• Title/Summary/Keyword: Second-order rate constant

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Isolation and Identification of Succinic Semialdehyde Dehydrogenase Inhibitory Compound from the Rhizome of Gastrodia elata Blume

  • Baek, Nam-In;Choi, Soo-Young;Park, Jin-Kyu;Cho, Sung-Woo;Ahn, Eun-Mi;Jeon, Seong-Gyu;Lee, Byung-Ryong;Bahn, Jae-Hoon;Kim, Yong-Kyu;Shon, Il-Hwan
    • Archives of Pharmacal Research
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    • v.22 no.2
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    • pp.219-224
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    • 1999
  • In our search for the anticonvulsant consitutent of Gastrodia elata repeated column chromatographies guided by activity assay led to isolation of an active compound, which was identified as gastrodin on the basis of spectral data. Brain succinic semialdehyde dehydrogenase (SSADH) was inactivated by preincubation with gastrodin in a time-dependent manner and the reaction was monitored by absorption and fluorescene spectroscopic methods. The inactivation followed pseudo-first-order kinetics with the second-rate order constant of $1.2{\times}10^{3} M^{-1} min^{-1}$. The time course of the reaction was significantly affected by the coenzyme NAD^{+}$, which affected complete protection against the loss of the catalytic activity, whereas substrate succinic semialdehyde failed to prevent the inactivation of the enzyme. It is postulated that the gastrodin is able to elevate the neurotransmitter GABA levels in central nervous system by inhibitory action on one of the GABA degradative enzymes, SSADH.

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Alkali Metal Ion Catalysis and Inhibition in Nucleophilic Substitution Reactions of 3,4-Dinitrophenyl Diphenylphosphinothioate with Alkali Metal Ethoxides in Anhydrous Ethanol: Effect of Changing Electrophilic Center from P=O to P=S

  • An, Jun-Sung;NamKoong, Gil;Kang, Ji-Sun;Um, Ik-Hwan
    • Bulletin of the Korean Chemical Society
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    • v.32 no.7
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    • pp.2423-2427
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    • 2011
  • Pseudo-first-order rate constants ($k_{obsd}$) have been measured spectrophotometrically for nucleophilic substitution reactions of 3,4-dinitrophenyl diphenylphosphinothioate 9 with alkali metal ethoxides (EtOM, M = Li, Na, K) in anhydrous ethanol at $25.0{\pm}0.1^{\circ}C$. The plot of $k_{obsd}$ vs. [EtOM] is linear for the reaction of 9 with EtOK. However, the plot curves downwardly for those with EtOLi and EtONa while it curves upwardly for the one with EtOK in the presence of 18-crown-6-ether (18C6). Dissection of $k_{obsd}$ into $k_{EtO^-}$ and $k_{EtOM}$ (i.e., the second-order rate constant for the reaction with dissociated $EtO^-$ and ion-paired EtOM, respectively) has revealed that the reactivity increases in the order $k_{EtOLi}$ < $k_{EtONa}$ < $k_{EtO^-}$ ${\approx}$ $k_{EtOK}$ < $k_{EtOK/18C6}$, indicating that the reaction is inhibited by $Li^+$ and $Na^+$ ions but is catalyzed by 18C6-crowned $K^+$ ion. The reactivity order found for the reactions of 9 contrasts to that reported previously for the corresponding reactions of 1, i.e., $k_{EtOLi}$ > $k_{EtONa}$ > $E_{EtOK}$ > $k_{EtO^-}$ ${\approx}$ $k_{EtOK/18C6}$, indicating that the effect of changing the electrophilic center from P=O to P=S on the role of $M^+$ ions is significant. A four-membered cyclic transition-state has been proposed to account for the $M^+$ ion effects found in this study, e.g., the polarizable sulfur atom of the P=S bond in 9 interacts strongly with the soft 18C6-crowned $K^+$ ion while it interacts weakly with the hard $Li^+$ and $Na^+$ ions.

