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Long Reaction Times (long + reaction_time)
Selected AbstractsPreparation and characterization of biodegradable poly(trimethylenecarbonate-,-caprolactone)-block-poly(p -dioxanone) copolymersJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 13 2005J.-T. Hong Abstract A series of poly(trimethylenecarbonate-,-caprolactone)-block-poly(p- dioxanone) copolymers were prepared with varying feed rations by using two step polymerization reactions. Poly(trimethylenecarbonate)(,-caprolactone) random copolymer was synthesized with stannous-2-ethylhexanoate and followed by adding p- dioxanone monomer as the other block. The ring opening polymerization was carried out at high temperature and long reaction time to get high molecular weight polymers. The monofilament fibers were obtained using conventional melting spun methods. The copolymers were identified by 1H and 13C NMR spectroscopy and gel permeation chromatography (GPC). The physicochemical properties, such as viscosity, molecular weight, melting point, glass transition temperature, and crystallinity, were studied. The hydrolytic degradation of copolymers was studied in a phosphate buffer solution, pH = 7.2, 37 °C, and a biological absorbable test was performed in rats. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 2790,2799, 2005 [source] Glacier response in the European Alps to Heinrich Event 1 cooling: the Gschnitz stadial,JOURNAL OF QUATERNARY SCIENCE, Issue 2 2006Susan Ivy-Ochs Abstract The Gschnitz stadial was a period of regionally extensive glacier advance in the European Alps that lies temporally between the breakdown of the Last Glacial Maximum piedmont lobes and the beginning of the Břlling warm interval. Moraines of the Gschnitz stadial are found in medium to small catchments, are steep-walled and blocky, and reflect a snowline lowering of 650,700,m in comparison to the Little Ice Age reference snowline. 10Be surface exposure dating of boulders from the moraine at the type locality at Trins (Gschnitz valley, Tyrol, Austria) shows that it stabilised no later than 15,400,±,1400,yr ago. The overall morphological situation and the long reaction time of the glacier suggest that the climatic downturn lasted about 500,±,300,yr, indicating that the Gschnitz cold period began approximately 15,900,±,1400,yr ago, if not somewhat earlier. This is consistent with published radiocarbon dates that imply that the stadial occurred sometime between 15,400 14C,yr BP (18,020,19,100,cal.,yr) and 13,250 14C,yr BP (15,360,16,015,cal.,yr). A palaeoclimatic interpretation of the Gschnitz glacier based on a simple glacier flow model and statistical glacier-climate models shows that precipitation was about one-third of modern-day precipitation and summer temperatures were about 10,K lower than today. In comparison, during the Younger Dryas, precipitation in this area was only about 10% less and Ts (summer temperature) was only 3.5,4,K lower than modern values. Based on the age of the moraine and the cold and dry climate at that time, we suggest that the Gschnitz stadial was the response of Alpine glaciers to cooling of the North Atlantic Ocean associated with Heinrich Event 1. Copyright © 2005 John Wiley & Sons, Ltd. [source] Gold Catalysis: Alkylideneoxazolines and -oxazoles from Intramolecular Hydroamination of an Alkyne by a TrichloroacetimidateEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 21 2006A. Stephen K. Hashmi Abstract Several propargylic trichloroacetimidates have been prepared and their reactions with gold catalysts studied. Only with the propargyl and the 1-methylpropargyl substituent was a selective cyclization observed; with gold(III) chloride in acetonitrile only the product of a fast hydroamination to 4-methylene-4,5-dihydrooxazoles was obtained, in chloroform the slower subsequent aromatization could not be prevented which delivered the oxazoles after long reaction times. Up to 3333 turnovers could be reached. With gold(I) catalysts in chloroform or dichloromethane selective hydroamination to 4-methylene-4,5-dihydrooxazoles without subsequent aromatization was exclusively observed. The gold(I) catalysts also allowed chemoselective cycloisomerization of N -propargylcarboxamides to 5-methylene-4,5-dihydrooxazoles. