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Kobs
Selected AbstractsSpatial and temporal habitat use of kob antelopes (Kobus kob kob, Erxleben 1777) in the Comoé National Park, Ivory Coast as revealed by radio trackingAFRICAN JOURNAL OF ECOLOGY, Issue 3 2001Frauke Fischer Abstract Spatial and temporal habitat use of kob antelopes (Kobus kob kob) have been investigated in the Comoé National Park (Ivory Coast, West Africa) by use of radio telemetry. A total of 23 kob were equipped with radio collars and radio tracked for up to 15 months. Home ranges of males were smaller and those of females larger than expected from theoretical models. Adult males used smaller areas than adult females and did not show seasonal home range shifts. Daily distances travelled did not differ between sexes. Kob walked less during the night than by day and covered shorter distances in the wet season. Whereas an increase in home range overlap between females resulted in higher rates of association among individuals, association of adults of mixed sexes was not correlated with the degree of home range overlap. Territorial behaviour of males and predator avoidance by females are suggested to explain the sex-specific differences in home range size of adults and the deviation from the predicted sizes. Predator avoidance is presumed as the main reason for the reduced walking distances at night as well as in the wet season. Reproductive behaviour and feeding ecology are assumed to determine the degree of association of conspecifics. Résumé On a étudié par radio-télémétrie l'utilisation spatiale et temporelle de l'habitat par les cobes (Kobus kob kob) au Parc National de Comoé (en Côte d'Ivoire, Afrique de l'Ouest). On a équipé un total de 23 cobes de colliers radio et on les a suivis pendant 15 mois (pour certains). L'espace vital des mâles était plus petit et celui des femelles plus grand que ce à quoi on s'attendait d'après les modèles théoriques. Les mâles adultes couvraient une zone plus réduite que les femelles adultes et ne déplaçaient pas leur espace vital en fonction des saisons. Les distances parcourues chaque jour étaient les mêmes pour les deux sexes. Les cobes se déplaçaient moins la nuit que le jour, et couvraient de plus courtes distances pendant la saison des pluies. Alors qu'une augmentation du recouvrement entre espaces vitaux des femelles aboutissait à un taux supérieur d'associations entre individus, l'association d'adultes des deux sexes n'était pas liée au taux de recouvrement des espaces vitaux. On suggère que le comportement territorial des mâles et l'évitement des prédateurs par les femelles pourraient expliquer les différences, spécifiques au sexe, de la dimension de l'espace vital des adultes et la déviation par rapport aux dimensions prévues. On suppose que l'évitement des prédateurs est la raison principale de la limitation des déplacements de nuit ainsi qu'en saison des pluies. On suppose que le comportement reproducteur et l'écologie alimentaire déterminent le degré d'association entre membres de la même espèce. [source] Characteristics and economic contribution of a developing recreational fishery in southern AngolaFISHERIES MANAGEMENT & ECOLOGY, Issue 1 2009W. M. POTTS Abstract, The characteristics and contribution of a developing recreational fishery to the local, regional and national economy of Angola were evaluated in 2006. Annual angling effort was 13 435 h, while the estimated total catch of the three target species [leerfish, Lichia amia (L.), west coast dusky kob, Argyrosomus coronus (Griffiths & Heemstra) and shad, Pomatomus saltatrix (L.)], was 5913 fish with a mass of 27 975 kg. Catch per unit effort (CPUE) for all teleost species combined was 0.44 fish per angler h,1 and 2.08 kg per angler h,1. Total harvest of the three species was 576 fish with a total mass of 2221.6 kg. The total contribution of this recreational fishery (mostly anglers from South Africa) to the local economy was US$ 1007 per harvested fish and US$ 243 per harvested kg. This equated to a contribution to the local, regional and national economies of US$ 151 685, US$ 44 767 and US$ 344 364 respectively. Although the regional contribution was less than half of the national contribution, it was regionally significant when the low population density and the general absence of other formal sector employment opportunities are considered. As a result of the largely undisturbed nature of the southern Angolan coastline, the catch, effort and CPUE information was considered suitable as a baseline for a cost-effective method of future fisheries monitoring in the region. [source] Introducing size limits as a management tool for the recreational line fishery of silver kob, Argyrosomus inodorus (Griffiths and Heemstra), in Namibian watersFISHERIES MANAGEMENT & ECOLOGY, Issue 3 2001C. H. Kirchner Individual silver kob Argyrosomus inodorus (Griffiths and Heemstra) first mature at just over 1 yr of age and the median age at maturity is approximately 1.5 yr. Spawning of silver kob was observed in the southern and central region of the stock's range, but little spawning activity was found in silver kob sampled from the northern region. The spawning period is protracted over 6 months (October,March), which coincides with warmer water temperatures (>15 °C) and the occurrence of large-sized spawning silver kob in the southern and central part of Namibia. Implementing a minimum size limit for the silver kob fishery is not recommended as it will have serious economic implications for the coastal communities. The protection of the spawning areas, Meob Bay and Sandwich, should be continued and a strict bag limit on large-sized silver kob is recommended for the Namibian silver kob recreational fishery. [source] Effect of short term exposure to the anaesthetic 2-phenoxyethanol on plasma osmolality of juvenile dusky kob, Argyrosomus japonicus (Sciaenidae)JOURNAL OF APPLIED ICHTHYOLOGY, Issue 3 2008A. K. Bernatzeder Summary The plasma osmolality of early juvenile dusky kob, Argyrosomus japonicus, exposed