• Title/Summary/Keyword: Kinetic Constants

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Soluble Epoxide Hydrolase Inhibitory Activity from Euphorbia supina Rafin

  • Luyen, Bui Thi Thuy;Thao, Nguyen Phuong;Tai, Bui Huu;Dat, Le Duc;Kim, Ji Eun;Yang, Seo Young;Kwon, Se Uk;Lee, Young Mi;Kim, Young Ho
    • Natural Product Sciences
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    • v.21 no.3
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    • pp.176-184
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    • 2015
  • In our search for natural soluble epoxide hydrolase (sEH) inhibitors from plants, an extract of the dried whole plants of Euphorbia supina Rafin was found to significantly inhibit sEH activity in vitro. Phytochemical investigation of E. supina resulted in isolation of 17 compounds (1 - 17), including triterpenes (1 - 4), phenolic compounds (5 - 8), and flavonoid derivatives (9 - 17). The structures of the isolated compounds were established mainly by extensive analysis of the 1D and 2D NMR, and MS data. All of the isolated compounds were evaluated for their sEH inhibitory activity. Among the isolated phenolic compounds, 8 was identified as a significant inhibitor of sEH, with an IC50 value of 15.4 ± 1.3 μM. Additionally, a kinetic analysis of isolated compounds (2, 5, 8 - 11, 13, and 17) indicated that the inhibitory effects of flavonoid derivatives 10 and 11 were of mixed-type, with inhibitory constants (Ki) ranging from 3.6 ± 0.8 to 21.8 ± 1.0 μM, whereas compounds 2, 5, 8, 9, 13, and 17 were non-competitive inhibitors with inhibition Ki values ranging from 3.3 ± 0.2 to 39.5 ± 0.0 μM.

Carotenoid Destruction and Nonenzymatic Browning during Red Pepper Drying as functions of Average Moisture Content and Temperature (고추 건조과정에 있어서 평균 수분함량 및 온도에 따른 Carotenoid파괴 및 비효소적 갈변)

  • Lee, Dong-Sun;Kim, Hyun-Ku
    • Korean Journal of Food Science and Technology
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    • v.21 no.3
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    • pp.425-429
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    • 1989
  • Functional relationships of carotenoid destruction and nonenzymatic browning during red pepper drying were established by the dynamic test using the moisture-temperature-quality history curve in actual drying experiments. The dependence of the rate constants on temperature and moisture content was established and analysed assuming that carotenoid destruction and nonenzymatic browning are the first order and the zero order reaction, respectively. Carotenoid destruction rate constant was high at high moisture and high temperature, and had a minimum value at some intermediate moisture content. As dependence of rate constant on temperature, activation energy of carotenoid decolorization ranged from 7.7 to 27.4 kcal/mol, showing higher value at higher moisture content. Nonenzymatic browning showed higher rate at higher temperature and higher moisture content. Activation energy of browning was in the range of 7.5-20.2 kcal/mol with higher value at higher moisture level.

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A Study on Solvent Extraction of Metal by Salicylaldoxime (Salicylaldoxime에 의한 금속 추출에 관한 연구)

  • Shin, Jeong-Ho;Park, Sang-Wook;Park, Dae-Won;Lee, Kyung-Soo;Jeong, Kap-Seop
    • Applied Chemistry for Engineering
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    • v.4 no.1
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    • pp.46-53
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    • 1993
  • The kinetic and equilibrium characteristics of copper extraction by salicylaldoxime in chloroform and benzene were investigated. Equilibrium constants such as dissociation constant, distribution coefficient of salicylaldoxime and stability constant, distribution coefficient and molar extinction coefficient of oxime-Cu chelate were determined from absorbance. Extracted species of Cu-chelate were found to be ${\bar{CuR_2}}$. Overall initial extraction rate of copper by salicylaldoxime in chloroform was expressed by the following equation : $R=k[Cu^{2+}]{\bar{[HR]}}^{0.5}/[H^+]^{0.4}$.

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Recycling of Crosslinked Polypropylene and Crosslinked Polyethylene in Supercritical Methanol (초임계 메탄올에서 가교폴리프로필렌과 가교폴리에틸렌의 재활용성 비교)

  • Lee, Hong-Shik;Jeong, Ju Hyeong;Hong, Soon Man;Koo, Chong Min;Cho, Hang-Kyu;Lee, Youn-Woo
    • Korean Chemical Engineering Research
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    • v.50 no.1
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    • pp.88-92
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    • 2012
  • Decrosslinking of crosslinked polypropylene(XLPP) in supercritical methanol was investigated compared with that of crosslinked polyethylene(XLPE). Effect of reaction temperature and initial gel contents was studied using a batch reactor. Gel contents of samples before and after reaction were measured for quantitative analysis. As reaction temperature and initial gel contents increased, the decrosslinking rate increased. The rate of decrosslinking reaction is dependent linearly on the gel contents. Experimental results indicated that the decrosslinking of XLPP was faster than that of XLPE, and it was confirmed quantitatively by the calculation of kinetic constants. In conclusion, it is considered that XLPP has better recyclability than XLPE.

