The reaction kinetics for the oxidation of l ‐histidine by permanganate ions have been investigated spectrophotometrically in sulfuric acid medium at constant ionic strength and temperature. The order with respect to permanganate ions was found to be unity and second in acid concentration, whereas a fractional order is observed with respect to histidine. The reaction was observed to proceed through formation of a 1:1 intermediate complex between oxidant and substrate. The effect of the acid concentration suggests that the reaction is acid catalyzed. Increasing the ionic strength has no significant effect on the rate. The influence of temperature on the rate of reaction was studied. The presence of metal ion catalysts was found to accelerate the oxidation rate, and the order of effectiveness of the ions was Cu2+ > Ni2+ > Zn2+. The final oxidation products were identified as aldehyde (2‐imidazole acetaldehyde), ammonium ion, manganese(II), and carbon dioxide. Based on the kinetic results, a plausible reaction mechanism is proposed. The activation parameters were determined and discussed with respect to a slow reaction step. 相似文献
The thermal properties of the complexes of cinchomeronic and dinicotinic acid with several divalent metal ions were determined by thermogravimetry (TG) and differential thermal analysis (DTA).For the thermal stability of the anhydrous compounds a sequence may be observed for the metal ions with cinchomeronic (3,4-H2PC) and dinicotinic acid (3,5-H2PC): The thermal stability of the pyridine carboxylic acid for each metal of the series is: dinicotinic > cinchomeronicThe activation energy values for each thermal reaction were also calculated, using the Coats and Redfern algorism, by the Univac 1108 computer, by a program properly implemented for the statistical analysis of the data to obtain the reaction order and the activation parameters with the relative confidence limits. 相似文献
The hammerhead ribozyme is one of the best studied ribozymes, but it still presents challenges for our understanding of RNA catalysis. It catalyzes a transesterification reaction that converts a 5',3' diester to a 2',3' cyclic phosphate diester via an S(N)2 mechanism. Thus, the overall reaction corresponds to that catalyzed by bovine pancreatic ribonuclease. However, an essential distinguishing aspect is that metal ions are not involved in RNase catalysis but appear to be important in ribozymes. Although various techniques have been used to assign specific functions to metals in the hammerhead ribozyme, their number and roles in catalysis is not clear. Two recent theoretical studies on RNA catalysis examined the reaction mechanism of a single-metal-ion model. A two-metal-ion model, which is supported by experiment and based on ab initio and density functional theory calculations, is described here. The proposed mechanism of the reaction has four chemical steps with three intermediates and four transition states along the reaction pathway. Reaction profiles are calculated in the gas phase and in solution. The early steps of the reaction are found to be fast (with low activation barriers), and the last step, corresponding to the departure of the leaving group, is rate limiting. This two-metal-ion model differs from the models proposed previously in that the two metal ions function not only as Lewis acids but also as general acids/bases. Comparison with experiment shows good agreement with thermodynamic and kinetic data. A detailed analysis based on natural bond orbitals (NBOs) and natural energy decomposition (NEDA) provides insights into the role of metal ions and other factors important for catalysis. 相似文献
The rate constants of para-/orthohydrogen (p-/o-H2) nuclear spin isomerization have been measured by means of 1H NMR in deuterated solvents at 298.2 K. The indicated reaction is catalyzed by paramagnetic complex ions giving rate constants that are proportional to the concentrations of the catalysts. The second-order rate constants are directly proportional to the squares of the magnetic moments for the solvated metal complexes for two classifications: M(solv)m2+, M = 3d transition metals; Ln(solv)n3+, where in 1:9 D2O-CD3CN the aqua complexes are the predominant species, Ln = lanthanides. The other 3d transition metal complexes with different ligands show rate constants that also depend on the sizes of ligands. Whereas the correlation between the second-order rate constants and magnetic moments is consistent with Wigner's theory, the size of catalyst shows a more modest effect on the rate constants than expected. The effective collision radii of the complexes, calculated from the rate constants, proved to be approximately constant for each series of solvated metal complexes. 相似文献
