• 제목/요약/키워드: dissociation rate constant

검색결과 32건 처리시간 0.024초

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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    • 제10권3호
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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.

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)- (Antimuscarine-like Action of Licorice Alkaloidal Fraction on Intestinal Smooth Muscle -Studies of Alkaloid of Glycyrrhiza glabra L. III-)

  • 김명석;오진섭;홍사악
    • 대한약리학회지
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    • 제5권2호
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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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2, 4-Heptadione에 의한 Cu(II)의 용매추출특성 (Solvent Extraction of Cu(II) by 2,4-Heptadione in Chloroform)

  • 신정호;정갑섭;이상훈;박상욱;박대원
    • 공업화학
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    • 제4권4호
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    • pp.672-682
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    • 1993
  • sodium amide에 의한 methylpropyl ketone과 ethyl acetate의 반응으로 2, 4-heptadione(이하 24HTD)을 합성하고, 클로로포름 용매하에 Cu(II)의 용매추출 실험으로부터 추출평형 및 추출속도 특성을 고찰하였다. 흡광도와 Cu(II)의 농도변화 측정으로부터 24HTD의 분배계수와 해리정수, 24HTD와 Cu 착화합물의 안정도 상수, 분배계수 및 총괄추출 평형정수 등을 구하고 추출기구를 구명하였다. 24HTD에 의한 Cu(II)의 추출 화학종은 1:2의 형태인 $CuR_2$였으며, 24HTD-클로로포름에 의한 Cu(II)의 총괄 초기 추출속도는 $R_0=k[\bar{HR}]([Cu^{2+}]/[H^+])^{0.5}$로 표시되었다.

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

  • 이근재;조현모;조재흥
    • 한국광학회지
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    • 제28권1호
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    • pp.9-15
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    • 2017
  • 실리콘 기판으로 만든 바이오센서에서 펩타이드-항체의 접합 동특성을 회전 타원분광계로 정밀하게 측정하고 분석하였다. 극도로 낮은 몰농도의 펩타이드를 측정할 때, 시료가 놓이는 바이오센서의 표면의 불완전한 편평도와 완충용액 굴절률 변화로 인한 측정오차를 줄이기 위하여 금속박막의 유리 프리즘 대신에 실리콘 기판 위에 덱스트란 SAM을 직접 적층하여 바이오센서를 만들었다. $100{\mu}l/min$의 완충용액 주입속도에서 바이오센서에 올려진 항체 및 펩타이드의 접합특성을 각각 측정하였다. 리터당 5 ng의 낮은 항체농도에서도 항체-덱스트란 SAM 사이의 동특성을 쉽게 측정할 수 있었다. 또한 100 nM까지의 펩타이드에 대한 미세한 흡착 및 해리 특성을 정밀하게 측정할 수 있었으며, 접합 동특성 식에 이 실험결과를 피팅하여 흡착계수와 해리계수를 구할 수 있었다. 이 결과로부터 펩타이드의 평형상태의 해리상수인 $K_D$는 97 nM이었고, 이 수치는 Class I에 속함을 알 수 있었다.

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

  • 신정호;박상욱;박대원;이경수;정갑섭
    • 공업화학
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    • 제4권1호
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    • pp.46-53
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    • 1993
  • salicylaldoxime에 의한 Cu의 용매추출에 있어서 추출평형 및 추출속도 등을 고찰하였다. 흡광도 측정으로부터 oxime의 분배정수와 해리정수를 구하고, oxime-Cu착화합물의 안정도 상수와 분배정수, 분자흡광계수 및 추출평형정수를 결정하였다. chloroform 및 benzene 용매하에 salicylaldoxime에 의한 Cu의 추출 화학종은 1:2의 형태인 ${\bar{CuR_2}}$였으며, 초기 추출속도실험으로부터 salicylaldoxime-chloroform에 의한 Cu의 총괄추출속도는 $R=k[Cu^{2+}]{\bar{[HR]}}^{0.5}/[H^+]^{0.4}$로 표시 되었다.

