• Title/Summary/Keyword: order of reaction

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Chemical Modification of Serratia marcescens Acetolactate Synthase with Cys, Trp, and Arg Modifying Reagents

  • Choi, Ho-Il;Kim, Soung-Soo
    • BMB Reports
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    • v.28 no.1
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    • pp.40-45
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    • 1995
  • Acetolactate synthase purified from Serratia marcescens ATCC 25419 was rapidly inactivated by the thiol specific reagent p-chloromercuribenzoate (PCMB), the tryptophan specific reagent N-bromosuccinimide (NBS), and the arginine modifying reagent phenylglyoxal (PGO). Inactivation by PCMB was prevented by both ${\alpha}$-ketobutyrate and pyruvate, and the second order rate constant for the inactivation was $2480\;M^{-1}{\cdot}min^{-1}$. The reaction order with respect to PCMB was 0.94. The inactivation of the enzyme by NBS was also substantially reduced by both ${\alpha}$-ketobutyrate and pyruvate. The second order rate constant for inactivation by NBS was $15,000\;M^{-1}{\cdot}min^{-1}$, and the reaction order was 2.0. On the other hand, inactivation by PGO was partially prevented by ${\alpha}$-ketobutyrate, but not by pyruvate. The second order rate constant for the inactivation was $1480\;M^{-1}{\cdot}min^{-1}$ and the order of reaction with respect to PGO was 0.75. These results suggest that essential cysteine, tryptophan and arginine are located at or near the substrate binding site.

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N-Oxidation of Pyrazines by Bromamine-B in Perchloric Acid Medium: Kinetic and Mechanistic Approach

  • Puttaswamy;Shubha, J.P.
    • Bulletin of the Korean Chemical Society
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    • v.30 no.9
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    • pp.1939-1945
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    • 2009
  • Kinetic investigations on the oxidation of pyrazine and four 2-substituted pyrazines viz., 2-methylpyrazine, 2-ethylpyrazine, 2-methoxypyrazine and 2-aminopyrazine by bromamine-B (BAB) to the respective N-oxides have been studied in HCl$O_4$ medium at 303 K. The reactions show identical kinetics being first-order each in $[BAB]_o\;and\;[pyrazine]_o$, and a fractional- order dependence on $[H^+]$. Effect of ionic strength of the medium and addition of benzenesulfonamide or halide ions showed no significant effect on the reaction rate. The dielectric effect is positive. The solvent isotope effect was studied using $D_2$O. The reaction has been studied at different temperatures and activation parameters for the composite reaction have been evaluated from the Arrhenius plots. The reaction showed 1:1 stoichiometry and the oxidation products of pyrazines were characterized as their respective N-oxides. Under comparable experimental conditions, the oxidation rate of pyrazines increased in the order: 2-aminopyrazine > 2-methoxypyrazine > 2-ethylpyrazine > 2-methylpyrazine > pyrazine. The rates correlate with the Hammett $\sigma$ relationship and the reaction constant $\rho$ was found to be -0.8, indicating that electron donating centres enhance the rate of reaction. An isokinetic temperature of $\beta$ = 333 K, indicated that the reaction was enthalpy controlled. A mechanism consistent with the experimental results has been proposed in which the rate determining step is the formation of an intermediate complex between the substrate and the diprotonated species of the oxidant. The related rate law in consistent with observed results has been deduced.

Reaction Mechanism and Kinetics of Degradation for Refractory Organic Pollutants in Water by Ultrasonic Irradiation

  • Sohn, Jong-Ryeul;Moon, Kyung-Hwan
    • Proceedings of the Korean Environmental Health Society Conference
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    • 2003.06a
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    • pp.123-127
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    • 2003
  • This experiment was performed to investigate the characteristics of sonolytic reaction as the basic data for development of the ultrasonic AOP(Advanced Oxidation Process) process from which the refractory organic compounds in aqueous solution which are not readily removed by the existing conventional wastewater treatment processes can be destructed and removed. Trichloroethylene (TCE), benzene, and 2,4-dichlorophenol(DCP) were used as the samples, and their destruction efficiency were measured in terms of experimental parameters of the initial solution concentration, initial solution pH, reaction temperature, acoustic frequencies and intensities. Results showed that the destruction efficiencies of all of the sample materials were above 80% within 120 minutes of sonolytic reaction in all reaction condition. The reaction order of these three compounds was verified as Pseudo first order. From the fore-mentioned results, it can be concluded that the refractory organic compounds could be removed by the ultrasonic irradiation with radicals, such as H$.$and OH$.$causing the high increase of pressure and temperature. Finally, it appears that the new AOP technology using ultrasonic irradiation can be applied to the treatment of refractory substances which are difficult to be decomposed by the conventional methods.

