수용액 및 물-유기용매 혼합용매에서의 Hg$^{2+}$ 에 의한 Co(Ⅲ) 착물의 수화반응

오창언,윤두천,도명기,Oh Chang Eon,Yoon Doo Cheon,Doh Myung Ki 대한화학회 1990 대한화학회지 Vol.34 No.5

Observed rate constants (k$_{obs.}$) for Hg$^{2+}$-catalysed aquation of cis-[Co(en)$_2$(OH$_2$)Cl]$^{2+}$, [Co(NH$_3$)$_5$Cl]$^{2+}$, cis-[Co(NH$_3$)$_4$(OH$_2$)Cl]$^{2+}$, and [Co(NH$_2$CH$_3$)$_5$Cl]$^{2+}$ were measured at various concentrations of Hg$^{2+}$. The k$_{obs.}$ was increased with increasing the concentrations of Hg$^{2+}$. The k$_{obs.}$ were related to mechanistically derived rate constants by the relationship; Rate = k$_2$K[complex][Hg$^{2+}$]. Various mixed aqueous-organic solvent have been successfully employed for Hg$^{2+}$-catalysed aquation of octahedral myetal complexes. From the slope of the plot of log k againt Y (solvent ionizing power), the mechanism on the aquation of Co(Ⅲ) complexes by Hg$^{2+}$ has been suggested to be I$_d$-mechanism. The change in a rate on aquation of each Co(Ⅲ) complex was related to the ligand field parameters (${\Delta}$), for Co(Ⅲ) complexes. 촉매로서 Hg$^{2+}$을 사용한 수화반응에서 cis-[Co(en)$_2$(OH$_2$)Cl]$^{2+}$, [Co(NH$_3$)$_5$Cl]$^{2+}$, cis-[Co(NH$_3$)$_4$(OH$_2$)Cl]$^{2+}$ 및 [Co(NH$_2$CH$_3$)$_5$Cl]$^{2+}$착물들은 Hg$^{2+}$의 농도가 증가할수록 관측속도상수(k$_{obs}$)의 값이 증가하였다. Hg$^{2+}$에 의한 수화반응의 속도법칙은 Rate = k$_2$K[complex][Hg$^{2+}$]이었고, 그 메카니즘이 연구되었다. 또한 여러가지 유기용매-물 혼합용매에서 Co(Ⅲ)착물의 Hg$^{2+}$에 의한 수화반응이 연구되었다. 용매의 성질인 Y (solvent ionizing power)값에 대한 log k를 도시하여 그 기울기인 m값을 얻었다. 그 m값으로부터 수화반응의 메카니즘을 추정하였다. 속도론적인 자료로부터 Hg$^{2+}$에 의한 Co(Ⅲ)착물의 수화반응이 I$_{d^-}$메카니즘으로 제안되었다. 각 Co(Ⅲ)착물의 속도의 차이는 여러가지 리간드가 배위된 Co(Ⅲ)착물의 리간드장파라메타(${\Delta}$)값과 관계가 있었다.

Equaatiorial-Skew [Co(TRDTRA)(OH₂)] 착물과 CN, NO₂그리고 NCS 이온간의 치환반응

都命基,趙榮在,李東鎭,吳昌彦,金東曄 嶺南大學校 基礎科學硏究所 1992 基礎科學硏究 Vol.12 No.-

Equatorial-Skew형[Co(TRDTRA)(OH₂)]착물과 ??,?? 그리고 ?? 이온 간의 치환반응결과 생성된 차물의 치환반응성 및 구조를 전자흡수 스펙트럼과 Yamatera 이론에 따라 조사하였다. 속도론적 자료로부터 착물과 ??,?? 그리고 ?? 이온의 반응차수는 각각 1차이며 총괄 반응차수는 2차임을 알 수 있었다. ?? 및 ?? 이온에서 생성된 착물의 구조는 이성질화 반응이 동반된 Polar-Chair 형이며, ?? 이온의 경우에는 이성질화 반응이 동반되지 않은 Equatorial-Skew 형임을 알 수 있었다. The substitution reaction and structrue of products obtained from the reaction of Equatorial-Skew-[Co(TRDTRA)(OH??)](TRDTRA=trimethylenediaminetriacetate) with ??,??, and NCS ions have been investigated by means of electronic absorption spectroscopy and theoretical calculation based on the Yamatera`s theory. According to kinetic data, the substitution reaction order for the complexes such as ??,?? and ?? was the first order, respectively, and overall reaction order was second order. It has been determined that the structure of products having ?? and ?? ions was Polar-Chair type complexes which were accompanying with isomerization and having ?? ion was Equatorial-Skew type complex which was not accompanying with isomerization.