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006) [source] Mixed Isobutylphobane/N-Heterocyclic Carbene Ruthenium- Indenylidene Complexes: Synthesis and Catalytic Evaluation in Olefin Metathesis ReactionsADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 11-12 2010Xavier Sauvage Abstract Two new second generation ruthenium(II) dichloride-indenylidene complexes [RuCl2(9-isobutylphosphabicyclo[3.3.1]nonane)(NHC)(3-phenyl-1-indenylidene)], where NHC=1,3-bis(2,4,6-trimethylphenyl)imidazolin-2-ylidene (SIMes) or its unsaturated imidazol-2-ylidene analogue (IMes), were isolated in high yields upon heating a tetrahydrofuran (THF) solution of the diphosphane complex [RuCl2(isobutylphobane)2(3-phenyl-1-indenylidene)] with a two-fold excess of the corresponding imidazol(in)ium-2-carboxylate zwitterions. Both products were characterized by 1H, 13C, and 31P,NMR spectroscopy, and the molecular structure of [RuCl2(isobutylphobane)(SIMes)(3-phenyl-1-indenylidene)] was determined by X-ray diffraction analysis. A close inspection of the packing structure revealed the presence of different types of intra- and intermolecular interactions that enhanced the global stability of the crystals, while low temperature NMR experiments showed the existence of two distinct rotational isomers due to the unsymmetrical nature of the phobane ligand. The catalytic activity of both compounds was assessed in olefin metathesis using benchmark ring-opening metathesis polymerization, ring-closing metathesis (RCM), and cross-metathesis reactions, and compared with those of related first and second generation ruthenium-benzylidene and indenylidene catalyst precursors. Kinetic studies confirmed the high thermal stability of the mixed isobutylphobane/N-heterocyclic carbene complexes, which suffered from a slow initiation efficiency compared to other catalytic systems based on the tricyclohexylphosphane ligand. However, the remarkable robustness of [RuCl2(isobutylphobane)(SIMes)(3-phenyl-1-indenylidene)] was beneficial for performing the RCM of diethyl 2,2-bis(2-methylallyl)malonate. Monitoring the formation of the ruthenium-methylidene active species [RuCl2(isobutylphobane)(SIMes)(CH2)] derived from this precursor further demonstrated its ability to sustain long reaction times and high temperatures required to carry out the RCM of tetrasubstituted olefins. [source] Synthesis of Diacylglycerols Containing CLA by Lipase-Catalyzed EsterificationJOURNAL OF FOOD SCIENCE, Issue 7 2006In-Hwan Kim ABSTRACT:, Diacylglycerols (DAG) were prepared by esterification of glycerol with conjugated linoleic acid (CLA) in the presence of an immobilized 1,3-regiospecific lipase from Rhizomucor miehei and vacuum conditions. The effects of several parameters, namely, temperature, enzyme loading, stirring speed, and vacuum, on the concentration and the purity of the DAG were studied. The reaction temperature influenced both the reaction rate and the concentration of the DAG. The rate of DAG synthesis increased as the enzyme loading increased. However, for high enzyme loadings, the concentration of triacylglycerols (TAG) increased significantly at long reaction times and, as a result, the purity of the DAG decreased. When the stirring speed increased from 150 to 450 rpm, the DAG concentration increased significantly. However, at stirring speeds above 450 rpm, no significant increases in DAG concentration were observed. When the pressure was decreased from 20 to 3 mmHg, the maximum concentration of DAG increased from 76.0% to 80.5%. No increase in the DAG concentration was observed when the pressure was decreased from 3 to 1 mm Hg, even though a slightly higher DAG purity was achieved at 1 mm Hg. For the range of absolute pressures tested, the concentrations of 1,2-DAG were less than 1%. [source] Drug substances presented as sulfonic acid salts: overview of utility, safety and regulationJOURNAL OF PHARMACY AND PHARMACOLOGY: AN INTERNATI ONAL JOURNAL OF PHARMACEUTICAL SCIENCE, Issue 3 2009David P. Elder Abstract Objectives Controlling genotoxic impurities represents a significant challenge to both industry and regulators. The potential