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Effects of Hydro-thermal Reaction Temperature on Anaerobic Biodegradability of Piggery Manure Hydrolysate

  • Kim, Ho;Jeon, Yong-Woo
    • Korean Journal of Soil Science and Fertilizer
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    • v.48 no.6
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    • pp.602-609
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    • 2015
  • In order to enhance a biogas production by the hydro-thermal pre-treatment of piggery manure, the effects of hydro-thermal reaction temperature at thermal hydrolysis of piggery manure on the methane potential and anaerobic biodegradability of thermal hydrolysate were analyzed. The increase of hydro-thermal reaction temperature from $170^{\circ}C$ to $220^{\circ}C$ caused the enhancement of hydrolysis efficiency, and most of organic matters were present in soluble forms. However, the methane potentials ($B_u-TCOD$) of hydrolysate were decreased from 0.239 to $0.188Nm^3kg^{-1}-TCOD_{added}$ by increasing hydro-thermal reaction temperature from $170^{\circ}C$ to $220^{\circ}C$, and also the anaerobic biodegradability (DTCOD) decreased from 74.6% to 58.6% with increase of hydro-thermal reaction temperature. The increase of hydro-thermal reaction temperature from $170^{\circ}C$ to $220^{\circ}C$ resulted in the decrease of easily biodegradable organic matter content, while persistent organic matter contents increased.

The Catalytic Effects of o-Iodosobenzoate Ion on Hydrolysis of p-Nitrophenylvalate in ETAMs Solution (ETAMs 용액내에서 p-Nitrophenylvalate의 가수분해반응에 미치는 o-Iodosobenzoate Ion의 촉매효과)

  • Kim, Jeung-Bea
    • Journal of Environmental Science International
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    • v.20 no.1
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    • pp.119-126
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    • 2011
  • In this study, reaction model and reactions rate accelerated by o-iodosobenzoate ion(IB$^{\ominus}$) on hydrolysis reaction of p-nitrophenyl valate(NPV) using ethyl tri-octyl ammonium mesylate(ETAMs) for quaternary ammonium salts, the phase transfer catalysis(PTC) reagent, were investigated. The effect of IB$^{\ominus}$ on hydrolysis reaction rate constant of NPV was weak without ETAMs solutions. Otherwise, in ETAMs solutions, the hydrolysis reactions exhibit higher first order kinetics with respect to the nucleophile, IB$^{\ominus}$, and ETAMs, suggesting that reactions are occurring in small aggregates of the three species including the substrate(NPV), whereas the reaction of NPV with OH$^{\ominus}$ is not catalyzed by ETAMs. Different concentrations of NPV were tested to measure the change of rate constants to investigate the effect of NPV as substrate and the results showed that the effect was weak. This means the reaction would be the first order kinetics with respect to the nucleophile. This behavior for the drastic rate-enhancement of the hydrolysis is referred as 'Aggregation complex model' for reaction of hydrophobic organic ester with o-iodosobenzoate ion(IB$^{\ominus}$) in hydrophobic quarternary ammonium salt(ETAMs) solutions.

Cure Kinetics of amine-cured tetraglycidyl-4,4'-diaminodiphenylmethane epoxy blends with a new polyetherimide (반응성 열가소성 수지로 개질된 TGDDM/DDS 시스템의 Cure Kinetics)

  • Hwang Seungchul;Lee JungHoon;Kim Donghyon;Kim Woho;Kim Minyoung
    • Proceedings of the Korean Society For Composite Materials Conference
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    • 2004.04a
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    • pp.214-217
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    • 2004
  • The cure kinetics of blends of epoxy(tetraglycidyl-4,4'-diaminodiphenylmethane ; TGDDM)/curing agent(diaminodiphenyl sulfone ; DDS) resin with amine terminated polyetherimide-CTBN-amine terminated polyetherimide triblock copolymer(ABA) were studied using differential scanning calorimetry under isothermal conditions to determine the reaction parameters such as activation energy and reaction constants. By increasing the amount of ABA in the blends, the final cure conversion was decreased. Lower values of the final cure conversions in the epoxy/ABA blends indicated that ABA hinders the cure reaction between the epoxy and curing agents. 1be value of the reaction order, m, for the initial autocatlytic reaction was not affected by blending ABA with epoxy resin, and the value was approximately 1.0. The value of n for the nth order component in the autocatalytic analysis was increased by increasing the amount of ABA in the blends, and the value increased from 2.0-3.4. A diffusion controlled reaction was observed as the cure conversion increased and the rate equation was successfully analyzed by incorporating the diffusion control term for the epoxy/DDS/ABA blends.

