Synthesis,characterization and catalytic activities of a reusable polymer-anchored palladium(II) complex: effective catalytic hydrogenation of various organic substrates

A poly(3,6-dibenzaldimino N-vinyl carbazole) Pd(II) complex has been synthesized and characterized by physicochemical and spectroscopic techniques. The complex was found to be highly active toward hydrogenation reactions of various organic substrates under atmospheric pressure at ambient temperature. A tentative reaction mechanism is proposed on the basis of kinetic studies and isolation of reactive intermediates. The catalyst shows good conversion rates, thermal stability and recyclability.     

Oxidative coupling of methane on alkali metal-containing catalysts

MgO, MgHPO₂, MgCl₂, silica gel, SiO₂ (aerogel), zeolite H-ZSM-5 and various modified compounds of Li, Na, K, Be and Mn have been examined. Effect of temperature, space velocity and partial pressure of oxygen on the selectivity to C₂ and carbon oxides formation was studied in detail in the presence of NaCl-MnO/MgO. Paper presented at the II European Congress on Catalysis (EUROPACAT-II), Maastricht (The Netherlands), 3–8 September, 1995 and the VIII International Symposium on Relations between Homogeneous and Heterogeneous Catalysis, Balatonfüred (Hungary), 10–14 September, 1995.     

Synthesis,characterization, and catalytic activity of a polymer-supported copper(II) complex with a thiosemicarbazone ligand

A thiosemicarbazone Cu(II) complex anchored to a polystyrene framework has been synthesized and characterized by analytical and spectroscopic techniques. The complex was found to be a highly active catalyst for the oxidation of various organic substrates including alkenes and alcohols using H₂O₂ as oxidant. The reaction conditions were optimized with respect to temperature, solvent, oxidant, catalyst amount, and substrate to peroxide ratio. The heterogeneous catalyst was reused five times without significant loss of activity. A comparison between the catalytic activities of this polymer-supported Cu(II) complex and its homogeneous analogue was carried out.     

Cloud point and solid phase extraction of vanadium in surface and bottled mineral water samples using 8-hydroxyquinoline as a complexing reagent

Cloud point extraction (CPE) and solid phase extraction (SPE) methods were developed for the determination of ??g l^?1 of vanadium ions in surface, tap and bottled mineral water samples, based on the rapid reaction of vanadium(V) with 8- hydroxyquinoline (8-quinolinol) at pH 3?C5. Both the sensitive extraction methods were successfully employed for the preconcentration of V in real samples. For CPE, V complexed with 8-quinolinol and then was entrapped in non-ionic surfactant Triton X-114, while for SPE, V was adsorbed on XAD -2 impregnated with 8-quinolinol. The experimental conditions for SPE (pH, eluent, and contact time between the liquid sample and the resin) and CPE (pH of sample solution, concentration of 8- quinolinol and Triton X-114, equilibration temperature and time period for shaking) were investigated in detail. The validity of SPE/CPE of V was checked by certified reference material of water (SRM-1643e). The extracted surfactant-rich phase (200 ??l) was mixed with 200 ??l of HNO₃ in ethanol and this final volume was injected into electrothermal atomic absorption spectrometry with different modifiers. Under these conditions, the preconcentration of 25 ml sample solution allowed the raising of an enrichment factor of 100 and 10 folds for CPE and SPE, respectively. The concentration of V in surface water (river and lake), tap water and bottled mineral water samples was found to be in the range of 1.30?C19.9, 1.05?C5.25 and 0.67?C1.21 ??g l^?1, respectively.     

Characteristics investigation on heat transfer growth of sonochemically synthesized ZnO-DW based nanofluids inside square heat exchanger

Journal of Thermal Analysis and Calorimetry - In recent decades, the growth of heat transfer using nanomaterials in the conventional base fluid has caught the attention of researchers...     

Catechol oxidase activity of a series of new dinuclear copper(II) complexes with 3,5-DTBC and TCC as substrates: syntheses, X-ray crystal structures, spectroscopic characterization of the adducts and kinetic studies