for formation of genotoxic short-chain alkyl esters of sulfonic acids during synthesis of sulfonic acid salts is a long-standing regulatory concern. This review provides a general overview of the utility of sulfonic acids as salt-forming moieties and discusses strategies for effectively minimizing the potential for alkyl sulfonate formation during the synthesis and processing of sulfonate salt active pharmaceutical ingredients. The potential implications of the recent establishment of a substantial human threshold dose for ethyl methanesulfonate for the safety assessment of alkyl sulfonates in general are also discussed. Key findings The formation of alkyl sulfonates requires highly acidic conditions, possibly combined with long reaction times and/or elevated temperatures, to generate significant amounts, and these conditions are most unlikely to be present in the synthesis of active pharmaceutical ingredient sulfonate salts. It is possible to design salt formation conditions, using a short-chain alcohol as solvent, to manufacture sulfonate salts that are essentially free of alkyl sulfonate impurities. Processes using non-acidic conditions such as ethanol recrystallization or wet granulation should not raise any concerns of alkyl sulfonate formation. Summary An understanding of the mechanism of formation of alkyl sulfonates is critical in order to avoid restricting or over-controlling sulfonic acid salts, which have many technical advantages as pharmaceutical counterions. Recent regulatory acceptance of a human threshold limit dose of 2 mg/kg per day for ethyl methanesulfonate, indicating that its toxicological risks have previously been considerably overestimated, could signal the beginning of the end over safety concerns on alkyl sulfonate residues, thus removing a major constraint from the exploitation of sulfonic acid counterions. [source] Controlled synthesis of poly(dimethylsiloxane) homopolymers using high-vacuum anionic polymerization techniquesJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 18 2009Mario D. Ninago Abstract The controlled synthesis of poly(dimethylsiloxane) homopolymers (PDMS) using hexamethyl(cyclotrisiloxane) monomer (D3), a mixture of ciclohexane/tetrahydrofuran 50/50 v/v and sec- Bu,Li+ as initiator was studied using different experimental conditions, and whole-sealed glass reactors according to standards procedures in high-vacuum anionic polymerization. It was observed that polydispersity indexes (PD) and conversions strongly depend on temperature and reaction times. For PDMS homopolymers with molar masses below 100,000 g/mol, high conversion (>90%) and PD < 1.1 can be achieved at long reaction times (24 h) and mild temperature conditions (below or up to 30 °C). On the other hand, to synthesize PDMS homopolymers with molar masses higher than 100,000 g/mol and PD < 1.1 it is necessary to increase the temperature up to 50 °C and decrease the reaction time (8 h). However, under these reaction conditions, it was observed that the conversion decreases (about 65,70% conversion is achieved). Apparently, the competition between propagation and secondary reactions (redistribution, backbiting, and reshuffling) depends on the molar masses desired. According to the results obtained in this study,which were compared with others found in the scientific literature,propagation is favored when Mn < 100,000 g/mol, whereas secondary reactions seem to become important for higher molar masses. Nevertheless, model PDMS homopolymers with high molar masses can still be obtained increasing the reaction temperature and shortening the total reaction time. It seems that the combined effect of these two facts favors propagation against secondary reactions, and provides model PDMS homopolymers with molar masses quite close to the expected ones. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 4774,4783, 2009 [source] Use of recombinant rotavirus VP6 nanotubes as a multifunctional template for the synthesis of nanobiomaterials functionalized with metalsBIOTECHNOLOGY & BIOENGINEERING, Issue 5 2009Germán Plascencia-Villa Abstract The structural characteristics and predefined constant size and shape of viral assemblies make them useful tools for nanobiotechnology, in particular as scaffolds for constructing highly organized novel nanomaterials. In this work it is shown for the first time that nanotubes formed by recombinant rotavirus VP6 protein can be used as scaffolds for the synthesis of hybrid nanocomposites. Rotavirus VP6 was produced by the insect cell-baculovirus expression vector system. Nanotubes of several micrometers in length and various diameters in the nanometer range were functionalized with Ag, Au, Pt, and Pd through strong (sodium borohydride) or mild (sodium citrate) chemical reduction. The nanocomposites obtained were characterized by transmission electron microscopy (TEM), high-resolution TEM (HRTEM) with energy dispersive spectroscopy (EDS), dynamic light scattering, and their characteristic plasmon resonance. The outer surface of VP6 nanotubes had intrinsic affinity to metal deposition that allowed in situ synthesis of nanoparticles. Furthermore, the use of preassembled recombinant protein structures resulted in highly ordered integrated materials. It was possible to obtain different extents and characteristics of the metal coverage by manipulating the reaction conditions. TEM revealed either a continuous coverage with an electrodense thin film when using sodium citrate as reductant or a discrete coverage with well-dispersed metal nanoparticles of diameters between 2 and 9,nm when using sodium borohydride and short reaction times. At long reaction times and using sodium borohydride, the metal nanoparticles coalesced and resulted in a thick metal layer. HRTEM-EDS confirmed the identity of the metal nanoparticles. Compared to other non-recombinant viral scaffolds used until now, the recombinant VP6 nanotubes employed here have important advantages, including a longer axial dimension, a dynamic multifunctional hollow structure, and the possibility of producing them massively by a safe and efficient bioprocess. Such characteristics confer important potential applications in nanotechnology to the novel nanobiomaterials produced here. Biotechnol. Bioeng. 2009; 104: 871,881. © 2009 Wiley Periodicals, Inc. [source] Mechanistic limitations in the synthesis of polyesters by lipase-catalyzed ring-opening polymerizationBIOTECHNOLOGY & BIOENGINEERING, Issue 1 2003Anna A. Panova Abstract Lipase-catalyzed polymerization of caprolactone (CL) in toluene with methoxy-poly(ethylene glycol) (MPEG) and water as initiators was characterized in detail for mechanistic insight. 1H NMR analysis of polycaprolactone chains (PCL), dicaprolactone, degree of esterification of MPEG, and fractions of PCL chains initiated by MPEG and water were used to follow the reactions. The data were analyzed with the kinetic scheme involving formation of the acylenzyme and its consequent reaction with MPEG, water, or PCL to yield the MPEG- or water-initiated PCL chains, or increase in PCL length. A limit for MPEG initiator esterification in lipase-catalyzed CL polymerization was observed and was explained by preferential reaction of PCL propagation over MPEG esterification at long reaction times and low MPEG concentrations. Slower monomer conversion in concentrated monomer solutions was explained by decreased partitioning of PCL between the solvent and the enzyme. This effect resulted in inhibition of the lipase by the reaction product, PCL chains, and/or insufficient diffusion of monomer to the enzyme active site. High monomer/initiators ratio in these solutions did not yield longer polymer chains due to decreased monomer conversion and the corresponding decrease in product yields; lower yields were also observed for chain initiation by MPEG and water. A shift in the reaction rate-limiting step from formation of acylenzyme in dilute CL solutions to its deacylation in concentrated CL solutions yielded higher PCL polydispersity due to increased initiation by water. Enhanced intramolecular cyclization was also observed. Endgroup composition of PCL chains was influenced by the concentration of monomer, ratio of initiators (MPEG and water), and reaction time, yielding PCL chains initiated exclusively by MPEG at "infinite reaction times." © 2003 Wiley Periodicals, Inc. Biotechnol Bioeng 84: 103,113, 2003. [source] | ||||||||||