to 2-phenoxyethanol and control fish that were pithed prior to sampling, was investigated. Exposure to 2-phenoxyethanol, after 2, 4, 6, 8 and 10 min, did not alter plasma osmolality (Friedman test; P = 0.976). There was no significant relationship between the size of fish within the range 133,170 mm SL (40,85 g) and plasma osmolality. Finally, there was no significant difference in plasma osmolality between anaesthetized fish and the control group that were pithed directly after removal from the tanks. Anaesthetizing juvenile dusky kob with 2-phenoxyethanol prior to blood sampling did not affect plasma osmolality. [source] Spatial and temporal habitat use of kob antelopes (Kobus kob kob, Erxleben 1777) in the Comoé National Park, Ivory Coast as revealed by radio trackingAFRICAN JOURNAL OF ECOLOGY, Issue 3 2001Frauke Fischer Abstract Spatial and temporal habitat use of kob antelopes (Kobus kob kob) have been investigated in the Comoé National Park (Ivory Coast, West Africa) by use of radio telemetry. A total of 23 kob were equipped with radio collars and radio tracked for up to 15 months. Home ranges of males were smaller and those of females larger than expected from theoretical models. Adult males used smaller areas than adult females and did not show seasonal home range shifts. Daily distances travelled did not differ between sexes. Kob walked less during the night than by day and covered shorter distances in the wet season. Whereas an increase in home range overlap between females resulted in higher rates of association among individuals, association of adults of mixed sexes was not correlated with the degree of home range overlap. Territorial behaviour of males and predator avoidance by females are suggested to explain the sex-specific differences in home range size of adults and the deviation from the predicted sizes. Predator avoidance is presumed as the main reason for the reduced walking distances at night as well as in the wet season. Reproductive behaviour and feeding ecology are assumed to determine the degree of association of conspecifics. Résumé On a étudié par radio-télémétrie l'utilisation spatiale et temporelle de l'habitat par les cobes (Kobus kob kob) au Parc National de Comoé (en Côte d'Ivoire, Afrique de l'Ouest). On a équipé un total de 23 cobes de colliers radio et on les a suivis pendant 15 mois (pour certains). L'espace vital des mâles était plus petit et celui des femelles plus grand que ce à quoi on s'attendait d'après les modèles théoriques. Les mâles adultes couvraient une zone plus réduite que les femelles adultes et ne déplaçaient pas leur espace vital en fonction des saisons. Les distances parcourues chaque jour étaient les mêmes pour les deux sexes. Les cobes se déplaçaient moins la nuit que le jour, et couvraient de plus courtes distances pendant la saison des pluies. Alors qu'une augmentation du recouvrement entre espaces vitaux des femelles aboutissait à un taux supérieur d'associations entre individus, l'association d'adultes des deux sexes n'était pas liée au taux de recouvrement des espaces vitaux. On suggère que le comportement territorial des mâles et l'évitement des prédateurs par les femelles pourraient expliquer les différences, spécifiques au sexe, de la dimension de l'espace vital des adultes et la déviation par rapport aux dimensions prévues. On suppose que l'évitement des prédateurs est la raison principale de la limitation des déplacements de nuit ainsi qu'en saison des pluies. On suppose que le comportement reproducteur et l'écologie alimentaire déterminent le degré d'association entre membres de la même espèce. [source] Kinetic Study of the Oxidation of Catechols in the Presence of Some Aza-crown Ethers by Digital Simulation of Cyclic VoltammogramsELECTROANALYSIS, Issue 9 2009Davood Nematollahi Abstract The electrochemical oxidation of catechols (1) have been studied in the presence of diaza-18-crown-6 (DA18C6) (3a), diaza-15-crown-5 (DA15C5) (3b), and aza-15-crown-5 (A15C5) (3c) as nucleophiles in aqueous solution, by means of cyclic voltammetry and controlled-potential coulometry. The results indicate the participation of electrochemically generated o -benzoquinones (2) in Michael-type reaction with aza-crown ethers (3) to form the corresponding new o -benzoquinone-aza-crown ether adducts (5). Based on ECE mechanism, the observed homogeneous rate constants (kobs) of the reaction of o -bezoquinones (2) with aza-crown ethers (3) were estimated by comparing the experimental cyclic voltammograms with the digital simulated results. The calculated observed homogeneous rate constants (kobs) was found to vary in the order DA18C6>DA15C5>A15C5. [source] Kinetics of Bis(p -nitrophenyl)phosphate (BNPP) Hydrolysis Reactions with Trivalent Lanthanide Complexes of N -Hydroxyethyl(ethylenediamine)- N,N,,N, -triacetate (HEDTA),EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 8 2009C. Allen Chang Abstract Kinetic studies of hydrolysis reactions of BNPP [sodium bis(p -nitrophenyl)phosphate] with trivalent lanthanide (Ln3+) complexes of HEDTA [HEDTA = N -hydroxyethyl(ethylenediamine)- N,N,,N, -triacetate] were performed at pH 6.96,11.34 and 25 °C by a spectrophotometric method and by HPLC analysis. The reaction rates increase with increasing atomic number of lanthanide and solution pH from PrHEDTA to EuHEDTA and then decrease for heavier LnHEDTA complexes. Plots of pseudo-first-order rate constants (kobs) vs. pH could be fitted to the equation kobs = kLnL(OH)[LnL]T/{1,+,exp[,2.303(pH,,,pKh)]}, where kLnL(OH) is the rate constant for the reaction of LnHEDTA(OH), with BNPP, Kh is the hydrolysis constant of LnHEDTA, and [LnL]T is the total concentration of LnHEDTA. The pKh values obtained by the kinetic method are in the range 8.2,10.3 and are similar to those measured by potentiometric methods. At [LnL]T = 10,70 mM and pH 10.5, most of the observed pseudo-first-order rate constants could be fitted to a simple saturation kinetic model, kobs = k1K[LnHEDTA(OH),]/{1 + K[LnHEDTA(OH),]}, where K is the equilibrium constant for the formation for LnHEDTA(OH),BNPP and is in the range 2,147 M,1. The k1 values are in the range 1.12,×,10,5,2.71,×,10,3 s,1. The kobs data for TbHEDTA and HoHEDTA were fitted to a quadratic equation. It was observed that the dinuclear species are more reactive. ESI mass spectrometry confirmed that the reaction between BNPP and EuHEDTA is a simple hydrolysis but not a transesterification, presumably because the three inner-sphere coordinated water molecules are far away from the coordinated hydroxyethyl group. Hydrolysis is likely to occur by proton transfer from one inner-sphere coordinated water molecule to the deprotonated ethyl oxide group followed by nucleophilic attack of the resulting hydroxide ion on the bonded BNPP anion.