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Degradation of Ascorbic acid in Limited Dissolved Oxygen Environment (제한된 산소 존재중의 Ascorbin 산의 분해에 대하여)

  • Rhee, Sook-Hee
    • Journal of Nutrition and Health
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    • v.9 no.4
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    • pp.54-58
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    • 1976
  • Deterioration of ascorbic acid content is the important factor in the food quality. The degradation of ascorbic acid undergoes as a first-order of reaction in the presence of excess oxygen content. However, under the limited oxygen content, ascorbic acid decomposes as a psudo-first order of reaction. The ascorbic acid, in this study, under the limited dissolved oxygen content in the presesce of iron(III) and copper(II) decomposed as first-order reaction with a little influence in rate constant and the light was an accelerating factor on the ascorbic acid degradation.

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Effects of Excipients on Colour Fading of FD & C Yellow No. 5 and FD & C Red No. 2 by Use Tintometer (Tintometer를 이용한 FD & C Yellow No. 5와 FD & C Red No.2의 퇴색에 미치는 부형제의 영향에 관한 연구)

  • Kim, Jung-Woo
    • Journal of Pharmaceutical Investigation
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    • v.5 no.2
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    • pp.57-62
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    • 1975
  • It was many differances to evaluate of the effect of excipients on colour fading in FD & C Yellow No.5 by use Tintometer and nearly is not effective in FD & C Red No. 2. When we observed colour fading in suger coating formulations by tintometer, FD & C Red No.2 was appeared to follow zero order reaction and FD & C Yellow No. 5 was not follow zero order reaction or first order reaction. Also, we could know the tendency of colour fading by visible spectrum, but it was net suitable method for this experiment more than by tintometer. The relative colour fading effect of the surfactants(Polysorbate) was as follows: Tween 60> Tween 80> Tween 20. In addition to, Benzalkonium chloride was reacted with FD & C Yellow No.5, so the stronger colour was appeared. On the other hand, the weaker colour was appeared in FD & C Red No.2. While, the sunscreening agents was not almost effective in colour fading of FD & Yellow No. 5 and FD & C Red No. 2.

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The Kinetics and Mechanism for the Oxidation of Nicotinic Acid by Peroxomonosulfate in Acidic Aqueous Medium

  • Agrawal, Anju;Sailani, Riya;Gupta, Beena;Khandelwal, C.L.;Sharma, P.D.
    • Journal of the Korean Chemical Society
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    • v.56 no.2
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    • pp.212-216
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    • 2012
  • The kinetics of oxidation of nicotinic acid by peroxomonosulfate (PMS) has been studied in acetate buffers. Stoichiometry of the reaction corresponds to the reaction of one mole of the oxidant with a mole of nicotinic acid. N${\rightarrow}$O product has been confirmed both by UV visible and IR spectroscopy. The reaction is second order viz. first order with respect to each reactant. Activation parameters have also been evaluated. A plausible reaction mechanism is mentioned and the derived kinetic rate law accounts for experimental observations.

Effects of Added Anions on the Reaction of Nitrous Acid with Hydrogen Peroxide

  • Park, Jong-Yoon;Choi, Eun-Jin;Park, Joon-Woo
    • Bulletin of the Korean Chemical Society
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    • v.13 no.1
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    • pp.37-41
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    • 1992
  • The reactions of nitrous acid with hydrogen peroxide in acidic aqueous solution in the presence of several added anions have been studied at $0^{\circ}C$ and pH 2-4 to investigate the nucleophilic catalysis of these anions. From the dependence of reaction rates on the anion concentrations, significant catalytic effects were found for $Cl^-,\;Br^-,\;SCN^-$, in order of effect $SCN^-\;{\approx}\;Br^->Cl^-$, while no observable effect was found for ${ClO_4}^-$ and ${NO_3}^-$. These results support O-nitrosation reaction is the rate-determining step and NOX formed in the presence of an anion ($X^-$) also acts as a nitrosating agent and accelerates the overall reaction rate. The order of reactivity was found to be NOCl>NOBr>NOSCN, which is consistent with the results of N-nitrosation and S-nitrosation reactions.