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Reaction Parameters (reaction + parameter)
Kinds of Reaction Parameters Selected AbstractsMechanism of Hydride Abstraction by Cyclopentadienone-Ligated Carbonylmetal Complexes (M = Ru, Fe)EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 2 2009Megan K. Thorson Abstract Cyclopentadienone-ligated ruthenium complexes, such as Shvo's catalyst, are known to oxidize reversibly alcohols to the corresponding carbonyl compounds. The mechanism of this reaction has been the subject of some controversy, but it is generally believed to proceed through concerted transfer of proton and hydride, respectively, to the cyclopentadienone ligand and the ruthenium center. In this paper we further study the hydride transfer process as an example of a coordinatively directed hydride abstraction by adding quantitative understanding to some features of this mechanism that are not well understood. We find that an oxidant as weak as acetone can be used to re-oxidize the intermediate ruthenium hydride without catalyst re-oxidation becoming rate-limiting. Furthermore, C,H cleavage is a significantly electrophilic event, as demonstrated by a Hammett reaction parameter of , = ,0.89. We then describe how the application of our mechanistic insights obtained from the study have enabled us to extend the ligand-directed hydride abstraction strategy to include a rare example of an iron(0) oxidation catalyst.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) [source] A PM3/d specific reaction parameterization for iron atom in the hydrogen abstraction catalyzed by soybean lipoxygenase-1JOURNAL OF COMPUTATIONAL CHEMISTRY, Issue 6 2007Ismael Tejero Abstract This paper reports a specific reaction parameter (SRP) PM3/d model for iron that can reproduce the DFT/MM results of the hydrogen abstraction reaction from the C11 position of linoleic acid by the Soybean lipoxygenase-1 enzyme. A suite of nonlinear optimization methods is outlined for semiempirical parameter development based on integrated evolutionary (genetic) and direction set minimization algorithms. The PM3/d-SRP Fe parameters are derived along three consecutive steps. The final parameterization step includes the effect of the whole enzyme in order to get a better quantum mechanical/molecular mechanical description. © 2007 Wiley Periodicals, Inc. J Comput Chem, 2007 [source] Thermal and mass transients in the developing region of a homogeneous tubular chemical reactorAICHE JOURNAL, Issue 3 2010Mohammad K. Alkam Abstract The current investigation presents a finite difference simulation of a homogeneous tubular reactor under laminar flow conditions. The present simulation considers the unsteady operation where transients in flow hydrodynamics, temperature field, and species concentrations have been considered. Flow development in the entrance region of the present reactor has been considered. Present results exhibit reactant concentration and mixing cup temperature profiles for a variety of operating conditions. Effects of several parameters on the performance of the current reactor have been examined, including, reaction parameter, order of reaction, and Schmidt number. © 2009 American Institute of Chemical Engineers AIChE J, 2009 [source] Trajectory planning for boundary controlled parabolic PDEs with varying parameters defined on a parallelepipedPROCEEDINGS IN APPLIED MATHEMATICS & MECHANICS, Issue 1 2009Thomas Meurer The trajectory planning and feedforward tracking control problem is considered for a boundary controlled diffusion-reaction system with a spatially and time varying reaction parameter defined on a 3-dimensional parallelepiped. For this, an implicit state and input parametrization in terms of a basic output via a Volterra-type integral equation with operator kernel is determined, which is solved recursively by means of a series ansatz. The absolute and uniform convergence of the resulting series is verified by restricting the reaction parameter and the basic output to a certain but broad Gevrey class. Hence, assigning an admissible desired trajectory for the basic output directly yields the respective feedforward control, which is required to realize a desired spatio-temporal transition path. (© 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] Spectroelectrochemical and Voltammetric Studies of L -DOPAELECTROANALYSIS, Issue 2 2003Xiaoqiang Liu Abstract The electrooxidation of L -dopa at GC electrode was studied by in situ UV-vis spectroelectrochemistry (SEC) and cyclic voltammetry. The mechanism of electrooxidation and some reaction parameters were obtained. The results showed that the whole electrooxidation reaction of L -dopa at glassy carbon (GC) electrode was an irreversible electrochemical process followed by a chemical reaction in neutral solution (EC mechanism). The spectroelectrochemical data were treated by the double logarithm method together with nonlinear regression, from which the formal potential E0=228,mV, the apparent electron-transfer number of the electrooxidation