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야마사키 가츠 선문대학교 신학대학 2001 선문대학교 신학대학논문집 Vol.2001 No.-
유물사관의 공산주의와 통일사상의 두익사상을 알아보고자 한다. 이 논문을 쓰기 위해 보다 많은 자료와 폭넓은 자료를 구하기 위해 인터넷을 사용할 것이며 참고 문헌 식으로 전문 서적을 바탕으로 삼아 연구 할 것이다. 여러 측면에서 주제를 생각해 보고 연구하기 위해 노력할 것이다. Over the years, there has been enormous interest in developing metal complexes that hydrolyze phosphate backbone of DNA. Recently, several metal complexes have been reported with high efficiencies in hydrolyzing phosphate esters such as BNPP. Although some of them could even cleave ss- and ds-DNA, the mechanisms were not clearly elucidated. Those that cleave DNA hydrolytically have yet to be developed. Until now, only a few metal complexes including cis-diaquo(tetraamine) Co(Ⅲ) complexes have been thoroughly studied in their hydrolytic mechanisms. Among them, cis-diaquo Co(Ⅲ)(cyclen) complex (cyclen; 1,4,7,10-tetraazacyclododecane) was highly efficient in hydrolyzing phosphate esters such as BNPP and dimethyl phosphate as well. The proposed mechanism involved a coordination of the substrate, followed by nucleophilic attack of the bound cobalt hydroxide on the bound substrate, forming a four-membered ring chelates. Catalytic efficiency of the metal complexes was largely dependent on the easy formation of the strained four-membered ring chelates and it has been nicely shown with the trpn[tris(aminopropyl)amine], tren(tris(aminoethyl)amine], where their cobalt complexes showed 300 times of rate difference in hydrolyzing BNPP. One way to increase the catalytic efficiency of metal complex is to design ligand system that can force the four-membered ring chelate to be formed easily. Taking this into consideration, we have prepared a series of ligand based on the structure of cyclen. Cyclen was chosen because it was a little less active but much more stable than trpn under the reaction conditions used. The trpn cobalt complex is far the most active catalyst in that series yet the ligand deligation often occurs during the hydrolysis. One (mcyclen) or two(trans-dimethyl and cis-dimethylcyclen: tmcyclen, cmcyclen) methyl groups are introduced into nitrogens of cyclen. Herein we report on the reactivities of cobalt complexes 1, 2, 3 for hydrolyzing BNPP and its implication on structural requirements of efficient catalysts.