수용액에서 $Hg^{2+}$에 의한 trans-[Co(3,2,3-tet)X$_2]^+$ (3,2,3-tet = 4,7-diazadecane-1,10-diamine, $X_2\;=\;Cl_2,\;(NO_2)Cl,\;Br_2,\;(NO_2)Br,\;(NO_3)_2)$ 착물의 아쿠아 반응

윤두천,오창언,도명기,Doo Cheon Yoon,Chang Eon Oh,Myung Ki Doh 대한화학회 1993 대한화학회지 Vol.37 No.11

수용액상에서 $Hg^{2+}$에 의한 trans-[Co(3,2,3-tet)$X_2]^+$ (3,2,3-tet = 4,7-diazadecane-1,10-diamine, $X_2\;=\;Cl_2,\;(NO_2)Cl,\;Br_2,\;(NO_2)Br,\;(NO_3)_2)$ 착물의 아쿠아 반응이 연구되었다. 생성물을 확인하고 반응메카니즘을 추정하기 위하여 크로마토그래피를 사용하였고 전자흡수 스펙트럼을 측정하였다. 그 결과 네자리 리간드인 3,2,3-tet가 배위된 여러가지 $trans-[Co(3,2,3-tet)X_2]^+$ 착물은 각각 아쿠아된 trans-[Co(3,2,3-tet)$(OH_2)_2]^{3+}$ 착물을 거쳐 cis-${\beta}$-[Co(3,2,3-tet)$(OH_2)_2]^{3+}$ 착물이 생성되었다. $Hg^{2+}$에 의한 trans-$[Co(3,2,3-tet)Cl_2]^+$ 착물과 trans-[Co(3,2,3-tet)$(NO_2)Cl]^+$ 착물의 아쿠아 반응에 대한 메카니즘을 추정하기 위하여 속도론적 조사를 하였따. 그 결과 $trans-[Co(3,2,3-tet)Cl_2]^+$ 착물은 D(dissociative)-메카니즘으로 진행되었고, trans-[Co(3,2,3-tet)$(NO2_)Cl]^+ $착물은 $I_d$(interchange dissociative)-메카니즘으로 진행되었다. 그리고 입체화학적인 거동을 조사하기 위하여 라세미(R,R:S,S)3,2,3-tet 대신에 키랄성이 R,R인 3,2,3,-tet를 배위시킨 trans-$[Co(R,R-3,2,3-tet)Cl_2]^+$ 착물에 $Hg^{2+}$를 용리시켰을 때 아쿠아 반응에 대한 원편광이색성(circular dichroism) 스펙트럼을 측정하여 그 절대구조를 확인한 결과 ${\Delta}-cis-{\beta}$-[Co(R,R-3,2,3-tet)$(OH_2)_2]^{3+}$ 착물이 생성되었다. $Hg^{2+}$-induced aquation trans-[Co(3,2,3-tet)$X_2]^+$(3,2,3-tet = 4,7-diazadecane-1,10-diamine, $X_2\;=\;Cl_2,\;(NO_2)Cl,\;Br_2,\;(NO_2)Br,\;(NO_3)_2)$ complexes was investigated in aqueous solution. The products and the reaction mechanism were confirmed by chromatography, UV/Vis. spectrum, and circular dichroism (CD) spectrum. From the results, $Hg^{2+}$-induced aquation of 3,2,3-tet system has been produced cis-${\beta}$ complex via trans complex. The kinetic studies on $Hg^{2+}$-induced aquation of trans-[Co(3,2,3-tet)$Cl_2]^+$ complex and trans-[Co(3,2,3-tet)$(NO_2)Cl]^+$ complex were also carried out to study the reaction mechanism. The results show that trans-[Co(3,2,3-tet)$Cl_2]^+$ complex undergoes the D(dissociative)-mechanism and trans-[Co(3,2,3-tet)$(NO_2)Cl]^+$ complex $I_d$(interchange dissociavite)-mechanism. In order to confirm steric course for the reaction mechanism, $Hg^{2+}$-induced aquation on trans-[Co(R,R-3,2,3-tet)$Cl_2]^+$ complex to which chiral R,R-3,2,3-tet was coordinated instead of the racemic(R,R:S,S) 3,2,3-tet was used has been examined by CD spectrum. From the results, the final complex was confirmed to be ${\Delta}-cis-{\beta}$-[Co(R,R-3,2,3-tet)$(OH_2)_2]^{3+}$ complex indicating the chirality was retained through whole process.

