Kinetic Experiments (kinetic + experiment)

Distribution by Scientific Domains
Distribution within Chemistry

Selected Abstracts

Evolution of Permanent Deformations (or Memory) in Nafion 117 Membranes with Changes in Temperature, Relative Humidity and Time, and Its Importance in the Development of Medium Temperature PEMFCs,

FUEL CELLS, Issue 4 2009
G. Alberti
Abstract An important problem for medium temperature polymer electrolyte fuel cells (MT PEMFCs) operating in the temperature range 90,140,°C is the short time-life of proton conducting membranes. To shed some light on the empirical annealing treatments used for increasing the membrane durability, a systematic research on the effects of thermal treatments of Nafion 117 membranes was undertaken with the hope that the information obtained could be useful for a better understanding of the real limits for MT PEMFCs. Kinetic experiments showed that, for each couple of T,RH values, the water taken up from the membrane reaches a constant value only after long times of equilibration (,200,h). Taking into account that the enlargements provoked by the water-uptake remain as permanent deformations when the samples are cooled, it was found that the evolution of the deformations provoked by changes in temperature and RH can be conveniently estimated at 20,°C by determining the water taken up after equilibration in liquid water. By relating the counter-elastic index of the matrix (nc(m)) to the extent of these deformations, a set of equations were obtained which allowed us to predict their evolution with changes of temperature and relative humidity. A good agreement with experimental values was found. The importance of this discovery for the development of MT PEMFCs is discussed. [source]

Studies on the cellular uptake of substance P and lysine-rich, KLA-derived model peptides,

Johannes Oehlke
Abstract In the last decade many peptides have been shown to be internalized into various cell types by different, poorly characterized mechanisms. This review focuses on uptake studies with substance P (SP) aimed at unravelling the mechanism of peptide-induced mast cell degranulation, and on the characterization of the cellular uptake of designed KLA-derived model peptides. Studies on structure,activity relationships and receptor autoradiography failed to detect specific peptide receptors for the undecapeptide SP on mast cells. In view of these findings, a direct interaction of cationic peptides with heterotrimeric G proteins without the participation of a receptor has been proposed. Such a process would require insertion into and translocation of peptides across the plasma membrane. In order to clarify whether a transport of cationic peptides into rat peritoneal mast cells is possible, transport studies were performed by confocal laser scanning microscopy (CLSM) using fluorescence-labeled Arg3,Orn7 -SP and its D -amino acid analog, all- D -Arg3,Orn7 -SP, as well as by electron microscopic autoradiography using 3H-labelled SP and 125I-labelled all- D -SP. The results obtained by CLSM directly showed translocation of SP peptides into pertussis toxin-treated cells. Kinetic experiments indicated that the translocation process was rapid, occurring within a few seconds. Mast cell degranulation induced by analog of magainin 2 amide, neuropeptide Y and the model peptide acetyl-KLALKLALKALKAALKLA-amide was also found to be very fast, pointing to an extensive translocation of the peptides. In order to learn more about structural requirements for the cellular uptake of peptides, the translocation behavior of a set of systematically modified KLA-based model peptides has been studied in detail. By two different protocols for determining the amount of internalized peptide, evidence was found that the structure of the peptides only marginally affects their uptake, whereas the efflux of cationic, amphipathic peptides is strikingly diminished, thus allowing their enrichment within the cells. Although the mechanism of cellular uptake, consisting of energy-dependent and -independent contributions, is not well understood, KLA-derived peptides have been shown to deliver various cargos (PNAs, peptides) into cells. The results obtained with SP- and KLA-derived peptides are discussed in the context of the current literature. Copyright © 2004 John Wiley & Sons, Ltd. [source]