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) [source] Efficient Increase of DNA Cleavage Activity of a Diiron(III) Complex by a Conjugating Acridine GroupEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 34 2007Xiao-Qiang Chen Abstract A new diferric complex, Fe2Lb, in which a DNA intercalator (acridine) is linked to a precursor diferric complex (Fe2La), has been designed and synthesised as a hydrolytic cleaving agent of DNA. Compared with Fe2La (without the DNA intercalator) (La: 2,6-bis{[(2-hydroxybenzyl)(pyridin-2-yl)methylamino]methyl}-4-methylphenol), Fe2Lb [Lb: 5-(acridin-9-yl)- N -(3,5-bis{[(2-hydroxybenzyl)(pyridin-2-yl)methylamino]methyl}-4-hydroxybenzyl)pentanamide] leads to a 14-fold increase in the cleavage efficiency of plasmid DNA due to the binding interaction between DNA and the acridine moiety. The interaction has been demonstrated by UV/Vis absorption, CD spectroscopy, viscidity experiments and thermal denaturation studies. The hydrolytic mechanism is supported by evidence from T4 DNA ligase assay, reactive oxygen species (ROS) quenching and BNPP [bis(4-nitrophenyl) phosphate, a DNA model] cleavage experiments. The pH dependence of the BNPP cleavage by Fe2La in aqueous buffer media shows a bell-shaped pH,kobs profile with an optimum point around a pH of 7.0 which is in good agreement with the maximum point of the pH-dependent relative concentration curve of active species from the pH titration experiments. The determination of the initial rates at a pH of 7.36 as a function of substrate concentration reveals saturation kinetics with Michaelis,Menten-like behaviour and Fe2La shows a rate acceleration increase of 4.7,×,106 times in the hydrolysis of BNPP. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source] The Reaction of (Bipyridyl)palladium(II) Complexes with Thiourea , Influence of DNA and Other Polyanions on the Rate of ReactionEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 2 2005Matteo Cusumano Abstract [Pd(bipy)(py)2](PF6)2 reacts stepwise with excess thiourea to give [Pd(tu)4](PF6)2. The kinetics of the second step, which refers to the replacement of bipyridyl in [Pd(bipy)(tu)2](PF6)2, have been studied in water and in the presence of calf thymus DNA, sodium polyriboadenylate, sodium polyvinylsulfonate or sodium polymetaphosphate at 25 °C and pH = 7 and a fixed sodium chloride concentration. The reaction follows a first order course and a plot of kobs against [thiourea]2 affords a straight line with a small intercept. DNA inhibits the process without altering the rate law. The kobs values decrease systematically on increasing the DNA concentration eventually tending to a limiting value. The values are larger at higher ionic strengths and the other polyanions show similar behaviour. The influence of DNA on the kinetics can be related to steric inhibition caused by noncovalent binding with the complex. Upon interaction with DNA, [Pd(bipy)(tu)2]2+ gives rise to immediate spectroscopic changes in the UV/Vis region as well as induced circular dichroism suggesting that the complex, like similar platinum(II) and palladium(II) species of bipyridyl, intercalates with the double helix. Such a type of interaction hampers the attack of the nucleophile at the metal centre inhibiting the reaction. The decrease in the rate of ligand substitution upon decreasing salt concentration but at a given DNA concentration is due to the influence of ionic strength on the complex,DNA interaction. The reactivity inhibition by single-stranded poly(A), polyvinylsulfonate or polymetaphosphate can be accounted for in terms of self-aggregation of the complex induced by the polyanion. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005) [source] Kinetic Studies of the Oxidative Addition and Transmetallation Steps Involved in the Cross-Coupling of Alkynyl Stannanes with Aryl Iodides Catalysed by ,2 -(Dimethyl fumarate)(iminophosphane)palladium(0) ComplexesEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 4 2004Bruno Crociani Abstract The complexes [Pd(,2 -dmfu)(P,N)] {dmfu = dimethyl fumarate; P,N = 2-(PPh2)C6H4,1-CH=NR, R = C6H4OMe-4 (1a), CHMe2 (2a), C6H3Me2 -2,6 (3a), C6H3(CHMe2)2 -2,6 (4a)} undergo dynamic processes in solution which consist of a P,N ligand site exchange through initial rupture of the Pd,N bond at lower energy and an olefin dissociation-association at higher energy. According to equilibrium constant values for olefin replacement, the complex [Pd(,2 -fn)(P,N)] (fn = fumaronitrile, 1b) has a greater thermodynamic stability than its dmfu analogue 1a. The kinetics of the oxidative addition of ArI (Ar = C6H4CF3 -4) to 1a and 2a lead to the products [PdI(Ar)(P,N)] (1c, 2c) and obey the rate law, kobs = k1A + k2A[ArI]. The k1A step involves oxidative addition to a reactive species [Pd(solvent)(P,N)] formed from dmfu dissociation. The k2A step is better interpreted in terms of oxidative addition to a species [Pd(,2 -dmfu)(solvent)(,1 -P,N)] formed in a pre-equilibrium step from Pd,N bond breaking. The complexes 1c and 2c react with PhC,CSnBu3 in the presence of an activated olefin (ol = dmfu, fn) to yield the palladium(0) derivatives [Pd(,2 -ol)(P,N)] along with ISnBu3 and PhC,CAr. The kinetics of the transmetallation step, which is rate-determining for the overall reaction, obey the rate law: kobs = k2T[PhC,CSnBu3]. The k2T values are markedly enhanced in more polar solvents such as CH3CN and DMF. The solvent effect and the activation parameters suggest an associative SE2 mechanism with substantial charge separation in the transition state. The kinetic data of the above reactions in various solvents indicate that, for the cross-coupling of PhC,CSnBu3 with ArI catalysed by 1a or 2a, the rate-determining step is represented by the oxidative addition and that CH3CN is the solvent in which the highest rates are observed. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004) [source] SN2 Displacement by Bromide Ions in Dichloromethane , The Role of Reverse MicellesEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 18 2006Lucia Brinchi Abstract Reverse micellar systems are of interest as reaction media because they are powerful models for biological compartmentalization, enzymatic catalysis and separation of biomolecules. Solutions of ionic surfactants in apolar solvents may contain reverse micelles, but they may also contain ion pairs, or small clusters, with waters of hydration. We studied the bimolecular reaction in CH2Cl2 solutions of cationic tetraalkylammonium bromide salts (onium salts), such as cetyltrimethylammonium bromide (CTABr), cetyltripropylammonium bromide (CTPABr) and tetra- n -butylammonium bromide (TBABr). Methylnaphthalene-2-sulfonate (,-MeONs), its 6-sulfonate derivative (,-MeONsS,) as the 2,6-lutidinium salt and methyl-5- N,N,N,trimethylammonium naphthalene-1-sulfonate (,-MeONsNT+) as the trifluoromethanesulfonate salt react with Br, in CH2Cl2. First-order rate constants, kobs, increase linearly and similarly for the three substrates with increasing concentrations of the onium salts. Reactions are faster with TBABr than they are with CTPABr and CTABr, and the reactivity of the three substrates is in the order: ,-MeONsNT+ >> ,-MeONsS, > ,-MeONs. The reactions are inhibited by the addition of H2O, but CTABr tolerates H2O in large excess. At [H2O]/[CTABr] = w0 , 6, "water-pool" reverse micelles form, and kobs for all three substrates is then independent of w0. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006) [source] Solvolysis of Some Arenediazonium Salts in Binary EtOH/H2O Mixtures under Acidic ConditionsEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 17 2003Román Pazo-Llorente Abstract We have determined the product distribution, the rate constants for dediazoniation product formation, and the solvolytic rate constants for 2-, 3-, and 4-methylbenzenediazonium ions (2-, 3-, and 4-MBD, respectively) loss in acidic ethanol/water mixtures over the whole composition range by a combination of spectrophotometric (UV/Vis) and high performance liquid chromatography (HPLC) measurements. The observed rate constants (kobs) for substrate loss are equal to those for product formation, and they remain essentially constant (2-MBD) with changing solvent composition but increase by a factor of ,2 (4MBD) on going from water to 100% EtOH. Up to four dediazoniation products , cresols (ArOH), chlorotoluene (ArCl), methylphenetole (ArOEt), and toluene (ArH) , were detected, depending on the solvent composition; the major dediazoniation products were the ArOH and ArOEt derivatives. The product selectivity (S) of the reaction towards nucleophiles is low and essentially constant with changing solvent composition, and good linear correlations between log kobs and YCl (solvent ionizing power) were observed for the three ArN2+ ions. All data are consistent with the rate-determining formation of an aryl cation, which reacts immediately with available nucleophiles. The data suggest that the distribution of neutral and anionic nucleophiles in the neighborhood of the ground state arenediazonium ion remains essentially unchanged upon dediazoniation, the observed product distribution reflecting the concentrations of nucleophiles in their immediate environment (i.e., in the first solvation shells of the arenediazonium ions). (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003) [source] Micellar Effects on the Reaction between an Arenediazonium Ion and the Antioxidants Gallic Acid and Octyl GallateHELVETICA CHIMICA ACTA, Issue 1 2008Losada Barreiro, Sonia Abstract The effect of sodium dodecyl sulfate (SDS) micelles on the reaction between the 3-methylbenzenediazonium (3MBD) ion and either the hydrophilic antioxidant gallic acid (GA) or the hydrophobic analogue octyl gallate (OG) have been investigated as a function of pH. Titration of GA in the absence and presence of SDS micelles showed that the micelles do not alter the first ionization equilibrium of GA. Analysis of the dependence of the observed rate constant (kobs) with pH shows that the reactive species are GA2, and OG,. Kinetics results in the absence and presence of SDS micelles suggest that SDS aggregates do not alter the expected reaction pathway. SDS Micelles inhibit the spontaneous decomposition of 3MBD as well as the reaction between 3MBD and either GA or OG, and upon increasing the SDS concentration, with kobs approaching the value for the thermal decomposition of 3MBD in the presence of SDS. Our results are consistent with the prediction of the pseudophase model and show that the origin of the inhibition for the reaction with GA is different to that for the reaction with OG; in the former case, the observed inhibition can be rationalized in terms of the micelle-induced electrostatic separation of reactants in the micellar Stern layer, whereas the observed inhibition in the reaction with OG is a consequence of the dilution effect caused by increasing SDS concentration, decreasing the local OG, concentration in the Stern layer. [source] Preferential solvational effects on the Cr(VI) oxidation of benzylamines in benzene/2-methylpropan-2-ol mixturesINTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 3 2010A. Thirumoorthi Imidazolium fluorochromate (IFC) oxidation of 11 meta- and para-substituted benzylamines, in varying mole fractions of benzene/2-methylpropan-2-ol binary