산자수 증가를 위한 번식돈의 단계별 사양관리

임주상 충남대학교 농과대학 1999 논문집 Vol.- No.5

제70회 발명교실 - 뉴 바인다 시스템 발명인

임주상 한국발명진흥회 1989 發明特許 Vol.14 No.12

$Hg^{2+}$수용액에서 $[Co(en)_2Cl_2]^+$의 아쿠아 반응속도론과 메카니즘

박병각,임주상,성낙정,이일봉,김광진,강성구,Byung-Kak Park,Joo-Sang Lim,Sung Nak-Jung,Il-Bong Lee,Kwang-Jin Kim,Sung-Gu Kang 대한화학회 1988 대한화학회지 Vol.32 No.4

$Hg^{2+}$수용액내에서 $[Co(en)_2Cl_2]^+$의 Cl이 $H_2O$로 치환되는 속도를 UV/vis 분광광도계로 측정하여$Hg^{2+}$를 고려했을때의 속도식을 결정하고, 촉매가 관여한 타당한 반응메카니즘을 제안하였다. 그리고 생성물에서 분리 할 수 없는 cis-형과 trans-형이 생성될 때 이들 이성질체의 비율계산식을 만들고 이식에 의하여 이들 이성질체의 비율을 결정하였다. 본 연구에서 $Hg^{2+}$에 대한 반응차수는 cis-$[Co(en)_2Cl_2]^+$경우 1차이고 trans-$[Co(en)_2Cl_2]^+$경우 2차이다. 그리고 cis형 보다는 trans-형의 경우 더 빠른 반응으로 나타났고 생성물은 cis-형이 약 97%이고 trans-형이 약 3%정도 생성되었다. 이러한 속도자료와 활성화파라메타로 부터 본 반응계가 Id 메카니즘으로 반응이 진행되는 타당한 반응메카니즘을 제안하였다. An experimental investigation is made to determine the mechanism of the aquation of $[Co(en)_2Cl_2]^+$ in $Hg^{2+}$ aqueous solution. The progress of reaction is followed UV/vis-spectrophotometrically by a measurment of the absorbance at a specific wavelength of Co(III) complex as a function of time. The aquation of cis-$[Co(en)_2Cl_2]^+$ and trans-$[Co(en)_2Cl_2]^+$ has been found to be first order and second order with respect to the concentration of $Hg^{2+}$ catalyst, respectively. It has been found that the reaction rate for aquation of the trans-form is faster than that of cis-form, and that the product of either cis-form or trans-form is always in the mixture ratio of 97 % to 3 %. Plausible reaction mechanism is proposed for the reaction system on the basis of kinetic data and activation parameters. Theoretical rate equation derived from the proposed mechanism is consistent with the observed one.

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.

산촉매 하에서 [Co(NH₃)₄(C₂O₄)]+ 와 Fe(Ⅱ)와의 산화-환원 반응에 대한 반응속도와 메타니즘

朴柄珏,林周相,姜成九 嶺南大學校附設 基礎科學硏究所 1988 基礎科學硏究 Vol.8 No.-

Kinetic study was carried out for the redox reaction of [Co(NH₃)₄(C₂O₄)]+ with Fe(Ⅱ) in acidic solution by UV/vis-spectrophotometric method. It has been found that the reaction order for H+ catalyst is the first order in lower H+ concentration range than 0.5mol/ℓ, while second order in the higher one than 0.5mol/ℓ. This redox reaction system is first order with respect to each of the two substracts. Accordingly overall reaction was the third and forth order. It was found that the H+ act as the first order, the values of rate constant, ΔH? and ΔS? is 2.2079×10 ? ℓ²·mol?. sec?, 13.40Kcal/mol and -17.33e. u., and H+ act the second order, these values is 2.4490×10? ℓ³·mol?·sec?, 15.39Kcal/mol and -20.60 e. u., respectively. The result of EHMO calculation appears to be the preferred trigonal bipyramidal intermediate. On the basis of kinetic data and EHMO calculation, we suggest that the redox reaction system proceed via innersphere mechanism.

