Kinetic Investigations (kinetic + investigation)

Distribution by Scientific Domains

Selected Abstracts

Kinetic investigation on the reactions of p -toluenesulfonyl chloride with p -substituted benzoic acid(s) in the presence of triethylamine in aprotic solvents

Subbiah Ananthalakshmi
Second-order rate constants of the reactions of p -toluenesulfonyl chloride with p -substituted benzoic acids in the presence of triethylamine in acetonitrile/acetone under equimolar and pseudo-first-order conditions have been determined by the conductometric method using the Guggenheim principle at 25, 30, 35, and 40°C. The reactions follow second order with respect to the whole and first order with respect to each of the reactants. The order of reactivity of the substituents in benzoic acid is rationalized. Activation parameters are obtained by applying the usual methods. The Hammett plot has been found nonlinear, whereas the Bronsted plot shows good correlation. This may be explained on the basis of electronic effects of substituents on the reaction center. Kinetic data and the product analyses indicate that the reaction proceeds through direct nucleophilic attack on the sulfur center. © 2009 Wiley Periodicals, Inc. Int J Chem Kinet 41: 303,308, 2009 [source]

Kinetic investigation on the oxidation of nitrite by oxochromium(V) ion in aqueous and micellar systems

Mookandi Kanthimathi
The kinetics of oxidation of nitrite by [O = CrV (5-chlorosalen)]+ complex has been studied spectrophotometrically at [CrV] = 0.5 × 10,3 M, [NO2,] = 0.01,0.1 M, [H+] = 0.0001,0.05 M, I = 0.15 M, and T = 25°C in the presence of cationic surfactant, cetyl pyridium chloride (CPC), and anionic surfactant, sodium dodecyl sulfate (SDS),in aqueous acidic medium. The oxygen atom transfer reaction from O = CrV to nitrite ion is influenced by the ionic nature of the micelle. The redox reaction is accelerated in presence of CPC and slowed down by 40 times in presence of SDS. The mechanism of the reaction involves an inner-sphere process involving the formation of an intermediate followed by oxo transfer process. © 2003 Wiley Periodicals, Inc. Int J Chem Kinet 36: 79,86 2004 [source]

Surface modification of nylon-6 fibers for medical applications

S. E. Shalaby
Abstract Hydroxyethylmethacrylate (HEMA) is considered to be one of the important vinyl monomers. The ability of polyhydroxyethyl-methacylate (PHEMA) graft sites to consecutive chemical modification makes the use of nylon-6 fibers grafted with PHEMA a feasible bed for immobilization of a wide range of biologically active reagents, specially enzymes, drugs, cells, and immunadsorbents. Stemming from the above discussions, in this article, the graft copolymerization of HEMA onto modified nylon-6 fibers containing Polydiallyldimethylammonium chloride (PDADMAC) in the presence of Cu2+,K2S2O8 as a redox initiating system was carried out, with very high rate and almost without homopolymer formation. The factors affecting the grafting reaction (monomer, K2S2O8 and cupric ion concentrations, the amount of PDADMAC as well as the reaction temperature) were studied. Kinetic investigation revealed that the rate of grafting (Rp) of HEMA onto modified nylon-6 fibers is proportional to [HEMA]1, [CuSO4.5H2O] 0.7, [PDADMAC]0.4, and [K2S2O8]1.4. The overall activation energy was calculated (71 KJ/mol). The fine structure, surface topography, thermal and electrical properties of parent and grafted nylon-6 fibers were investigated. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 3788,3796, 2007 [source]

