Polyamine류와 Imidazole 유도체가 배위된 Cu(II)착물의 저해효과에 관한 ZINDO/1 연구

김정성,최진태,김창만,송영대 大邱大學校附設 基礎科學硏究所 1998 基礎科學硏究 Vol.15 No.2

The investigation of the inhibitory activity on some Cu(II) complexes with polyamines and imidazole derivatives is performed by ZINDO/1 calculations. It was found that good correlation between enthalpy of formation of the Cu(ll) complexes and experimental inhibitory activity(IA) and the weaker bond strength of between central metal and ligand appears, the higher IA becomes. These results showed that the Cu(II) complexes have weak bond strength with the exception of the following very stable compounds: square planar [Cu(N-Proplm)₂(NCS)₂](N-Proplm=N-propylimidazole), distorted octahedral [Cu(bipy)₂(NCS)₂](bipy=2,2'-bipyridine), and five coordinate [Cu(Me6tren)(NCS)]^(+)(Me_(6)tren=tri(2-dimethylaminoethyl)amine). The degree of bond strength of Cu(II) complexes will be related to the IoglA value experimental inhibitory activity coefficient(IA).

Fe(II)착물의 금속-리간드 사이의 결합에너지와 실측 리간드화열과의 상관성에 관한 EHT-ZINDO/1 연구

김정성,송영대,최진태 大邱大學校附設 基礎科學硏究所 1997 基礎科學硏究 Vol.14 No.1

The correlation was investigated between the observed heat of ligation and calculated bond energy for octahedral Fe(II) complexes by EHMO(Extended Hückel Molecular Orbital) and ZINDO/1(Zerner's Intermediated Neglected of Differential Overlap) method. The net charge of Fe²+ ion of octahedral [Fe(H₂O)_(5)_(-)_(x)(NH₃]²+ complexes(x = 0, 1, …, 6) is decreased with substituting NH₃for H₂O molecule. It was found that a good relationship exists between the observed heat of ligation and the calculated quantum chemical quantity, net charge of central atom, enthalpy of formation, total dissociation energy. From this fact, we can obtain a linear equation △H_(obs) = -0.2858q_(Fc) + 0.8813, △H_(obs) = 0.0031H_(f) + 0.5725, △H_(obs) = 0.00476E_(diss) + 0.6434, respectively, theoretical equation.

Spiropyran과 그의 유도체들중 6-nitrospirobenzopyran의 Photomerocyanine에 관한 AM1연구

김정성,송영대,최진태 大邱大學校附設 基礎科學硏究所 1998 基礎科學硏究 Vol.15 No.1

Semiempirical AM1 quantum chemical calculation were carried out for the spiropyran and its derivatives and for the merocyanine-form four isomer of 6-nitrospirobenzopyran(2H-1-benzopyran-2-2'-indoline) to reveal the thermal back reaction of the photochromic spiropyran. The correlation was investigated between C and O of spiropyran and its derivatives by AM1(Austin Model 1) method. The bond length of C-O for spiropyran and its derivatives is decreased with substituting donating group for withdrawing group. It was found that a good relationship exists between the bond length of C-O for spiropyran and its derivatives and the calculated quantum chemical quantities, binding energy(E_(bind)), enthalpy of formation(Hr), dipole moment(μo ), and difference between HOMO and LUMO energy(ΔE) for spiropyran and its derivatives and for the merocyanine-form four isomer of 6-nitrospirobenzopyran.

