$Hg^{2+}$이온 水溶液 內에서의 Chloropentaamminecobalt(III)의 置換反應速度와 메카니즘 (제 1 보)

박병각,이재원,임주상,Byung-Kak Park,Jae-Weon Lee,Joo-Sang Lim 대한화학회 1986 대한화학회지 Vol.30 No.3

Chloropentaamminecobalt(III)의 $Cl^-$리간드와 물 分子의 置換反應에서 H$g^{2+}$ 이온 觸媒의 역할을 알기 위하여 UV分光法으로 速度論的 硏究를 하였다. 觸媒촉매가 一次일차 反應반응形式형식으로 反應반응에 관여함을 알았으며, 觸媒촉매를 考慮 했을때의 速度常數 $k_{obs}$는 3.366$l{\cdot}mol^{-1}sec^{-1}$의 값을 얻었다. 아울러 總括反應은 二次反應 임을 알았으며, $S_N2$ 反應機構로 進行되는 反應 메카니즘을 提案하였다. Kinetic studies were carried out for the substitution of $H-2$O for $Cl^-$ ligand of chloropentaamminecobalt(III) in the presence of $Hg^{2+}$ catalyst by UV spectrophotometer. It has been found that $Hg^{2+}$ ion appears first order dependence and the overall reaction is second order. The reaction system can be believed to occur via $S_N2$ reaction, because the calculated rate equation for our presumed $S_N2$ mechanism is in agreement with the observed one.

Sodium Dodecyl Sulfate의 분해반응에 대한 속도론적 연구

이길준,김종용,박병각 嶺南大學校 環境問題硏究所 1994 環境硏究 Vol.14 No.1

하천수에서 분리해 낸 SDS(Sodium Dodecyl Sulfate) 분해균주에 의하여 분해균주량의 변화와 SDS의 농도변화를 주어 SDS를 분해시킬 때 그 분해반응을 속도론적으로 연구하였다. 실험결과 SDS의 분해를 BOD로 표시하여 분해률을 측정한 속도식은 1차로 나타남을 알 수 있었다. 그리고 분해균주량의 변화와 SDS농도의 변화에 따른 속도상수는 분해규준량에는 영향을 받지 않으나 SDS의 농도에는 영향을 받음을 알 수 있었다. 그리고 활성화에너지는 5.304kcal/mol, 활성화 파라메타인 ???와 ???는 각각 4.69kcal/mol, -56.90 e.u.임을 알았다. Kinetic studies were carried out for change in BOD of SDS degradating microorganism isolated from river water. It is found that the decomposition of SDS is first order. Rate constants for the decomposition of SDS and its degrading microorganism found not to have an influence on variation of SDS-degrading microorganism but have an influence on SDS concentration. And thermodynamic parameters, Ea, ???? and ????, were obtained the value of 5.304kcal/mol, 4.69kcal/mol and -56.90 e.u., respectively.

發癌物質과 非發癌物質의 DNA-Modifying Activity에 대한 量子生物學的 解釋

李佶俊,林周相,宋寧大,徐榮培,朴柄珏 嶺南大學校 基礎科學硏究所 1990 基礎科學硏究 Vol.10 No.-

LCAOMO calculation has been carried out for thirty chemical carcinogens and nine metabolites of them. The LUMO electron density which is a measure of ability electron to be accepted and observed DNA-Modifying activity which is a measure of mutation relationship was considered. It was found that the sum of LUMO electron density of 1, 2, 4-positions of a relevant trans-butadiene type (F??) in the compound was correlative to DNA-Modifying activity. This means that carcinogenesis closely relate to mutagensis, since the LUMO electron density is a measure of carcinogenic activity of carcinogens as shown earlier. It was also found that LUMO electron density of 1, 2, 4-positions in compounds increase with their metabolic activation. This is in agreement with the experimental result that carcinogen is more electrophilic as metabolic activation. In conclusion, it may be possible to give a theoretical interpretation on the mutation of chemical carcinogens and explain theoretically the fact that the compound have a strong elestrophilicity on metabolic activation.

隣接基에 따른 SN_1反應과 E_1反應의 優劣性에 硏究 (第1報)

朴柄珏,沈相喆,李武相 경북대학교 공과대학 1973 工大硏究誌 Vol.2 No.-

A close relation between SN₁and E₁reactions and the competitive character of these two processes were studied. The predominance of either one reaction over the other has been investigated by an extended Hu‥ckel method using hypothetical model in transition states. The calculations show that the reactions in the alcohol solvent agree with experimental results. The comparison of the electronic energies and population analyses of 2-bromo-butane and 2-bromo-2-methyl butane in their transition state models were made. The result turned out to be the predominance of E_1 over SN_1 reactions for 2-bromo-butane and the predominance of SN_1 over E_1 reactions for 2-bromo-2-methyl-butane.