Synthesis of well-defined photoresist materials by SET-LRP

Sven Fleischmann
Abstract Single electron transfer-living radical polymerization (SET-LRP) provides an excellent tool for the straightforward synthesis of well-defined macromolecules. Heterogeneous Cu(0)- catalysis is employed to synthesize a novel photoresist material with high control over the molecular architecture. Poly(,-butyrolactone methacrylate)- co -(methyladamantly methacrylate) was synthesized. Kinetic experiments were conducted demonstrating that both monomers, ,-butyrolactone methacrylate (GBLMA) and methyl adamantly methacrylate (MAMA), are successfully homopolymerized. In both cases polymerization kinetic is of first order and the molecular weights increase linearly with conversion. The choice of a proper solvent was decisive for the SET-LRP process and organic solvent mixtures were found to be most suitable. Also, the kinetic of the copolymerization of GBLMA and MAMA was investigated. Following first order kinetics in overall monomer consumption and exhibiting a linear relationship between molecular weights and conversion a "living" process was established. This allowed for the straightforward synthesis of well-defined photoresist polymers. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2251,2255, 2010 [source]

Catalytic effect of dissolved humic acids on the chemical degradation of phenylurea herbicides

Stefano Salvestrini
Abstract BACKGROUND: Although biodegradation seems to be the main cause of herbicide degradation, abiotic degradation can also be important for chemicals such as phenylureas, which are subject to catalysed soil reactions. The aim of this work is to investigate the effect of dissolved humic acids (HAs), normally present in natural waters, on the hydrolysis of phenylurea herbicides, and it presents a kinetic model that takes into account the role of adsorption. RESULTS: The linearity of the adsorption isotherms indicates that phenylurea,humic acid interaction can be considered in terms of a repartition-like equilibrium of phenylurea between water and HAs. Kinetic experiments show that the degradation rates of phenylureas increase with HA concentration. CONCLUSION: The kinetic equation adopted adequately describes the experimental data trend, allowing the evaluation of the catalytic effect of HAs on the chemical degradation of phenylureas. Carboxyl groups of HAs seem to play a leading role in the catalysis. The kinetic equation derived in this work could be helpful in predicting the persistence of phenylureas and of related compounds in natural water. Copyright © 2008 Society of Chemical Industry [source]

A unified mechanism for protein folding: Predetermined pathways with optional errors

Mallela M.G. Krishna
Abstract There is a fundamental conflict between two different views of how proteins fold. Kinetic experiments and theoretical calculations are often interpreted in terms of different population fractions folding through different intermediates in independent unrelated pathways (IUP model). However, detailed structural information indicates that all of the protein population folds through a sequence of intermediates predetermined by the foldon substructure of the target protein and a sequential stabilization principle. These contrary views can be resolved by a predetermined pathway,optional error (PPOE) hypothesis. The hypothesis is that any pathway intermediate can incorporate a chance misfolding error that blocks folding and must be reversed for productive folding to continue. Different fractions of the protein population will then block at different steps, populate different intermediates, and fold at different rates, giving the appearance of multiple unrelated pathways. A test of the hypothesis matches the two models against extensive kinetic folding results for hen lysozyme which have been widely cited in support of independent parallel pathways. The PPOE model succeeds with fewer fitting constants. The fitted PPOE reaction scheme leads to known folding behavior, whereas the IUP properties are contradicted by experiment. The appearance of a conflict with multipath theoretical models seems to be due to their different focus, namely on multitrack microscopic behavior versus cooperative macroscopic behavior. The integration of three well-documented principles in the PPOE model (cooperative foldons, sequential stabilization, optional errors) provides a unifying explanation for how proteins fold and why they fold in that way. [source]

Src kinase activation: A switched electrostatic network

Elif Ozkirimli
Abstract Src tyrosine kinases are essential in numerous cell signaling pathways, and improper functioning of these enzymes has been implicated in many diseases. The activity of Src kinases is regulated by conformational activation, which involves several structural changes within the catalytic domain (CD): the orientation of two lobes of CD; rearrangement of the activation loop (A-loop); and movement of an ,-helix (,C), which is located at the interface between the two lobes, into or away from the catalytic cleft. Conformational activation was investigated using biased molecular dynamics to explore the transition pathway between the active and the down-regulated conformation of CD for the Src-kinase family member Lyn kinase, and to gain insight into the interdependence of these changes. Lobe opening is observed to be a facile motion, whereas movement of the A-loop motion is more complex requiring secondary structure changes as well as communication with ,C. A key result is that the conformational transition involves a switch in an electrostatic network of six polar residues between the active and the down-regulated conformations. The exchange between interactions links the three main motions of the CD. Kinetic experiments that would demonstrate the contribution of the switched electrostatic network to the enzyme mechanism are proposed. Possible implications for regulation conferred by interdomain interactions are also discussed. [source]

