• Title/Summary/Keyword: dissociation rate constant

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A Gas Phase Kinetic Study on the Thermal Decomposition of $ClCH_2CH_2CH_2Br$

  • Kim, Sung-Hoon;Choo, Kwang-Yul;Jung, Kyung-Hoon
    • Bulletin of the Korean Chemical Society
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    • v.10 no.3
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    • pp.262-269
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    • 1989
  • The gas phase thermal decomposition of 1-bromo-3-chloropropane in the presence of radical inhibitor was studied by using the conventional static system. The mechanism of unimolecular elimination channel is shown below. [...] In this scheme, the total molecular dissociation rate constant, ($k_1\;+\;k_2$), for the decomposition of $BrCH_2CH_2CH_2Cl$ was determined by pyrolyzing the $BrCH_2CH_2CH_2Cl$ in the temperature range of $380-420^{\circ}C$ and in the pressure range of 10∼100 torr. To obtain $k_3\;and\;k_4,\;and\;to\;obtain\;k_1\;and\;k_2$ independently, the thermal decompositions of allyl chloride and allyl bromide were also studied. The Arrhenius parameters for each step are as follows; $log\;A_{\infty}\;=\;14.20(sec^{-1}),\;E_a$ = 56.10(kcal/mol) for reaction path 1; $log\;A_{\infty}\;=\;12.54(sec^{-1}),\;E_a$ = 49.75(kcal/mol) for reaction path 2; $log\;A_{\infty}\;=\;13.41(sec^{-1}),\;E_a$ = 50.04(kcal/mol) for reaction path 3; $log\;A_{\infty}\;=\;12.43(sec^{-1}),\;E_a$ = 52.78(kcal/mol) for reaction path 4; Finally, the experimentally observed pressure dependence of the rate constants in each step is compared with the theoretically predicted values that are obtained by the RRKM calculations.

Antimuscarine-like Action of Licorice Alkaloidal Fraction on Intestinal Smooth Muscle -Studies of Alkaloid of Glycyrrhiza glabra L. III- (감초(甘草) Alkaloidal Fraction 의 평활근(平滑筋)에 대(對)한 Acetylcholine 길항작용(拮抗作用) -감초 알카로이드에 관한 연구 (제 3 보)-)

  • Kim, Myung-Suk;Oh, Jin-Sup;Hong, Sa-Ack
    • The Korean Journal of Pharmacology
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    • v.5 no.2
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    • pp.121-127
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    • 1969
  • Antimuscarinic agent like antispasmodic actions of licorice alkaloidal fraction, obtained from the Glycyrrhiza glabra L., was compared with that of atropine quantitatively. For this purpose, the author calculated the kinetic constants and $ED_{50}$ for acetylcholine antagonism by these drugs on rat ileum and guinea-fig ileum longitudinal muscle according to Paton's theoretical equations describing the combination of an antagonist drug with its receptors. The results are as follows. 1. On rat ileum. a) Licorice alkaloidal fraction $K_1$ (association rate constant)=$4.078{\times}10^2\;(s^{-1}\;gm^{-1}\;ml)$ $K_2$ (dissociation rate constant)=$6.986{\times}10^{-4}\;(s^{-1})$ $ED_{50}(K_2/K_1)=1.772{\times}10^{-6}(gm/ml)$ b) Atropine $K_1=5.136{\times}10^6$, $K_2=7.714{\times}10^{-4}$, $ED_{50}=1.408{\times}10^{-10}$ 2. On guinea-pig ileum longitudinal muscle a) Licorice alkaloidal fraction $K_1=1.30{\times}10^2$, $K_2=1.25{\times}10^{-3}$ $ED_{50}=9.58{\times}10^{-6}$ b) Atropine $K_1=5.75{\times}10^6$, $K_2=1.54{\times}10^{-3}$ $ED_{50}=2.68{\times}10^{-10}$ Above results present that 1 r of licorice alkaloidal fraction has equal fotency of acetylcholine antagonism with $8.5{\times}10^{-5}r$ of atropine on rat ileum, $2.8{\times}10^{-5}r$ on guinea-pig ileum longitudinal muscle. This facts suggest that the site and numbers of licorice alkaloid receptors of guinea-pig ileum are different from that of rat ileum. Besides, it also gives a suggestion that licorice alkaloidal fraction may be a partial antagonist on guinea-pig ileum in this experimental conditions.