Structure of Export Competition between Asian NIEs and Japan in the U.S. Import Market and Exchange Rate Effects (한국(韓國)의 아시아신흥공업국(新興工業國) 및 일본(日本)과의 대미수출경쟁(對美輸出競爭) : 환율효과(換率效果)를 중심(中心)으로)

  • Jwa, Sung-hee
    • KDI Journal of Economic Policy
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    • v.12 no.2
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    • pp.3-49
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    • 1990
  • This paper analyzes U.S. demand for imports from Asian NIEs and Japan, utilizing the Almost Ideal Demand System (AIDS) developed by Deaton and Muellbauer, with an emphasis on the effect of changes in the exchange rate. The empirical model assumes a two-stage budgeting process in which the first stage represents the allocation of total U.S. demand among three groups: the Asian NIEs and Japan, six Western developed countries, and the U.S. domestic non-tradables and import competing sector. The second stage represents the allocation of total U.S. imports from the Asian NIEs and Japan among them, by country. According to the AIDS model, the share equation for the Asia NIEs and Japan in U.S. nominal GNP is estimated as a single equation for the first stage. The share equations for those five countries in total U.S. imports are estimated as a system with the general demand restrictions of homogeneity, symmetry and adding-up, together with polynomially distributed lag restrictions. The negativity condition is also satisfied for all cases. The overall results of these complicated estimations, using quarterly data from the first quarter of 1972 to the fourth quarter of 1989, are quite promising in terms of the significance of individual estimators and other statistics. The conclusions drawn from the estimation results and the derived demand elasticities can be summarized as follows: First, the exports of each Asian NIE to the U.S. are competitive with (substitutes for) Japan's exports, while complementary to the exports of fellow NIEs, with the exception of the competitive relation between Hong Kong and Singapore. Second, the exports of each Asian NIE and of Japan to the U.S. are competitive with those of Western developed countries' to the U.S, while they are complementary to the U.S.' non-tradables and import-competing sector. Third, as far as both the first and second stages of budgeting are coneidered, the imports from each Asian NIE and Japan are luxuries in total U.S. consumption. However, when only the second budgeting stage is considered, the imports from Japan and Singapore are luxuries in U.S. imports from the NIEs and Japan, while those of Korea, Taiwan and Hong Kong are necessities. Fourth, the above results may be evidenced more concretely in their implied exchange rate effects. It appears that, in general, a change in the yen-dollar exchange rate will have at least as great an impact, on an NIE's share and volume of exports to the U.S. though in the opposite direction, as a change in the exchange rate of the NIE's own currency $vis-{\grave{a}}-vis$ the dollar. Asian NIEs, therefore, should counteract yen-dollar movements in order to stabilize their exports to the U.S.. More specifically, Korea should depreciate the value of the won relative to the dollar by approximately the same proportion as the depreciation rate of the yen $vis-{\grave{a}}-vis$ the dollar, in order to maintain the volume of Korean exports to the U.S.. In the worst case scenario, Korea should devalue the won by three times the maguitude of the yen's depreciation rate, in order to keep market share in the aforementioned five countries' total exports to the U.S.. Finally, this study provides additional information which may support empirical findings on the competitive relations among the Asian NIEs and Japan. The correlation matrices among the strutures of those five countries' exports to the U.S.. during the 1970s and 1980s were estimated, with the export structure constructed as the shares of each of the 29 industrial sectors' exports as defined by the 3 digit KSIC in total exports to the U.S. from each individual country. In general, the correlation between each of the four Asian NIEs and Japan, and that between Hong Kong and Singapore, are all far below .5, while the ones among the Asian NIEs themselves (except for the one between Hong Kong and Singapore) all greatly exceed .5. If there exists a tendency on the part of the U.S. to import goods in each specific sector from different countries in a relatively constant proportion, the export structures of those countries will probably exhibit a high correlation. To take this hypothesis to the extreme, if the U.S. maintained an absolutely fixed ratio between its imports from any two countries for each of the 29 sectors, the correlation between the export structures of these two countries would be perfect. Therefore, since any two goods purchased in a fixed proportion could be classified as close complements, a high correlation between export structures will imply a complementary relationship between them. Conversely, low correlation would imply a competitive relationship. According to this interpretation, the pattern formed by the correlation coefficients among the five countries' export structures to the U.S. are consistent with the empirical findings of the regression analysis.