백금착물 (II) 의 항암성에 관한 분자궤도론적 해석 (제1보)

박병각,여환진,Byung-Kak Park,Yeo Hwhan-Jin 대한화학회 1985 대한화학회지 Vol.29 No.4

본 연구에서는 백금착물, $[PtA_2Cl_2]\;(A:\;NH_3$ 및 en과 그 유도체)형의 항암성 메카니즘의 첫 단계에서 두 개의 염소 원자가 분리된다고 가정하고 이 분리의 용이성을 Extended Huckel법에 의해서 양자화학적 양을 조사하였다. 백금착물의 전체에너지가 높을수록, Pt의 d-전자의 전이가 용이할수록, Cl의 net charge의 (-)값이 클수록, Pt-Cl사이의 Cl의 이탈이 용이하여진다고 생각된다. 그리고 실험적으로 항암성이 있다고 보고된 Pt(II)착물에서 Cl의 이탈용이도가 컸다. 따라서 $PtLCl_2$형 항암제(L:NH$_3$, en)$에서 항암작용의 첫 단계로서 Cl의 해리과정이 중요하다고 예측된다. Extended Huckel Calculation of cis-and trans-dichloro diammine platinum(II), dichloroethylene diamine platinum(II) and their N-mono, di, tri and tetra-methylated or ethylated ones were carried out to investigate their anticancer activity. It was found that the net charge of two chlorine atoms in cis-isomers are greater than those in trans-ones and Pt-Cl bond energies of the former are less than that of the latter, indicating that Pt-Cl bond in cis-isomers has greater ionic character than that in trans-ones and Cl atoms in the former are easier to dissociated as Cl- than those in the latter. Also, the values of $b_{2g}-b_{1g}$ energy difference, ${\Delta}_1$ were found to be greater in cis-isomers than in trans-one without exceptions. For the substitution of methyl for H atom in ammine and ethylenediamine Pt-Cl bond strength shows the tendency to increase with increasing in number of methyl group. Accordingly, We believe that two Cl atoms in $PtLCl_2$-complexes (L: NH$_3$, en) are dissociated in the first step of the action of anticancer.

二中心 Hu¨ckel M.O.法의 應用(Ⅴ) : 아민의 알킬기 置換에 따른 아미노산과의 �타이드 結合에 관한 硏究 Study on the peptide bond formation of substituted alkylamines with various amino acids

朴柄珏,李武相,郭永佑 慶北大學校 1976 論文集 Vol.21 No.-

二中心 Hu‥ckel法을 使用해서, 筆者들은 amine의 alkyl 置換體, 1次, 2次, 3次 amine과 glycine, alanine, valine의 結合에너지 및 電子密度를 計算했다. 그 結果 amine에 alkyl基가 置換될 수록 amino酸과 peptide結合 形成이 어려웠다. 그리고 amine에 alkyl基간 置換에 따른 電子效果도 볼 수 있었으며 amino酸 간의 peptide 結合에서 생기는 化合物의 容易度를 짐작 할 수 있었다. 그러므로 σ 電子密度에 依해서 peptide 結合의 反應 mechanism을 짐작할 수 있었다. Two-Center Hu‥ckel M.O. method is used to calculate σ-bond energies, and σ-electron densities for alkyl substituted amines, pri-amine, sec-amine and t-amine, also glycine, alanine and valine amino acids. It is concluded that in the peptide bone formation the more alkyl group substituted amines with previous mentioned amino acids make more difficult. And it could be known the electron inductive effects in the alkyl substituted amines. By comparing σ-electron densities the facility of reaction with two amino acids and reaction mechanism could be predicted.

