• Title/Summary/Keyword: Hydrolysis mechanism

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Kinetics and Mechanism of the Hydrolysis of Imidoyl Halides (Imidoyl Halide의 가수분해 반응메카니즘과 그의 반응속도론적 연구)

  • Tae-Rin Kim;Jin-Hee Kim;Byung-Doo Chang;Kwang-Il Lee;Ung-Cho Kim
    • Journal of the Korean Chemical Society
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    • v.20 no.1
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    • pp.48-55
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    • 1976
  • The rate constants of the derivatives of N-(2,4-dinitrophenyl)-benzimidoyl chloride were determined at various pH and a rate equation which can be applied over wide pH range was obtained. The reaction mechanism of hydrolysis of N-(2,4-dinitrophenyl)-benzimidoyl chloride which has not been studied carefully earlier in acidic and basic solution can be fullly explained by the rate equation obtained. The rate equation reveals that, beow pH 7.00, the hydrolysis of benzimidoyl chloride proceeds through $S_N2$ reaction to form a carbonium ion intermediate.Above pH 8.5, however, the hydrolysis proceeds through the $S_N2$ type reaction which depends on hydroxide ion and imidoyl chloride concentration. At pH 7.0∼8.5, two reactions occur competitively.

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Kinetic Studies on the Mechanism of Hydrolysis of 2-Phenyl-4H,5H-3-methyl-3-thiazolinium Perchlorate Derivatives (2-Phenyl-4H,5H-3-methyl-3-thiazolinium Perchlorate 유도체의 가수분해 반응 메카니즘에 관한 반응속도론적 연구)

  • Kim, Tae-Rin;Lee, So-Young;Han, Man-So;Pyun, Sang-Yong;Lee, Seok-Hee
    • Journal of the Korean Chemical Society
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    • v.44 no.2
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    • pp.120-126
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    • 2000
  • The rate constants for the hydrolysis of 2-phenyl-4H,5H-3-methyl-3-thiazolinium perchlorate(PTP) derivatives were detemined by the use of ultraviolet visible spectrophotometer in water. The rate equations which could be applied over a wide pH ranges were obtained. On the basis of rate equation, hydrolysis product analysis, general base catalysis, and substituent effect, a plausible mechanism of the hydrolysis is proposed: Below pH 4.0, the reaction is initiated by addition of water, while above pH 9.0, Michael type nucleophilic addition takes place. In the pH range of $4.5{\sim}8.0$, these two reactions appear to occur competitively.

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Kinetics and hydrolysis mechanism of insecticide O,O-diethyl-O-(1-phenyl-3-trifluoromethylpyrazol-5-yl)phosphorothioate (Flupyrazofos) (살충제 O,O-diethyl-O-(1-phenyl-3-trifluoromethylpyrazol-5-yl)-phosphorothioate(Flupyrazofos)의 가수분해 반응 메커니즘)

  • Sung, Nack-Do
    • The Korean Journal of Pesticide Science
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    • v.6 no.3
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    • pp.218-223
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    • 2002
  • The rate of hydrolysis of insecticide, O,O-diethyl-O-(1-phenyl-3-trifluoromethylpyrazol-5-yl)phosphorothioate (Flupyrazofos) have been investigated in 25% (v/v) aqueous dioxane (${\mu}=0.1M$) at $45^{\circ}C$. The hydrolysis mechanism of flupyrazofos proceeds through the specific acid ($A_{AC}2$) catalysis below pH 4.0, specific base ($B_{AC}2$) catalysis above pH 11.0 and general acid & base ($B_{AC}2$) catalysis between pH 5.0 and pH 10.0 via trigonal-bipyramidal ($d^2sp^3$) intermediate as evidence by solvent effect ($|m|{\ll}|{\ell}|$), rate equation ($kt=ko+k_H+ [H_3O^+]+k_{OH}[OH^-]$) and product analysis. The half-life ($T\frac{1}{2}$) of hydrolytic degradation in neutral media at $45^{\circ}C$ was ca. 3 months.