$Hg^{2+}$ 수용액 내에서 cis-[Co(en)$_2$YCl]$^{r+}$ (Y = $NH_3$, NO$_2^-$, NCS$^-$, $H_2O$)의 아쿠아 반응속도와 반응메카니즘

박병각,임주상,Byung-Kak Park,Joo-Sang Lim 대한화학회 1988 대한화학회지 Vol.32 No.5

$Hg^{2+}$ 수용액내에서 cis-[$Co(en)_2YCl$]$^{r+}$ (Y = $NH_3$, $NO_2^-$, NCS$^-$, $H_2O$)의 아쿠아 반응속도를 UV/vis 분광광도계로 측정하여 반응속도식을 결정하였으며, 확장분자궤도법(Extended Huckel Molecular Orbital Method)에 의해 Co(Ⅲ) 전이금속착물의 양자화학적값을 계산하고 실험에서 구한 반응속도와의 상관성을 조사하여 촉매가 관련한 타당한 반응메카니즘을 제안하였다. 본 연구에서 Co(Ⅲ) 전이금속착물과 $Hg^{2+}$에 대하여 각각 1차반응이고, 반응속도는 Co(Ⅲ) 중심금속의 알짜전하 크기와 병행성이 있으며, 이들의 반응속도는 Y의 종류에 따라 $NH_3$ < NCS$^-$ < H$_2$O < NO$_2^-$의 순으로 증가되었다. 그리고 이들 생성물의 cis-이성질체가 약 95${\%}$, trans-이성질체가 약 5${\%}$정도 생성되었다. 또한 EHMO법에 의해 계산된 알짜전하와 결합차수로부터 본 반응계는 결합깨어짐보다 결합형성이 우선되어 H$_2$0가 Co(Ⅲ) 중심금속에 공격하는 단계가 속도결정 단계가 됨을 알았다. 이러한 사실과 실험에서 구한 속도자료 그리고 활성화파라메타값으로부터 Id 메카니즘으로 진행되는 타당한 반응메카니즘을 제안하였다. Kinetic studies and theoretical investigations were made to illustrate the mechanism of the aquation of cis-[Co(en)$_2$YCl]$^{r+}$ (Y = NH$_3$, NO$_2^-$, NCS$^-$, $H_2O$) in $Hg^{2+}$ aqueous solution UV/vis-spectrophotometrically. The aquation of cis-[Co(en)$_2$YCl]$^{r+}$ have been found to be the second order for overall reaction as first order for each of substrate and Hg$^{2+}$+ catalyst. The reaction rate was increased in the order of Y=NH$_3$ < NCS$^-$- < $H_2O$ < $NO_2^-$, which are neighboring group of Cl. The step of bond formation was found to be the rate determining one, because the net charge of central metal ion run parallel with the observed rate constant. On the basis of rate determining step, kinetic data and the observed activation parameters, we have proposed the Id mechanism for the reaction system. The rate equation derived from the proposed mechanism has been in agreement with the observed rate equation.

第一轉移金屬錯物의 리간드化 엔탈피의 量子化學的 解釋

朴柄珏,林周相,宋寧大,禹泰河 嶺南大學校附設 基礎科學硏究所 1989 基礎科學硏究 Vol.9 No.-

The relation was examined among enthalpy of ligation(ΔH), Δ? values, and total reduced energy partition by using Extended Huckel Molecular Orbital Theory for the first series of bivalent transition metal complexes. It was found that the reduced energy partition is directly propotional to the ionic radius of central metal of both M(H₂O)?? and M(H₂O)₄(en) complexes(M=Fe²+, Co²+, Ni²+, Cu²+). The ?? values was found to be propotional to the ionic radius of central metal of M(H₂O)?? complexes, while being inversely propotional to M(H₂O)₄(en) complexes. Accordingly, we suggest that enthalpy of ligation could be related to the calculated Δ? values.

化學發癌 物質의 發癌 能力에 關한 反應性 指數의 理論的 硏究

李一峯,宋寧大,林周相,崔茂悅,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.-

There are many theoretical indices for chemical carcinogenicity. Among the various indices, the LUMO electron density and approximate superdelocalizability have taken to compared and discussed for the carcinogenicity of PAHs, aromatic amines and Azo-compounds. The sum of LUMO electron density of the trans-butadiene type 1, 2, 4 positions in a molecule has been known to be in more agreement with the observed values than those of approximate superdelocalizability. It is suggested that any trans-butadiene type 1, 2, 4 positions play an importmant role in the elucidation of mechanism of chemical carcinogenesis.