?? 착물의 구조적 특성

김복조,윤두천,박기훈,주언정,오창언 嶺南大學校 基礎科學 硏究所 1998 基礎科學硏究 Vol.18 No.-

Five-coordinated complex of Cu(Ⅱ) complex, [CuCl(1,10-phenanthroline)₂]·Cl·6H₂O·CH₃OH, was synthesized by adding an aqueous solution of Cu(Ⅱ) to a methanol solution of 1,10-phenanthroline. Its crystal structure was detemined by single crystal X-ray crystallography. Crystal data are are as fllow: [CuCl(phen)₂]·Cl·6H₂O·CH₃OH, monoclinic, space group C2/c (#15), a = 23.309(5), b = 30.270(6), c = 7.491(2) A, B = 97.83(2)˚, V = 5236 A³, Z = 8,2745 data with I >3σ(I) (R = 00.64, Rw = 0.087). In the crystal structure of ??, the Cu(Ⅱ)is five-coordianted with four nitrogen and one chlorine atom. The geometry around Cu(Ⅱ) is somewhat distorted trigonal bipyramid and Cu(Ⅱ) is locted nearly (0.0280 A˚) on the least-squares plane of the two nitrogen atoms and one chlorine atom.

정신분열병에 대한 리스페리돈의 효과 및 안정성

이민수,김용구,김영훈,연병길,오병훈,윤도준,윤진상,이철,정희연,강병조,김광수,김동언,김명정,김상훈,김희철,나철,노승호,민경준,박기창,박두병,백기청,백인호,손봉기,손진욱,양병환,양창국,우행원,이정호,이종범,이홍식,임기영,전태연,정영조,정영철,정인과,정인원,지익성,채정호,한상익,한선호,한진희,서광윤 大韓神經精神醫學會 1998 신경정신의학 Vol.37 No.1