트리아릴포스포늄 염과 카르보닐 화합물 사이의 위티그 반응의 입체선택성에 대한 고압 효과

김정성,최정훈,지진영,김창만,김용훈 대구대학교 기초과학연구소 1999 基礎科學硏究 Vol.15 No.3

The Wittig reactions of triarylphosphonium ylides with various carbonyl compounds under high pressure were carried out to investigate its effect on the cis-trans stereochemical outcome. Generally, the cis-stereoselectivities at atmospheric pressure are known to be resulted from smaller steric hindrance of α-carbon of carbonyl group with hydrogens of phenyl residue of triphenylphosphonium ylide and in oxaphosphetane intermediate stage. Thus, the steric interactions between triphenylphosphonium ylide and carbonyl compounds in the transition state can be maximized. And, the reactions of semistabilized ylide and stabilized ylide at atmospheric pressure generate mainly thermodynamically more stable trans-alkane after formation of betaine intermediate. The reactions at high pressure, however, can generate cis-alkene more exclusively through oxaphosphentane intermediate,directly without the formation of betaine intermediate by reducing distance between ylide and carbonyl compound. Reaction between benzyl triphenylphosphonium ylide, a semistabilized ylide, and butyraldehyde at atmospheric pressure gave cis-1-phenyl-1-pentene with 34/66 of Z/E stereoselectivity, but when pressurized at 10000 bar, cis-alkene with 69/31 the Z/E ratio was excellently yielded than trans-alkene. In the case of Wittig reaction of ethoxyacetyl triphenylphosphonium ylide, a stabilized ylide, with butyraldehyde, Z/E stereoselectivity at 10000 bar was inversed in contrast to atmospheric pressure.

한국 노동시장 경제활동상태 변화의 결정요인 분석 및 시사점

김정성 국회입법조사처 2018 입법과 정책 Vol.10 No.1

This study attempts to analyze main determinants of labor market transition in Korea. In particular, this study tries to decompose the determinants into structural factor and the others such as economic cycle. The results from TVP-SVAR model indicates mismatch from employment implying regular and irregular worker discrimination and mismatch from wage explain well the change of labor market transition. Specially, the transitions, unemployment from employment and inactive from employment, are mostly captured by both mismatches of wage and employment. The estimation from the model also shows that the effects of the mismatches are growing in recent period. Considering the result from this paper, the policy efforts to compromise labor market mismatches are necessary. 본 연구의 목적은 한국 노동시장에서 경제활동상태 변화를 야기하는 구조적요인의 영향력을 측정하는 것이다. 이를 위해 본고에서는 기존 연구와 달리 5개 부문의 미스매치를 반영한 구조적요인을 모형 내에 명시적으로 고려함으로써 그 영향력을 보다 정교하게 측정하고자 하였다. TVP-SVAR 모형 추정 결과, 정규직과 비정규직간 고용형태별 미스매치와 임금별 미스매치가 우리나라 경제활동상태 변화 중 취업에서 실업, 취업에서 비경제활동으로의 노동력 이동을 잘 설명하는 것으로 나타났다. 특히 이러한 구조적요인의 영향력이 최근 들어 더욱 확대되고 있는 것으로 분석되었다. 본 연구의 결과에 비추어우리나라 노동시장 상황을 개선하기 위해 경기 부양에만 집중하기 보다는 고용형태‧임금 등의 측면에서 근로자와 사용자간 미스매치를 완화하기 위한 노력이 절실하다는 시사점을 얻을 수 있다.

Kinetics of Ligand Substitution Reactions in Vanadium(III) Complexes with Multidentate Ligand

김정성,HIROSHI TOMIYASU 大邱大學校附設 基礎科學硏究所 1993 基礎科學硏究 Vol.10 No.-

The kinetics of ligand substitution reactions in V(Gly)3 (Gly = Glycine) with various multidentate ligands, nitrilotriacetate (NTA) and ethylendiaminetetraacetate (EOM) have been atudied spectre photometrically. The rates of EDTA and NTA substitutions depend on the entering species. The value of the second order rate constants are k11= 3.0 x 10-2 M-1 s-1(1 M = 1 mol dm 3) for H2edta, k21 = 0.24 M-1 s'1 for Hnta and 1.9 x 10-2 M-1 s-1 for H2nta as an entering ligand, respectively at 250C. Large negative values of activation entropies are interpreted by associative mechanism.

