Home About us Contact
|
Home About us Contact | ||
|
|
||
Full Conversion (full + conversion)
Selected AbstractsFacile Functionalization and Phase Reduction Route of Magnetic Iron Oxide Nanoparticles for Conjugation of Matrix Metalloproteinase,ADVANCED ENGINEERING MATERIALS, Issue 6 2010Dan Li Abstract A protocol for the simultaneous functionalization and phase reduction route of iron oxide magnetic nanoparticles (MNPs) and its further bioconjugation is presented. It was found that surface functionalization of maghemite (,-Fe2O3) nanoparticles with mercaptopropyltrimethoxysilane (MPTMS) under anoxic environment at above 80,°C promotes in situ conversion to magnetite (Fe3O4). Full conversion to Fe3O4, as probed by Mössbauer spectroscopy, with accompanied increase in the composite saturation magnetization, was achieved at 120,°C. By controlling the MPTMS concentration, the resultant silane-MNPs morphology can be tuned from having homogeneous thin layer (<1,nm) to thick continuous silane with embedded MNP multicores. Likewise the amount of surface distal thiol moieties was dependent on the silanization conditions. The density of distal thiols (i.e., amount of thiol per surface area) and resultant aggregate size have direct impact on the attachment, as well as the activity and reusability of the conjugated matrix metalloproteinase (MMP-2, using sulfo-SMCC as crosslinker). The work has important implication to the field of magneto-chemotherapeutics, where spatial control of conjugated active biomolecules under magnetic field and T2 -weighted MRI contrast can be achieved simultaneously. [source] Highly Selective Cobalt-Catalyzed Hydrovinylation of StyreneADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 13 2009Michiel M. Abstract Phosphine complexes of cobalt halide salts activated by diethylaluminum chloride are shown to yield highly active catalysts in the hydrovinylation of styrene, with unprecedented high selectivity to the desired product 3-phenyl-1-butene (3P1B). Double-bond isomerization, a common problem in codimerization reactions, only occurs after full conversion with these catalyst systems, even at elevated temperature. The most active catalysts are based on cobalt halide species combined with either C1 - or C2 -bridged diphosphines, heterodonor P,N or P,O ligands, flexible bidentate phosphine ligands or monodentate phosphine ligands. Kinetic investigations show an order >1 in catalyst, which indicates either the involvement of dinuclear species in the catalytic cycle or partial catalyst decomposition via a bimolecular pathway. [source] Homogeneous Hydrogenation of Tri- and Tetrasubstituted Olefins: Comparison of Iridium-Phospinooxazoline [Ir-PHOX] Complexes and Crabtree Catalysts with Hexafluorophosphate (PF6) and Tetrakis[3,5-bis(trifluoromethyl)phenyl]borate (BArF) as CounterionsADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 1 2008Bettina Wüstenberg Abstract Four iridium complexes with achiral phosphino-oxazoline (PHOX) ligands were readily prepared in two steps starting from commercially available phenyloxazolines. The air-stable complexes with tetrakis[3,5-bis(trifluoromethyl)phenyl]borate (BArF) as counterion showed high reactivity in the hydrogenation of a range of tri- and tetrasubstituted olefins. The best results were obtained with an iridium complex (11) derived from a dicyclohexylphosphino-oxazoline ligand bearing no additional substituents in the oxazoline ring. With several substrates, which gave only low conversion with the Crabtree catalyst, [Ir(Py)(PCy3)(COD)]PF6, full conversion was observed. The productivity of the Crabtree catalyst could be strongly increased by replacing the hexafluorophosphate anion with tetrakis[3,5-bis(trifluoromethyl)phenyl]borate. In one case, in the hydrogenation of a tetraalkyl-substituted CC bond, [Ir(Py)(PCy3)(COD)]BArF gave higher conversion than catalyst 11. However, with several other substrates complex 11 proved to be superior. [source] Ferrocenyl-functionalized long chain branched polydienesJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 10 2009Frederik Wurm Abstract A convenient two-step approach for the synthesis of ferrocenyl-functionalized long chain branched polydienes, based on both butadiene and isoprene, respectively, is presented. Classical living anionic polymerization was used to synthesize different ABn type poly(diene) macromonomers with moderate molecular weights between 1700 and 3200 g/mol and narrow polydispersity. Quantitative end-capping with chlorodimethylsilane resulted in the desired ABn macromonomer structures. In the ensuing Pt-catalyzed hydrosilylation polyaddition, branched, functionalized polydienes were obtained by a concurrent ABn + AR type of copolymerization with mono- and difunctional ferrocenyl silanes (fcSiMe2H or fc2SiMeH). Molecular weights of the branched polymers were in the range of 10,000 to 44,000 g/mol (SEC/MALLS). Because of the large number of functional end groups, high loading with ferrocene units up to 63 wt % of ferrocene was achieved. Detailed studies showed full conversion of the functional silanes and incorporation into the branched polymer. Further studies using DSC, TGA, and cyclovoltammetry (CV) measurements have been performed. Electrochemical studies demonstrated different electrochemical properties for fcSiMe2 - and fc2SiMe-units. The CVs of polymers modified with diferrocenylsilane units exhibit the pattern of communicating ferrocenyl sites with two distinct, separate oxidation waves. The polymers were also deposited on an electrode surface and the electrodes investigated via CV, showing formation of electroactive films with promising results for the use of the materials in biosensors. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2518,2529, 2009 [source] Kinetics of self-condensing vinyl hyperbranched polymerization in three-dimensional spaceJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 13 2008Xuehao He Abstract Self-condensing vinyl hyperbranched polymerization (SCVP) with A-B* type monomer is simulated applying Monte Carlo method using 3d bond fluctuation lattice model in three-dimensional space. The kinetics of SCVP with zero active energy of reaction is studied in detail. It is found that the maximal number,average and weight,average polymerization degrees and the maximal molecular weight distribution, at varying the initial monomer concentration and double bond conversion, are about 52, 190, and 3.93, respectively, which are much lower than theoretical values. The maximal average fraction of branching points is about 0.27, obtained at full conversion at the initial monomer concentration of 0.75. The simulation demonstrated the importance of steric effects and intramolecular cyclization in self-condensing vinyl hyperbranched polymerization. The results are also compared with experiments qualitatively and a good agreement is achieved. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 4486,4494, 2008 [source] Star polystyrenes by anionic star,star coupling reactions with divinylbenzeneJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 8 2006Hyung-Jae Lee Abstract The incremental addition of divinylbenzene was used to generate star polystyrenes in a nearly full conversion of a living polystyrenyl anion. The dramatic increase in the molecular weight of the star polystyrenes with a limited supply of the living polystyrene supported the formation of gradient-star polystyrenes through star,star coupling. The stoichiometric analysis of the star polymers revealed that their connection polymer had a shorter length than their branch polymer. The measured solution viscosity of the gradient-star polymers greatly deviated from a linear correlation with the molecular weight and was in parallel to a theoretical simulation based on a highly branched structure of the gradient-star polymer. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2579,2586, 2006 [source] Accelerated Heck reaction using ortho -palladated complex with controlled microwave heatingAPPLIED ORGANOMETALLIC CHEMISTRY, Issue 12 2009Abdol R. Hajipour Abstract Palladium-catalyzed Heck couplings utilizing [Pd{C6H2(CH2CH2NH2)-(OMe)2,3,4} (µ-Br)]2 palladacycle catalyst and microwave irradiation lead to formation of different coupling products. This complex is an active and efficient catalyst for the Heck reaction of aryl iodides, bromides and even less reactive chlorides. The cross-coupled products were produced in excellent yields. The reaction time was reduced from hours to minutes and full conversion was achieved under microwave irradiation. Copyright © 2009 John Wiley & Sons, Ltd. [source] Heterogeneous Versus Homogeneous Palladium Catalysts for Ligandless Mizoroki,Heck Reactions: A Comparison of Batch/Microwave and Continuous-Flow ProcessingCHEMISTRY - A EUROPEAN JOURNAL, Issue 4 2009Abstract Mizoroki,Heck couplings of aryl iodides and bromides with butyl acrylate were investigated as model systems to perform transition-metal-catalyzed transformations in continuous-flow mode. As a suitable ligandless catalyst system for the Mizoroki,Heck couplings both heterogeneous and homogeneous Pd catalysts (Pd/C and Pd acetate) were considered. In batch mode, full conversion with excellent selectivity for coupling was achieved applying high-temperature microwave conditions with Pd levels as low as 10,3,mol,%. In continuous-flow mode with Pd/C as a catalyst, significant Pd leaching from the heterogeneous catalyst was observed as these Mizoroki,Heck couplings proceed by a homogeneous mechanism involving soluble Pd colloids/nanoparticles. By applying low levels of Pd acetate as homogeneous Pd precatalyst, successful continuous-flow Mizoroki,Heck transformations were performed in a high-temperature/pressure flow reactor. For both aryl iodides and bromides, high isolated product yields of the cinnamic esters were obtained. Mechanistic issues involving the Pd-catalyzed Mizoroki,Heck reactions are discussed. [source] Screening of a Modular Sugar-Based Phosphite,Oxazoline Ligand Library in Asymmetric Pd-Catalyzed Heck ReactionsCHEMISTRY - A EUROPEAN JOURNAL, Issue 12 2007Yvette Mata Abstract We have synthesised a library of phosphite,oxazoline ligands derived from readily available D -glucosamine. These ligands have been successfully screened in the palladium-catalysed Heck reaction of several substrates with high regio- (up to 99,%) and enantioselectivities (ee's up to 99,%) as well as with improved activities under standard thermal conditions. The results indicate that the catalytic performance is highly affected by the oxazoline and biarylphosphite substituents and the axial chirality of the biaryl moiety of the ligand. The Heck reactions were also performed under microwave irradiation conditions, allowing a considerably shorter reaction time (full conversion in minutes) maintaining the excellent regio- and enantioselectivities. [source] Asymmetric Hydrogenation of Quinoxalines Catalyzed by Iridium/PipPhosADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 16 2009Abstract A catalyst made in situ from the (cyclooctadiene)iridium chloride dimer, [Ir(COD)Cl]2, and the monodentate phosphoramidite ligand (S)-PipPhos was used in the enantioselective hydrogenation of 2- and 2,6-substituted quinoxalines. In the presence of piperidine hydrochloride as additive full conversions and enantioselectivities of up to 96% are obtained. [source] | |||||||||||||