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Solvent Extraction of Cu(II) by 2,4-Heptadione in Chloroform (2, 4-Heptadione에 의한 Cu(II)의 용매추출특성)

  • Shin, Jeong-Ho;Jeong, Kap-Seop;Lee, Sang-Hoon;Park, Sang-Wook;Park, Dae-Weon
    • Applied Chemistry for Engineering
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    • v.4 no.4
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    • pp.672-682
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    • 1993
  • 2, 4-Heptadione(abbreviated to 24HTD) was synthesized from methylpropyl ketone and ethyl acetate with sodium amide, and the equilibrium and the kinetic characteristics of copper extraction by 24HTD-chloroform were investigated. Equilibrium constants such as the dissociation constant and the distribution coefficient of 24HTD and the stability constant of the 24HTD-Cu chelate were evaluated from the spectrophotometry, and the overall equilibrium constant of the extraction was also determined. The extracted species of the 24HTD-Cu chelate was found to be $CuR_2$ and the initial rate of the extraction of coupper by 24HTD in chloroform was expressed by $R_0=k[\bar{HR}]([Cu^{2+}]/[H^+])^{0.5}$.

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Measurement and Analysis of the Dynamics of Peptide-Antibody Interactions Using an Ellipsometric Biosensor Based on a Silicon Substrate (실리콘 기판을 사용한 바이오센서와 회전 타원분광계를 이용한 펩타이드-항체 접합의 동특성 측정과 분석)

  • Lee, Geun-Jae;Cho, Hyun Mo;Jo, Jae Heung
    • Korean Journal of Optics and Photonics
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    • v.28 no.1
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    • pp.9-15
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    • 2017
  • We precisely measured and analyzed the dynamics of peptide-antibody interactions, using an ellipsometric biosensor based on a silicon substrate. To reduce the signal error due to the imperfect flatness of the substrate for extremely low concentrations of peptide, we fabricated the biosensor with a silicon substrate coated with Dextran SAM, instead of a glass prism coated with a thin metallic thin film. At an injection speed of $100{\mu}l/min$ of buffer liquid, we detected the dynamics of antibody-Dextran SAM or peptide-antibody fixed on biosensor, respectively. We detected the dynamics of antibody-Dextran SAM interactions down to a low concentration of 5 ng per liter, and we precisely measured the dynamics of association and dissociation of peptide and antibody down to 100 nM of peptide. We obtained the rate constants for association and dissociation from fitting the data by using deduced dynamical equation. As a result, we obtained an equilibrium constant for dissociation of 97 nM of peptide-antibody complex, which belongs to Class I.

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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Rat Liver $AT_1$ Receptor Binding Analysis for Drug Screening

  • Lee, Sunghou;Lee, Buyean;Hwasup Shin;Jaeyang Kong
    • Biomolecules & Therapeutics
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    • v.3 no.1
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    • pp.21-27
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    • 1995
  • The only compounds with antagonistic activity via AT$_1$receptor, one of two subtypes of angiotensin II (AII) receptor, have been demonstrated to block the vasoconstriction effects of AII and thereby provide therapeutic potential. This initiated the search for compounds with high specific affinity to AT$_1$receptor and their effective screening methods. The radioligand binding assay for the AII receptor is regarded as the primary method for the evaluation of AT$_1$receptor antagonists for their activity. In this paper, we characterized the liver AT$_1$receptor and describe the efficient method of the radioligand binding assay using rat liver as a source of AT$_1$receptor. Equilibrium binding studies with rat adrenal cortex, adrenal medulla, liver and bovine adrenal showed that the specific bindings of [$^3$H] AII were saturable in all tissues and the Scatchard plots of those data were linear, suggesting a single population of binding sites. Hill slopes were very near to the unity in all tissues. Kinetic studies of [$^3$H) AII binding in rat liver homogenates yielded two association rate constants, 4.10$\times$10$^{7}$ M$^{-1}$ min$^{-1}$ and 4.02$\times$10$^{9}$ M$^{-1}$ min$^{-1}$ , with a single dissociation rate constant, 7.07$\times$10$^{-3}$ min-$^{-1}$ , possibly due to the partial dissociation phenomenon. The rank order of inhibition potencies of [$^3$H] AII binding in rat liver was AII>Sarile>Losartan>PD 123177. Rat liver homogenates revealed to have very high density of homogeneous population of the AT$_1$receptor subtype, as the specifically bound [$^3$H] AII was not inhibited by PD 123177, the nonpeptide antagonist of AT$_2$. The results of this study demonstrated that the liver homogenates from rats could be the best receptor preparation for the AT$_1$receptor binding assay and provide an efficient system for the screening of newly synthesized candidate compounds of AT$_1$receptor antagonist.