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Adsorption Kinetic and Thermodynamic Studies of Tricyclazole on Granular Activated Carbon (입상 활성탄에 대한 트리사이크라졸의 흡착동력학 및 열역학적 연구)

  • Lee, Jong-Jib;Cho, Jung-Ho;Kim, H.T.
    • Journal of Korean Society of Environmental Engineers
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    • v.33 no.9
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    • pp.623-629
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    • 2011
  • The adsorption characteristics of tricyclazole by granular activated carbon were experimently investigated in the batch adsorption. Kinetic studies of adsorption of tricyclazole were carried out at 298, 308 and 318 K, using aqueous solutions with 250, 500 and 1,000 mg/L initial concentration of tricyclazole. It was established that the adsorption equilibrium of tricyclazole on granular activated carbon was successfully fitted by Freundlich isotherm equation at 298 K. The pseudo first order and pseudo second order models were used to evaluate the kinetic data and the pseudo second order kinetic model was the best with good correlation. Values of the rate constant ($k_2$) have been calculated as 0.1076, 0.0531, and 0.0309 g/mg h at 250, 500 and 1,000 mg/L initial concentration of tricyclazole, respectively. Thermodynamic parameter such as activation energy, standard enthalpy, standard entropy and standard free energy were evaluated. The positive value for enthalpy, -66.43 kJ/mol indicated that adsorption interaction of tricyclazole on activated carbon was an exothermic process. The estimated values for standard free energy were -5.08~-8.10 kJ/mol over activated carbon at 200 mg/L, indicated toward a exothermic process.

Adsorption Characteristics of Brilliant Green by Coconut Based Activated Carbon : Equilibrium, Kinetic and Thermodynamic Parameter Studies (야자계 입상 활성탄에 의한 brilliant green의 흡착 특성 : 평형, 동력학 및 열역학 파라미터에 관한 연구)

  • Lee, Jong-Jib
    • Clean Technology
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    • v.25 no.3
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    • pp.198-205
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    • 2019
  • The adsorption equilibrium, kinetic, and thermodynamic parameters of brilliant green adsorbed by coconut based granular activated carbon were determined from various initial concentrations ($300{\sim}500mg\;L^{-1}$), contact time (1 ~ 12 h), and adsorption temperature (303 ~ 323 K) through batch experiments. The equilibrium adsorption data were analyzed by Langmuir, Freundlich, Temkin, Harkins-Jura, and Elovich isotherm models. The estimated Langmuir dimensionless separation factor ($R_L=0.018{\sim}0.040$) and Freundlich constant ($n^{-1}=0.176{\sim}0.206$) show that adsorption of brilliant green by activated carbon is an effective treatment process. Adsorption heat constants ($B=12.43{\sim}17.15J\;mol^{-1}$) estimated by the Temkin equation corresponded to physical adsorption. The isothermal parameter ($A_{HJ}$) by the Harkins-Jura equation showed that the heterogeneous pore distribution increased with increasing temperature. The maximum adsorption capacity by the Elovich equation was found to be much smaller than the experimental value. The adsorption process was best described by the pseudo second order model, and intraparticle diffusion was a rate limiting step in the adsorption process. The intraparticle diffusion rate constant increased because the dye activity increased with increases in the initial concentration. Also, as the initial concentration increased, the influence of the boundary layer also increased. Negative Gibbs free energy ($-10.3{\sim}-11.4kJ\;mol^{-1}$), positive enthalpy change ($18.63kJ\;mol^{-1}$), and activation energy ($26.28kJ\;mol^{-1}$) indicate respectively that the adsorption process is spontaneous, endothermic, and physical adsorption.

