• 제목/요약/키워드: Dissociation constants

검색결과 127건 처리시간 0.025초

수용성 폴리파라시클로판류와 약물과의 상호작용(제 3보)-수용액 중 수용성 폴리파라시클로판류와 형광 소수 나프탈렌 유도체류와의 복합체 형성- (Interactions between Water-Soluble Polyparacyclophanes and Drugs (III) -Complex Formation of Water-Soluble Polyparacyclophanes with Fluorescent Hydrophobic Naphthalene Derivatives in Aqueous Solution-)

  • 전인구;이민화
    • Journal of Pharmaceutical Investigation
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    • 제19권2호
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    • pp.71-79
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    • 1989
  • Complex formation of water-soluble polyparacyclophanes bearing two diphenylmethane or two diphenyl ether skeletons with l-anilinonaphthalene-8-sulfonate (ANS) and 2-p-toluidinylnaphthalene-6-sulfonate (TNS) was investigated quantitatively to develop useful host compounds comparing with ${\alpha}\;-\;and\;{\beta}-cyc1odextrins$$({\alpha}-\;and\;{\beta}-CyDs$) in aqueous solution. Benesi-Hildebrand type analysis of the fluorescent intensity showed that the dissociation constants (Kd) of paracyclophane-ANS complexes were $1.55\;{\times}\;10^{-4}M$ for 1,6,20,25-tetraaza[6.1.6.1]paracyclophane(CPM 44) and $1.23\;{\times}\;10^{-4}M$ for 1,7,21,27-tetraaza[7.1.7.1]paracyclophane (CPM 55), and those of paracyclophane-TNS complexes were $6.99\;{\times}\;10^{-6}M$ for CPM 44 and $6.23\;{\times}\;10^{-5}M$ for CPM 55, in 1:1 molar ratio. On the other hand, the Kd values of 1,7,21,27-tetraaza-14,34-dioxa[7.1.7.1]paracyclophane (CPE 55)-ANS, 1,8,22,29-tetraaza-15,36-dioxa[8.1.8.1]paracyclophane (CPE 66)-ANS, CPE 55-TNS, CPE 66-TNS complexes were $1.75\;{\times}\;10^{-3}M$, $3.07\;{\times}\;10^{-3}M$, $3.75\;{\times}\;10^{-3}M$ and $2.15\;{\times}\;10^{-3}M$, respectively. On the contrary, the Kd values of ${\alpha}-CyD-ANS$, ${\beta}-CyD-ANS$, ${\alpha}-CyD-TNS$ and ${\beta}-CyD-TNS$ complexes were found to be $3.98\;{\times}\;10^{-2}M$, $1.05\;{\times}\;10^{-2}M$, $1.38\;{\times}\;10^{-2}M$ and $3.52\;{\times}\;10^{-4}M$, respectively. These results mean that the complexation of CPMs with ANS or TNS is by 5.6-1,975 fold stronger than that for ${\alpha}-or\;{\beta}-CyDs$, and the complex formation of CPEs with ANS or TNS is nearly same as or somewhat stronger than that for ${\alpha}-or\;{\beta}-CyDs$. From the Kd values determined at different temperatures, thermodynamic parameters were calculated and the complexation was found to be a spontaneous exothermic reaction. The effects of pH on Kd values of CPM 44-ANS, and CPM 55-ANS complexes were negligible in the range of pH 1.2-1.8. However, the Kd values of these complexes increased significantly with increasing ionic strength.

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히스티딜기등을 포함하는 미셀성 계면활성제를 촉매로 사용한 파라니트로페닐 에스테르의 가수분해반응에 관한 연구 (A Study on the Hydrolysis of p-Nitrophenyl Carboxylates by Micellar Surfactants Catalysts Involving Histidyl Residue)