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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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    • 제3권1호
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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.
    • 대한의용생체공학회:의공학회지
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    • 제14권1호
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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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DNA 모델인 Bis(p-nitrophenyl)phosphate에 대한 2핵 Ni(II) 착 화합물의 촉매 가수분해 반응에서 물 분자와 금속 이온의 역할 (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)

  • 성낙도;윤기섭
    • Applied Biological Chemistry
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    • 제48권2호
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    • pp.115-119
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    • 2005
  • DNA 모델 화합물인 bis(p-nitrophenyl)phosphate(BNPP)에 대한 2핵 닉켈(II) 착 화합물, ${\mu}-aquapentaaqua[{\mu}-3,6-bis(6'-methyl-2'-pyridyl)pyridazine]chlorodinickel(II)$ trichloride trihydrate(APNT)의 촉매 가수분해 반응성을 검토하였다. APNT의 산 해리 상수는 각각 $pKa_1=7.9$$pKa_2=9.6$이었으며 BNPP의 가수분해반응 결과, pH 7.0과 $50^{\circ}C$에서 무 촉매인 경우에 비하여 가수분해 속도를 약 37만 배 가량 촉진시킴을 확인하였다. 그리고 pH-rate profile로부터 실험 사실을 합리적으로 설명할 수 있는 APNT에 의한 BNPP의 촉매 가수분해 반응에 대한 일련의 catalytic cycle을 제안하였다. 따라서 반응의 각 단계에서 2핵 닉켈(II) 착 화합물의 금속 이온들은 phosphoryl group의 전달 속도를 촉진하였고 물 분자는 친핵체와 양성자 전달체로 작용하였다.

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

  • 신상구;김명석;임정규
    • 대한약리학회지
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    • 제18권2호
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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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중성자에 조사된 Mn-Mo-Ni 저합금강의 열처리 회복거동 (Thermal Recovery Behaviors of Neutron Irradiated Mn-Mo-Ni Low Alloy Steel)

  • 장기옥;지세환;심철무;박승식;김종오
    • 한국재료학회지
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    • 제9권3호
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    • pp.327-332
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    • 1999
  • 중성자에 조사 $(fluence: 2.3\times10^{19}ncm^{-2}, 553 K, E\geq1.0 MeV)$된 Mn-Mo-Ni 저 합금강 모재의 열처리 회복 거동을 조사하기 위하여 등시소둔과 등온소둔을 수행하여 회복 활성화에너지, 회복 반응차수 그리고 회복 반응률상수를 결정하였다. 열처리 후 회복은 비커스 미세 고온경도기로 측정하였고 실험결과를 이용, 열처리 회복단계, 회복결함들의 거동 및 회복 kinetics을 분석하였다. 실험결과 2단계의 회복구간(stage I : 703-753K, stage II : 813K-873K)이 나타났으며 각 단계의 회복활성화 에너지는 2.50 eV(1단계) 및 2.93 eV(2단계)이었다. 조사재와 비조사재의 등시소둔 곡선의 비교를 통하여 813K에서 RAH(radiation anneal hardening) 피크를 확인할 수 있었다. 743K 및 833K에서 수행한 등온소둔 결과, 회복의 60%가 모두 120분 이내에 일어나는 것으로 관찰되었다. 회복 반응차수는 두 회복구간에서 모두 2로 나타났으며 회복 반응율상수는 $3.4\times10^{-4}min^{-1}$(1단계)과 $7.1\times10^{-4}min^{-1}$(2단계) 이었다. 이상의 결과와 기 발표된 자료들을 함께 분석한 결과, 본 재료의 회복은 오랜 중성자조사로 형성된 점결함 집합체들이 열처리에 의한 분해와 Fe 기지에 격자간 원자로 존재하던 self-interstitial들과 vacancy들의 재결합에 의해 일어나는 것으로 해석된다.

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