reaction ,n=0.376 (R=0.99, SD=0.26), the standard electrochemical rate constant k0=(3.93±0.12)×10,4,cm s,1 (SD=1.02×10,2), and the formation equilibrium constant of the following chemical reaction kc=(5.38±0.34)×10,1,s,1 (SD=1.02×10,2) were also obtained. [source] The Thermal Decomposition of Three Magnetic Acetates at Their Autogenic Pressure Yields Different Products.EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 14 2007Abstract We report on the one-stage, reproducible, solvent-free, competent and straightforward approach for the synthesis of fullerene-like Ni@C, Co@C, and Fe3O4@C core-shell nanostructures that can be scaled up. The single precursor reactions of low cost acetates of Fe, Co and Ni are separately conducted at a relatively low temperature (700 °C) in a closed Swagelok reactor, as compared to other methods for the formation of graphitic layers. It is worth mentioning that although identical reaction parameters are employed, using the three acetate precursors, the graphitic carbon is coated on nanosized metallic Ni and Co cores, while Fe tends to form Fe3O4, maintaining the same core-shell morphology. The systematic morphological, compositional, structural characterization and the room temperature magnetic susceptibility measurements of the as-made particles are carried out on a vibrating sample magnetometer. The plausible mechanism is based on the comparison between the dissociation products of three acetate precursors, their obtained experimental data, and calculations on the enthalpy and free energy changes.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source] Bottom-Up Synthesis of Biologically Active Multilayer Films Using Inkjet-Printed TemplatesADVANCED FUNCTIONAL MATERIALS, Issue 9 2010Joshua D. Swartz Abstract As a non-invasive, rapid prototyping technique, piezoelectric inkjet printing using the Dimatix Materials Printer (DMP) is incorporated to template 2D biologically active surfaces. In these studies, a bioinspired ink is synthesized and printed directly onto gold-coated silicon nitride substrates and into polymer-coated 96-well plates. Once deposited on a surface, these patterns are reacted with varying concentrations of a model enzyme glucose oxidase in the presence of a silica precursor, monosilicic acid. The reaction mechanism and order of reactant products within and along the patterns are shown to directly affect the integrity and overall microstructure of the biologically active films. Using profilometry measurements and scanning electron microscopy, a biologically active platform is optimized without significantly compromising the activity of the enzyme. In fact, enzyme activity, constrained within a thin film, is reported for the first time over variable reaction parameters. When compared to the enzyme free in solution, the immobilized enzyme is 25.9% active, where nearly 100% of the activity is retained after repeated usage. [source] Controlled Synthesis of CdSe Nanowires by Solution,Liquid,Solid MethodADVANCED FUNCTIONAL MATERIALS, Issue 22 2009Zhen Li Abstract Semiconductor nanowires prepared by wet chemical methods are a relatively new field of 1D electronic systems, where the dimensions can be controlled by changing the reaction parameters using solution chemistry. Here, the solution,liquid,solid approach where the nanowire growth is governed by low-melting-point catalyst particles, such as Bi nanocrystals, is presented. In particular, the focus is on the preparation and characterization of CdSe nanowires, a material which serves a prototype structure for many kinds of low dimensional semiconductor systems. To investigate the influence of different reaction parameters on the structural and optical properties of the nanowires, a comprehensive synthetic study is presented, and the results are compared with those reported in literature. How the interplay between different reaction parameters affects the diameter, length, crystal structure, and the optical properties of the resultant nanowires are demonstrated. The structural properties are mainly determined by competing reaction pathways, such as the growth of Bi nanocatalysts, the formation and catalytic growth of nanowires, and the formation and uncatalytic growth of quantum dots. Systematic variation of the reaction parameters (e.g., molecular precursors, concentration and concentration ratios, organic ligands, or reaction time, and temperature) enables control of the nanowire diameter from 6 to 33,nm, while their length can be adjusted between several tens of nanometers and tens of micrometers. The obtained CdSe nanowires exhibit an admixture of wurtzite (W) and zinc blende (ZB) structure, which is investigated by X-ray diffraction. The diameter-dependent band gaps of these nanowires can be varied between 650 and 700,nm while their fluorescence intensities are mainly governed by the Cd/Se precursor ratio and the ligands used. [source] Lewis Basic Ionic Liquids-Catalyzed Conversion of Carbon Dioxide to Cyclic CarbonatesADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 