  • 구원회;홍춘표
    • 대한화학회지
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    • 제33권1호
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    • pp.3-10
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    • 1989
  • 파파인효소의 가수분해반응을 이해하기 위하여 파파인의 활성점에 모여 있는 히스티딘, 시스테인, 및 히스테인-시스테인을 포함하는 양이온성 펩티드-계면활성제를 합성하였다. 이것을 촉매로 사용하여 PNPL을 가수분해 시킬때 pH 7.40에서 촉매의 효율성은 $N^{+}C_{2}AlaC^{12}$과 비교하여 $N^{+}C_{2}HisC_{12}$, $N^{+}C_{2}HisC_{12}$, $N^{+}C_{2}HisCysC_{12}$, 순으로 현저한 증가를 나타내고 그 이유는 $N^{+}C_{2}HisC_{12}$는 이미다졸기, $N^{+}C_{2}CysC_{12}$는 티올기 영향이며, 가장 좋은 촉매효율을 나타내는 $N^{+}C_{2}HisCysC_{12}$은 이미다졸기와 티올기의 상호작용때문이다. 가수분해반응을 촉진시키는 펩티드-계면활성제의 이미다졸기와 티올기들의 활동성을 나타내는 해리상수, pKa는 각각 6.49, 10.50 이고, 기능기에 의한 속도상수, $k^{\ast}_m$는 각각 $7.91{\times}10^{-4}S^{-1}$, $6.00{\times}10^{-4}S^{-1}$이었다. 가수분해에 대한 혼합미셀계의 촉매효과는 파라니트로페닐 에스테르의 알킬기의 탄소수가 증가함에 따라 증가하므로 기능기의 작용외에는 미셀의 소수성 부분과 기질사이의 상호작용에 의하여도 증가됨을 알았다.

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Association between a M-Iacking mutant D75N of pharaonis phoborhodopsin and its transducer is stronger than the complex of the wild-type pigment: Implication of the signal transduction

  • Sudo, Yuki;Iwamoto, Masayuki;Shimono, Kazumi;Kamo, Naoki
    • Journal of Photoscience
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    • 제9권2호
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    • pp.314-316
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    • 2002
  • In halobacterial membrane, pharaonis phoborhodopsin (or pharaonis sensory rhdopsin II, psRII) forms a complex with its transducer pHtrII. Flash-photolyis of D75N mutant did not yield M-intermediate but an O-like intermediate is observed. We examined the interaction between D75N of ppR and t-Htr (truncated pHtrII). These formed a complex in the presence of n-dodecyl-$\beta$-D-maltoside, and the association accelerated the decay of the 0 of D75N from 15 to 56 s$\^$-1/. From the decay time constants under varying ratios of D75N and t-Htr, n, the molar ratio of D75N/t-Htr in the complex, and K$\_$D/, the dissociation constant, were estimated. The value of n was unity and K$\_$D/ was estimated to 146 nM. This K$\_$D/ value can be considered as the association between the photo-intermediate and t-Htr, which is deduced by the method of estimation. Previously we (Photochem. Photobiol. 74, 489-494 (2001)) reported K$\_$D/ of 15 $\mu$M for the interaction between the wild-type and t-Htr by means of the change of M-decay rates. Therefore, this value should be the K$\_$D/ value for the interaction between M of the wild-type and t-Htr.

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The Slow and Tight Binding of MR-387A to Aminopeptidase N

  • CHUNG, MYUNG-CHUL;HYO-KON CHUN;HO-JAE LEE;CHOONG-HWAN LEE;SU-IL KIM;YUNG-HEE KHO
    • Journal of Microbiology and Biotechnology
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    • 제6권4호
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    • pp.250-254
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    • 1996
  • MR-387A [(2S, 3R)-2-hydroxy-3-amino-4-phenylbutanoyl-L-valyl-L-prolyl-(2, 4-trans)- L-4-hydroxy-proline] reversibly inhibits aminopeptidase N (BC 3.4.11.2) in a process that is remarkable for its unusual degree of time dependence. The time required to inactivate the enzyme by 50$%$ ($t_{1/2}$) for establishing steady-state levels of $EI^*$complex was approximately 5 minutes. This indicates that the inhibition is a slow-binding process. In dissociation experiments of $EI^*$ complex, enzymic activity was regained slowly in a quadratic equation, indicating that the inhibition of aminopeptidase N by MR-387A is tight-binding and reversible. Thus, the binding of MR-387A by aminopeptidase N is slow and tight, with $K_{i}$ (for initial collision complex, EI) and $K_i{^*}$ (for final tightened complex, $EI^*$) of $2.2\times10^{-8}$ M (from Lineweaver-Burk plot) and $4.4\times10^{-10}$ M (from rate constants), respectively. These data indicate that MR-387A and aminopeptidase N are bound approximately 200-fold more tightly in the final $EI^*$complex than in the initial collision EI complex.