Study on of Process Parameters for Adsorption of Reactive Orange 16 Dye by Activated Carbon (활성탄에 의한 Reactive Orange 16 염료 흡착에 대한 공정 파라미터 연구)

  • Lee, Jong Jib
    • Journal of the Korea Academia-Industrial cooperation Society
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    • v.21 no.7
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    • pp.667-674
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    • 2020
  • The adsorption of reactive orange 16 (RO 16) dye by activated carbon was investigated using the amount of adsorbent, pH, initial concentration, contact time and temperature as adsorption variables. The investigated process parameters were separation coefficient, rate constant, rate controlling step, activation energy, enthalpy, entropy, and free energy. The adsorption of RO 16 was the highest at pH 3 due to the electrostatic attraction between the cations (H+) on the surface of the activated carbon and the sulfonate ions and hydroxy ions possessed by RO 16. Isotherm data were fitted into Langmuir, Freundlich and Temkin isotherm models by applying the evaluated separation factor of Langmuir (RL=0.459~0.491) and Freundlich (1/n=0.398~0.441). Therefore, the adsorption operation of RO 16 by activated carbon was confirmed as an appropriate removal method. Temkin's adsorption energy indicated that this adsorption process was physical adsorption. The adsorption kinetics studies showed that the adsorption of RO 16 follows the pseudo-second-order kinetic model and that the rate controlling step in the adsorption process was the intraparticle diffusion step. The positive enthalpy change indicated an endothermic process. The negative Gibbs free energy change decreased in the order of -3.16 <-11.60 <-14.01 kJ/mol as the temperature increased. Therefore, it was shown that the spontaneity of the adsorption process of RO 16 increases with increasing temperature.

An Investigation of Higher Order Forces on a Vertical Truncated Cylinder

  • Boo, Sung-Youn
    • Proceedings of the Korea Committee for Ocean Resources and Engineering Conference
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    • 2003.05a
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    • pp.214-214
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    • 2003
  • During a model test of Hutton TLP, a "ringing" response was first observed about 20 years ago. This phenomenon is a resonant build up over the time of wave period and this burst-like motion can cause the extreme load on the TLP tether. It is often detected in the large and steep irregular waves but the generation mechanism leading to the "ringing" is not yet well understood. According to the research since then, the higher order harmonic components may account for the "ringing" on the floating offshore structures. The main purpose of the present research is, thus, to measure the higher harmonic forces exerted on a vertical truncated circular column and to compare them with available data. A vertical truncated cylinder with a diameter of 3.5inch and a draft of 10.5inch is used as a test structure, which is a scaled model of ISSC TLP column. The cylinder is installed at a distance of 45ft from the wave maker in order to avoid parasitic waves created in the wave flap. Attached to the upper part of the cylinder are two force gages to measure the horizontal (surge) and vertical (heave) forces on the cylinder. The incoming waves are Stokes waves with a slope ranging from 0.06 to 0.24. The forces and waves are measured for 60 seconds with a sampling rate of 50 Hz. Among the recorded data, the first 10 waves are excluded because of transient behavior of the waves and the next The horizontal and vertical forces are analyzed up to 5th order harmonics. The horizontal forces are then compared to the values from the theoretical model called "FNV model". In addition, force transfer functions are also investigated. Major findings in this research are below. 1) The first order forces measured are slightly larger than the theoretical values of "FNV model" 2) The "FNV model" considerably overpredicts the second order forces. 3) The larger the amplitude and more extreme the wave slope, the smaller the predictions are compared to the experimental. 4) The higher harmonic forces are significantly smaller than the first harmonic force for all wave parameters. 5) The normalized forces vs. waves slopes are almost constant in the lower harmonics but vary a lot in the higher harmonics. 6) The trend of forces is more nonlinear in the horizontal forces than in the vertical forces as the wave slope increases. 7) The part of the results above is also observed by other researchers and confirmed again through the present work.

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AN EXPERIMENTAL STUDY ON THE FATIGUE FRACTURE OF LAMINATE PORCELAIN (치과용 라미네이트 도재의 피로파괴에 관한 실험적 연구)