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Increase In Mean Alveolar Pressure Due To Asymmetric Airway Geometry During High Frequency Ventilation

  • Cha, Eun-J.;Lee, Tae-S.;Goo, Yong-S.;Song, Young-J.
    • Journal of Biomedical Engineering Research
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    • v.14 no.1
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    • pp.89-96
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    • 1993
  • During high frequency ventilation (HFV), mean alveolar pressure has been measured to increase with mean airway opening pressure controlled at a constant level in both humans and experimental animals. Since this phenomenon could potentiate barotrauma limiting advantages of HFV, the present study theoretically predicted the difference between menu alveolar and airway opening pressures ($MP_{alv}$). In a Weibel's trumpet airway model, approximated formula for $MP_{alv}$ was derived based on momentum conservation assuming a uniform velocity profile. The prediction, equation was a func pion of gas density($\rho$), mean flow rate(Q), and diameter of the airway opening where the pressure measurement was made($D_0$) : $MP_{alv}=4{\rho}(Q/D_0^{2})^2$. This was a result of the difference in crosssectional area between the alveoli and the airway opening. A simple aireway model experiment was performed and the results well fitted to the prediction, which demonstrated the validity of the present analysis. Previously reported $MP_{alv}$ data from anesthetized dogs in supine position were comparable to the predicted values, indicating that the observed dissociation between mean alveolar and airway opening pressures during HFV can be explained by this innate geometric (or cross-sectional area) asymmetry of the airways. In lateral position, however, the prediction substantially underestimated the measurements suggesting involvement of other important physiological mechanisms.

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The Roles of Metal Ions and Water Molecules in the Hydrolysis of Bis(p-nitrophenyl)phosphate as a DNA Model Catalyzed by Dinuclear Ni(II) Complex (DNA 모델인 Bis(p-nitrophenyl)phosphate에 대한 2핵 Ni(II) 착 화합물의 촉매 가수분해 반응에서 물 분자와 금속 이온의 역할)

  • Sung, Nack-Do;Yun, Ki-Seob
    • Applied Biological Chemistry
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    • v.48 no.2
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    • pp.115-119
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    • 2005
  • The catalytic hydrolysis reactivities of dinuclear nickel (II) complex, ${\mu}-aquapentaaqua[{\mu}-3,6-bis(6'-methyl-2'-pyridyl)pyridazine]chlorodinickel\;(II)$ trichloride trihydrate (APNT) for bis(p-nitrophenyl) phosphate (BNPP) as a DNA model compound were investigated. The dissociation constants of APNT were $pKa_1=7.9$ and $pKa_2=9.6$, respectively. The hydrolysis rate constant of BNPP compound by APNT was showed the rate enhancement of about 370,000 times in the case of none catalyst at pH 7.0 and $50^{\circ}C$. Based on the findings, we proposed the catalytic cycle for the hydrolysis of BNPP by APNT complex. The metal ions of dinuclear nickel (II) complex significantly enhance the transfer rate of phosphoryl group in the catalytic process and the water molecules as nucleophile and proton transfer agent act in different steps.