13 2010Zhen-Zhen Yang Abstract A series of easily prepared Lewis basic ionic liquids were developed for cyclic carbonate synthesis from epoxide and carbon dioxide at low pressure without utilization of any organic solvents or additives. Notably, quantitative yields together with excellent selectivity were attained when 1,8-diazabicyclo[5.4.0]undec-7-enium chloride ([HDBU]Cl) was used as a catalyst. Furthermore, the catalyst could be recycled over five times without appreciable loss of catalytic activity. The effects of the catalyst structure and various reaction parameters on the catalytic performance were investigated in detail. This protocol was found to be applicable to a variety of epoxides producing the corresponding cyclic carbonates in high yields and selectivity. Therefore, this solvent-free process thus represents an environmentally friendly example for the catalytic conversion of carbon dioxide into value-added chemicals by employing Lewis basic ionic liquids as catalyst. A possible catalytic cycle for the hydrogen bond-assisted ring-opening of epoxide and activation of carbon dioxide induced by the nucleophilic tertiary nitrogen of the ionic liquid was also proposed. [source] Novel Palladium-Catalysed Hydroamination of Myrcene and Catalyst Separation by Thermomorphic Solvent SystemsADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 11-12 2010Arno Behr Abstract Hydroamination is an elegant and atom economical reaction to convert alkenes into amines. One of the few technical realisations of this reaction is the hydroamination of myrcene to diethylgeranylamine, an important precursor of (,)-menthol. However, this so-called "Takasago process" is catalysed by high amounts of alkali metals, especially lithium, which makes it a relatively expensive approach. In the present work, the hydroamination of myrcene with morpholine is catalysed by palladium complexes with bidentate ligands such as bis(diphenylphosphino)butane (DPPB) or bis(2-diphenylphosphinophenyl) ether (DPEphos). The systematic optimisation of the reaction parameters under single-phase conditions led to yields of the 1,4-adducts of higher than 90%. The only side products proved to be the telomers of myrcene, whose formation could be decreased by using appropriate reaction conditions. The method of temperature-dependent solvent systems was successfully applied to separate the palladium catalyst from the amines with a palladium leaching lower than 1.0%. [source] Metal-Free and Copper-Promoted Single-Pot Hydrocarboxylation of Cycloalkanes to Carboxylic Acids in Aqueous MediumADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 17 2009Marina Abstract A simple and effective method for the transformation, under mild conditions and in aqueous medium, of various cycloalkanes (cyclopentane, cyclohexane, methylcyclohexane, cis - and trans -1,2-dimethylcyclohexane, cycloheptane, cyclooctane and adamantane) into the corresponding cycloalkanecarboxylic acids bearing one more carbon atom, is achieved. This method is characterized by a single-pot, low-temperature hydrocarboxylation reaction of the cycloalkane with carbon monoxide, water and potassium peroxodisulfate in water/acetonitrile medium, proceeding either in the absence or in the presence of a metal promoter. The influence of various reaction parameters, such as type and amount of metal promoter, solvent composition, temperature, time, carbon monoxide pressure, oxidant and cycloalkane, is investigated, leading to an optimization of the cyclohexane and cyclopentane carboxylations. The highest efficiency is observed in the systems promoted by a tetracopper(II) triethanolaminate-derived complex, which also shows different bond and stereoselectivity parameters (compared to the metal-free systems) in the carboxylations of methylcyclohexane and stereoisomeric 1,2-dimethylcyclohexanes. A free radical mechanism is proposed for the carboxylation of cyclohexane as a model substrate, involving the formation of an acyl radical, its oxidation and consequent hydroxylation by water. Relevant features of the present hydrocarboxylation method, besides the operation in aqueous medium, include the exceptional metal-free and acid-solvent-free reaction conditions, a rare hydroxylating role of water, substrate versatility, low temperatures (ca. 50,°C) and a rather high efficiency (up to 72% carboxylic acid yields based on cycloalkane). [source] Induction of chemical and moisture resistance in Saccharum spontaneum L fiber through graft copolymerization with methyl methacrylate and study of morphological changesJOURNAL OF APPLIED POLYMER SCIENCE, Issue 3 2009Balbir Singh Kaith Abstract In this article, morphological modification of Saccharum spontaneum L, a natural fiber through graft copolymerization with methylmethacrylate using ferrous ammonium sulfate,potassium per sulfate redox initiator has been reported. Different reaction parameters such as reaction temperature, time, initiator molar ratio, monomer concentration, pH and solvent were optimized to get maximum graft yield (144%). The graft copolymers thus formed were characterized by Fourier transform infrared, scanning electron microscopy, X-ray diffraction and thermogravimetric, differential thermal analysis, and differential thermogravimetric techniques. Graft copolymer has been found to be more moisture resistant and also showed higher chemical and thermal resistance. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009 [source] Miniemulsion polymerization of a fluorinated acrylate copolymer: Kinetic studies and nanolatex morphology characterizationJOURNAL OF APPLIED POLYMER SCIENCE, Issue 1 2007Qinghua Zhang Abstract A stable fluoroacrylate copolymer emulsion was successfully prepared by miniemulsion polymerization with fluoroacrylate, lauryl methylacrylate, and methyl methacrylate as monomers. Extremely hydrophobic fluoroacrylate, instead of conventional cosurfactants, was used as a reactive cosurfactant to stabilize the miniemulsions. The results indicated that fluoroacrylate retarded Ostwald ripening and allowed the production of stable miniemulsions. The chemical compositions of the copolymer were studied with Fourier transform infrared and 1H-NMR. The average composition of the copolymers prepared with miniemulsions was in good agreement with the feed ratio according to 1H-NMR from the integration ratios corresponding to typical protons of the individual monomers. The particle size distribution and morphology of the latex particles were determined with laser particle analysis and transmission electron microscopy. The particle size of the latex underwent no change in the process of miniemulsion polymerization, but the particle size distributions were broader than those of conventional emulsion polymerization. The effects of various reaction parameters, including the temperature and concentrations of the emulsifier and initiator, on the miniemulsion polymerization were also investigated, and the polymerization rate and conversion increased with increasing concentrations of nonylphenol polyethoxylate (with an average of 40 ethylene oxide units per molecule), cetyltrimethylammonium, and 2,2,-azobisisobutyronitrile. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 641,647, 2007 [source] Optimization of the reaction parameters of epoxidation of rapeseed oil with peracetic acidJOURNAL OF CHEMICAL TECHNOLOGY & BIOTECHNOLOGY, Issue 8 2010Eugeniusz Milchert Abstract BACKGROUND: The epoxidation of vegetable oils has been a subject of interest for many years; epoxidized oils are frequently used as plasticizers and as renewable materials for the manufacture of alcohols, glycols and many other complex compounds with excellent antioxidant and antifriction properties. In this work the epoxidation process of rapeseed oil (RO) with peracetic acid generated in situ by the reaction of 30 wt% hydrogen peroxide and acetic acid has been studied. Optimization studies were performed by application of a statistical experimental design method utilizing a rotatable-uniform design. RESULTS: The significant parameters for the RO epoxidation process were established as temperature, molar ratio of hydrogen peroxide to rapeseed oil, molar ratio of acetic acid to rapeseed oil and reaction time. The process description was based on five response functions: iodine number, epoxy number, conversion, yield and selectivity. The highest values of all functions with the exception of selectivity were achieved for the same values of parameters: temperature 65 °C, molar ratio of hydrogen peroxide to RO 11.1:1 mol mol,1, molar ratio of acetic acid to RO 1.89:1 mol mol,1 and reaction time 6 h. CONCLUSION: In summary, these optimum parameters allow one to obtain epoxidized rapeseed oil with a yield of 66.2 mol% at an oil conversion of 91.0 mol% in mild and relatively safe conditions. The epoxy number of the product was 0.207 mol per 100 g, whereas the iodine number was 0.027 mol per 100 g. Copyright © 2010 Society of Chemical Industry [source] Lipase-catalyzed ethanolysis of soybean oil in a solvent-free system using central composite design and response surface methodologyJOURNAL OF CHEMICAL TECHNOLOGY & BIOTECHNOLOGY, Issue 6 2008Rafael Costa Rodrigues Abstract BACKGROUND: In this work we describe the synthesis of ethyl esters, commonly known as biodiesel, using refined soybean oil and ethanol in a solvent-free system catalyzed by lipase from Thermomyces lanuginosus. Central composite design and response surface methodology (RSM) were employed to optimize the biodiesel synthesis parameters, which were: reaction time, temperature, substrate molar ratio, enzyme content, and added water, measured as percentage of yield conversion. RESULTS: The optimal conditions obtained were: temperature, 31.5 °C; reaction time, 7 h; substrate molar ratio, 7.5:1 ethanol:soybean oil; enzyme content, 15% (g enzyme g,1 oil); added water, 4% (g water g,1 oil). The experimental yield conversion obtained under these conditions was 96%, which is very close to the maximum predicted value of 94.4%. The reaction time-course at the optimal