$Hg^{2+}$수용액에서 $cis-[Co(en)_2(NH_3)Cl]^{2+}$의 아쿠아반응에 대한 속도론적 연구

박병각,이길준,이재원,임주상,Byung-Kak Park,Gil-Jun Lee,Jae-Weon Lee,Joo-Sang Lim 대한화학회 1988 대한화학회지 Vol.32 No.3

$Hg^{2+}$촉매 존재하에서 cis-amminechlorobis(ethylenediamine)cobalt(III)의 Cl이 $H_2O$로 치환되는 반응을 전자흡수 스펙트라로 속도론적 연구를 하였다. 그 결과 $cis-[Co(en)_2(NH_3)Cl]^{2+}$에 대해서 각각 1차인 총괄반응이 2차반응이다. 활성화 파라메타인 ${\Delta}H^{\neq}$와 ${\Delta}S^{\neq}$는 각각 12.9 kcal/mol, -19.3 e.u 이고 $Hg^{2+}$에 의한 반응속도상수는 $1.65{\times}10^{-2}l/mol.sec$가 됨을 알았다. 이러한 속도 자료로부터 본 반응계의 Cl이 $H_2O$로 치환되는 반응은 촉매인 $Hg^{2+}$가 관여하는 Id 메카니즘을 제안하였다. A kinetic study was made to determine the mechanism of the aquation of $cis-[Co(en)_2(NH_3)Cl]^{2+}\;in\;Hg^{2+}$ aqueous solution. The progress of reaction was followed UV/vis-spectrophotometrically by a measurement of the absorbance at a specific wave length (530nm) of $cis-[Co(en)_2(NH_3)Cl]^{2+}$ as a function of time. The experimental results have shown that the reaction rate is dependent upon the concentration of $Hg^{2+}$ that act as a catalyst. And it was found that the overall reaction proceed with second order, first order with respect to Co(III) complex and $Hg^{2+}$. Activation parameters, ${\Delta}H^{\neq}\;and\;{\Delta}S^{\neq}$, were obtained as 12.9 kcal/mol and -19.3 e.u., respectively. We have proposed a plausible reaction mechanism which is consistent with the observed rate equation.

벤젠-아조-이미다졸型 染料의 合成 및 最大吸光波長의 分子軌道論的 解釋

박병각,임용진,김우식,Byung Kak Park,Young Jin Lim,Woo Sik Kim 대한화학회 1978 대한화학회지 Vol.22 No.4

Gelatin 水溶液에서의 [Ni(H$_2O)_6]^{2+}$ 와 [CN]$^-$로 부터 [Ni(CN)$_4]^{2-}$生成에 관한 速度論的 硏究

박병각,이일봉,임주상,이길준,Park Byung-Kak,Il-Bong Lee,Joo-Sang Lim,Gil-Jun Lee 대한화학회 1987 대한화학회지 Vol.31 No.5

反應系 $[Ni(H_2O)_6]^{2+}+4CN^-{\rightleftharpoons}[Ni(CN)_4]^{2-}$를 Counductivity-meter를 이용해서 0.005% Gelatin 水溶額에서 反應速度論을 硏究하였다. $[Ni(CN)_4]^{2-}$와 [CN]$^-$의 反應으로 부터 $[Ni(CN)_4]^{2-}$ 生成速度는 $[Ni(H_2O)_6]^{2+}$에 대해서 1次, [CN]$^-$에 대해서 4次인 총괄反應이 5次로 進行됨을 알았으며, 또한 活性化 파라메타 ${\Delta}H^{\neq}$ 와 ${\Delta}S^{\neq}$는 각각 5.15kcal/mole , -35.07 e.u가 되었다. 그리고 이들의 資料로 부터 이 反應系의 타당한 生成메카니즘을 제안하였다. Kinetics studies on the reaction system of $[Ni(H_2O)_6]^{2+}+4CN^-{\rightleftharpoons}[Ni(CN)_4]^{2-}$ have been carried out in 0.005% gelatin solution at $25^{\circ}C$ by means of conductometry. The fifth-order kinetics were observed in the formation rate of $[Ni(CN)_4]^{2-}$ from the reaction of [Ni(H$_2O)_6]^{2+}$ and [CN]$^-$. The reaction was found first order in $[Ni(H_2O)_6]^{2+}$ and fourth order in [CN]$^-$. ${\Delta}H^{\neq}$ and ${\Delta}S^{\neq}$ were obtained the values of 5.15kcal/mole and -35.07 e.u., respectively. We have proposed the possible mechanism from the data obtained.

Styrene과 Maleic anhydride의 Copolymerization

朴柄珏,沈相喆 경북대학교 교육대학원 1973 논문집 Vol.4 No.-

The alternating copolymer of styrene and maleic anhydride was synthesized in the various solutions such as thiophene-free benzene, acetone carbontetrachloride, cyclohexanone, mercaptan. In this paper, however, the experiment that none was attempted in the bromobenzene solution is carried out under I_2 catalyzer, and also we are proposed the alternating copolymerization mechanism under I_2 catalyzer.