mixtures, is first order in IFC and acid and zero order in substrate. The Hammett correlation yielded a U-shaped curve, indicating a change in the relative importance of bond formation and bond fission in the transition state. The rate data failed to correlate with macroscopic solvent parameters such as ,r and E. The correlation of kobs with Kamlet,Taft solvatochromic parameters suggests that H-bonding between the reacting species and the solvent plays a major role in governing the reactivity. © 2010 Wiley Periodicals, Inc. Int J Chem Kinet 42: 159,167, 2010 [source] Studies on the oxygen atom transfer reactions of peroxomonosulfate: Oxidation of glycolic acidINTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 3 2009S. Shailaja The kinetics of oxidation of glycolic acid, an ,-hydroxy acid, by peroxomonosulfate (PMS) was studied in the presence of Ni(II) and Cu(II) ions and in acidic pH range 4.05,5.89. The metal glycolate, not the glycolic acid (GLYCA), is oxidized by PMS. The rate is first order in [PMS] and metal ion concentrations. The oxidation of nickel glycolate is zero-order in [GLYCA] and inverse first order in [H+]. The increase of [GLYCA] decreases the rate in copper glycolate, and the rate constants initially increase and then remain constant with pH. The results suggest that the metal glycolate ML+ reacts with PMS through a metal-peroxide intermediate, which transforms slowly into a hydroperoxide intermediate by the oxygen atom transfer to hydroxyl group of the chelated GLYCA. The effect of hydrogen ion concentrations on kobs suggests that the structure of the metal-peroxide intermediates may be different in Ni(II) and Cu(II) glycolates. © 2008 Wiley Periodicals, Inc. Int J Chem Kinet 41: 160,167, 2009 [source] Kinetic and mechanistic investigation into the influence of chelate substituents on the substitution reactions of platinum(II) terpyridine complexesINTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 12 2008Deogratius Jaganyi The substitution kinetics of the complexes [Pt{4,-(o -CH3 -Ph)-terpy} Cl]SbF6 (CH3PhPtCl(Sb)), [Pt{4,-(o -CH3 -Ph)-terpy}Cl]CF3SO3 (CH3PhPtCl(CF)), [Pt(4,-Ph-terpy)Cl]SbF6 (PhPtCl), [Pt(terpy)Cl]Cl·2H2O (PtCl), [Pt{4,-(o -Cl-Ph)-terpy}Cl]SbF6 (ClPhPtCl), and [Pt{4,-(o -CF3 -Ph)-terpy}Cl]SbF6 (CF3PhPtCl), where terpy is 2,2,:6,,2,-terpyridine, with the nucleophiles thiourea (TU), N,N,-dimethylthiourea (DMTU), and N,N,N,,N,-tetramethylthiourea (TMTU) were investigated in methanol as a solvent. The substitution reactions of the chloride displacement from the metal complexes by the nucleophiles were investigated as a function of nucleophile concentration and temperature under pseudo-first-order conditions using the stopped-flow technique. The reactions followed the simple rate law kobs = k2[Nu]. The results indicate that the introduction of substituents in the ortho position of the phenyl group on the ancillary ring of the terpy unit does influence the extent of ,-backbonding in the terpy ring. This controls the electrophilicity of the platinum center, which in turn controls the lability of the chloro-leaving group. The strength of the electron-donating or -withdrawing ability of the substituents correlates with the reactivity of the complexes. Electron-donating substituents decrease the rate of substitution, whereas electron-withdrawing substituents increase the rate of substitution. This was supported by DFT calculations at the B3LYP/LACVP+** level of theory, which showed that most of the electron density of the HOMO is concentrated on the phenyl ligand rather than on the metal center in the case of the strongest electron-withdrawing substituent in CF3PhPtCl. The opposite was found to be true with the strongest electron-donating substituent in CH3PhPtCl. Thiourea was found to be the best nucleophile with N,N,N,,N,-tetramethylthiourea being the weakest due to steric effects. The temperature dependence studies support an associative mode of activation. © 2008 Wiley Periodicals, Inc. Int J Chem Kinet 40: 808,818, 2008 [source] Dediazoniation of 1-naphthalenediazonium tetrafluoroborate in aqueous acid and in micellar solutionsINTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 6 2008Carlos Bravo-Diaz We have measured the rates and product yields of dediazoniation of 1-naphthalenediazonium (1ND) tetrafluoroborate in the presence and absence of sodium dodecyl sulfate (SDS) micellar aggregates by employing a combination of UV,vis spectroscopy and high-performance liquid chromatography (HPLC) measurements. Kinetic data were obtained by a derivatization procedure with product yields were determined by HPLC. HPLC chromatograms show that in aqueous acid and in micellar solutions only one dediazoniation product is formed in significant quantities, 1-naphthol (NOH), and the observed rate constants (kobs) are the same when 1ND loss is monitored spectrometrically and when NOH formation is monitored by HPLC. Activation parameters were obtained both in the presence and absence of SDS micellar aggregates. In both the systems, the enthalpies of activation are high and the entropies of activation are positive. The enthalpy of activation in the absence of SDS is very similar to that in the presence of SDS micelles, but the entropy of activation is lower by a factor of 4. As a consequence, SDS micelles speed up the thermal decomposition of 1ND and increase kobs by a factor of 1.5 when [SDS] = 0.02 M. In contrast, results obtained in the presence of complexing systems such as crown ethers and polyethers show significant stabilization of the parent arenediazonium ions. Kinetic and HPLC data are consistent with the heterolytic DN + AN mechanism that involves the rate-determining fragmentation of the arenediazonium ion into a very reactive phenyl cation that reacts competitively with available nucleophiles. © 2008 Wiley Periodicals, Inc. Int J Chem Kinet 40: 301,309, 2008 [source] Nucleophilic heteroaromatic substitution: Kinetics of the reactions of nitropyridines with aliphatic amines in dipolar aprotic solventsINTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 3 2008Chukwuemeka Isanbor Rate data are reported for the reactions of 2-chloro-5-nitropyridine 2a, 2-chloro-3-nitropyridine 2b, and the corresponding 2-phenoxy derivatives 2c with n -butylamine, pyrrolidine and piperidine and 2d with n -butylamine and pyrrolidine in dimethyl sulfoxide (DMSO) as solvent. The same reactions in acetonitrile had been reported earlier (Crampton et al., Eur J Org Chem 2007, 1378,1383). Values in these solvents are compared with those of 2,4-dinitrochlorobenzene 3a, 2,6-dinitrochlorobenzene 3b, and the corresponding nitroactivated diphenyl ethers 3c and 3d. Reactions with n -butylamine in both solvents gave values of kobs, which increase linearly with amine concentration indicating that nucleophilic attack is rate limiting. The only exception is the reactions in acetonitrile with 2c where base catalysis was observed. Values of k1, the rate constant for the nucleophilic attack, decrease in the order pyrrolidine > piperidine > n -butylamine. In acetonitrile, kinetic data show that k/k ratios are more than unity while the inverse is the case in DMSO. With the phenoxy derivatives, substitution was the only process observed. Base catalysis detected in the reactions of the 1-phenoxy derivatives is attributed to rate-limiting deprotonation of the initially formed zwitterionic intermediate. Our results shed more light on fundamental aspects of activation, hydrogen bonding, and steric effects associated with an aza or a nitro group in the molecules investigated as it affects the nucleophilic aromatic substitution (SNAr) reaction pathways. © 2008 Wiley Periodicals, Inc. Int J Chem Kinet 40: 125,135, 2008 [source] Estimation of homogeneous rate constants of reaction of electrochemically generated ortho -benzoquinones with 1,3-indandioneINTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 11 2007Davood Nematollahi Electrochemical oxidation of some catechol derivatives has been studied in the presence of 1,3-indandione as nucleophile in aqueous solution, by means of cyclic voltammetry and controlled-potential coulometry. The results indicate the participation of electrochemically produced o -benzoquinones in the Michael reaction with 1,3-indandione to form the corresponding new catechol derivatives. On the basis of the EC mechanism, the observed homogeneous rate constants (kobs) of reaction of produced o -benzoquinones with 3-indandione were estimated by comparing the experimental cyclic voltammograms with the digitally simulated results. © 2007 Wiley Periodicals, Inc. Int J Chem Kinet 39: 605,613, 2007 [source] Micellar and salt effects on the interaction of [Cu(II)-Gly-Gly]+ with ninhydrinINTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 10 2007Mohd. Akram The effect of cationic micelles of cetyltrimethylammonium bromide (CTAB) on the kinetics of interaction of copper dipeptide complex [Cu(II)-Gly-Gly]+ with ninhydrin has been studied spectrophotometrically at 70°C and pH 5.0. The reaction follows first- and fractional-order kinetics, respectively, in complex and ninhydrin. The reaction is catalyzed by CTAB micelles, and the maximum rate enhancement is about twofold. The results obtained in the micellar medium are treated quantitatively in terms of the kinetic pseudophase and Piszkiewicz models. The rate constants (kobs or k,), micellar-binding constants (kS for [Cu(II)-Gly-Gly]+, kN for ninhydrin), and index of cooperativity (n) have been evaluated. A mechanism is proposed in accordance with the experimental results. The influence of different inorganic (NaCl, NaBr, Na2SO4) and organic (NaBenz, NaSal) salts on the reaction rate has also been seen, and it is found that tightly bound/incorporated counterions are the most effective. © 2007 Wiley Periodicals, Inc. Int J Chem Kinet 39: 556,564, 2007 [source] The reactivity of Ni(II) toward aspartic and glutamic monohydroxamatesINTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 9 2006Fawzia Al-Sogair The formation of complexes of Ni(II) with aspartic and glutamic acid hydroxamates was determined by potentiometric methods at I = 0.15 M NaCl and T = 25°C. The equilibrium study of Ni(II) with ASX or GLX revealed that the predominant species formed in solution were (M:L:H+): (1:1:0), (1:1:1), (2:1:0), and (2:1:1) in the whole pH range (,3,11). The formation of polymeric species was not observed. The octahedral structures were predicted in which the ligands act as tridentate ligands. The kinetics of complex formation between Ni(II) with ASX system as well as Ni(II) with GLX were also studied in a wide pH range. The observed rate constants for the Ni(II)-hydroxamates were found to be dependent on the total concentration of hydroxamates at a given pH through the following relations: kobs = Y0 + Z(TASX) and kobs = Y0 + Z(TGLX) + W(TGLX)2. The trans effect of the hydroxyl group present in the reacting species of Ni(OH)+ as well as a ring closure resulted from ligand chelation are introduced as explanations for the rate constants obtained for the reactions of Ni(II) with ASX or GLX. © 2006 Wiley Periodicals, Inc. Int J Chem Kinet 38: 540,552, 2006 [source] Kinetics and mechanism of the oxidation of some ,-hydroxy acids by 2,2,-bipyridinium chlorochromateINTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 4 2002Vinita Kumbhat The oxidation of glycolic, lactic, malic, and a few substituted mandelic acids by 2,2,-bipyridinium chlorochromate (BPCC) in dimethylsulphoxide leads to the formation of corresponding oxoacids. The reaction is first order each in BPCC and the hydroxy acids. The reaction is catalyzed by the hydrogen ions. The hydrogen ion dependence has the form: kobs = a + b [H+]. The oxidation of ,-deuteriomandelic acid exhibited a substantial primary kinetic isotope effect (kH/kd = 5.29 at 303 K). Oxidation of p -methylmandelic acid was studied in 19 different organic solvents. The solvent effect has been analyzed by using Kamlet's and Swain's multiparametric equations. A mechanism involving a hydride ion transfer via a chromate ester is