Oxidation of cyclohexene under 1 atmospheric pressure of molecular oxygen at 70℃ in the absence of solvent catalyzed by PAMAM-SA-M(Where PAMAM=polyamidoamine;SA=salicyaldehyde;M=metal ions Fe^3 ,Co^2 ,Ni^2 ,Mn^2 ,Cu^2 ,Zn^2 ,respectively) dendrimers, afforded 2-cyclohexen-1-ol 1,2-cyclohexen-1-one 2,7-oxabicyclo [4,1,0] heptane 3 and 7-oxabicyl [4,1,0] heptan-2-one 4 as the major products. The factors that affect this reaction are also discussed. 相似文献
The oxidative degradation of isotactic polypropylene films coated on well-defined Cu(Cu2O), CuO0.67, and CuO films in a temperature range of 90–120°C in a quartz-spoon-gauge-reaction vessel was studied. This catalytic reaction has been compared with the oxidation of polypropylene without copper or oxide films. The reaction vessel contained, if needed, P2O5 and/or KOH as “getters” for H2O and CO2, these substances could be menitored continuously. Cu(Cu2O) films were transformed during oxidation of the polymer to yellow CuO0.67 below 100°C and above this temperature to black CuO in the presence of H2O and CO2, whereas in the absence of these compounds CuO was formed below 100°C and CuO0.67 at 120°C. Characteristic autoxidation curves obtained in the absence of H2O and CO2 showed induction periods that were shorter for copper oxide-polymer interfaces than for glass-polymer interfaces (i.e., for uncatalyzed oxidation). Abnormalities were observed for Cu(Cu2O)-polymer interfaces because of further oxidation of Cu during the reaction. The rates of oxygen consumption were faster for CuO0.67-polymer and CuO-polymer than for the uncatalyzed reaction; the catalytic action of CuO0.67 was somewhat larger than that of CuO. The important observation was made that the mechanism of oxidation is not the same in the absence and presence of reaction products; that is, H2O and CO2. This was confirmed by ion beam scattering experiments, which also revealed that an oxidation-reduction process takes place at Cu and their oxide interfaces. A mechanism for the catalytic oxidation process, based on the ease by which copper ions are released from the metal oxides at the interface, was formulated. These ions diffuse subsequently as actions of carboxylate anions into the bulk of the polymer. Arrhenius equations of oxygen consumption are given for all cases; the energy of activation calculated for the initiation of the uncatalyzed oxidation agrees with its literature value. The energy of activation for the initiation of the catalyzed reaction was a few kilocalories lower than that for the uncatalyzed reaction. Catalytic action is mainly operative for the initiation reaction at the interface and for the decomposition of hydroperoxides by copper ions. Preventing the delivery of copper ions to the polymer would be the most efficient way of inhibiting the catalysis. 相似文献
Oxidation of iodide ions by K3Fe(CN)6, catalyzed by hydrogen ions obtained from hydrochloric acid was found to be further catalyzed by iridium(III) chloride. Rate,
when the reaction is catalyzed only by the hydrogen ions, was separated from the rate when iridium(III) and H+ions both, catalyze the reaction. Reactions studied separately in the presence as well as in the absence of IrCl3 under similar conditions were found to follow second order kinetics with respect to [I−]. While the rate showed direct proportionality with respect to [K3Fe(CN)6] and [IrCl3]. At low concentrations the reaction shows direct proportionality with respect to [H+] which tends to become proportional to the square of hydrogen ions at higher concentrations. Strong retarding affect of externally
added hexacyanoferrate(II) ions was observed in the beginning but further addition affects the rate to a little extent. Changes
in [Cl−] and also ionic strength of the medium have no effect on the rate. With the help of the intercept of catalyst graph, the
extent of the reaction, which takes place without adding iridium(III), was calculated and was found to be in accordance with
the values obtained from the separately studied reactions in which only H+ ions catalyze the reaction. It is proposed that iridium forms a complex, which slowly disproportionates into the rate-determining
step. Thermodynamic parameters at four different temperatures were calculated. 相似文献
A highly efficient catalyst Fe–Co/sulfonated polystyrene (Fe–Co/SPS) was introduced and synthesized, which catalyzed BV oxidation of ketones with aqueous hydrogen peroxide to give the corresponding lactones in high yield and selectivity. Solid acid catalyst of Fe–Co/SPS has been prepared by using the 98-wt% sulfuric acid as the sulfonating agent and CoCl2 combined FeCl3 as sources of metal ions. Various physical–chemical characterizations including FT-IR, XRD, SEM and TGA, revealed that bimetallic ions Fe3+–Co2+ species in the sulfonated polystyrene framework were responsible for the catalytic activities. The BV reaction catalyzed by Fe–Co/SPS highlighted the special effects between metal ions and protonic acids as well as solvent-free heterogeneous catalytic oxidation with excellent conversion. 相似文献