• 대한화학회지
• /
• 제29권6호
• /
• pp.623-628
• /
• 1985

산성용매에서 몰리브덴-옥살산 결합의 고리열림이 일어난 다음 티오시안산과 반응하는 속도를 460nm에서 분광학적으로 측정하였다. 산성용매에서 몰리브덴-옥살산의 해리와 이 해리된 착물과 티오시안산의 반응속도를 티오시안산 및 수소이온농도에 따라 연구하였다. 몰티브덴에 결합된 옥살산리간드에 양성자첨가가 되고 이 양성자 첨가된 착물은 티오시안산이온과 반응을 빠르게 한다. 이들 결과에서부터 산성용매에서 옥살산리간드의 치환은 몰리브덴닐산소의 트란스에 결합된 산소의 결합이 끊어지는 과정과 관련되는 해리메카니즘에 의해서 설명할 수 있다.

• 대한화학회지
• /
• 제46권2호
• /
• pp.99-116
• /
• 2002

Thiazolylazo 화합물과 barbituric산, uracil, thiouracil, citrazinic산 chromotrotropic산, gallict산, pyrogallol 그리고 salicylic산의 Co(II), Ni(II) 그리고 Cu(II) 착화합물의 제조하였고, $^1H$ NMR, IR, 그리고 전기 흡수 스펙트럼에 대한 pHdudgid에 의하여 규명하였다. 이온화형태, 전기적 전이 그리고 해리상수에 대하여 설명하였다. 구리 착화합물은 등방형 ESR스펙트럼이었으며 자기적으로 궤도 기여를 갖는 묽은 성질이었다. 상세한 DTA데이타를 얻었고, 그 결과를 토론하였다.

• Archives of Pharmacal Research
• /
• 제18권3호
• /
• pp.169-172
• /
• 1995

The changes in blood pressure may relate to the alterations of the responsiveness to vasoconstrictors and vasodilators, and these alterations can arise the modifications in the properties of angiotensin II (AII) receptor. In order to examine the changes of AII receptor in the hypertensive mechanism of renin-dependent hypertensive rats (RHRs; two-kidney, one-ligated type), we compared the equilibrium binding characteristics of $[^3H]$All in adrenal cortex and medulla from RHRs and normotensive rats. The dissociation constants of AII binding in both tissues of RHRs were very similar to those in the respective tissue of normotensive rats. However, the maximum binding was increased from 805 to 1050 fmole/mg protein in the adrenal cortex of RHRs, and decreased from 172 to 126 fmole/mg protein in the adrenal medulla of RHRs. These results imply that the up- and down-regulation of the All receptor population on the cell surface of adrenal glands from RHRs are consorted with the elevation of blood pressure and the activation of renin-angiotensin system.

• Molecules and Cells
• /
• 제27권2호
• /
• pp.225-235
• /
• 2009

Antibody phage display provides a powerful and efficient tool for the discovery and development of monoclonal antibodies for therapeutic and other applications. Antibody clones from synthetic libraries with optimized design features have several distinct advantages that include high stability, high levels of expression, and ease of downstream optimization and engineering. In this study, a fully synthetic human scFv library with six diversified CDRs was constructed by polymerase chain reaction assembly of overlapping oligonucleotides. In order to maximize the functional diversity of the library, a ${\beta}$-lactamase selection strategy was employed in which the assembled scFv gene repertoire was fused to the 5'-end of the ${\beta}$-lactamase gene, and in-frame scFv clones were enriched by carbenicillin selection. A final library with an estimated total diversity of $7.6{\times}10^9$, greater than 70% functional diversity, and diversification of all six CDRs was obtained after insertion of fully randomized CDR-H3 sequences into this proofread repertoire. The performance of the library was validated using a number of target antigens, against which multiple unique scFv sequences with dissociation constants in the nanomolar range were isolated.

• Bulletin of the Korean Chemical Society
• /
• 제6권4호
• /
• pp.196-202
• /
• 1985

A Very Low Pressure Reactor (VLPR) is constructed for the kinetic study of atom-molecule bimolecular elementary reactions. The basic principles and the versatility of the method are described. By using the VLPR technique the forward (k1) and the reverse (k-1) rate constants for Br atom reaction with trimethylsilane are studied; Br + $(CH_3)_3$SiH k1 ${\leftrightarrow}$ k-1 HBr + $(CH_3)_3$Si. From the kinetic data and the entropy estimation the bond dissociation energy for Si-H bond in trimethylsilane is calculated to be 90.1 kcal/mole $({\pm}1.1$ kcal/mole). The Arrhenius parameters for k1 are found to be log A = 10.6 l/mole·sec, $E_a$ = 4.4 kcal/mole respectively. For the comparison purpose analogous reaction for carbon compound ; Br + $(CH_3)_3$CH ${\rightarrow}$ HBr + $(CH_3)_3$C was also studied. The corresponding rate constant and equilibrium constant at $25^{\circ}C$ are found to be 2.67 ${\times}$ $10^6l$/mole${\cdot}$sec and 160 respectively.