산성용액내에서 trans-[Co(en)$_2$(NO$_2$)Cl]$^+$ 와 [Fe(H$_2$O)$_6$]$^{2+}$ 와의 산화환원반응에 대한 속도론적 연구

박병각,우태하,임주상,송영대,Park Byung-Kak,Woo Tae-Ha,Lim Joo-Sang,Song Yeung-Dae 대한화학회 1990 대한화학회지 Vol.34 No.5

산성용액내에서 trans-[$Co(en)_2(NO_2)Cl]^+$ 착물과 [$Fe(H_20)_6]^{2+}$ 착물과의 산화환원반응 속도를 UV/vis-분광광도계로 측정하여 $H^+$가 관여한 반응속도상수 k$_H^+$, 반응차수 및 열역학적 활성화파라메타를 구하였다. Co(III), Fe(II)에 대해 각각 1차, H$^+$에 대해서 1차로 진행되는 총괄반응이 3차 반응이고 이 때, $H^+$가 작용한 속도상수 $k_H^+$는 6.7 ${\times}\;10^{-1}$ $L^2$/mol$^2$·min이였고 $E_a$, ${\{Delta}H^{\neq}$는 14.5 Kcal/mol, 13.8 Kcal/mol ${\{Delta}S^{\neq}$는 -18.3 e.u였다. 이러한 실험자료로부터 내부권 반응임을 알았으며 그 메카니즘을 제안하였다. Proton behavior was investgated for the redox reaction of trans-[$Co(en)_2(NO_2)Cl]^+$ with aqueous Fe(II) in acidic solution by UV/vis-spectrophotometric method. The reaction order of proton is first one and the rate constant(k$_H^+$) is 6.7 ${\times}\;10^{-1}L^2/mol^2{\cdot}min$. The values of $E_a$, ${\{Delta}H^{\neq}$, ${\{Delta}S^{\neq}$ are 14.5 Kcal/mol, 13.8 Kcal/mol and -18.3e.u., respectively. As the result of analysis of kinetic data, it has been found that this reaction proceeds through inner-sphere mechanism.

산 촉매하에서 cis-$[Co(en)_2(N_3)_2]^+$ 와 Fe(II) 와의 산화-환원반응에 대한 반응속도와 메카니즘

박병각,김광진,임주상,Byung-Kak Park,Kwang-Jin Kim,Joo-Sang Lim 대한화학회 1989 대한화학회지 Vol.33 No.3

산 용액내에서 cis-$[Co(en)_2(N_3)_2]^+$와 Fe(II)간의 산화-환원 반응속도를 UV/vis-분광광도계로 측정하였다. 여기서 촉매 $H^+$가 관여한 반응속도상수와 각 반응물의 반응차수 그리고 활성화파라메타를 구하여 이들 자료를 바탕으로 타당한 반응메카니즘을 제안하였다. 본 연구의 실험결과를 보면, Co(III)와 Fe(II) 그리고 $H^+$에 대해서 각각 1차로 총괄반응이 3차 반응이다. 이때 반응속도상수 $K_H^+$는 $3.27{\times}10^{-2}l^2{\cdot}mol^{-2}{\cdot}sec^{-1}$이였다. 그리고 활성화에너지 $E_a$는 14.8Kcal/mol, 활성화엔탈피 ${\Delta}H^{\neq}$는 14.2Kcal/mol, 활성화엔트로피 ${\Delta}S^{\neq}$는 -16.7e.u.였다. 이러한 실험적 사실을 바탕으로, 본 반응계에서 $H^+$가 촉매로 작용하여 내부권(inner-sphere) 메카니즘으로 산화-환원반응이 진행되는 타당한 반응메카니즘을 제안하였다. A kinetic study was carried out for the redox reaction of cis-$[Co(en)_2(N_3)_2]^+$ with Fe(II) in acidic solution by spectrophotometric methods. This redox reaction system have been found to show a third order for overall reaction as the respective first order with respect to reactant cis-$[Co(en)_2(N_3)_2]^+$, Fe(II), and $H^+$ catalyst. The activation parameters, ${\Delta}H^{\neq}$ and ${\Delta}S^{\neq}$, were obtained as 14.2Kcal/mol and -16.7 e.u., respectively. On the basis of the kinetic data, we suggest that the redox reaction system proceeds via inner sphere mechanism. The rate equation derived from the proposed mechanism is in agreement with the observed rate equation.