows catecholase activity i.e. oxidation of a broad range of catechols to quinones through the four-electron reduction of molecular oxygen to water. Studies on the model compounds mimicking the catecholase activity are very useful and promising for the development of new, more efficient bioinspired catalysts, for in vitro oxidation reactions. In this study, a new tetradentate asymmetrical Schiff-base and its Cu(II) complex were synthesized by condensation of 4-nitro-1,2-phenylenediamine with 6-formyl-7-hydroxy-5-methoxy-2-methylbenzopyran-4-one and by using an appropriate Cu(II) salt, respectively. The prepared compounds were characterized by elemental analysis, FT-IR, NMR, UV-Vis and magnetic susceptibility. The catecholase-mimicking activity of the new Schiff Base Cu(II) complex was performed for the oxidation of 3,5-di-tert-butylcatechol (3,5-DTBC) in methanol at 25 °C, where the electronic spectra were recorded at different time intervals. The yield of the quinone (3,5-DTBQ) was determined from the measured absorbance at 400 nm of the resulting solution. The compatibility of catalytic reaction with Michaelis-Menten kinetics was also investigated. In conclusion, we have found that our new Schiff Base Cu(II) complex presents a significant capacity to catalyze the oxidation reaction of the catechol to o-quinone.

Keywords: catecholase activity, Michaelis-Menten kinetics, Schiff base, transition metals

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6902 Electrochemical Sensor Based on Poly(Pyrogallol) for the Simultaneous Detection of Phenolic Compounds and Nitrite in Wastewater

Authors: Majid Farsadrooh, Najmeh Sabbaghi, Seyed Mohammad Mostashari, Abolhasan Moradi

Abstract:

Phenolic compounds are chief environmental contaminants on account of their hazardous and toxic nature on human health. The preparation of sensitive and potent chemosensors to monitor emerging pollution in water and effluent samples has received great consideration. A novel and versatile nanocomposite sensor based on poly pyrogallol is presented for the first time in this study, and its electrochemical behavior for simultaneous detection of hydroquinone (HQ), catechol (CT), and resorcinol (RS) in the presence of nitrite is evaluated. The physicochemical characteristics of the fabricated nanocomposite were investigated by emission-scanning electron microscopy (FE-SEM), energy-dispersive X-ray spectroscopy (EDS), and Brunauer-Emmett-Teller (BET). The electrochemical response of the proposed sensor to the detection of HQ, CT, RS, and nitrite is studied using cyclic voltammetry (CV), chronoamperometry (CA), differential pulse voltammetry (DPV), and electrochemical impedance spectroscopy (EIS). The kinetic characterization of the prepared sensor showed that both adsorption and diffusion processes can control reactions at the electrode. In the optimized conditions, the new chemosensor provides a wide linear range of 0.5-236.3, 0.8-236.3, 0.9-236.3, and 1.2-236.3 μM with a low limit of detection of 21.1, 51.4, 98.9, and 110.8 nM (S/N = 3) for HQ, CT and RS, and nitrite, respectively. Remarkably, the electrochemical sensor has outstanding selectivity, repeatability, and stability and is successfully employed for the detection of RS, CT, HQ, and nitrite in real water samples with the recovery of 96.2%–102.4%, 97.8%-102.6%, 98.0%–102.4% and 98.4%–103.2% for RS, CT, HQ, and nitrite, respectively. These outcomes illustrate that poly pyrogallol is a promising candidate for effective electrochemical detection of dihydroxybenzene isomers in the presence of nitrite.

Keywords: electrochemical sensor, poly pyrogallol, phenolic compounds, simultaneous determination

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6901 Investigating Water-Oxidation Using a Ru(III) Carboxamide Water Coordinated Complex

Authors: Yosra M. Badiei, Evelyn Ortiz, Marisa Portenti, David Szalda

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Water-oxidation half-reaction is a critical reaction that can be driven by a sustainable energy source (e.g., solar or wind) and be coupled with a chemical fuel making reaction which stores the released electrons and protons from water (e.g., H₂ or methanol). The use of molecular water-oxidation catalysts (WOC) allow the rationale design of redox active metal centers and provides a better understanding of their structure-activity-relationship. Herein, the structure of a Ru(III) complex bearing a doubly deprotonated N,N'-bis(aryl)pyridine-2,6-dicarboxamide ligand which contains a water molecule in its primary coordination sphere was elucidated by single-crystal X-ray diffraction. Further spectroscopic experimental data and pH-dependent electrochemical studies reveal its water-oxidation reactivity. Emphasis on mechanistic details for O₂ formation of this complex will be addressed.