• Bulletin of the Korean Chemical Society
• /
• 제10권3호
• /
• pp.262-269
• /
• 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.

• 대한화학회지
• /
• 제44권5호
• /
• pp.403-409
• /
• 2000

1,4,7,10-tetraaza13,16-dioxacyclooctadecane-N,N',N",N'"-tetraacetic acid (1), 1,4,7,10-tetraaza-13,16-dioxactclootadecane-N,N',N",N'"-tramethylacetic acid (2), 및 1,4,7,10-tetraaza-13,16-dixacyclooc-tedecane-N,N',N",N'"-tetrapropionic acid (3)와 $Zn^{2+}$ 착물의 형성 및 해리 속도를 멈춤-흐름법 및 분광학적방법으로 측정하였다. 측정 조건을 온도 25.0$\pm$0.1 $^{\circ}C$ 및 이온강도 0.10 M NaClO4 이었다. $Zn^{2+}$이온과 1과 2의 형성 반응은 빠르게 중간 생성물($ZnH_3L^+$)를 형성한다. 여기서 $Zn^{2+}$ 이온은 부분적으로 배위되어 있고 속도 결정 단계는 최종 생성물이었다. pH범위 4.76-5.76에서, 2가 양성자($H_2L^{2-}$) 형태가 매우 낮은 농도임에도 불구하고 속도론적으로 활성화종임을 알 수 있었다. 또한 중간체 착물의 안정도 상수(log$K_{(ZnH_3L^+)}$)와 고유 물분자-보조 속도상수(KOH)가 속도론적 자료로부터 계산되었다. $Zn^{2+}$이온과 1,2, 및 3의 해리 반응은 아세테이트 완충 용액 하에서 청소군 $Cu^{2+}$ 이온을 이용하여 측정하였다. 모든 착물의 해리 반응은 산-무관 및 산-촉매 반응으로 진행됨을 알 수 있었다. $Zn^{2+}$ 착물의 해리 속도에 영향을 미치는 완충 용액 및 $Cu^{2+}$농도의 효과를 알아보았으며, 아울러 리간드 효과를 곁가지에 매달려있는 치환기와 킬레이트 고리크리로 논하였다.

• 분석과학
• /
• 제13권2호
• /
• pp.173-178
• /
• 2000

두 개의 페놀기를 포함하는 열린 고리형태의 1, 14-Bis(2-hydroxybenzyl)-2, 6, 9, 12-tetraazatetradecane(bsated) 리간드를 염산염의 형태로 분리하여 원소 분석, 질량 스펙트럼 및 핵자기공명법으로 분석하였다. 합성된 리간드의 산 해리상수($logK^n{_H}$)와 $Cu^{2+}$, $Ni^{2+}$, $Co^{2+}$ 및 $Zn^{2+}$에 대한 안정도 상수($logK_{ML}$)를 전위차 적정법으로 결정하였다. 이때 온도는 $25^{\circ}C$ 및 이온강도는 0.10M($KNO_3$)로 고정시켰다. [Cu(bsated)] $(ClO_4)_2$ X-ray구조의 crystal data는 다음과 같다: Monoclinic space group $P2_1/n$, $a=17.856(4){\AA}$, $b=17.709(1){\AA}$, $c=8.539(2){\AA}$, $V=2700(2){\AA}$ with Z=4. tetrabutylammonium perchlorate 전해질의 dimethyl sulfoxide 용액속에서 [Cu(bsated)]$(ClO_4)_2$ 착물의 전기화학적 특성을 순환 전압-전류법 (CV)과 normal pulse voltammertry (NPV, 정상펄스전압전류법)으로 측정하였다.

• Biomolecules & Therapeutics
• /
• 제3권1호
• /
• pp.21-27
• /
• 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.

• 대한화학회지
• /
• 제33권4호
• /
• pp.366-370
• /
• 1989

새로운 거대고리 리간드 1,15,18-triaza-3,4 : 12,13-dibenzo-5,8,11-trioxa-cycloeicosane(NdienOdien$H_4$=$N_3O_3$)를 합성하여 $25^{\circ}C$ 95% 메탄올 용액에서 전위차계를 이용하여 양성자 첨가반응의 평형상수를 구한 결과 log $K_1$ ; log $K_2$ ; log $K_3$는 9.1; 8.1; 3.6이었다. 또한 위의 리간드와 이미 합성된 리간드 1,12,15-triaza-3,4;9,10-dibenzo-5,8-dioxa-cycloheptadecane(NdienOen$H_4$=$N_3O_2$)를 각각 Ni(II), Cu(II)의 금속이온과의 착물을 합성하여 수용액에서 산을 가해 착물의 산해리반응 속도 상수를 여러온도에서 분광광도법으로 측정하였다. 또한 활성화에너지($E_a$)와 활성화파라메타 ${\Delta}H^{\neq}$, ${\Delta}S^{\neq}$를 구하였다. 그리고 이들의 자료로부터 이 반응계의 타당한 해리메카니즘을 제안하였다.