values indicated that 5 h was necessary to obtain high yield conversions. CONCLUSION: A high yield conversion was obtained under the optimized conditions, with relative low enzyme content and short time. Comparison of predicted and experimental values showed good correspondence, implying that the empirical model derived from RSM can be used to adequately describe the relationship between the reaction parameters and the response (yield conversion) in lipase-catalyzed biodiesel synthesis. Copyright © 2008 Society of Chemical Industry [source] Preparation and animal biodistribution of 166Ho labeled DOTA for possible use in intravascular radiation therapy (IVRT)JOURNAL OF LABELLED COMPOUNDS AND RADIOPHARMACEUTICALS, Issue 3 2003Tapas Das Owing to its favorable decay characteristics (T1/2=27 h, E,(max)=1.85 MeV, E,=81 keV) and its availability with a specific activity of 3.7,4.4 GBq/mg from a moderate flux reactor, 166Ho can be considered as a potential radionuclide for intravascular radiation therapy (IVRT) using liquid-filled balloons. In the present work, studies on the use of 166Ho labeled 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid (DOTA) as a possible agent for IVRT for the prevention of restenosis has been initiated. 166Ho was obtained by irradiating natural Ho2O3 powder and DOTA was synthesized by a multistep procedure. The optimum protocol of radiolabeling of DOTA with 166Ho was achieved by varying different reaction parameters. The complex was found to retain its stability for 7 days at room temperature. Bioevaluation studies carried out in Wistar rats showed that >95% of the injected activity was excreted within 3 h p.i. with almost no retention in any major organ. Both radiochemical and biological studies showed that 166Ho labeled DOTA can be further explored as a potential agent for IVRT. Copyright © 2002 John Wiley & Sons, Ltd. [source] Modeling and inferential control of the batch acetylation of celluloseAICHE JOURNAL, Issue 6 2006Anshul Dubey Abstract The batch acetylation of cellulose involves two main stages, acetylation followed by hydrolysis. Mathematical models were constructed for these processes using reaction parameters obtained from earlier publications. The two models were then combined, along with a model predicting the cellulose feedstock moisture content. The overall temperature profiles as well as the final degree of acetylation and polymerization were shown to match the data obtained from a commercial process. From the results of the model and the observations made in a typical process, it has been established that this process is highly sensitive to disturbances in the input streams that can result in unacceptable final properties of the batch. Because the exact disturbance occurring in a batch cannot be identified and measured, inferential control is used to formulate an intrabatch control strategy. Support vector regression is used to make predictions on the final properties of the batch. These predictions, along with the model of the hydrolysis stage, are used to estimate the inputs that, when applied during hydrolysis, can counter the disturbances caused during the acetylation stage. Simulations show that this hydrolysis control strategy can improve the average batch properties of cellulose acetate required for subsequent processing. © 2006 American Institute of Chemical Engineers AIChE J, 2006 [source] Kinetic parameters for step and flash imprint lithography photopolymerizationAICHE JOURNAL, Issue 2 2006Michael D. Dickey Abstract Step and Flash Imprint Lithography (SFIL) is a high-resolution, yet low-cost nanopatterning technique that employs an acrylate-based, free-radical photo-polymerization to replicate a patterned template onto a substrate. Modeling the photo-polymerization requires knowledge of the values of several reaction parameters, which are unique to the acrylate formulation used in SFIL. The values of these parameters were experimentally determined for use in a previously described kinetic model. The rate coefficient for initiation, kI, was determined by measuring the absorbance spectrum of the initiator, Darocur® 1173, and convolving it with the intensity spectrum from the irradiation source. The reaction coefficients kp and kt were measured using the dark polymerization method. The experimental values of both parameters were then mathematically modeled to reflect the changes that occur as a function of conversion. Measuring the kinetic parameters provides insight into the fundamental steps involved in the polymerization. © 2005 American Institute of Chemical Engineers AIChE J, 2006 [source] Ethylene polymerization and ethylene/hexene copolymerization with vanadium(III) catalysts bearing heteroatom-containing salicylaldiminato ligandsJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 14 2009Ji-Qian Wu Abstract A series of novel vanadium(III) complexes bearing heteroatom-containing group-substituted salicylaldiminato ligands [RNCH(ArO)]VCl2(THF)2 (Ar = C6H4, R = C3H2NS, 2a; C7H4NS, 2c; C7H5N2, 2d; Ar = C6H2tBu2 (2,4), R = C3H2NS, 2b) have been synthesized and characterized. Structure of complex 2c was further confirmed by X-ray crystallographic analysis. The complexes were investigated as the catalysts for ethylene polymerization in the presence of Et2AlCl. Complexes 2a,d exhibited high catalytic activities (up to 22.8 kg polyethylene/mmolV h bar), and affording polymer with unimodal molecular weight distributions at 25,70 °C in the first 5-min polymerization, whereas produced bimodal molecular weight distribution polymers at 70 °C when polymerization time prolonged to 30 min. The catalyst structure plays an important role in controlling the molecular weight and molecular weight distribution of the resultant polymers produced in 30 min polymerization. In addition, ethylene/hexene copolymerizations with catalysts 2a,d were also explored in the presence of Et2AlCl, which leads to the high molecular weight and unimodal distributions copolymers with high comonomer incorporation. Catalytic activity, comonomer incorporation, and polymer molecular weight can be controlled over a wide range by the variation of catalyst structure and the reaction parameters, such as comonomer feed concentration, polymerization time, and polymerization reaction temperature. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 3573,3582, 2009 [source] Synthesis and reactivity of allyl nickel(II) N -heterocyclic carbene enolate complexesJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 16 2007Stefan Benson Abstract Two new N -heterocyclic carbene enolate nickel(II) allyl complexes have been prepared and their activity towards ethylene polymerization was investigated. It was found that in the presence of diethyl zinc, the carbene enolate complex bearing a nitro substituent produces highly linear polyethylene of modest molecular weight and high polydispersity. The influence of the reaction parameters on catalytic activity and the characteristics of the resulting polymer were investigated through systematic variation of the time, temperature, and diethyl zinc concentration. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45:3637,3647, 2007 [source] Vinyl polymerization of norbornene by bis(nitro-substituted-salicylaldiminate)nickel(II)/methylaluminoxane catalystsJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 4 2006Carlo Carlini Abstract The polymerization of norbornene has been investigated in the presence of different bis(salicylaldiminate)nickel(II) precursors activated by methylaluminoxane. These systems are highly active in affording nonstereoregular vinyl-type polynorbornenes (PNBs) with high molecular weights. The productivity of the catalytic systems is strongly enhanced (up to 35,000 kg of PNB/mol of Ni × h) when electron-withdrawing nitro groups are introduced on the phenol moiety. On the contrary, the presence of bulky alkyl groups on the N -aryl moiety of the ligand does not substantially affect the activity or characteristics of the resulting PNBs. The catalytic performances are also markedly influenced by the reaction parameters, such as the nature of the solvent, the reaction time, and the monomer/Ni and Al/Ni molar ratios. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1514,1521, 2006 [source] Ethylene/,-olefin copolymerization with bis(,-enaminoketonato) titanium complexes activated with modified methylaluminoxaneJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 24 2005Li-Ming Tang Abstract Copolymerizations of ethylene with ,-olefins (i.e., 1-hexene, 1-octene, allylbenzene, and 4-phenyl-1-butene) using the bis(,-enaminoketonato) titanium complexes [(Ph)NC(R2)CHC(R1)O]2TiCl2 (1a: R1 = CF3, R2 = CH3; 1b: R1 = Ph, R2 = CF3; and 1c: R1 = t -Bu, R2 = CF3), activated with modified methylaluminoxane as a cocatalyst, have been investigated. The catalyst activity, comonomer incorporation, and molecular weight, and molecular weight distribution of the polymers produced can be controlled over a wide range by the variation of the catalyst structure, ,-olefin, and reaction parameters such as the comonomer feed concentration. The substituents R1 and R2 of the ligands affect considerably both the catalyst activity and comonomer incorporation. Precatalyst 1a exhibits high catalytic activity and produces high-molecular-weight copolymers with high ,-olefin insertion. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 6323,6330, 2005 [source] Synthesis of highly crosslinked monodisperse polymer particles: Effect of reaction parameters on the size and size distributionJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 23 2002J. Choi Abstract Monodisperse polystyrene particles crosslinked with different concentrations of divinylbenzene were synthesized in the 3.2,9.1 ,m size range by dispersion polymerization in an isopropyl alcohol/toluene mixed-dispersion medium with poly(N -vinylpyrrolidone) as a steric stabilizer and 2,2,-azobisisobutyronitrile as a radical initiator. The effects of the reaction parameters such as the crosslinking agent concentration, media solvency (controlled by varying the amount of toluene addition), the initiator concentration, and the stabilizer concentration on the particle size and size distribution were investigated with reference particles with a monodisperse size distribution and crosslinked by 1.5 wt % divinylbenzene. The appropriate increase in media solvency was a prerequisite for preparing crosslinked particles without coagulated and/or odd-shaped particles. The investigation of the effects of the polymerization parameters also shows that only specific sets of conditions produce particles with a monodisperse size distribution. The glass-transition temperatures of the particles increased with increasing divinylbenzene concentration. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 4368,4377, 2002 [source] Physico-enzymatic production of monoacylglycerols enriched with very-long-chain polyunsaturated fatty acidsJOURNAL OF THE SCIENCE OF FOOD AND AGRICULTURE, Issue 2 2008Ratchapol Pawongrat Abstract BACKGROUND: Monoacylglycerols (MAG) containing polyunsaturated fatty acids (PUFA), especially eicosapentaenoic acid (EPA) and docosahexaenoic acid (DHA), have interesting applications. The enzymatic processing of such MAG directly from fish oils is highly interesting, integrating the processing of MAG and concentration of EPA and DHA. The aim of this study was to develop an efficient enzymatic glycerolysis system together with physical fractionation for the production of PUFA-MAG from tuna oil. RESULTS: Novozym 435 was eventually selected after evaluation together with immobilized lipase AK in a tertiary alcohol-based system. A further evaluation of solvent mixtures involving tertiary alcohols was made, taking ease of operation into consideration. It turned out that a number of mixtures gave a similar performance to that of tert -butanol (TB). Basic reaction parameters were thoroughly evaluated. In the batch reaction system with TB as solvent, the recommended conditions were: glycerol/tuna oil 4:1 (mol/mol), TB/tuna oil 2:1 (wt/wt), 15 wt% Novozym 435, and temperature 40 °C. Under these conditions, the yield of MAG was up to 90% after 3 h incubation. Crude MAG from the production was fractionated to produce MAG with higher EPA and DHA content. Using acetone as solvent at 0 °C led to ca 50% yield of MAG but contained EPA and DHA up to 71% in comparison with ca 30% in tuna oil. CONCLUSION: Potentially practical process steps have been developed for the production of MAG containing a high content of EPA and DHA from natural fish oils with high efficiency and simplicity. Copyright © 2007 Society of Chemical Industry [source] Papain hydrolysates of casein: molecular weight profile and encapsulation in lipospheresJOURNAL OF THE SCIENCE OF FOOD AND AGRICULTURE, Issue 14 2004Cristiane MS Barbosa Abstract Some reaction parameters were tested in the hydrolysis of casein by papain, in order to prepare hydrolysates with high oligopeptide contents, for either dietetic or pharmaceutical purposes. Five casein hydrolysates were prepared and then fractionated by size-exclusion HPLC. The rapid correct fraction area method was used for quantifying peptides and free amino acids. Among the five reaction conditions tested, three produced similar peptide profiles. However, the use of a temperature of 37°C and an E:S ratio of 2% is probably the most economical condition for use in large-scale manufacture. With the aim of masking the bitterness of these preparations, a new method, based on the encapsulation in lipospheres, was used. Also, second derivative spectrophotometry was used for the first time to measure the extent of encapsulation of protein hydrolysates, which changed from 50% to 83%. Moreover, the efficiency of this system was evaluated by analysing other parameters, which showed a reduction of hydrophobicity and bitterness of all samples, as well as good chemical stability during 60 days of storage under refrigeration. The electron microscopical analysis of liposheres showed an average size around 5.0 ± 1.0 µm. Copyright © 2004 Society of Chemical Industry [source] Study of Laser-Induced Photopolymerizations by Optical PyrometryMACROMOLECULAR CHEMISTRY AND PHYSICS, Issue 15 2004Patrick Lin Abstract Summary: Studies of the 355 nm laser induced free radical and cationic photopolymerization reactions of mono- and multifunctional monomers were conducted. These investigations were carried out with the aid of a specially constructed optical pyrometry instrument that provides rapid, reproducible temperature versus time profiles for these fast photopolymerization reactions. Using this technique, the effects of various reaction parameters and monomer structures on the rate and extent of the photopolymerization reactions were examined. Optical pyrometry instrument for the monitoring of laser-induced photopolymerizations. [source] Dispersion copolymerization of methyl methacrylate and acrylic acid in polar media: effects of reaction parameters on the particle size and size distribution of the copolymer microspheresPOLYMER INTERNATIONAL, Issue 