proposed. © 2002 Wiley Periodicals, Inc. Int J Chem Kinet 34: 248,254, 2002 [source] Enhanced reactivity in the ammonolysis of phenyl thiolacetates in aqueous mediumINTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 1 2002D. Rajarathnam The ammonolysis of several substituted phenyl thiolacetates is kinetically studied in aqueous medium, 18°C, ionic strength 0.1 M (KCl). By following the leaving groups spectrophotometrically (,max = 260,410 nm), under excess free ammonia, pseudo-first-order rate coefficients (kobs) are obtained. The plots of (kobs , kH) against free ammonia concentration are linear at constant pH. The macroscopic nucleophilic substitution rate coefficients (kN) are obtained as the slopes of these plots and found to be pH-independent for all the thiolesters. The Brönsted-type plot (log kN against pKa of leaving groups) and the Hammett plot (log kN against , values of substituents) obtained for the title reactions of thiolesters are linear with slope values of ,lg = ,0.34 and , = 0.74 respectively. From the magnitude of these values, experimental data, the kinetic law, and the analysis of products, it is deduced that the ammonolysis of thiolesters proceeds through a simple bimolecular nucleophilic substitution pathway with a zwitterionic tetrahedral addition intermediate (T±), whereby its formation is rate-determining (k1 step). Comparison of this reaction of thiolesters with a similar reaction of analogue oxyesters shows a mechanistic difference. Further, for thiolesters there is a rate enhancement with larger kN values. The change in mechanism and enhanced reactivity observed by substitution of the oxygen atom by sulphur atom on the phenyl moiety are discussed in detail. © 2001 John Wiley & Sons, Inc. Int J Chem Kinet 34: 18,26, 2002 [source] Kinetics and mechanism of alkaline hydrolysis of 4-nitrophthalimide in the absence and presence of cationic micellesINTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 7 2001M. Niyaz Khan Pseudo-first-order rate constants (kobs) for alkaline hydrolysis of 4-nitrophthalimide (NPTH) decreased by nearly 8- and 6-fold with the increase in the total concentration of cetyltrimethyl-ammonium bromide ([CTABr]T) from 0 to 0.02 M at 0.01 and 0.05 M NaOH, respectively. These observations are explained in terms of the pseudophase model and pseudophase ion-exchange model of micelle. The increase in the contents of CH3CN from 1 to 70% v/v and CH3OH from 0 to 80% v/v in mixed aqueous solvents decreases kobs by nearly 12- and 11-fold, respectively. The values of kobs increase by nearly 27% with the increase in the ionic strength from 0.03 to 3.0 M. The mechanism of alkaline hydrolysis of NPTH involves the reactions between HO, and nonionized NPTH as well as between HO, and ionized NPTH. The micellar inhibition of the rate of alkaline hydrolysis of NPTH is attributed to medium polarity effect. © 2001 John Wiley & Sons, Inc. Int J Chem Kinet 33: 407,414, 2001 [source] An empirical approach to study the occurrence of ion exchange in the ionic micellar-mediated semi-ionic reactions: Kinetics of the rate of reaction of piperidine with ionized phenyl salicylate in the presence of cationic micellesINTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 5 2001M. Niyaz Khan Pseudo-first-order rate constants (kobs),obtained for the cleavage of ionized phenyl salicylate (PS,) at constant [NaOH], [MeCN], [CTAZ]T (total concentration of cetyltrimethylammonium chloride and bromide), [Pip]T (total concentration of piperidine), and varying concentrations of sodium cinnamate, acetate, and butanoate ([NaX]),follow the relationship: kobs = (k0 + , K[NaX])/(1 + K[NaX]), where , and K are empirical parameters. The values of , are almost independent of [CTAZ]T, while K values decrease with the increase in [CTAZ]T within its range 0.006,0.020 M. The values of , and K are explained in terms of pseudophase model of micelle coupled with an empirical relationship: KS = KS0/(1 + ,X/S [NaX]), where KS is the CTAZ micellar binding constant of PS, in the presence of NaX. © 2001 John Wiley & Sons, Inc. Int J Chem Kinet 33: 288,294, 2001 [source] KINETICS AND HYDROLYSIS PARAMETERS OF TOTAL FRUCTOOLIGOSACCHARIDES OF ONION BULBS: EFFECTS OF TEMPERATURE REGIMES AND CULTIVARSJOURNAL OF FOOD BIOCHEMISTRY, Issue 1 2007NOUREDDINE BENKEBLIA ABSTRACT This work studied the percentage of hydrolysis, observed hydrolysis rate constant (kobs), half-life time (t1/2) and kinetics of degradation of the total fructooligosaccharides (FOS) of three different onion bulb cultivars (Yellow Spanish, Red Amposta and Tenshin) kept during 6 months under three temperature regimes, 10, 15 and 20C. The percentage of hydrolysis of FOS was higher at 20C than at 10C and ranged from 47 to 58% at 10C, from 63 to 68% at 15C and from 74 to 83% at 20C. The kobs ranged from 27 × 10,3 to 36 × 10,3/week at 10C and from 41 × 10,3/week to 47 × 10,3/week at 15C, while at 20C, it was high and was about kobs 56 × 10,3/week.. The t1/2 decreased when temperature increased, and varied from 19.5 to 26.0 weeks at 10C, from 14.6 to 16.8 weeks at 15C and from 9.4 to 12.3 weeks at 20C, indicating that high degree of polymerization (DP) FOS have shorter lives than low DP FOS. Linear regression and kinetics of hydrolysis have shown that FOS hydrolysis is higher at 20C, with a coefficient of regression ranging between 0.87 and 0.99. Apparently, FOS hydrolysis is temperature independent, and storage time had more effect on the higher DP FOS than on the lower DP FOS. [source] Butanolysis of 2-methylbenzenediazonium ions: product distribution, rate constants of product formation, and activation parametersJOURNAL OF PHYSICAL ORGANIC CHEMISTRY, Issue 5 2009M. José Pastoriza-Gallego Abstract We have determined the product distributions, the rate constants of product formation and substrate loss, and the activation parameters for the butanolysis of 2-methylbenzenediazonium, 2MBD, tetrafluoroborate in aqueous 1-Butanol (BuOH) solutions by combining UV,VIS spectroscopy, high performance liquid chromatography (HPLC), and a derivatization protocol that traps unreacted 2MBD as a stable azo dye. BuOH/H2O solutions are miscible over a narrow composition range, but in reverse micelles composed of sodium dodecyl sulfate, SDS, BuOH, and water, are miscible between 45,80%. Two major and two minor dediazoniation products are observed, 2-cresol, ArOH, 2-butyl-tolyl-ether, ArOBu, and small amounts of 2-chlorobenzene, ArCl (from HCl added to control solution acidity) and toluene, ArH (a reduction product). Product yields depend on experimental conditions, but quantitative conversion to products is achieved over the entire composition ranges investigated. The observed rate constants, kobs, obtained by monitoring 2MBD loss or by monitoring ArOH or ArOBu formation, are the same and they are only modestly affected by changes in the solution composition. The activation parameters obtained from the effect of temperature on kobs show that the enthalpy of activation is relatively high compared to those found in bimolecular reactions and the entropy of activation is small but positive. The results suggest that 2MBD is mainly sampling in the BuOH-H2O rich interfacial region of the reverse micelle and are consistent with 2MBD decomposing through a DN,+,AN mechanism, i.e., a rate limiting formation of an aryl cation that reacts immediately with nucleophiles. Copyright © 2008 John Wiley & Sons, Ltd. [source] Amide and lactam hydrolysis of N -(2-hydroxyacetyl)-2-pyrrolidone: effective catalysis,JOURNAL OF PHYSICAL ORGANIC CHEMISTRY, Issue 11 2006Lisaedy García Borboa Abstract When N -(2-hydroxyacetyl)-2-pyrrolidone (open form) is dissolved in water at pH,>,8, irreversible cleavage of the exocyclic and endocyclic amide CN bond occurs. The latter rupture corresponds to the lactam opening yielding N -(4-hydroxyacetyl)butanoic acid (NBA). NBA is produced from the ester hydrolysis of the ester-amide macrocycle that is in equilibrium with the cyclol form of the open form. We have previously reported this latter equilibrium for N -(2-aminoacetyl)-2-lactams. 2-pyrrolidone (lactam) and glycolic acid are produced from direct hydrolysis of the open form by means of the amide exocyclic cleavage. The [NBA]/[lactam] ratio increases at higher pH since the NBA production is second order with respect to [OH,] while the corresponding lactam formation is only first order. The obtained kobs is hence the sum of the rate constants that yield lactam and NBA, respectively. This kobs is uncatalyzed and specific base catalyzed with unusually high rate constants of 2.1,×,10,6,s,1 and 0.025,M,1,s,1, respectively. The stability of the corresponding tetrahedral intermediate formed and the intramolecular alkoxy nucleophilic attack on the lactam carbonyl group combined with an effective protonation of the lactam nitrogen that promotes the CN cleavage, contribute to increase the reaction rates and lactam opening. Rate constants for the two parallel reactions are obtained from kobs and [NBA]/[lactam] versus pH plots. Copyright © 2006 John Wiley & Sons, Ltd. [source] Effects of non-ionic and mixed non-ionic,cationic micelles on the rate of aqueous cleavages of phenyl benzoate and phenyl salicylate in alkaline mediumJOURNAL OF PHYSICAL ORGANIC CHEMISTRY, Issue 5 2004M. Niyaz Khan Abstract Pseudo-first-order rate constants (kobs) for the hydrolysis of phenyl salicylate (PSH) and phenyl benzoate (PB) in the alkaline medium show a monotonic decrease with the increase in [C16E20]T (total concentration of Brij 58) at constant [CH3CN] and [NaOH]. This micellar effect is explained in terms of the pseudophase model of micelles. These results show a characteristic difference between the effects of [C16E20]T and previously published effects of [C12E23]T (total concentration of Brij 35) on the rates of aqueous cleavage of PSH and PB at [CnEm]T/[NaOH],,3. The values of kobs, obtained at different [C16E20]T in the presence of a constant amount of CTABr, follow the empirical relationship kobs=(k0+,K[C16E20]T)/(1+K[C16E20]T), where , and K are empirical parameters. The values of , are not affected whereas the values of K decrease with increase in [CTABr]T in a mixed C16E20,CTABr micellar system. The values of , at different [CTABr]T show that ,>k0 for hydrolysis of PSH and , Effects of non-ionic and mixed cationic,non-ionic micelles on the rate of alkaline hydrolysis of phthalimideJOURNAL OF PHYSICAL ORGANIC CHEMISTRY, Issue 7 2002M. Niyaz Khan Abstract Pseudo-first-order rate constants (kobs) for the alkaline hydrolysis of phthalimide (PTH) show a monotonic decrease with the increase in [C16E20]T (total concentration of Brij 58) at constant [CH3CN] and [NaOH]. This micellar effect is explained in terms of the pseudophase model of micelles. The rate of hydrolysis of PTH in C16E20 micellar pseudophase appears to be negligible compared with that in the aqueous pseudophase. The values of kobs for C12E23 (Brij 35) show a sharp decrease at very low values of [C12E23]T followed by a very slow decrease with increase in [C12E23]T at relatively higher values of the latter. The rate of hydrolysis becomes too slow to monitor at [C12E23]T ,0.04,M in the absence of cetyltrimethylammonium bromide (CTABr) and at [C12E23]T ,0.05,M in the presence of 0.006,0.02,M CTABr at 0.02,M NaOH whereas such characteristic behavior is kinetically absent with C16E20. The values of kobs, obtained at different [NIS]T (where NIS represents C16E20 and C12E23) in the presence of a constant amount of CTABr, follow the empirical relationship kobs,=,(k0,+,kK[NIS]T)/(1,+,K[NIS]T) where k and K are empirical parameters. The values of k are only slightly affected whereas the values of K decrease with increase in [CTABr]T for the mixed C16E20,CTABr micellar system. The rate of hydrolysis of PTH at ,0.01,M C12E23 and ,0.01,M CTABr reveals the formation of phthalic anhydride whereas this was not observed in the mixed C16E20,CTABr micellar system under similar experimental conditions. Copyright © 2002 John Wiley & Sons, Ltd. [source]
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