N-terminal extension changes the folding mechanism of the FK506-binding protein

Alla Korepanova
Abstract Many of the protein fusion systems used to enhance the yield of recombinant proteins result in the addition of a small number of amino acid residues onto the desired protein. Here, we investigate the effect of short (three amino acid) N-terminal extensions on the equilibrium denaturation and kinetic folding and unfolding reactions of the FK506-binding protein (FKBP) and compare the results obtained with data collected on an FKBP variant lacking this extension. Isothermal equilibrium denaturation experiments demonstrated that the N-terminal extension had a slight destabilizing effect. NMR investigations showed that the N-terminal extension slightly perturbed the protein structure near the site of the extension, with lesser effects being propagated into the single ,-helix of FKBP. These structural perturbations probably account for the differential stability. In contrast to the relatively minor equilibrium effects, the N-terminal extension generated a kinetic-folding intermediate that is not observed in the shorter construct. Kinetic experiments performed on a construct with a different amino acid sequence in the extension showed that the length and the sequence of the extension both contribute to the observed equilibrium and kinetic effects. These results point to an important role for the N terminus in the folding of FKBP and suggest that a biological consequence of N-terminal methionine removal observed in many eukaryotic and prokaryotic proteins is to increase the folding efficiency of the polypeptide chain. [source]

Life-cycle kinetic model for endospore-forming bacteria, including germination and sporulation

Seongjun Park
Abstract We develop a mechanistic life-cycle model for endospore-forming bacteria (EFB) and test the model with experiments with a Bacillus mixed culture. The model integrates and quantifies how sporulation and germination are triggered by depletion or presence of a limiting substrate, while both substrates affect the rate of vegetative growth by a multiplicative model. Kinetic experiments show the accumulation of small spherical spores after the triggering substrate is depleted, substantially more rapid decay during sporulation than for normal decay of vegetative cells, and a higher specific substrate utilization rate for the germinating cells than that for growth of vegetative cells. Model simulations capture all of these experimental trends. According to model predictions, when a batch reactor is started, seeding with EFB spores instead of active EFB delays the onset of rapid chemical oxygen demand (COD) utilization and biomass growth, but the end points are the same. Simulated results with low aeration intensity show that germination can consume some substrate without dissolved oxygen (DO) depletion. Biotechnol. Bioeng. 2009; 104: 1012,1024. © 2009 Wiley Periodicals, Inc. [source]

A Kinetic Model for Suspended and Attached Growth of a Defined Mixed Culture

Kawai Tam
Kinetic experiments were carried out in a semicontinuous wastewater treatment process called self-cycling fermentation (SCF) using a defined mixed culture and various concentrations of synthetic brewery wastewater. The same consortium, which had been previously identified as Acinetobacter sp., Enterobacter sp., and Candida sp., were used in these experiments. The overall rate of substrate removal was attributable to both suspended microbes and the biofilm that formed during the treatment process. A rate expression was developed for the SCF system for a range of synthetic wastewaters containing glucose and various initial concentrations of ethanol and maltose. The data indicated that substrate removal by the suspended cells was directly related to the biomass concentration. However, substrate removal by the biofilm was apparently not affected by the biofilm thickness and was a function of substrate concentration only. [source]

Optimization of the nitroxide-mediated radical polymerization conditions for styrene and tert -butyl acrylate in an automated parallel synthesizer

C. Remzi Becer
Abstract Automated parallel synthesizers provide fast and comparable screening of different polymerization parameters under similar conditions. In addition, these robotic systems eliminate handling errors, which may affect the results of a kinetic experiment more than the effect of an important parameter. The polymerization temperature and N,N - tert -butyl- N -[1,-diethylphosphono-2,2,-dimethylpropyl]nitroxide concentration were optimized for the homopolymerization of both styrene and tert -butyl acrylate to improve the control over the polymerization while reasonable polymerization rates were retained. Subsequently, polystyrene and poly(tert -butyl acrylate) macro initiators were synthesized according to the knowledge obtained from the screening results. These macroinitiators were used for the preparation of block copolymers consisting of styrene and tert -butyl acrylate. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6202,6213, 2006 [source]