연구목적 : 본 시험의 목적은 임상시험 시작전에 연구자들을 대상으로 PANSS Workshop을 통하여 PANSS, ESRS에 대한 국내에서의 표준화 작업을 구축하고 새로운 정신병 치료제인 리스페리돈의 효과와 안정성을 재확인하여 리스페리돈 사용에 대한 적정화를 이루는데 있다. 연구방법 : 1996년 4월부터 1996년 9월까지 국내 39개 대학병원 정신과에 입원중인 혹은 증상이 악화되어 입원하는 정신분열병 환자 377명을 대상으로 다시설 개방 연구를 시행하였다. 1주일간의 약물 배설기간을 가진후, 리스페리돈을 8주간 투여하였고, 기준점, 1주, 2주, 4주, 그리고 8주후에 평가되었다. 용량은 제1일에는 리스페리돈 1mg씩 1일 2회, 제2일에는 2mg씩 1일 2회, 제3∼7일에는 3mg씩 1일 2회 투여하였다. 이후 환자의 임상상태에 따라 임의로 증량할 수 있으며, 최대 일일 16mg을 초과하지 않도록 하였다. 추체외로 증상을 조절하기 위한 투약을 허용하였다. 임상증상 및 부작용의 평가는 PANSS(Positive and Negative Syndrome Scale), CGI(Clinical Global Impression) 그리고 ESRS(Extrapyramidal Symptom Rating Scale)을 사용하였다. 연구결과 : 377명중 343명(91%)이 8주간의 연구를 완결하였다. 치료 종결시점인 8주후 PANSS 총점수가 20% 이상 호전된 경우를 약물 반응군으로 정의할때, 약물반응군은 81.3%였다. 리스페리돈에 반응하는 예측인자로는 발병연령, 이전의 입원 횟수, 유병기간이 관련 있었다. 리스페리돈은 1주후부터 PANSS양성, 음성, 및 일반정신병리 점수상에 유의한 호전을 보여 효과가 빨랐다. CGI의 경우도 기준점에 비해 1주후부터 유의한 감소를 나타내었다. ESRS의 경우, 파킨슨 평가점수는 기준점과 비교해 투여 1주, 2주, 4주후 유의하게 증가되었다가 8주후 기준점과 차이가 없었다. Dystonia 평가점수는 1주후만 유의한 증가를 보였으며, dyskinesia 평가점수는 유의한 차이가 없었다. 혈압, 맥박수의 생명징후 및 일반 혈액학 검사, 생화학적 검사, 심전도 검사에서 유의한 변화는 없었다. 결 론 : 이상의 다시설 개방 임상 연구를 통해 리스페리돈은 정신분열병 환자에서 양성증상뿐만 아니라 음성증상 및 전반적인 증상에도 효과적인 것으로 사료된다. 보다 명확한 평가를 위해서는 다른 항정신병약물과의 이중맹검 연구가 필요할 것으로 생각되며, 또한 장기적 치료에 대한 평가도 함께 이루어져야 하겠다. Objective : The purpose of this study was to investigate the efficacy and safety of risperidone in the treatment of Korean schizophrenic patients. Method : This multicenter open study included 377 schizophrenic patients drawn from 39 university hospitals. After a wash-out period of 1 week, the schizophrenic patients were treated with risperidone for 8 weeks and evaluated at 5 points ; at baseline, and 1, 2, 4 and 8 weeks of treatment. The dose was increased from 2mg/day(1mg twice daily) to 6mg/day(3mg twice daily) during the first week and adjusted to a maximum of 16mg/day over the next 7 weeks according to the patient's clinical response. Medication to control extrapyramidal symptoms was permitted. The psychiatric and neurological status of the patients was assessed by PANSS, CGI, and ESRS scales. Results : 343(91%) of 377 patients completed the 8-week trial period. Clinical improvement, as defined by a 20% or more reduction in total PANSS score at end point, was shown by 81.3% of patients. The predictors of response to risperidone were associated older age, shorter duration of illness, fewer previous hospitalization. Risperidone had rapid onset of action ; a significant decrease of the total PANSS and three PANSS factor(positive, negative, general), and CGI was already noticed at the end of first week. For the ESRS, parkinsonism rating scores were significantly increased until week 4 comparing with baseline. Dystonia rating scores were significantly increased until week 1, and dyskinesia rating scores were not significantly changed during the study. Laboratory parameters including vital sign, EKG, hematological, and biochemical values showed no significant changes during the trial. Conclusions : This study suggests that risperidone is generally safe and effective against both the positive and negative symptoms in our group of patients.