Kinetic investigation of the RAFT polymerization of p -acetoxystyrene

Solène I. Cauët
Abstract The kinetics of the RAFT polymerization of p -acetoxystyrene using a trithiocarbonate chain transfer agent, S -1-dodecyl- S,-(,,,,-dimethyl-,,-acetic acid)trithiocarbonate, DDMAT, was investigated. Parameters including temperature, percentage initiator, concentration, monomer-to-chain transfer agent ratio, and solvent were varied and their impact on the rate of polymerization and quality of the final polymer examined. Linear kinetic plots, linear increase of Mn with monomer conversion, and low final molecular weight dispersities were used as criteria for the selection of optimized polymerization conditions, which included a temperature of 70 or 80 °C with 10 mol % AIBN initiator in bulk for low conversions or in 1,4-dioxane at a monomer-to-solvent volume ratio of 1:1 for higher conversions This study opens the way for the use of DDMAT as a chain transfer agent for RAFT polymerization to incorporate p -acetoxystyrene together with other functional monomers into well-defined copolymers, block copolymers, and nanostructures. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2517,2524, 2010 [source]

Highly Selective Cobalt-Catalyzed Hydrovinylation of Styrene

Michiel 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]

Synthesis of Phenyl Arylsulfonyl-alkyl-dithiocarbamates and Their Hydrolytic Reactivity in Hydroxide and Hydroperoxide Media

Fátima Norberto
Abstract Eight previously unreported phenyl arylsulfonyl-alkyl-dithiocarbamates were synthesized by treatment of arylsulfonamides with phenyl chlorodithioformate in an adaptation of a general amine acylation method. A kinetic investigation of their alkaline hydrolysis was performed and the experimental data are discussed. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005) [source]

Equilibrium and kinetic investigation of the interaction of model palladium(II) complex with biorelevant ligands

Mohamed M. Shoukry
Pd(DME)Cl2 complex was synthesized and characterized, where DME is 2-{[2-(dimethylamino)ethyl]-methylamino}ethanol. Stoichiometry and stability constants of the complexes formed between various biologically relevant ligands (amino acids, peptides, DNA constituents, and dicarboxylic acids) and [Pd(DME)(H2O)2]2+ are investigated at 25°C and at constant 0.1 M ionic strength. The effect of dielectric constant of the medium on the stability constant of Pd(DME)-CBDCA complex, where CBDCA is cyclobutanedicarboxylate, is also reported. The concentration distribution diagrams of the various species formed are evaluated. The kinetics of base hydrolysis of amino acid esters coordinated to Pd(DME)2+ complex is investigated. The effect of the temperature on the kinetics of base hydrolysis of glycine methyl ester complex is studied. © 2010 Wiley Periodicals, Inc. Int J Chem Kinet 42: 608,618, 2010 [source]

Kinetic study on the prooxidative effect of vitamin C on the autoxidation of glycerol trioleate in micelles

Zai-Qun Liu
Abstract Vitamin C (L -ascorbic acid) protects human health by scavenging toxic free radicals and other reactive oxygen species formed in cell metabolism. The surplus supplementation of vitamin C, however, may be harmful to health because the level of 8-oxoguanine and 8-oxoadenine in lymphocyte DNA varies remarkably. In the process of the kinetic investigation on the 2,2,-azobis(2-amidinopropane dihydrochloride) (AAPH)-induced autoxidation of glycerol trioleate (GtH) in the micelles of cetyl trimethyl ammonium bromide (CTAB), sodium dodecyl sulfate (SDS) and Triton X-100, the addition of vitamin C accelerates the autoxidation of GtH even in the absence of the free radical initiator, AAPH. The initiating rate, Ri, of vitamin C (VC)-induced autoxidation of GtH is related to the micelle charge, i.e. Ri,=,14.4,×,10,6 [VC] s,1 in SDS (anionic micelle), Ri,=,1961,×,10,6 [VC] s,1 in Triton X-100 (neutral micelle) and Ri is a maximum in CTAB (cationic micelle) when the vitamin C concentration is ,300,µM. Thus, vitamin C can initiate autoxidation of GtH in micelles, especially in the neutral one. Moreover, the attempt to explore whether ,-tocopherol (TocH) could rectify vitamin C-induced autoxidation of GtH leads us to find that the rate constant of TocH reacting with the anionic radical of vitamin C (VC.,), k,inh, is ,103M,1,s,1, which is less than that of the ,-tocopherol radical (Toc.) with vitamin C (kinh,=,,105,M,1,s,1). Thus, the equilibrium constant of the reaction Toc.+VC,,TocH+VC., is prone strongly to the regeneration of Toc. by vitamin C rather than the reverse reaction. Copyright © 2006 John Wiley & Sons, Ltd. [source]