A series of dinuclear copper(II) complexes has been synthesized with the aim to investigate their applicability as potential structure and function models for the active site of catechol oxidase enzyme. They have been characterized by routine physicochemical techniques as well as by X-ray single-crystal structure analysis: [Cu 2(H 2L2 (2))(OH)(H 2O)(NO 3)](NO 3) 3.2H 2O ( 1), [Cu(HL1 (4))(H 2O)(NO 3)] 2(NO 3) 2.2H 2O ( 2), [Cu(L1 (1))(H 2O)(NO 3)] 2 ( 3), [Cu 2(L2 (3))(OH)(H 2O) 2](NO 3) 2, ( 4) and [Cu 2(L2 (1))(N 3) 3] ( 5) [L1 = 2-formyl-4-methyl-6R-iminomethyl-phenolato and L2 = 2,6-bis(R-iminomethyl)-4-methyl-phenolato; for L1 (1) and L2 (1), R = N-propylmorpholine; for L2 (2), R = N-ethylpiperazine; for L2 (3), R = N-ethylpyrrolidine, and for L1 (4), R = N-ethylmorpholine]. Dinuclear 1 and 4 possess two "end-off" compartmental ligands with exogenous mu-hydroxido and endogenous mu-phenoxido groups leading to intermetallic distances of 2.9794(15) and 2.9435(9) A, respectively; 2 and 3 are formed by two tridentate compartmental ligands where the copper centers are connected by endogenous phenoxido bridges with Cu-Cu separations of 3.0213(13) and 3.0152(15) A, respectively; 5 is built by an end-off compartmental ligand having exogenous mu-azido and endogenous mu-phenoxido groups with a Cu-Cu distance of 3.133(2) A (mean of two independent molecules). The catecholase activity of all of the complexes has been investigated in acetonitrile and methanol medium by UV-vis spectrophotometric study using 3,5-di- tert-butylcatechol (3,5-DTBC) and tetrachlorocatechol (TCC) as substrates. In acetonitrile medium, the conversion of 3,5-DTBC to 3,5-di- tert-butylbenzoquinone (3,5-DTBQ) catalyzed by 1- 5 is observed to proceed via the formation of two enzyme-substrate adducts, ES1 and ES2, detected spectroscopically for the first time. In methanol medium no such enzyme-substrate adduct has been detected, and the 3,5-DTBC to 3,5-DTBQ conversion is observed to be catalyzed by 1- 5 very efficiently. The substrate TCC forms an adduct with 2- 5 without performing further oxidation to TCQ due to the high reduction potential of TCC (in comparison with 3,5-DTBC). But most interestingly, 1 is observed to be effective even in TCC oxidation, a process never reported earlier. Kinetic experiments have been performed to determine initial rate of reactions (3,5-DTBC as substrate, in methanol medium) and the activity sequence is 1 > 5 > 2 = 4 > 3. A treatment on the basis of Michaelis-Menten model has been applied for kinetic study, suggesting that all five complexes exhibit very high turnover number, especially 1, which exhibits turnover number or K cat of 3.24 x 10 (4) (h (-1)), which is approximately 3.5 times higher than the most efficient catalyst reported to date for catecholase activity in methanol medium.     

Speciation of arsenic by ion chromatography inductively coupled plasma mass spectrometry using ammonium eluents

A method based on ion chromatography (IC) and inductively coupled plasma MS (ICP-MS) was developed for the speciation of arsenic in water and soil extracts. An anion-exchange column (G3154A/101) was used to separate As(III), As(V), dimethylarsinic acid (DMA), and monomethylarsonic acid (MMA) with excellent resolution. Various ammonium salts, including NH4H2PO4, (NH4)2HPO4, (NH4)2CO3, and NH4HCO3, were examined as eluents to reduce matrix interference from chloride and to solve clogging problems. The best arsenic speciation was obtained within 9 min with excellent resolution and without interference from high chloride concentrations using an eluent containing 7.5 mM (NH4)2HPO4 at pH 7.9. The detection limits for the target arsenic species ranged from 0.1 to 0.4 microg/L with direct injection of sample without matrix elimination. The proposed method was effectively demonstrated by determining arsenic species in contaminated waters and soils of Bangladesh.     

Ultrasound-assisted pseudodigestion for toxic metals determination in fish muscles followed by electrothermal atomic absorption spectrophotometry: multivariate strategy

A simple and efficient procedure for the determination of arsenic (As), cadmium (Cd), and lead (Pb) in the edible parts of freshwater fish by ultrasonic-assisted acid pseudodigestion (USD) was developed. A Plackett-Burman experimental design was used as a multivariate strategy for the evaluation of the effects of several variables at once. Five variables--sonication time, sample mass of muscle tissue, temperature of the ultrasonic bath, mL of nitric acid, and mL of a mixture of acid and oxidant--were regarded as factors. From these studies, certain variables showed up as significant, and they were optimized by a 23+star central composite design, which involved 16 experiments. Optimum values of the variables were selected for the development of USD to determine the contents of As, Cd, and Pb in fish muscles used as pollution bioindicators from Lake Manchar (Sindh, Pakistan). The determination of the 3 toxic metals under study was performed by electrothermal atomic absorption spectrometry. The accuracy of the optimized procedure was evaluated by analysis of certified reference materials BCR 185R bovine liver and by comparison with conventional wet acid digestion methodology. The result obtained by the optimized method showed good agreement with the certified values and sufficiently high recovery. No significant differences were observed for P = 0.05. Relative standard deviation values (average of 10 separate determinations) were 1.21, 5.52, and 5.32% for As, Cd, and Pb, respectively.     

Selective oxidation of sulfides and oxidative bromination of organic substrates catalyzed by polymer anchored Cu(II) complex

A new polymer-anchored Cu(II) complex has been synthesized and characterized. The catalytic performance of the complex has been tested for the oxidation of sulfides and in oxidative bromination reaction with hydrogen peroxide as the oxidant. Sulfides have been selectively oxidized to the corresponding sulfoxides in excellent yields and in the presence of KBr as the bromine source, organic substrates have been selectively converted to mono bromo substituted compounds using polymer-anchored Cu(II) catalyst. This catalyst showed excellent catalytic activity, high selectivity, and recyclability. The polymer-anchored Cu(II) catalyst could be easily recovered by filtration and reused more than five times without appreciable loss of its initial activity.