The Study on $Na^+-Ca^{++}$ Exchange in Heart Mitochondria (심근 Mitochondria의 $Na^+-Ca^{++}$교환에 관한 연구)

  • Shin, Sang-Goo;Kim, Myung-Suk;Lim, Jung-Kyoo
    • The Korean Journal of Pharmacology
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    • v.18 no.2
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    • pp.89-102
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    • 1982
  • The $Na^+-and\;K^+-induced\;Ca^{++}$ release was measured isotopically by millipore filter technique in pig heart mitochondria. With EGTA-quenching technique, the characteristics of mitochondrial $Ca^{++}-pool$ and the sources of $Ca^{++}$ released from mitochondria by $Na^+\;or\;K^+$ were analyzed. The mitochondrial $Ca^{++}-pool$ could be distinctly divided into two components: internal and external ones which were represented either by uptake through inner membrane, or by energy independent passive binding to external surface of mitochondria, respectively. In energized mitochondria, a large portion of $Ca^{++}$was transported into internal pool with little external binding, while in de-enerigzed state, a large portion of transported $Ca^{++}$ existed in the external pool with limited amount of $Ca^{++}$ in the internal pool which was possibly transported through the $Ca^{++}-carrier$ present in the inner membrane. $Na^+$ induced the $Ca^{++}$ release from both internal pool and external pool and external binding pool of mitochondria. In contrast, $K^+$ did not affect $Ca^{++}$ of the internal pool, but, displaced $Ca^{++}$ bound to external surface of the mitochondria. When the $Ca^{++}-reuptake$ was blocked by EGTA, the $Ca^{++}$ release from the internal pool by $Na^+$ was rapid; the rate of $Ca^{++}-efflux$ appeared to be a function of $[Na^+]^2$ and about 8mM $Na^+$ was required to elicit half-maximal velocity of $Ca^{++}-efflux$. So it was revealed that $Ca^{++}-efflux$ velocity was particulary sensitive to small changes of the $Na^+$ concentration in physiological range. Energy independent $Ca^{++}-binding$ sites of mitochondrial external surface showed unique characteristics. The total number of external $Ca^{++}-binding$ sites of pig heart mitochondria was 29 nmoles per mg protein and the dissociation constant(Kd) was $34{\mu}M$. The $Ca^{++}-binding$ to the external sites seemed to be competitively inhibited by $Na^+\;and\;K^+$; the inhibition constant(Ki) were 9.7 mM and 7.1 mM respectively. Considering the intracellular ion concentrations and large proportion of $Ca^{++}$ uptake in energized mitochondria, the external $Ca^{++}-binding$ pool of the mitochondria did not seem to play a significant role on the regulation of intracellular free $Ca^{++}$ concentration. From this experiment, it was suggested that a small change of intracellular free $Na^+$ concentration might play a role on regulation of free $Ca^{++}$ concentration in cardiac cell by influencing $Ca^{++}-efflux$ from the internal pool of mitochondria.

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Thermal Recovery Behaviors of Neutron Irradiated Mn-Mo-Ni Low Alloy Steel (중성자에 조사된 Mn-Mo-Ni 저합금강의 열처리 회복거동)

  • Jang, Gi-Ok;Ji, Se-Hwan;Sim, Cheol-Mu;Park, Seung-Sik;Kim, Jong-O
    • Korean Journal of Materials Research
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    • v.9 no.3
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    • pp.327-332
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    • 1999
  • The recovery activation energy, the order of reaction and the recovery rate constant were detemined by isochronal and isothermal annealing treatment to investigate the recovery behaviors of neutron irradiated Mn-Mo-Ni low alloy steels$(fluence: 2.3\times10^{19}ncm^{-2}, 553K, E\geq1.0 MeV)$. Vickers microhardness tests were conducted to trace the recovery behavior after heat treatments. The results were analyzed in terms of recovery stages, behavior of responsible defects and recovery kinetics. It was shown that recovery occurred through two annealing stages(stage I : 703-753K, stage n : 813-873K) with re$\infty$very activation energies of 2.5 eV and 2.93 eV for each stage I and n, respectively. From the comparison of unirradiated and irradiated isochronal anneal curves, a radiation anneal hardening(RAH) peak was identified at around 813K. Most of recovery have occurred during about 120 min irrespective of isothermal annealing temperatures of 743K and 833K. Recovery rate constants were determined to be $3.4\times10^{-4}min^{-1} and 7.1\times10^{-4}min^{-1}$ for stage I and II, respectively. The order of reaction was about 2 for both recovery stages. Comparing the obtained data with those of previously reported results on neutron irradiated Mn- Mo- Ni steels, the thermal recovery be­havior of the present material seems to occur by the dissociation of point defect clusters formed during irradiation, and by the recombination process of self-interstitials and vacancies from dissociated vacancy clusters.

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