Single-Molecule Imaging Reveals the Mechanism Underlying Histone Loading of Schizosaccharomyces pombe AAA+ ATPase Abo1

  • Kang, Yujin;Cho, Carol;Lee, Kyung Suk;Song, Ji-Joon;Lee, Ja Yil
    • Molecules and Cells
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    • v.44 no.2
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    • pp.79-87
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    • 2021
  • Chromatin dynamics is essential for maintaining genomic integrity and regulating gene expression. Conserved bromodomain-containing AAA+ ATPases play important roles in nucleosome organization as histone chaperones. Recently, the high-resolution cryo-electron microscopy structures of Schizosaccharomyces pombe Abo1 revealed that it forms a hexameric ring and undergoes a conformational change upon ATP hydrolysis. In addition, single-molecule imaging demonstrated that Abo1 loads H3-H4 histones onto DNA in an ATP hydrolysis-dependent manner. However, the molecular mechanism by which Abo1 loads histones remains unknown. Here, we investigated the details concerning Abo1-mediated histone loading onto DNA and the Abo1-DNA interaction using single-molecule imaging techniques and biochemical assays. We show that Abo1 does not load H2A-H2B histones. Interestingly, Abo1 deposits multiple copies of H3-H4 histones as the DNA length increases and requires at least 80 bp DNA. Unexpectedly, Abo1 weakly binds DNA regardless of ATP, and neither histone nor DNA stimulates the ATP hydrolysis activity of Abo1. Based on our results, we propose an allosteric communication model in which the ATP hydrolysis of Abo1 changes the configuration of histones to facilitate their deposition onto DNA.

Kinetic Study on the Alkaline Hydrolysis of the Substituted Phenyl N,N-diethyl-P-benzylphosphonamidates (치환 Phenyl N,N-diethyl-P-benzylphosphonamidates의 염기성 가수분해 반응에 대한 속도론적 연구)

  • Shon, Kyoung Hwa;Shin, Gap Cheol
    • Journal of the Korean Chemical Society
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    • v.43 no.1
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    • pp.85-91
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    • 1999
  • The second order rate constants for the hydrolysis of substituted phenyl N,N-diethyl-P-benzylphosphonamidates (2,4-$(NO_2)_2$, 4-$NO_2$, 4-CN, 4-Cl, 4-H)in 20% dioxane-water (v/v) have been determined by UV/Vis spectrophotometric method at various temperatures. The activation parameters (Ea, ${\Delta}H^{\neq}$,${\Delta}S^{\neq}$) were calculated from the rate constants and the reaction constant ($\rho$) was also estimated by Hammett equation. The activation entropies of the title reactions show considerably negative values, this result is not consistent with a dissociative mechanism (EA) in which a positive or a slightly negative value of the entropy of activation should be expected. Further, kinetic evidence for an associative mechanism (AE) was obtained from the linear free energy relationship. By the results of kinetic study for the alkaline hydrolysis of substituted phenyl N,N-diethyl-P-benzylphosphonamidates, it may be concluded that these reactions proceed through an associative mechanism.

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Kinetics and Mechanism of the Hydrolysis of Enol Ester in Strong Acidic Solution (강산성용액에서 엔올에스테르의 가수분해에 대한 반응속도론적 연구)

  • Heo, Tae Seong;Yu, Gyeong Hwa
    • Journal of the Korean Chemical Society
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    • v.38 no.5
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    • pp.391-396
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    • 1994
  • The hydrolysis of $\alpha-benzoxystyrene(1)$ in strong acidic solution has been investigated kinetically. In perchloric acid concentration lower than 5.5 M($H_o$ < -3.0), hydration paramer $\omega$ = + 7.6, and $\Phi$ = + 0.54 were obtained. The solvent isotope effect $k_{H_2O}/K_{D_2O}$ is 0.72. The substituent effect was found to conform to the Hammett $\sigma^+$ constant with $\rho$ = -0.60. On the basis of these results and other evidence, the hydrolysis of the enol ester proceeds by $A_{AL}$2 type mechanism. In concentration greater than 5.5 M($H_o$ > -3.0), isotope effect, $k_{H_2O}/_{D_2O}$ is 3.32, substituent effect, $\rho$ is -1.60 and the rate is linear with the acidity function, $H_o$. Thus, the mechanism changes one involving initial, and rate-determining olefin protonation.

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