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Acid Additives (acid + additive)
Selected AbstractsEffect of Halide and Acid Additives on the Direct Synthesis of Hydrogen Peroxide using Supported Gold,Palladium CatalystsCHEMSUSCHEM CHEMISTRY AND SUSTAINABILITY, ENERGY & MATERIALS, Issue 6 2009Edwin Ntainjua N. Dr. Abstract Acidity is crucial: The effect of halide and acid addition on the direct synthesis of hydrogen peroxide is studied for magnesium oxide- and carbon-supported bimetallic gold,palladium catalysts. When using a Au,Pd/C catalyst, the acidity of the methanol/water solvent has a profound effect on the productivity (P). The effect of halide and acid addition on the direct synthesis of hydrogen peroxide is studied for magnesium oxide- and carbon-supported bimetallic gold,palladium catalysts. The addition of acids decreases the hydrogenation/decomposition of hydrogen peroxide, and the effect is particularly pronounced for the magnesium oxide-supported catalysts whilst for carbon-supported catalysts the pH requires close control to optimize hydrogen peroxide synthesis. The addition of bromide leads to a marked decrease in the hydrogenation/decomposition of hydrogen peroxide with either catalyst. These effects are discussed in terms of the structure of the gold,palladium alloy nanoparticles and the isoelectric point of the support. We conclude that with the highly active carbon-supported gold,palladium catalysts these additives are not required and that therefore this system presents the potential for the direct synthesis of hydrogen peroxide to be operated using green process technology. [source] Polymer-Supported Highly Enantioselective Catalyst for Nitro-Michael Addition: Tuning through Variation of the Number of H-Bond Donors and Spacer LengthADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 4 2009Lital Tuchman-Shukron Abstract Two series of polymer-bound bifunctional organocatalysts, based on chiral diamine scaffolds, were prepared by solid-phase synthesis. The series, incorporating a single hydrogen bond donor carbamate functionality, was notably more enantioselective in the Michael reaction of acetone and nitrostyrene than the series that includes a double hydrogen bond donor urea moiety, or the polymer-bound diamine that lacks sufficiently acidic protons. The best aminocarbamate catalyst promoted the addition of acetone to nitroolefins with enantioselectivity unmatched by known heterogeneous catalysts. Introduction of a short linear spacer between the support and the scaffold improves the activity but reduces the selectivity of the catalyst. Alternatively, an increase in the reaction yield could be induced by the benzoic acid additive. [source] Enantioselective Trifunctional Organocatalysts for Rate- Enhanced Aza-Morita,Baylis,Hillman Reactions at Room TemperatureADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 3 2009Jean-Marc Garnier Abstract A Brønsted acid-activated trifunctional organocatalyst, based on the BINAP scaffold, was used for the first time to catalyze aza-Morita-Baylis,Hillman reactions between N -tosylimines and methyl vinyl ketone with fast reaction rates and good enantioselectivity at room temperature. This trifunctional catalyst, containing a Lewis base, a Brønsted base, and a Brønsted acid, required acid activation to confer its enantioselectivity and rate improvement for both electron-rich and electron-deficient imine substrates. The role of the amino Lewis base of 1a was investigated and found to be the activity switch in response to an acid additive. The counterion of the acid additive was found to influence not only the excess ratio but also the sense of asymmetric induction. [source] Influence of fatty acid additives on the tribological performance of sunflower oilLUBRICATION SCIENCE, Issue 9 2010Patrick Baumgart Abstract Vegetable oils are potential substitutes for petroleum-based lubricants because they are environmentally friendly, renewable, less toxic and readily biodegradable. The addition of free fatty acids has been shown to increase the lubrication performance of vegetable oils at elevated temperatures. The purpose of this study was to evaluate the relationship between the length of the carbon chain in the fatty acid and its effectiveness as an additive for a range of elevated temperatures. Stearic, arachidic and behenic fatty acid additives were added to commercial sunflower oil. All fatty acid additives were shown to be effective in lowering the wear rate and coefficient of friction in ball-on-disc tribological tests. The overall carbon chain length was not observed to have a consistent influence on the effectiveness of the additive. All additives were less effective at temperatures above 100°C. Copyright © 2010 John Wiley & Sons, Ltd. [source] Effect of LiClO4 and LiCl Additives on the Kinetics of Anionic Polymerization of Methyl Methacrylate in Toluene-Tetrahydrofuran Mixed SolventMACROMOLECULAR CHEMISTRY AND PHYSICS, Issue 12 2003Mahua G. Dhara Abstract The kinetics of anionic polymerization of MMA has been studied at ,78,°C in toluene-THF (9:1 v/v) using 1,1,-diphenylhexyl lithium as initiator in the presence of lithium perchlorate and lithium chloride as Lewis acid additives. The control of the polymerization is lost in the absence of additives as evident from the non-linear first-order time-conversion plot and polymers with broad multimodal molecular weight distribution. The presence of LiClO4 and LiCl in 10:1 and 5:1 ratio, respectively, over the initiator brings about sufficient control, yielding polymers of narrow unimodal distribution throughout the polymerization. The reaction in the presence of the additives follows first-order kinetics free of termination and transfer. Moreover, the order with respect to the active centers is found to be almost unity, which signifies a probable disaggregation of ion-pairs to a single complexed propagating species. GPC elugrams at different conversions for MMA polymerization in the presence of LiClO4. [source] Peroxidase activity of bacterial cytochrome P450 enzymes: Modulation by fatty acids and organic solventsBIOTECHNOLOGY JOURNAL, Issue 8 2010Kersten S. Rabe Abstract The modulation of peroxidase activity by fatty acid additives and organic cosolvents was determined and compared for four bacterial cytochrome P450 enzymes, thermostable P450 CYP119A1, the P450 domain of CYP102A1 (BMP), CYP152A1 (P450bs,), and CYP101A1 (P450cam). Utilizing a high-throughput microplate assay, we were able to readily screen more than 100 combinations of enzymes, additives and cosolvents in a convenient and highly reproducible assay format. We found that, in general, CYP119A1 and BMP showed an increase in peroxidative activity in the presence of fatty acids, whereas CYP152A1 revealed a decrease in activity and CYP101A1 was only slightly affected. In particular, we observed that the conversion of the fluorogenic peroxidase substrate Amplex Red by CYP119A1 and BMP was increased by a factor of 38 or 11, respectively, when isopropanol and lauric acid were present in the reaction mixture. The activity of CYP119A1 could thus be modulated to reach more than 90% of the activity of CYP152A1 without effectors, which is the system with the highest peroxidative activity. For all P450s investigated we found distinctive reactivity patterns, which suggest similarities in the binding site of CYP119A1 and BMP in contrast with the other two proteins studied. Therefore, this study points towards a role of fatty acids as activators for CYP enzymes in addition to being mere substrates. In general, our detailed description of fatty acid- and organic solvent-effects is of practical interest because it illustrates that optimization of modulators and cosolvents can lead to significantly increased yields in biocatalysis. [source] | ||||||||||