A model predicting waterborne cadmium bioaccumulation in Gammarus pulex: The effects of dissolved organic ligands, calcium, and temperature

Bastien Pellet
Abstract Metal bioavailability depends on the presence of organic ligands in the water and on the concentrations of competitive cations. The present study aims at testing whether the diffusive gradient in thin films technique (DGT) could be used to take into account Cd speciation and its consequences on bioavailability in a bioaccumulation model and whether the influences of the Ca concentration and temperature also should be considered. Four kinetic experiments were conducted on Gammarus pulex: a calibration of Cd turnover rates and of the DGT lability in mineral water, a study of the influence of ethylenediaminetetraacetic acid (EDTA) and humic acids (HA) on uptake rates, and two experiments testing the influence of the Ca concentrations and temperature on Cd uptake clearance rates (ku). In mineral water, where Cd was considered fully labile, the ku was 0.46 L g,1 d,1, and the depuration rate was 0.032 d,1. The initial Cd influxes were lowered significantly by additions of 10 ,g L,1 of EDTA or 10 mg L,1 of HA in the water but not at 5 mg L,1 HA, even if DGT measurements proved that Cd formed Cd,HA complexes in that treatment. Increasing Ca concentrations lowered ku values, and a competitive inhibition model between Ca and Cd fitted the data. A 30% enhancement of ku values was observed when the temperature was increased by 8°C, which appeared comparatively as a weak effect. Thus, taking into account the metal speciation and the influence of the Ca concentration should improve Cd bioaccumulation modeling in amphipods. In freshwater, where metal bioavailability is reduced by the presence of dissolved organic matter, forecasting Cd waterborne uptake using the labile concentrations should allow robust comparisons between laboratory and field studies. [source]

Kinetic mechanism for p38 MAP kinase ,

FEBS JOURNAL, Issue 18 2005
A partial rapid-equilibrium random-order ternary-complex mechanism for the phosphorylation of a protein substrate
p38 Mitogen-activated protein kinase alpha (p38 MAPK,) is a member of the MAPK family. It is activated by cellular stresses and has a number of cellular substrates whose coordinated regulation mediates inflammatory responses. In addition, it is a useful anti-inflammatory drug target that has a high specificity for Ser-Pro or Thr-Pro motifs in proteins and contains a number of transcription factors as well as protein kinases in its catalog of known substrates. Fundamental to signal transduction research is the understanding of the kinetic mechanisms of protein kinases and other protein modifying enzymes. To achieve this end, because peptides often make only a subset of the full range of interactions made by proteins, protein substrates must be utilized to fully elucidate kinetic mechanisms. We show using an untagged highly active form of p38 MAPK,, expressed and purified from Escherichia coli[Szafranska AE, Luo X & Dalby KN (2005) Anal Biochem336, 1,10) that at pH 7.5, 10 mm Mg2+ and 27 °C p38 MAPK, phosphorylates ATF2,115 through a partial rapid-equilibrium random-order ternary-complex mechanism. This mechanism is supported by a combination of steady-state substrate and inhibition kinetics, as well as microcalorimetry and published structural studies. The steady-state kinetic experiments suggest that magnesium adenosine triphosphate (MgATP), adenylyl (,,,-methylene) diphosphonic acid (MgAMP-PCP) and magnesium adenosine diphosphate (MgADP) bind p38 MAPK, with dissociation constants of KA = 360 µm, KI = 240 µm, and KI > 2000 µm, respectively. Calorimetry experiments suggest that MgAMP-PCP and MgADP bind the p38 MAPK,,ATF2,115 binary complex slightly more tightly than they do the free enzyme, with a dissociation constant of Kd , 70 µm. Interestingly, MgAMP-PCP exhibits a mixed inhibition pattern with respect to ATF2,115, whereas MgADP exhibits an uncompetitive-like pattern. This discrepancy occurs because MgADP, unlike MgAMP-PCP, binds the free enzyme weakly. Intriguingly, no inhibition by 2 mm adenine or 2 mm MgAMP was detected, suggesting that the presence of a ,-phosphate is essential for significant binding of an ATP analog to the enzyme. Surprisingly, we found that inhibition by the well-known p38 MAPK, inhibitor SB 203580 does not follow classical linear inhibition kinetics at concentrations >,100 nm, as previously suggested, demonstrating that caution must be used when interpreting kinetic experiments using this inhibitor. [source]