Keywords: water-oxidation, catalysis, ruthenium, artificial photosynthesis

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6900 Mordenite as Catalyst Support for Complete Volatile Organic Compounds Oxidation

Authors: Yuri A. Kalvachev, Totka D. Todorova

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Zeolite mordenite has been investigated as a transition metal support for the preparation of efficient catalysts in the oxidation of volatile organic compounds (VOCs). The highly crystalline mordenite samples were treated with hydrofluoric acid and ammonium fluoride to get hierarchical material with secondary porosity. The obtained supports by this method have a high active surface area, good diffusion properties and prevent the extraction of metal components during catalytic reactions. The active metal phases platinum and copper were loaded by impregnation on both mordenite materials (parent and acid treated counterparts). Monometalic Pt and Cu, and bimetallic Pt/Cu catalysts were obtained. The metal phases were fine dispersed as nanoparticles on the functional porous materials. The catalysts synthesized in this way were investigated in the reaction of complete oxidation of propane and benzene. Platinum, copper and platinum/copper were loaded and there catalytic activity was investigated and compared. All samples are characterized by X-ray diffraction analysis, nitrogen adsorption, scanning electron microscopy (SEM), X-ray photoelectron measurements (XPS) and temperature programed reduction (TPR). The catalytic activity of the samples obtained is investigated in the reaction of complete oxidation of propane and benzene by using of Gas Chromatography (GC). The oxidation of three organic molecules was investigated—methane, propane and benzene. The activity of metal loaded mordenite catalysts for methane oxidation is almost the same for parent and treated mordenite as a support. For bigger molecules as propane and benzene, the activity of catalysts based on treated mordenite is higher than those based on parent zeolite.

Keywords: metal loaded catalysts, mordenite, VOCs oxidation, zeolites

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6899 Alumina Supported Copper-manganese Catalysts for Combustion of Exhaust Gases: Catalysts Characterization

Authors: Krasimir I. Ivanov, Elitsa N. Kolentsova, Dimitar Y. Dimitrov, Georgi V. Avdeev, Tatyana T. Tabakova

Abstract:

In recent research copper and manganese systems were found to be the most active in CO and organic compounds oxidation among the base catalysts. The mixed copper manganese oxide has been widely studied in oxidation reactions because of their higher activity at low temperatures in comparison with single oxide catalysts. The results showed that the formation of spinel CuxMn3−xO4 in the oxidized catalyst is responsible for the activity even at room temperature. That is why most of the investigations are focused on the hopcalite catalyst (CuMn2O4) as the best copper-manganese catalyst. Now it’s known that this is true only for CO oxidation, but not for mixture of CO and VOCs. The purpose of this study is to investigate the alumina supported copper-manganese catalysts with different Cu/Mn molar ratio in terms of oxidation of CO, methanol and dimethyl ether. The catalysts were prepared by impregnation of γ-Al2O3 with copper and manganese nitrates and the catalytic activity measurements were carried out in continuous flow equipment with a four-channel isothermal stainless steel reactor. Gas mixtures on the input and output of the reactor were analyzed with a gas chromatograph, equipped with FID and TCD detectors. The texture characteristics were determined by low-temperature (- 196 oС) nitrogen adsorption in a Quantachrome Instruments NOVA 1200e (USA) specific surface area&pore analyzer. Thermal, XRD and TPR analyses were performed. It was established that the active component of the mixed Cu-Mn/γ–alumina catalysts strongly depends on the Cu/Mn molar ratio. Highly active alumina supported Cu-Mn catalysts for CO, methanol and DME oxidation were synthesized. While the hopcalite is the best catalyst for CO oxidation, the best compromise for simultaneous oxidation of all components is the catalyst with Cu/Mn molar ratio 1:5.