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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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붕소 착물 음이온의 이온쌍 추출 (제1보) (Ion-Pair Extraction of Boron Complex Anions (I). Methylene Blue-Tetrafluoroborate Complex)

  • 장호겸;김강진;김시중
    • 대한화학회지
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    • 제26권5호
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    • pp.326-332
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    • 1982
  • 플루오르화수소산 존재하에서 methylene blue의 양이온과 $BF_4^-$, 음이온이 이루는 착물을 1,2-dichloroethane과 nitrobenzene으로 용매추출하여 분광광도법으로 분석하였다. 적외선과 가시선 스펙트럼을 조사하여 이 착물은 1:1 조성비를 가지는 ion-pair로 존재하는 것으로 보이며 1,2-dichlorethane 중에서는 해리하지 않는 것을 알아냈다. 1,2-Dichlorethane에 대해서는 HF의 농도가 1.43${\times}10^{-2}$~ 2.86${\times}10^{-1}$M 범위에서 추출상수가 25$^{\circ}$C에서 1.1${\times}10^4M{-1}$로 일정한 값을 나타내었으며 nitrobenzene에 대하여는 대체로 10배 가량 큰 값을 가지지만 HF농도가 증가함에 약간씩 증가하였다.

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세륨(Ⅳ)에 의한 말론산의 산화반응에 관한 반응속도론적 연구 (Kinetic Studies on the Oxidation Reaction of Malonic Acid by Ceric Ion)

  • 김왕기
    • 대한화학회지
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    • 제38권10호
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    • pp.705-709
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    • 1994
  • 1M 황산용액에서 세륨(Ⅳ) 이온에 의한 말론산의 산화반응에 관한 반응속도를 분광광도법으로 연구하였다. 말론산이 과량으로 존재하는 조건하에서 측정된 유사일차 속도상수, $k_{obs}$는 말론산의 농도, [MA]에 따라 크게 의존함을 보였으며 $k_{obs}$ = (0.592[MA])/(1+14.5[MA]$^2$)의 관계를 만족하였다. 이에 근거하여 반응메카니즘을 제안하였다. 말론산의 산해리에 의해 생성된 enolate형 음이온과 Ce(Ⅳ)간의 전자이동반응이 반응속도 결정단계이며, MA의 고농도하에서 Ce(Ⅳ)과 enolate형 음이온간의 1:2 chelate생성반응에 의하여 Ce(Ⅳ)의 농도가 감소하여 산화반응이 억제됨을 알 수 있었다. 본 연구에서 제안된 메카니즘에 근거하여 Sengupta 등에 의해 연구된 pH 의존성을 설명할 수 있었다.

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HWE 방법에 의한 AgGaS$_2$/GaAs 단결정 박막 성장과 광학적 특성 (Growth and optic characteristics of AgGaS$_2$/GaAs single crystal thin film by hot wall epitaxy)

  • 이상열;홍광준;정준우
    • 한국전기전자재료학회:학술대회논문집
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    • 한국전기전자재료학회 2002년도 하계학술대회 논문집
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    • pp.281-287
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    • 2002
  • The stochiometric composition of AgGaS$_2$ polycrystal source materials for the AgGaS$_2$/GaAs epilayer was prepared from horizontal furnace. From the extrapolation method of X-ray diffraction patterns it was found that the polycrystal AgGaS$_2$ has tetragonal structure of which lattice constant a$\sub$0/ and c$\sub$0/ were 5.756 ${\AA}$ and 10.305 ${\AA}$, respectively. AgGaS$_2$/GaAs epilayer was deposited on throughly etched GaAs(100) substrate from mixed crystal AgGaS$_2$ by the Hot Wall Epitaxy (100) system. The source and substrate temperature were 590$^{\circ}C$ and 440$^{\circ}C$ respectively. The crystallinity of the grown AgGaS$_2$/GaAs epilayer was investigated by the DCRC (double crystal X-ray diffraction rocking curve). The optical energy gaps were found to be 2.61 eV for AgGaS$_2$/GaAs epilayer at room temperature. The temperature dependence of the photocurrent peak energy is well explained by the Varshni equation, then the constants in the Varshni equation are given by ${\alpha}$ : 8.695${\times}$10$\^$-4/ eV/K, and ${\beta}$ = 332 K. From the photocurrent spectra by illumination of polarized light of the AgGaS$_2$/GaAs epilayer, we have found that crystal field splitting ΔCr was 0.28 eV at 20 K. From the PL spectra at 20 K, the peaks corresponding to free and bound excitons and a broad emission band due to D-A pain are identified. The binding energy of the free excitons are determined to be 0.2676 eV and 0.2430 eV and the dissociation energy of the bound excitons to be 0.4695 eV.