Peculiar kinetics of the complex formation in the iron(III),sulfate system

Balázs Kormányos
The results of comprehensive equilibrium and kinetic studies of the iron(III),sulfate system in aqueous solutions at I = 1.0 M (NaClO4), in the concentration ranges of T = 0.15,0.3 mM, and at pH 0.7,2.5 are presented. The iron(III),containing species detected are FeOH2+ (=FeH,1), (FeOH) (=Fe2H,2), FeSO, and Fe(SO4) with formation constants of log , = ,2.84, log , = ,2.88, log , = 2.32, and log , = 3.83. The formation rate constants of the stepwise formation of the sulfate complexes are k1a = 4.4 × 103 M,1 s,1 for the step and k2 = 1.1 × 103 M,1 s,1 for the step. The mono-sulfate complex is also formed in the reaction with the k1b = 2.7 × 105 M,1 s,1 rate constant. The most surprising result is, however, that the 2 FeSO, Fe3+ + Fe(SO4) equilibrium is established well before the system as a whole reaches its equilibrium state, and the main path of the formation of Fe(SO4) is the above fast (on the stopped flow scale) equilibrium process. The use and advantages of our recently elaborated programs for the evaluation of equilibrium and kinetic experiments are briefly outlined. © 2008 Wiley Periodicals, Inc. Int J Chem Kinet 40: 114,124, 2008 [source]

Spectrophotometric variable-concentration kinetic experiments applied to inorganic reactions

Giuseppe Alibrandi
The dependence of the observed rate constant of inorganic substitution reactions on the concentration of nucleophilic reagents was obtained by single variable-parameter kinetic runs. The experiments were carried out spectrophotometrically, varying the concentration of the nucleophile inside the reaction vessel. Software and apparatus were developed for an easy and rapid performance. The method gives accurate results and a saving in time by a factor of up to 100 compared to conventional methods. © 2003 Wiley Periodicals, Inc. Int J Chem Kinet 35: 497,502, 2003 [source]

Kinetic Study of the Asymmetric Hydrogenation of Methyl Acetoacetate in the Presence of a Ruthenium Binaphthophosphepine Complex

Eva Öchsner
Abstract The asymmetric hydrogenation of methyl acetoacetate (MAA) in methanol using dibromobis{(S)-4-phenyl-4,5-dihydro-3H -dinaphtho[2,1- c: 1,,2,- e]phosphepine}-ruthenium was studied in detail. For the determination of the reaction network, data from kinetic experiments were compared to different possible reaction networks using the kinetic software Presto Kinetics. The simulation was optimised to describe the reaction accurately with a minimal set of process parameters and reaction equations. For the best model the reaction orders, collision factors and activation energy of all reaction steps were determined. Additionally, the influence of reaction temperature and hydrogen pressure on the enantiomeric excess (ee) of the reaction was studied. It was found that high reaction temperatures and high hydrogen pressures result in increasing enantioselectivities. [source]

Inter-subtype cross-neutralizing antibodies recognize epitopes on cell-associated HIV-1 virions

Helen Donners
Abstract HIV-1 infected individuals with cross-neutralizing antibodies against primary HIV-1 isolates belonging to Group M (env A-H) and O, are identified. To investigate the neutralization-kinetics of primary isolates with these antibodies, different neutralization assay conditions are compared. Each set is summarized as a/b/c where a is the time in hours for which antibody is incubated with virus, b is the time in hours allowed for virus to absorb to cells, c is the total culture period in days, from the cells' first exposure to virus, before antigen production (peripheral blood mononuclear cells) or number of fluorescent cells (GHOST) are measured. In HIV-infected individuals, neutralizing antibodies can be detected against a wide range of primary isolates (Group M; A,H and Group O) in PBMC-assays with short incubation phases (1/2/7 or 1/24/7). If cultures are extended (1/2/14 or 1/24/14), however, neutralization can be lost. In kinetic experiments, neutralization can even be seen without pre-incubation (a,=,0 hr). This study shows that neutralization of primary HIV isolates by cross-reactive antibodies can continue after the virus has bound to its target cell. This neutralization, however, is not an all or nothing loss in virus infectivity. Most often it leads only to a reduction in viral replication rates. J. Med. Virol. 69:173,181, 2003. © 2003 Wiley-Liss, Inc. [source]