Simultaneous Spark Plasma Synthesis and Densification of TiC,TiB2 Composites

Antonio M. Locci
The simultaneous synthesis and densification of dense TiC,TiB2 composite has been investigated starting from Ti, B4C, and C as reactants, and using the spark plasma sintering (SPS) technique. The optimal conditions for complete conversion of the reactants to the composite were determined for different applied DC current levels. A kinetic investigation performed allows us to conclude that solid-state diffusion is the mechanism governing the synthesis process. It is seen that TiC is the first phase formed, while TiB2 formation occurs afterward. Two intermediate boride phases, i.e. TiB and Ti3B4, are also formed but, as the SPS holding time was augmented, they were gradually and completely converted to TiB2. Moreover, it is found that in order to reach relatively high dense products, an electric current needs to be applied for time intervals longer than those required for obtaining complete conversion. A pure dense product (relative density ,98%) was obtained when an electric pulsed current of 1100 A and a mechanical pressure of 20 MPa were applied for about 4 min. [source]

Alloying with copper to reduce metal dusting of nickel

J. Zhang
Abstract Copper is thought to be noncatalytic to carbon deposition from gas atmospheres, and owing to its extremely low solubility for carbon, inert to the metal dusting reaction. Thus, the addition of copper to nickel, which forms a near perfect solid solution, may be able to suppress or greatly retard the metal dusting of the alloy, without the need for a protective oxide scale on the surface. The dusting behaviour of Ni-Cu alloys containing up to 50 wt% Cu, along with pure Cu, was investigated in a 68%CO-31%H2 -1%H2O gas mixture (aC: 19) at 680°C for up to 150 h. Surface analysis showed that two types of carbon deposits, graphite particle clusters and filaments, were observed on pure Ni and Ni-Cu alloys with Cu contents of up to 5 wt%. Alloys with more than 10 wt% Cu showed very little coking, forming filaments only. SEM and TEM analyses revealed metal particles encapsulated by graphite shells within the graphite particle clusters, and metal particles at filament tips or embedded along their lengths. A kinetic investigation showed that alloy dusting rates decreased significantly with increasing copper levels up to 10 wt%. At copper concentrations of more than 20 wt%, the rate of metal dusting was negligible. Although pure copper is not catalytic to carbon formation, scattered carbon nanotubes were observed on its surface. The effect of copper on alloy dusting rates is attributed to a dilution effect. [source]