Keywords: supported copper-manganese catalysts, CO, VOCs oxidation, combustion of exhaust gases

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6898 Electrochemical Studies of Nickel Nanoparticles Decorated the Surface of Some Conducting Polymers for Glucose Oxidation in Biofuel Cells

Authors: Z. Khalifa, K. M. Hassan, M. Abdel Azzem

Abstract:

Potential strategies for deriving useful forms of renewable high density energy from abundant energy stored in carbohydrates is direct conversion of glucose (GLU) to electrical power. A three novel versatile modified electrodes, synthesized by electrochemical polymerization of organic monomers on glassy carbon electrodes (GC), have been developed for biofuel cells results in stable and long-term power production. Electrocatalytic oxidation of glucose in alkaline solution on conducting polymers electrodes modified by incorporation of Ni nanoparticles (NiNPs) onto poly(1,5-aminonaphthalene) (1,5-PDAN), poly(1,8-diaminonaphthalene) (1,8-PDAN) and poly(1-amino-2-methyl-9,10-anthraquinone) (PAMAQ) was investigated. The electrocatalytic oxidation of glucose at NiNPs-modified 1,5-PDAN/GC, 1,8-PDAN/GC and PAMAQ/GC electrodes has been studied using voltammetry technique. The PDAN electrodes show a slight activity in the potential of interest. The prepared NiNPs/PAMAQ/GC catalyst showed a very interesting catalytic activity that was nicely comparable to the NiNPs/1,5-PDAN/GC, NiNPs/1,8-PDAN/GC modified electrodes. In advance, both shows a significant more catalytic activity compared to the reported data for electrodes for glucose electrocatalytic oxidation.

Keywords: biofuel cells, glucose oxidation, electrocatalysis, nanoparticles and modified electrodes

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6897 Isothermal and Cyclic Oxidation of the Ti-6Al-4V Alloy

Authors: Poonam Yadav, Dong Bok Lee

Abstract:

In this study, the Ti-6Al-4V alloy was isothermally and cyclically oxidized at 800oC for 40 hours in air, and its oxidation behavior was characterized in terms of its oxidation rate, scaling rate, and scale spallation tendency. The isothermal oxidation tests indicated that Ti-6Al-4V oxidized fast and almost linearly, forming thick oxide scales. However, the scales that formed during isothermal oxidation were adherent. The cyclic oxidation tests indicated that the scales that formed on Ti-6Al-4V were highly susceptible to spallation owing to the large growth stress arisen and the thermal stress imposed during thermal cyclings. The formed scales frequently delaminated into several pieces owing to the excessive stress aroused by the repetitive thermal shock. Particularly, excessive oxidation and heavy spallation occurred at the edge of Ti-6Al-4V during cyclic oxidation.

Keywords: cyclic, isothermal, oxidation, spallation

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6896 The Effect of Metabolites of Fusarium solani on the Activity of the PR-Proteins (Chitinase, β-1,3-Glucanase and Peroxidases) of Potato Tubers

Authors: A. K. Tursunova, O. V. Chebonenko, A. Zh. Amirkulova, A. O. Abaildayev, O. A. Sapko, Y. M. Dyo, A. Sh. Utarbaeva

Abstract:

Fusarium solani and its variants cause root and stem rot of plants. Dry rot is the most common disease of potato tubers during storage. The causative agents of fusariosis in contact with plants behave as antagonists, growth stimulants or parasites. The diversity of host-parasite relationships is explained by the parasite’s ability to produce a wide spectrum of biologically active compounds including toxins, enzymes, oligosaccharides, antibiotic substances, enniatins and gibberellins. Many of these metabolites contribute to the creation of compatible relations; others behave as elicitors, inducing various protective responses in plants. An important part of the strategy for developing plant resistance against pathogens is the activation of protein synthesis to produce protective ‘pathogenesis-related’ proteins. The family of PR-proteins known to confer the most protective response is chitinases (EC 3.2.1.14, Cht) and β-1,3-glucanases (EC 3.2.1.39, Glu). PR-proteins also include a large multigene family of peroxidases (EC 1.11.1.7, Pod), and increased activity of Pod and expression of the Pod genes leads to the development of resistance to a broad class of pathogens. Despite intensive research on the role of PR-proteins, the question of their participation in the mechanisms of formation of the F.solani–S.tuberosum pathosуstem is not sufficiently studied. Our aim was to investigate the effect of different classes of F. solani metabolites on the activity of chitinase, β-1,3-glucanases and peroxidases in tubers of Solanum tuberosum. Metabolite culture filtrate (CF) and cytoplasmic components were fractionated by extraction of the mycelium with organic solvents, salting out techniques, dialysis, column chromatography and ultrafiltration. Protein, lipid, carbohydrate and polyphenolic fractions of fungal metabolites were derived. Using enzymatic hydrolysis we obtained oligo glycans from fungal cell walls with different molecular weights. The activity of the metabolites was tested using potato tuber discs (d = 16mm, h = 5mm). The activity of PR-proteins of tubers was analyzed in a time course of 2–24 hours. The involvement of the analysed metabolites in the modulation of both early non-specific and late related to pathogenesis reactions was demonstrated. The most effective inducer was isolated from the CF (fraction of total phenolic compounds including naphtazarins). Induction of PR-activity by this fraction was: chitinase - 340-360%, glucanase - 435-450%, soluble forms of peroxidase - 400-560%, related forms of peroxidase - 215-237%. High-inducing activity was observed by the chloroform and acetonitrile extracts of the mycelium (induction of chitinase and glucanase activity was 176-240%, of soluble and bound forms of peroxidase - 190-400%). The fraction of oligo glycans mycelium cell walls of 1.2 kDa induced chitinase and β-1,3-glucanase to 239-320%; soluble forms and related peroxidase to 198-426%. Oligo glycans cell walls of 5-10 kDa had a weak suppressor effect - chitinase (21-25%) and glucanase (25-28%) activity; had no effect on soluble forms of peroxidase, but induced to 250-270% activity related forms. The CF polysaccharides of 8.5 kDa and 3.1 kDa inhibited synchronously the glucanase and chitinase specific response in step (after 24 hours at 42-50%) and the step response induced nonspecific peroxidase activity: soluble forms 4.8 -5.2 times, associated forms 1.4-1.6 times.