5 2003Jin-Xia Huang Abstract Micron-size functional crosslinked poly(methyl methacrylate) (PMMA) particles with narrow size distribution in the range of 1,5 µm were prepared by dispersion copolymerization in polar media with poly(N -vinylpyrrolidone)(PVP) as steric stabilizer, 2,2,-azobisisobutyronitrile(AIBN) as initiator and ethylene glycol dimethylacrylate (EGDMA) as crosslinking agent. The effects of functional comonomer acrylic acid (AA) concentration, contents in AIBN, EGDMA and PVP, media polarity as well as reaction temperature on the particle size and size distribution were investigated. Particle size initially increased, and then decreased with increasing AA concentration in the range of 0.7,3.5 mol l,1, having a maximum of 5.01 µm at the concentration of 2.1 mol l,1, while size distribution became broader. This was regarded as the result of different roles of PAA in the process. Particle size increased with decreasing media polarity and stabilizer concentration, and with increasing initiator concentration and reaction temperature. The resulting particle shapes were observed by transmission electron microscopy and the presence of carboxyl groups on the surface of the particles was confirmed by Fourier-transform infrared spectroscopy. Copyright © 2003 Society of Chemical Industry [source] Developing a novel alkaline anion exchange membrane derived from poly(ether-imide) for improved ionic conductivityPOLYMERS FOR ADVANCED TECHNOLOGIES, Issue 8 2010Guigui Wang Abstract We have developed a novel alkaline anion exchange membrane derived from poly(ether-imide) for improved ionic conductivity. The effects of several important parameters on the chloromethylation of the membrane were investigated. These parameters included reaction temperature, reaction time, concentration of chloromethylation agent, concentration of polymer, and the amount of catalyst. The quaternization of the synthesized chloromethylated polymer was studied as well. The results show that all the studied parameters exhibited significant impacts on chloromethylation. Among them, the concentration of the chloromethylation agent played a key role in increasing the chloromethyl functional group attachment onto the polymer. It was found that the gelation could be avoided if these reaction parameters were controlled. It was also found that using an appropriate quaternization approach could significantly improve the ionic conductivity and optimize the conductivity of the membrane even though the functional chloromethyl groups attached to the polymer are limited. Copyright © 2009 John Wiley & Sons, Ltd. [source] Synthesis of graft copolymers of xyloglucan and acrylonitrilePOLYMERS FOR ADVANCED TECHNOLOGIES, Issue 2 2008Anuradha Mishra Abstract Xyloglucan (XG), a water-soluble food grade polysaccharide is reported as a substrate for the graft copolymerization of acrylonitrile (AN). XG was extracted from tamarind seed mucilage. Polymerization was initiated both by ceric ion in aqueous medium under N2 atmosphere and with microwave (MW) irradiation. The progress of the reaction was monitored gravimetrically. The effect of different reaction parameters such as monomer concentration, level of ceric ammonium nitrate/HNO3 (CAN) initiator, reaction time and temperature, and MW power on the percent grafting (PG) was studied. Grafting of polyacrylonitrile (PAN) onto XG was confirmed by Fourier-transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), and scanning electron microscope (SEM) techniques have been used to study the thermal and morphological changes in the materials. Copyright © 2007 John Wiley & Sons, Ltd. [source] Preparation and swelling behavior of amphoteric superabsorbent composite with semi-IPN composed of poly(acrylic acid)/Ca-bentonite/poly(dimethyldiallylammonium chloride)POLYMERS FOR ADVANCED TECHNOLOGIES, Issue 3 2007Liuchun Zheng Abstract Amphoteric superabsorbent composite with semi-interpenetrating polymer networks (semi-IPN) composed of poly(acrylic acid) (PAA)/Ca-bentonite/poly(dimethyldiallylammonium chloride) (PDMDAAC) was prepared by a combination of intercalative polymerization and a sequential IPN method and the effects of reaction parameters on the swelling capacity were studied. PDMDAAC was used as a polycation to modify bentonite and form semi-IPN with lightly crosslinked PAA. FTIR and TG were used to characterize the amphoteric superabsorbent composites with semi-IPN. The thermal stability of the product was not degraded as in the case of using small molecular surfactant to modify bentonite. The contents of carboxylic groups and nitrogen had been determined. This indicated that the product with certain content of carboxylic groups and nitrogen is inclined to exhibit excellent swelling capacity. The presence of PDMDAAC improved the swelling capacity. The resulting amphoteric superabsorbent composite showed excellent swelling capacity of 1578,g/g in distilled water and 136,g/g in 0.9,wt% NaCl solution. Copyright © 2007 John Wiley & Sons, Ltd. [source] | ||||||||||||||||||||||||||||