라세미-〔Co(N)6〕3+및 라세미-〔 Co(N)5(O)〕2+형 착물에 대한 d-주석산용액의 입체선택성에 관한 연구

오창언,김복조 嶺南大學校附設 基礎科學硏究所 1985 基礎科學硏究 Vol.5 No.-

Chromatographic behaviors of some bis(ethylenediamine) cobalt(Ⅲ) complexes have been investigated by using SP-Sephadex C-25 cation exchange resin with 0.2M sodium d-tartrate aqueous solution as eluent. Metal complexes ?? and ?? were resolved completely with sodium d-tartrate aqueous solution. However, other metal complexes ?? and ?? were resolved partially and mot resolved, respectively. ?? which have -CH₃ group blocked the formation of C₃ axis was resolved partially. It means that the formation of C₃ axis was influenced by replaced -CH₃ group. With the effects of -CH₃ group, hence, it was resolved partially and stereoselectivity of eluent was greater for the Λ-isomer than for the Δ-isomer. Tris-chelate complexes ?? and ?? which have only one C?? axis were resolved completely and stereoselectivity of eluent on these complexes was greater for the Λ-isomer than for the Δ-isomer. ?? which have -CH₃ group blocked the formation of C₃ axis was not resolved.

Eluent의 농도변화에 따른 +2가 및 +3가 금속양이온착물의 용리순서에 관한 연구

吳昌彦 嶺南大學校府設 基礎科學硏究所 1983 基礎科學硏究 Vol.3 No.-

The elution behaviors of various metal complexes were studied in aqueous solution by measuring the retention volume on sp-sephadex C-25 cation exchange resin. The results obtained are summarized as follows. In the case of strongly hydrated complexes. a strongly hydrated anion has a greater tendency towards association than a weakly hydrated anion. In the weakly hydrated complexes, a weakly hydrated anion is associated more easily than a strongly hydrated anion. It was found that the elution behaviors of metal complexes were apparently affected by salt concentration, kinds of cations and anions in eluent.

수용액중에 있어서 d- 주석산염과 아키랄 ?? 착물의 회합

吳昌彦 嶺南大學校府設 基礎科學硏究所 1983 基礎科學硏究 Vol.3 No.-

Ion association constants K of ?? complexes; ??, ??, ??, ??, with aqueous d-tartrate ion solution were determined by measuring induced circular dichroism spectra change at 25℃, It was found that the K values of these complexes associated with d-tartrate ion increase with increasing number of ethylenediamine chelate ring. Also, it was proposed that circular dichroism weakly induced in these achiral complexes measured when the two hydroxyl oxygen atoms and one oxygen atom of carboxyl group of d-tartrate ion form hydrogen bonds with protons of N-H bonds of ligands.

용리제에 의한 금속착물의 크로마토그래피적인 분리

吳昌彦,尹斗千 嶺南大學校附設 基礎科學硏究所 1986 基礎科學硏究 Vol.6 No.-

The elution behaviors of cationic complexes were determined by measuring retention volumes on SP-Sephadex C-25 cation exchange resin. When cationic complexes were eluted in the low concentration of eluents, their elution order was accordance with the order of their increasing charges. At this time, the elution depends on the strength of adsorptivities between cationic complex and the resin. However the elution order of cationic complexes was reserved when they were eluted in the high concentration of eluents. On this occasion, cationic complexes have been eluted predominantly by ion-association between cationic complex and eluent. Hydrophilic complexes were associated more strongly with chloride ion than bromide ion. But hydrophobic complexes were opposed to above. In the comparision of sulfate ion and halide ions(Cl- and Br-), hydrophilic complexes were associated more easily with sulfate ion than halide ions(Cl- and Br-), and hydrophobic complexes were opposed to above.

기술수용모형에 의한 기업문화와 인터넷 활용에 관한 연구

고부언,오창수 동의대학교 경제경영전략연구소 2004 經濟經營硏究 Vol.2 No.1

This study aims at verifying the structural relationship amongst four types of culture : innovation-oriented culture; relationship-oriented culture; Task-oriented culture; and hierachey-oriented culture, the perceived ease of the computer use, the perceived usefulness of the task-related computer use, the attitude of the computer use, and the behavior of the computer use by applying enterprise culture to technology acceptance model which is established to model user acceptance of information systems. Business need to give higher-aged people the idea to easily use the computer for their jobs and operate the rewarding program which provides a variety of incentives connecting with computer programs in the case that the members proactively use computer for their jobs.