Keywords: fusarium solani, PR-proteins, peroxidase, solanum tuberosum

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6895 Structure-Activity Relationship of Gold Catalysts on Alumina Supported Cu-Ce Oxides for CO and Volatile Organic Compound Oxidation

Authors: Tatyana T. Tabakova, Elitsa N. Kolentsova, Dimitar Y. Dimitrov, Krasimir I. Ivanov, Yordanka G. Karakirova, Petya Cv. Petrova, Georgi V. Avdeev

Abstract:

The catalytic oxidation of CO and volatile organic compounds (VOCs) is considered as one of the most efficient ways to reduce harmful emissions from various chemical industries. The effectiveness of gold-based catalysts for many reactions of environmental significance was proven during the past three decades. The aim of this work was to combine the favorable features of Au and Cu-Ce mixed oxides in the design of new catalytic materials of improved efficiency and economic viability for removal of air pollutants in waste gases from formaldehyde production. Supported oxides of copper and cerium with Cu: Ce molar ratio 2:1 and 1:5 were prepared by wet impregnation of g-alumina. Gold (2 wt.%) catalysts were synthesized by a deposition-precipitation method. Catalysts characterization was carried out by texture measurements, powder X-ray diffraction, temperature programmed reduction and electron paramagnetic resonance spectroscopy. The catalytic activity in the oxidation of CO, CH3OH and (CH3)2O was measured using continuous flow equipment with fixed bed reactor. Both Cu-Ce/alumina samples demonstrated similar catalytic behavior. The addition of gold caused significant enhancement of CO and methanol oxidation activity (100 % degree of CO and CH3OH conversion at about 60 and 140 oC, respectively). The composition of Cu-Ce mixed oxides affected the performance of gold-based samples considerably. Gold catalyst on Cu-Ce/γ-Al2O3 1:5 exhibited higher activity for CO and CH3OH oxidation in comparison with Au on Cu-Ce/γ-Al2O3 2:1. The better performance of Au/Cu-Ce 1:5 was related to the availability of highly dispersed gold particles and copper oxide clusters in close contact with ceria.

Keywords: CO and VOCs oxidation, copper oxide, Ceria, gold catalysts

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6894 In vitro Inhibitory Action of an Aqueous Extract of Carob on the Release of Myeloperoxidase by Human Neutrophils

Authors: Kais Rtibi, Slimen Selmi, Jamel El-Benna, Lamjed Marzouki, Hichem Sebai

Abstract:

