Applied Biological Chemistry

The Korean Society for Applied Biological Chemistry (한국응용생명화학회)
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The Roles of Metal Ions and Water Molecules in the Hydrolysis of Bis(p-nitrophenyl)phosphate as a DNA Model Catalyzed by Dinuclear Ni(II) Complex

DNA 모델인 Bis(p-nitrophenyl)phosphate에 대한 2핵 Ni(II) 착 화합물의 촉매 가수분해 반응에서 물 분자와 금속 이온의 역할

  • Sung, Nack-Do (Research Center for Transgenic Cloned Pigs, Division of Applied Biology and Chemistry, College of Agricultural and Life Science, Chung-Nam National University) ;
  • Yun, Ki-Seob (Research Center for Transgenic Cloned Pigs, Division of Applied Biology and Chemistry, College of Agricultural and Life Science, Chung-Nam National University)
  • 성낙도 (충남대학교 형질전환복제돼지연구센터) ;
  • 윤기섭 (충남대학교 형질전환복제돼지연구센터, 농업생명과학대학 응용생물화학부)
  • Published : 2005.06.30
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Abstract

The catalytic hydrolysis reactivities of dinuclear nickel (II) complex, ${\mu}-aquapentaaqua[{\mu}-3,6-bis(6'-methyl-2'-pyridyl)pyridazine]chlorodinickel\;(II)$ trichloride trihydrate (APNT) for bis(p-nitrophenyl) phosphate (BNPP) as a DNA model compound were investigated. The dissociation constants of APNT were $pKa_1=7.9$ and $pKa_2=9.6$, respectively. The hydrolysis rate constant of BNPP compound by APNT was showed the rate enhancement of about 370,000 times in the case of none catalyst at pH 7.0 and $50^{\circ}C$. Based on the findings, we proposed the catalytic cycle for the hydrolysis of BNPP by APNT complex. The metal ions of dinuclear nickel (II) complex significantly enhance the transfer rate of phosphoryl group in the catalytic process and the water molecules as nucleophile and proton transfer agent act in different steps.

DNA 모델 화합물인 bis(p-nitrophenyl)phosphate(BNPP)에 대한 2핵 닉켈(II) 착 화합물, ${\mu}-aquapentaaqua[{\mu}-3,6-bis(6'-methyl-2'-pyridyl)pyridazine]chlorodinickel(II)$ trichloride trihydrate(APNT)의 촉매 가수분해 반응성을 검토하였다. APNT의 산 해리 상수는 각각 $pKa_1=7.9$ 및 $pKa_2=9.6$이었으며 BNPP의 가수분해반응 결과, pH 7.0과 $50^{\circ}C$에서 무 촉매인 경우에 비하여 가수분해 속도를 약 37만 배 가량 촉진시킴을 확인하였다. 그리고 pH-rate profile로부터 실험 사실을 합리적으로 설명할 수 있는 APNT에 의한 BNPP의 촉매 가수분해 반응에 대한 일련의 catalytic cycle을 제안하였다. 따라서 반응의 각 단계에서 2핵 닉켈(II) 착 화합물의 금속 이온들은 phosphoryl group의 전달 속도를 촉진하였고 물 분자는 친핵체와 양성자 전달체로 작용하였다.

Keywords

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