Amplicilin biosynthesis by immobilized enzyme

  • Kim, Young-Sik;Ryu, Dewy-D.Y.
    • Archives of Pharmacal Research
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    • v.3 no.1
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    • pp.7-12
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    • 1980
  • Ampliciline was synthesized from 6-amino-pencillanic acid (6-APA) and D-.alpha. phenylglycine methyl ester by using amplicilin synthesizing enzyme from Peudomonas melanogenum (IAM 1655). The whole cell enzyme was immobilized by entrapping it in the polyacrylamide gel lattices. The polymer used in the enzyme entrapment was made from 150 mg per ml of acrylamide monomer and 8 mg per ml of N, N'-methylenebisacrylamide. About 200 mg/whole cell enzyme was mixed in the polymer for entrapment. The maximal activity retention after immobilization was 56%. The optimal pH values for the whole cell enzyme and the immobilized whole cell enzyme were 6.0 and 5.9, respectively. The optimal temperature for the enzyme activity were the same for both type of preparations. The enzyme stabilities against pH and heat increased for immobilized whole cell enzyme. Immobilized cell was more stable especially in the acidic condition while both type were found to be very suceptible to thermal inactivation at a temperature above 4.deg.C. The kinetic constants obtained from Lineweaver-Burk plot based on two substate reaction mechanism showed somewhat higher value for immobilized whole cell enzyme as compared to the whole cell enzyme : the Km value for 6-APA were 7.0 mM and 12.5 mM while Km values for phenylglycine methyl ester were 4.5 mM and 8.2 mM, respectively. Using the immobilized whole cell enzyme packed in a column reactor, the productivity of ampiciline was studied by varying the flow rate of substrate solution. At the space velocity, SV, 0.14 hr$^{-1}$ the conversion was 45%. Operational stability found in terms of half life was 30 hr at SV = 0.2 hr.

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Kinetics and Mechanism of Triethylamine Catalysed Michael Addition of Benzenethiol to 1-(2-Nitrovinyl)benzene in Acetonitrile

  • Sarathi, P.A.;Gnanasekaran, C.;Shunmugasundaram, A.
    • Bulletin of the Korean Chemical Society
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    • v.29 no.4
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    • pp.790-794
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    • 2008
  • Nucleophilic addition reaction of benzenethiols (PhSH) to 1-(2-nitrovinyl) benzenes ($\beta$ NS) in the presence of triethylamine (TEA) has been studied in acetonitrile at 25 ${^{\circ}C}$. The rate is first order with respect to [PhSH], [TEA] and [$\beta$ NS]. The reaction is found to proceed with the formation of ion-pair between benzenethiol and TEA. A suitable mechanism with the formation of an adduct between ion-pair and substrate in a slow step followed by its rearrangement to 1,2-addition product in a fast step has been proposed and corresponding rate law derived. From the rate law, the rate constants for the interaction between ion-pair and $\beta$NS have been evaluated. Interestingly, in both para-substituted substrates and benzenethiols the rate increases with the electron-withdrawing power of the substituents. The positive sign of $\rho_x$ in benzenethiols has been explained. The magnitude of cross-interaction constant, $\rho_{xy}$ is small (0.08). The magnitude of the Hammett $\rho_x$ values is higher than that of the Bronsted, $\beta_x$ values for benzenethiols. The kinetic isotope effect, $k_H/k_D$, is found to be greater than unity. A suitable transition state with simultaneous formation of $C_\beta$ -H and $B_\alpha$ -S bonds involving the ion-pair and $\beta$NS in a single concerted step has been proposed to account for these observations.

Kinetic Studies of the Hydrolysis of 1-Arylpyrrole Imine (1-Arylpyrrole Imine의 가수분해 반응의 속도론적 연구)

  • Hak-Soo Lyu;Hee-Ju Chae
    • Journal of the Korean Chemical Society
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    • v.27 no.2
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    • pp.133-141
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    • 1983
  • The kinetics of the acid-catalyzed hydrolysis of a series of 1-aryl-2-pyrrylideneaniline (3) have been studied in 20% MeOH solution using UV spectrophotometer. Substituents in 3 showed a relatively small effect, with hydrolysis facilitated by electron withdrawing group. By obtaing linear plots of $log k_{obs}$ against Hammett ${\sigma}$ constants, it was able to show that substituents had a considerable contribution to the aromaticity of pyrrole compounds. The small positive ${\rho}$ values were consistent with the rate-determining addition of water to the protonated schiff base in the buffer solution of pH 4 to 8, whereas the addition of water to the free imine seemed to be the rate-determining in the solution of acidities greater than pH 8.