Investigation of mechanism of Al(OH)3 crystal growth

I. Nikoli
Abstract Crystallization of Al(OH)3 that occurs during the decomposition of caustic soda solutions is an important part of Bayer process for alumina production. Several phenomena, which influence the physicochemical characteristics of precipitated Al(OH)3, occur simultaneously during this process. They are nucleation, agglomeration, and crystal growth of Al(OH)3. In this article, we have investigated the mechanism of Al(OH)3 crystal growth from pure caustic soda solutions and in the presence of oxalic acid. The results have shown that the growth of Al(OH)3 crystals from caustic soda solutions follow the B,+,S model (birth and spread). New Al(OH)3 particles, formed during the decomposition process of pure caustic soda solutions, are characterized by regular hexagonal shape. The nuclei have the same geometry as the contact face. However, microstructural investigations of Al(OH)3 samples, obtained by crystallization from caustic soda solutions in the presence of oxalic acid, have shown the presence of nuclei of irregular shape in addition to regular ones. So, the presence of oxalic acid in the caustic soda solutions leads to a change in crystal habit. Besides, the results obtained by kinetic investigation confirmed the mentioned mechanism of Al(OH)3 crystal growth. La cristallisation de l'Al(OH)3 qui accompagne la décomposition de solutions de soude caustique est une caractéristique importante du procédé Bayer de production d'alumine. Plusieurs phénomènes influant sur les caractéristiques physicochimiques de l'Al(OH)3 précipité, se produisent simultanément lors de ce procédé. Ce sont la nucléation, l'agglomération et la croissance des cristaux de l'Al(OH)3. Dans cet article, nous avons étudié le mécanisme de croissance des cristaux de l'Al(OH)3 à partir de solutions de soude caustique pures et en présence d'acide oxalique. Les résultats montrent que la croissance des cristaux d'Al(OH)3 à partir des solutions de soude caustique suit le modèle B,+,S (naissance (birth),+,dispersion (spread)). Les nouvelles particules d'Al(OH)3, formées lors du procédé de décomposition des solutions de soude caustique, se caractérisent par une forme hexagonale régulière. Les nuclei ont la même géométrie que la face de contact. Cependant, des recherches sur la microstructure des échantillons d'Al(OH)3 obtenus par cristallisation à partir des solutions de soude caustique en présence d'acide oxalique, montrent la présence de nuclei de forme irrégulière en plus de ceux de forme régulière. Ainsi, la présence d'acide oxalique dans les solutions de soude caustique mène à un changement dans le comportement des cristaux. En outre, les résultats obtenus dans l'étude cinétique confirment ce mécanisme de croissance des cristaux d'Al(OH)3. [source]

Proton-Coupled Electron Transfer of Unsaturated Fatty Acids and Mechanistic Insight into Lipoxygenase

Shunichi Fukuzumi
Abstract A proton-coupled electron transfer (PCET) process plays an important role in the initial step of lipoxygenases to produce lipid radicals which can be oxygenated by reaction with O2 to yield the hydroperoxides stereoselectively. The EPR spectroscopic detection of free lipid radicals and the oxygenated radicals (peroxyl radicals) together with the analysis of the EPR spectra has revealed the origin of the stereo- and regiochemistry of the reaction between O2 and linoleyl (=,(2Z)-10-carboxy-1-[(1Z)-hept-1-enyl]dec-2-enyl) radical in lipoxygenases. The direct determination of the absolute rates of H-atom-transfer reactions from a series of unsaturated fatty acids to the cumylperoxyl (=,(1-methyl-1-phenylethyl)dioxy) radical by use of time-resolved EPR at low temperatures together with detailed kinetic investigations on both photoinduced and thermal electron-transfer oxidation of unsaturated fatty acids provides the solid energetic basis for the postulated PCET process in lipoxygenases. A strong interaction between linoleic acid (=,(9Z,12Z)-octadeca-9,12-dienoic acid) and the reactive center of the lipoxygenases (FeIIIOH) is suggested to be involved to make a PCET process to occur efficiently, when an inner-sphere electron transfer from linoleic acid to the FeIII state is strongly coupled with the proton transfer to the OH group. [source]

Palladium-Catalyzed Transformation of Renewable Oils into Diesel Components

Junxing Han
Abstract A size-controlled palladium nanoparticle catalyst prepared by adsorption of colloidal palladium nanoparticles on barium sulfate is efficient and highly selective in transforming vegetable oils into diesel-like fuel. Preliminary kinetic investigations using model compounds indicated that decarboxylation of aliphatic esters on palladium in a hydrogen-rich atmosphere showed a zero-order rate. Hydrogen temperature-programmed desorption measurements revealed that the high-temperature desorption of hydrogen species might be the rate-determining step. [source]

A Selective and Benign Synthesis of Functionalized Benzalacetones via Mizoroki,Heck Reaction Using Aryldiazonium Salts

Therese Stern
Abstract Palladium-catalyzed Mizoroki,Heck reactions were carried out in the presence of calcium carbonate in alcoholic solvents. Under these conditions an efficient preparation of functionalized benzalacetones was developed. The reactions were carried out at room temperature and aerobic conditions, giving the products within several minutes in up to 95% isolated yields. Furthermore, some kinetic investigations, mechanistic insights and considerations are presented. [source]