  • Park Charn-Woon;Bae Tae-Sung;Lee Sang-Don
    • The Journal of Korean Academy of Prosthodontics
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    • v.31 no.4
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    • pp.482-505
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    • 1993
  • The purpose of this study was to evaluate the fracture characteristics and the effect of resin bonding of laminate porcelain. In order to characterize the indentation-induced crack, Young's moduli and characteristic indentation dimensions were measured. The fatigue life under three point flexure test was measured using the electro-dynamic type fatigue machine, and the crack propagation with thermocycling was investigated on the condition of 15 second dwell time each in $5^{\circ}C\;and\;55^{\circ}C$ bath. The Vickers indentation pattern and the fracture surface were examined by an optical microscope and a scanning electron microscope (SEM). The results obtained were summarized as follows ; 1. Young's moduli(E) of the laminate porcelain and the resin cement used in this experiment were $62.56{\pm}3.79GPa$ and $15.01{\pm}0.12GPa$, respectively. 2. The initial crack size of the laminate porcelain was $69.19{\pm}5.94{\mu}m$ when an indentation load of 9.8N was applied, and the fracture toughness was $1.065{\pm}0.156MPa\;m^{1/2}$. 3. The fatigue life of laminate porcelain showed the constant fracture range at the stress level 27.46-35.30MPa. 4. When a cyclic flexure load was applied, the fatigue life of resin-bonded laminate porcelain was more decreased than that of laminate porcelain. 5. When a thermocycling was conducted, the crack growth rate of resin-bonded laminate porcelain was more increased than that of laminate porcelain. 6. Fracture surface showed the radial crack, the lateral crack, and the macroscopic crack branching region beneath the plastic deformation region when an indentation load of 9.8N was applied.

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Chemical Modification of Bovine Brain Succinic Semialdehyde Reductase by Diethylpyrocarbonate

  • Lee, Byung-Ryong;Jeon, Seong-Gyu;Bahn, Jae-Hoon;Choi, Kyung-Soon;Yoon, Byung-Hak;Ahn, Yoon-Kyung;Choi, Eun-A;Lee, Kil-Soo;Cho, Sung-Woo;Choi, Soo-Young
    • BMB Reports
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    • v.32 no.3
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    • pp.254-258
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    • 1999
  • The NADPH-dependent succinic semialdehyde reductase is one of the key enzymes in the brain GABA shunt, and it catalyzes the formation of the neuromodulator $\gamma$-hydroxybutyrate from succinic semi aldehyde. This enzyme was inactivated by diethylpyrocarbonate (DEP) with the second-order rate constant of $1.1{\times}10^3\;M^{-1}min^{-1}$ at pH 7.0, $25^{\circ}C$, showing a concomitant increase in absorbance at 242 nm due to the formation of N-carbethoxyhistidyl derivatives. Complete inactivation of succinic semialdehyde reductase required the modification of five histidyl residues per molecule of enzyme. However, only one residue was calculated to be essential for enzyme activity by a statistical analysis of the residual enzyme activity. The inactivation of the enzyme by DEP was prevented by preincubation of the enzyme with the coenzyme NADPH but not with the substrate succinic semialdehyde. These results suggest that an essential histidyl residue involved in the catalytic activity is located at or near the coenzyme binding site of the brain succinic semialdehyde reductase.

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Electrocatalytic Oxidation of NADH at the Modified Graphite Electrode Incorporating Gold Nano Particles (금 나노입자를 회합시킨 수식된 흑연전극으로 NADH의 전기촉매 산화반응)

  • Cha, Seong-Keuck;Han, Sung-Yub
    • Journal of the Korean Electrochemical Society
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    • v.10 no.1
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    • pp.1-6
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    • 2007
  • Mercaptopropionic acid(mpa) has been used to make self-assembled monolayer(SAMs) on the surface of graphite electrode incorporating gold nano particles, which are subsequently modified with dopamine(dopa). Such modified electrodes haying types of Gr(Au)/mpa-dopa were employed in the electrocatalytic oxidation of NADH. The responses of such modified electrodes were studied in terms of electron transfer kinetics and reaction procedure in the reaction. The reaction of the surface immobilized dopa with NADH was studied using the rotating disk electrode technique and a value of $5.06{\times}10^5M^{-1}s^{-1}$ was obtained for the second-order rate constant in 0.1 M phosphate buffer(pH=7.0), which was a $EC_{cat}$ and kinetic controlled procedure. But, the modified electrodes were diffusion controlled reaction having $4.64{\times}10^{-4}cm^2s^{-1}$ of the coefficient within $10^{-3}s$ after starting the reaction.