Contributions of hydrophobic domain interface interactions to the folding and stability of human ,D-crystallin

Shannon L. Flaugh
Abstract Human ,D-crystallin (H,D-Crys) is a monomeric eye lens protein composed of two highly homologous ,-sheet domains. The domains interact through interdomain side chain contacts forming two structurally distinct regions, a central hydrophobic cluster and peripheral residues. The hydrophobic cluster contains Met43, Phe56, and Ile81 from the N-terminal domain (N-td) and Val132, Leu145, and Val170 from the C-terminal domain (C-td). Equilibrium unfolding/refolding of wild-type H,D-Crys in guanidine hydrochloride (GuHCl) was best fit to a three-state model with transition midpoints of 2.2 and 2.8 M GuHCl. The two transitions likely corresponded to sequential unfolding/refolding of the N-td and the C-td. Previous kinetic experiments revealed that the C-td refolds more rapidly than the N-td. We constructed alanine substitutions of the hydrophobic interface residues to analyze their roles in folding and stability. After purification from E. coli, all mutant proteins adopted a native-like structure similar to wild type. The mutants F56A, I81A, V132A, and L145A had a destabilized N-td, causing greater population of the single folded domain intermediate. Compared to wild type, these mutants also had reduced rates for productive refolding of the N-td but not the C-td. These data suggest a refolding pathway where the domain interface residues of the refolded C-td act as a nucleating center for refolding of the N-td. Specificity of domain interface interactions is likely important for preventing incorrect associations in the high protein concentrations of the lens nucleus. [source]

Simulation and validation of ethanol removal from water in an adsorption packed bed: Isotherm and mass transfer parameter determination in batch studies

R. A. Jones
Abstract Preferential adsorption of ethanol from ethanol/water mixtures in batch equilibrium and kinetic experiments were carried out on a commercially available activated carbon adsorbent Filtrasorb 600 (F-600). A model based on finite difference method was developed and employed to determine the mass transfer parameters and equilibrium behaviour for the adsorption of ethanol from simple batch systems. The estimates of the adsorption isotherm along with the mass transfer parameters were used to simulate the transient performance that could be expected in a packed bed under various operating conditions (feed flow rate, feed concentration, and particle size). The applicability of the simulation results were found to be a good match with experimental packed bed experiments over the entire range of operating conditions tested. La cinétique et l'isotherme d'adsorption de l'éthanol des mélanges eau/éthanol lors d'expériences en discontinus ont été déterminées pour un adsorbant au charbon activé disponible dans le commerce, le Filtrasorb 600 (F-600). Un modèle basé sur la méthode des différences finies a été développé et utilisé pour déterminer les paramètres de transfert de matière et étudier le comportement à l'équilibre pour l'adsorption préférentielle de l'éthanol en systèmes discontinus. Les estimations de l'isotherme d'adsorption aussi bien que les paramètres de transfert de matière ont été utilisées pour simuler la performance en régime transitoire d'un lit d'adsorbant sous diverses conditions de fonctionnement (taux d'écoulement du mélange, concentration du mélange et la taille des particules). L'applicabilité des résultats de simulation s'est avérée tout à fait concordante avec les données expérimentales sous toutes les conditions de fonctionnement examinées. [source]

Self and nonself recognition of chiral catalysts: The origin of nonlinear effects in the amino-alcohol catalyzed asymmetric addition of diorganozincs to aldehydes