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HWE 방법에 의한 $AgGaS_2$ 박막성장과 광학적특성 (Growth and optical properties for $AgGaS_2$ epilayer by hot wall epitaxy)

  • 윤석진;홍광준
    • 한국전기전자재료학회:학술대회논문집
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    • 한국전기전자재료학회 2004년도 춘계학술대회 논문집 반도체 재료 센서 박막재료 전자세라믹스
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    • pp.56-59
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    • 2004
  • The stochiometric composition of $AgGaS_2$ polycrystal source materials for the $AgGaS_2/GaAs$ epilayer was prepared from horizontal furnace. From the extrapolation method of X-ray diffraction patterns it was found that the polycrystal $AgGaS_2$ has tetragonal structure of which lattice constant $a_0$ and $c_0$ were 5.756 ${\AA}$ and 10.305 ${\AA}$, respectively. $AgGaS_2/GaAs$ epilayer was deposited on throughly etched GaAs (100) substrate from mixed crystal $AgGaS_2$ by the Hot Wall Epitaxy (HWE) system. The source and substrate temperature were $590^{\circ}C$ and $440^{\circ}C$ respectively. The crystallinity of the grown $AgGaS_2/GaAs$ epilayer was investigated by the DCRC (double crystal X-ray diffraction rocking curve). The optical energy gaps were found to be 2.61 eV for $AgGaS_2/GaAs$ epilayer at room temperature. The temperature dependence of the photocurrent peak energy is well explained by the Varshni equation, then the constants in the Varshni equation are given by ${\alpha}=8.695{\times}10^{-4}eV/K$, and $\beta$=332 K. From the photocurrent spectra by illumination of polarized light of the $AgGaS_2/GaAs$ epilayer, we have found that crystal field splitting $\Delta$ Cr was 0.28 eV at 20 K. From the PL spectra at 20 K, the peaks corresponding to free and bound excitons and a broad emission band due to D-A pairs are identified. The binding energy of the free excitons are determined to be 0.2676 eV and 0.2430 eV and the dissociation energy of the bound excitons to be 0.4695 eV.

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탄산에틸렌-아세톤 혼합용액에서의 1-1 전해질의 전기전도도 (Conductances of 1-1 Electrolytes in Ethylene Carbonate-Acetone Mixtures)

  • 김시중;신영국
    • 대한화학회지
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    • 제27권3호
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    • pp.178-182
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    • 1983
  • 비양성자성 극성용매인 탄산에틸렌과 아세톤과의 혼합용매에서 NaI, KI,$ NH_4I,\;(CH_3)_4NI,\;(C_2H_5)_4NI$, NaPic(Pic:피크린산이온), KPic, $(C_4H_9)_4NB(ph)_4$의 전기전도도를 $25{\circ}C$에서 측정하였다. 한계당량전도도를 Fuoss-Kraus식에 의하여 구한 결과 그 크기의 순위는 혼합용매의 성분비에 관계없이 $(C_4H_9)_4NB(ph)_4이었다. 이 전해질들의 해리상수로 부터 탄산에틸렌-아세톤 혼합용매는 이들에 대하여 좋은 이온화용매임을 알 수 있었다. 한계이온당량 전도도의 순위, $Na^+는 용매화수의 역순위와 일치하였다. Nightingale 방법에 의하여 구한 각 이온의 유효 용매화반지름에 의하면 피크린산이온은 용매화되어 있지 않으며, 요오드화이온은 탄산에틸렌-아세톤 혼합용매에서 상당히 용매화되어 있음을 알 수 있었다.

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