Significance of cell kinetic parameters in the prognosis of malignant melanoma: a review

Pierre Vereecken
The maximum tumor thickness as measured by Breslow's method is the cornerstone prognostic criterion, but despite this, evolution of the disease in some patients remains unpredictable, confirming that new reliable prognostic factors are awaited. Cell kinetic evaluation has been shown to be a useful tool for assessing the prognosis of breast and gastrointestinal cancer patients. Indeed, in these fields, the mitotic index and MIB-1 expression index, which are indirect estimates of the growth fraction of tumor cell population, are commonly shown to correlate with tumor grade and patient survival and presented as prognostic factors. In melanoma, results of cell kinetic investigations are conflicting: some studies have established a link between high proliferative activity and a bad prognosis, whereas other reports suggest the opposite. The aim of this review is to discuss these findings. [source]

Mechanistic understanding of the photochromism of a hybrid dithienylethene,naphthopyran system by NMR spectroscopy

S. Delbaere
Abstract Detailed 1H NMR kinetic investigations of the photochemical and thermal behaviour of a recently described poly-photochromic molecule including both dithienylethene and naphthopyran groups are reported. The combination of two photochromic moieties allows the selective controlled extension of the conjugated pi-electron system and the modulation of the absorption behaviour between ,380 to ,750,nm. It is shown that the two photochromic entities are coupled and do not behave independently. Copyright © 2007 John Wiley & Sons, Ltd. [source]

Ion rotating motion in a gas-filled radio-frequency quadrupole ion guide as a new technique for structural and kinetic investigations of ions

Valeri V. Raznikov
An ion rotating excitation mode of operation of a segmented gas-filled radio-frequency quadrupole (RFQ) ion guide for a high-resolution orthogonal time-of-flight (TOF) mass spectrometer is described. It is shown theoretically, by computer simulation and experimentally, that ion rotating excitation in a gas-filled RFQ has several advantages over other types of ion oscillation excitation. The main advantages are an approximately twofold increase in average ion kinetic energy for the same maximal deviation from the RFQ axis and therefore an increase of about this factor of average internal excitation energy of ions, and the extended mass range of fragment ions that can be observed. The new method of ion decomposition by ion rotation around the axis of an RFQ ion guide was experimentally implemented and tested using a home-built ,SIN-COS' generator to supply the excitation voltage. This generator enables control of phase shift and amplitude of excitation voltages applied to quadrupole rods smoothly from the data acquisition program running on a PC. Copyright © 2001 John Wiley & Sons, Ltd. [source]

Probing active-site residues of pyranose 2-oxidase from Trametes multicolor by semi-rational protein design

Clara Salaheddin
Abstract D -Tagatose is a sweetener with low caloric and non-glycemic characteristics. It can be produced by an enzymatic oxidation of D -galactose specifically at C2 followed by chemical hydrogenation. Pyranose 2-oxidase (P2Ox) from Trametes multicolor catalyzes the oxidation of many aldopyranoses to their corresponding 2-keto derivatives. Since D -galactose is not the preferred substrate of P2Ox, semi-rational design was employed to improve the catalytic efficiency with this poor substrate. Saturation mutagenesis was applied on all positions in the active site of the enzyme, resulting in a library of mutants, which were screened for improved activity in a 96-well microtiter plate format. Mutants with higher activity than wild-type P2Ox were chosen for further kinetic investigations. Variant V546C was found to show a 2.5-fold increase of kcat with both D -glucose and D -galactose when oxygen was used as electron acceptor. Because of weak substrate binding, however, kcat/KM is lower for both sugar substrates compared to wild-type TmP2Ox. Furthermore, variants at position T169, i.e., T169S and T169N, showed an improvement of the catalytic characteristics of P2Ox with D -galactose. Batch conversion experiments of D -galactose to 2-keto- D -galactose were performed with wild-type TmP2O as well as with variants T169S, T169N, V546C and V546C/T169N to corroborate the kinetic properties determined by Michaelis-Menten kinetics. [source]