Ryoji Noyori
Abstract Asymmetric addition of dialkylzincs to aldehydes in the presence of (2S)-3- exo -(dimethylamino)isoborneol [(S)-DAIB] exhibits various nonclassical phenomena. The enantiomeric excess (ee) of the alkylation product, obtained with partially resolved DAIB, is much higher than that of the chiral amino alcohol, while the rate decreases considerably as the ee of DAIB is lowered. The asymmetric amplification effects reflect the relative turnover numbers of two enantiomorphic catalytic cycles, where an essential feature is the reversible homochiral and heterochiral dimerization of the coexisting enantiomeric DAIB-based Zn catalysts. The interplay between the thermodynamics of the monomer/dimer equilibration and the kinetics of alkylation reaction strongly affect the overall profile of asymmetric catalysis. The self and nonself recognition of the chiral Zn catalysts is a general phenomenon when (S)-DAIB is mixed with its enantiomer, diastereomer, or even an achiral ,-amino alcohol. The degree of nonlinearity is highly affected not only by the structures and purity of catalysts but also by various reaction parameters. The salient features have been clarified on the basis of molecular weight measurements, NMR and X-ray crystallographic studies of organozinc complexes, and kinetic experiments, as well as computer-aided quantitative analysis. © 2001 John Wiley & Sons, Inc. and The Japan Chemical Journal Forum Chem Rec 1:85,100, 2001 [source]

Kinetics and mechanism of Cr(VI) adsorption onto tea-leaves waste

Md. Salatul Islam Mozumder
Abstract Adsorption equilibrium and kinetic experiments have been conducted in batch mode to evaluate Cr(VI)-tea-leaves waste system. The equilibrium data followed the Langmuir adsorption isotherm and the adsorption was viewed as a physicochemical reversible process. A unified approach model was used to describe the adsorption system from both equilibrium and kinetic viewpoints. The model satisfactorily described both kinetic and equilibrium data. The adsorption and desorption rate constants were evaluated from the model fittings and were not dependent on initial concentration and adsorbent doses. pHzpc of the adsorbent was evaluated as 4.2 ± 0.1, and below that pH the adsorbent surface is positively charged. Adsorption of Cr(VI) was found highly pH-dependent, and the removal efficiency dropped sharply from 95 to 10% when pH of the system changed from 2 to 5. The surface functional groups of tea-leaves waste (before and after adsorption) were analyzed by Fourier transform infrared (FTIR) and the amine groups were found to take part in the adsorption of Cr(VI). The experimental result inferred that electrostatic attraction between the surface and the species is one of the major adsorption mechanisms for binding metal ions to the tea-leaves waste. Copyright © 2008 Curtin University of Technology and John Wiley & Sons, Ltd. [source]

Cyclic Carbonate Synthesis Catalysed by Bimetallic Aluminium,Salen Complexes

William Clegg Prof.
Abstract The development of bimetallic aluminium,salen complexes [{Al(salen)}2O] as catalysts for the synthesis of cyclic carbonates (including the commercially important ethylene and propylene carbonates) from a wide range of terminal epoxides in the presence of tetrabutylammonium bromide as a cocatalyst is reported. The bimetallic structure of one complex was confirmed by X-ray crystallography. The bimetallic complexes displayed exceptionally high catalytic activity and in the presence of tetrabutylammonium bromide could catalyse cyclic carbonate synthesis at atmospheric pressure and room temperature. Catalyst-reuse experiments demonstrated that one bimetallic complex was stable for over 60 reactions, though the tetrabutylammonium bromide decomposed in situ by a retro-Menschutkin reaction to form tributylamine and had to be regularly replaced. The mild reaction conditions allowed a full analysis of the reaction kinetics to be carried out and this showed that the reaction was first order in aluminium complex concentration, first order in epoxide concentration, first order in carbon dioxide concentration (except when used in excess) and unexpectedly second order in tetrabutylammonium bromide concentration. Further kinetic experiments demonstrated that the tributylamine formed in situ was involved in the catalysis and that addition of butyl bromide to reconvert the tributylamine into tetrabutylammonium bromide resulted in inhibition of the reaction. The reaction kinetics also indicated that no kinetic resolution of racemic epoxides was possible with this class of catalysts, even when the catalyst was derived from a chiral salen ligand. However, it was shown that if enantiomerically pure styrene oxide was used as substrate, then enantiomerically pure styrene carbonate was formed. On the basis of the kinetic and other experimental data, a catalytic cycle that explains why the bimetallic complexes display such high catalytic activity has been developed. [source]