Background: Myeloperoxidase (MPO) is a hemic enzyme found in high concentrations in the primary neutrophils granules. In addition to its peroxidase activity, it has a chlorination activity, using hydrogen peroxide and chloride ions to form hypochlorous acid, a strong oxidant, capable of chlorinating molecules. Bioactive compounds contained in medicinal plants could limit the action of this enzyme to reduce the reactive oxygen species production and its chlorination activity. The purpose of this study is to evaluate the effect of the carob aqueous extract (CAE) on the release of MPO by human neutrophils in vitro and its activity following stimulation of these cells by PMA. Methods: Neutrophils were isolated by simple sedimentation using the Dextran/Ficoll method. After stimulation with phorbol 12-myristate 13-acetate (PMA), neutrophils release the MPO by degranulation. The effect of CAE on the release of MPO was analyzed by the Western blot technique, while, its activity was determined by biochemical method using the method of 3,3', 5,5'- Tetramethylbenzidine (TMB) and hydrogen peroxide. The data were expressed as mean ± SEM. Results: The carob aqueous extract causes a decrease in MPO quantity and activity in a concentration-dependent manner which leads to a reduction of the production of the ROS (reactive oxygen species) and the protection of the molecules against oxidation and chlorination mechanisms. Conclusion: Thanks to its richness in bioactive compounds, the aqueous extract of carob could limit the development of damages related to the uncontrolled activity of MPO.

Keywords: carob, MPO, myeloperoxidase, neutrophils, PMA, phorbol 12-myristate 13-acetate

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6893 Serum Anti-Oxidation Enzymes Response to L-Carnitine Supplementation

Authors: Farah Nameni, Hamidreza Poursadra, Maasumeh Nurani Pilehrud

Abstract:

Exercise training induced Inflammation and stress. Antioxidant, for example L- Carnitine has beneficial effects in immune system and increased antioxidant enzymes activity. L- Carnitine protects the tissue against the oxidative side effect and helps the body to protect against stress during and after acute exercise. The aim of this study was to determine the effect of L-Carnitine on the blood enzymes: GPX SOD, CAT and GR response. In this study, 20 basketball players girls participated. Subjects were randomly assigned into two groups; placebo and supplementation. Antioxidadision enzymes (Superoxide Dismutase, Catalase, Glutathione Reductase, Glutathione Peroxidase) evaluated. L-Carnitine supplement group orally daily received 3000 mg powder for 14 dys. Then all participates trained basketball exercise acute. Blood samples were drawn vein before and immediately after exercise. Superoxide Dismutase, Catalase, Glutathione Reductase, Glutathione Peroxidase were measured, and data was analyzed using repeated measure ANOVA, Bonferroni and t-test. Our results showed: SOD, GPX and GPX (P < 0.05) have a significant increase. These results suggest L-Carnitine supplementation may increase GPX SOD, CAT, and basal anti oxidative capacity. L-Carnitine can modulate the alterations of exercise oxidative damage in girl basketball players.

Keywords: l-carnitine, GPX, SOD, CAT, exercise, GR, anti-oxidant

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6892 Co-Immobilization of Palladium Nanoparticles and Polyoxometalate into the Cavities of the Mesocellular Foams: A Biomimetic Cooperative Catalytic System for Aerobic Oxidation of Alcohols under Green Conditions

Authors: Saeed Chehri, Sirvan Moradi, Amin Rostami

Abstract:

Cooperative catalyst systems have been developed as highly promising sustainable alternatives to traditional catalysts. In these catalysts, two or more catalytic centers cooperate to reduce the energy of chemical transformations. In nature, such systems are abundantly seen in metalloenzymes that use metal and an organic cofactor. We have designed a reusable cooperative catalyst oxidation system consisting of palladium nanoparticles and polyoxometalate. This biomimetic cooperative catalytic system was synthesized by the stepwise immobilization of palladium nanoparticlesandpolyoxometalateinto the same cavity of siliceous mesocellularfoams (Pd-POM@MCF)and wascharacterizedby SEM, EDX, FT-IR, TGAand ICP techniques. POM-Pd@MCF/HQexhibits high activity toward aerobic oxidation of alcohols to the corresponding carbonyl compoundsin water solvent at room temperature. The major novelties and advantages of this oxidation method are as follows: (i) this is the first report of the co-immobilization of polyoxometalateand palladium for use as a robust and highlyefficient heterogeneouscooperative oxidative nanocatalyst system for aerobic oxidation of alcohols, (ii) oxidation of alcoholswere performed using an ideal oxidant with good to high yields in a green solvent at ambient temperature and (iii) the immobilization of the oxygen-activating catalyst(polyoxometalate) and oxidizing catalyst (Pd) onto MCF provide practical cooperative catalyst the system that can be reused several times without a significant loss of activity (vi) the methodsconform to several of the guiding principles of green chemistry.

Keywords: palladium nanoparticles, polyoxometalate, reusable cooperative catalytic system, biomimetic oxidation reaction

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