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Kinetic Studies on the Nucleophilic Addition of Thiourea to ${\beta}$-Nitrostyrene Derivatives (${\beta}$-Nitrostyrene 유도체에 대한 Thiourea의 친핵성 첨가반응에 관한 반응속도론적 연구)

  • Tae-Rin Kim;Yeun-Soo Chung;Myung-Sook Chung
    • Journal of the Korean Chemical Society
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    • v.35 no.3
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    • pp.268-274
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    • 1991
  • The rate constants for the nucleophilic addition reactions of thiourea to ${\beta}$-nitrostyrene derivatives(p-H, p-Cl, p-CH$_3$, p-OCH$_3$, p-NO$_2$) were determined by UV spectrophotometer and rate equations which can be applied over a wide pH ranges were obtained. On the basis of substituent effect, general base catalysis and rate equations, a reaction mechanism was proposed and revealed quantitively. Above pH 9.00, sulfide anion adds to the double bond(Michael type addition) and between pH 7.00 and 9.00, the neutral molecules and its anions add to the double bond competitively. Below pH 7.00, the addition reaction to double bond is initiated by the addition of neutral thiourea molecule.

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Kinetic Study on Nucleophilic Displacement Reactions of 2-Chloro-4-Nitrophenyl X-Substituted-Benzoates with Primary Amines: Reaction Mechanism and Origin of the α-Effect

  • Um, Tae-Il;Kim, Min-Young;Kim, Tae-Eun;Um, Ik-Hwan
    • Bulletin of the Korean Chemical Society
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    • v.35 no.2
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    • pp.436-440
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    • 2014
  • The ${\alpha}$-Effect; Ground state; Transition state; Intramolecular H-bonding; Yukawa-Tsuno plot; Second-order rate constants for aminolysis of 2-chloro-4-nitrophenyl X-substituted-benzoates (1a-h) have been measured spectrophotometrically in 80 mol % $H_2O/20$ mol % DMSO at $25.0^{\circ}C$. The Br${\emptyset}$nsted-type plot for the reactions of 2-chloro-4-nitrophenyl benzoate (1d) with a series of primary amines curves downward, which has been taken as evidence for a stepwise mechanism with a change in rate-determining step (RDS). The Hammett plots for the reactions of 1a-h with hydrazine and glycylglycine are nonlinear while the Yukawa-Tsuno plots exhibit excellent linearity with ${\rho}_X=1.22-1.35$ and ${\gamma}= 0.57-0.59$, indicating that the nonlinear Hammett plots are not due to a change in RDS but are caused by stabilization of substrates possessing an electron-donating group (EDG) through resonance interactions between the EDG and C=O bond of the substrates. The ${\alpha}$-effect exhibited by hydrazine increases as the substituent X changes from a strong EDG to a strong electron-withdrawing group (EWG). It has been concluded that destabilization of hydrazine through the electronic repulsion between the adjacent nonbonding electrons is not solely responsible for the substituent dependent ${\alpha}$-effect but stabilization of the transition state is also a plausible origin of the ${\alpha}$-effect.

Reductive Degradation Kinetics and Pathways of Chlorophenolic Organic Pollutants by Nickel-Coated Zero Valent Iron (니켈로 코팅된 영가금속을 이용한 염소계 페놀화합물의 반응경로 및 반응율 평가)

  • Shin, Seung-Chul;Kim, Young-Hun;Ko, Seok-Oh
    • Journal of Korean Society of Environmental Engineers
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    • v.28 no.5
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    • pp.487-493
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    • 2006
  • Reductive dechlorination of chlorophenols by nickel coated iron was investigated to understand the feasibility of using Ni/Fe for the in situ remediation of contaminated groundwater. Zero Valent Iron(ZVI) was amended with Ni(II) ions to form bimetal(Ni/Fe). Dechlorination of five chlorophenol compounds and formation of intermediates were examined using Ni/Fe. Rate constant for each reaction pathway was quantified by the numerical integration of a series of differential rate equation. Experimental results showed that the sequence of hydrodechlorination rate constant was in the order of 2-CP>4-CP>2,4-DCP>2,4,6-TCP>2,6-DCP. The hydrodechlorination pathways for the conversion of each chlorophenol compound involves a full dechlorination to phenol via both concerted and stepwise mechanisms. Reaction pathways and corresponding kinetic rate constants were suggested based on the experiments and numerical simulations.