피리딘과 요오드브롬사이의 電荷移動 錯物에 관한 熱力學的 硏究

김정성,최기준 대구대학교 기초과학연구소 1984 基礎科學硏究 Vol.1 No.-

Oxovanadium(Ⅳ)錯物에 對한 速度論的 硏究

김정성 대구대학교 산업기술연구소 1984 産業技術硏究 Vol.3 No.-

The Kinetics of various reactions for Oxovanadium VO^(2+)(Ⅳ)-complexes, exchange, substitution and formation reaction has been studied. Using spectrophotometric and stopped-flow measurement, both the entering ligand and VO^(2+)(Ⅳ) complexes were found to be the first order in every case. The results obtained from the study were: in case the rate constants was Kobs=1.82×10³s^(-1) (pH=6.7, at 25℃), the activation parameters were ΔH^(≠)=10.21Kcal/mole and ΔS^(≠)=-8.79eu and in case the rate constants were Kobs=4.31×10³ s^(-1)(pH=1.57, at 25℃) the activation parament ers were ΔH^(≠)=12.7Kcal/mole and ΔS^(≠)=-4.1 eu for formation. Ligand-substitution reaction on oxovanadium(Ⅳ) complexes are essentially associative. Furthermore, the charge of the entering ligands-Hmal and Ox^(2-) -is of particular importance in determining the ligand-exchange reactions with VO(Ox)^(2-)₂ and the rate of complex formation for VO^(2+) (aq) to form VO(Ox)^(2-)₂.

Kinetics and Mechanism of the Axial Ligation of Hemin. Activation Volume for the Dissociation of Imidazole from Monoimidazole Complex in N,N-Dimethylformamide

김정성,박윤열,HIROSHI TOMIYASU 大邱大學校附設 基礎科學硏究所 1993 基礎科學硏究 Vol.10 No.-

Unusual kinetic behavior was observed in the substitutions of hemin with imidazole and cyanide ion under conditions of [L] S 2[hemin] (L=substituting ligand) in N,N--dimethylformamide. The rates of these reactions were much slower than those the formations of mono- and bis-coordinate complexes. Based on the kinetic results, these slow reactions were interpreted in terms of the dissociations of mono-coordinate complex to solvated hemin. The activation volume was determined to be 24.3 -- 0.4 cm3 mol'1 for the reaction with imidazole by the high pressure stopped flow method. The large positive value of the activation volume strongly supports a limiting dissociative mechanism.

이소옥사졸과 그의 유도체들이 배위된 팔라듐(Ⅱ)과 백금(Ⅱ) 착물의 항암활성에 관한 이론적 연구

김정성,송영대,Kim, Jung-Sung,Song, Young-Dae 대한화학회 1998 대한화학회지 Vol.42 No.4

The palladium(II) and platinum(II) complexes(where, $([M(L)_2X_2]$, M=Pd(II), Pt(II); L=isoxazole(isox), 3,5-dimethylisoxazole(3,5-diMeisox), 3-methyl, 5-phenylisoxazole(3-Me, 5-Ph-isox), and 4-amino-3,5-dimethylisoxazole (4-ADI); X=Cl, Br) with isoxazole and its derivatives were investigated on antitumor activity by MM2 and EHMO calculation. Because for all the complexes the ${\sigma}MO$ energy level $(E_{{\sigma}(M-X)})$ between $d_x^{2-}_y^2$ orbital of central metal and px orbital of halogen atom is less than ${\sigma}MO$ energy level $(E_{{\sigma}(M-N)})$ between $d_x^{2-}_y^2$ orbital of central metal and px orbital of N atom, without exception. And judging, from the lower $(E_{\'{o}(m-x)})$ value in trans, the bonding strength was found to be weaker in trans isomer than in cis. For the Pd(II) and Pt(II) complexes which have planar ligands, it was shown that for all the complexes dissociation of X-atom in the Pd(II) complexes is easier than that of X-atom in the Pt(II) complexes in both cis- and trans-complexes. Therefore it suggests that the easier dissociation of $X^-$ ion has some relations with antitumor activity, and a linear equation with correlation coefficient of 0.96 was found between ${\Delta}E_{{\sigma}(N-X)}(E_{{\sigma}(M-N)}-E_{{\sigma}(M-X)})$ and inhibitory activity coefficient, logIA.