TY - JOUR
T1 - Active species for Ce(IV)-induced hydrolysis of phosphodiester linkage in cAMP and DNA
AU - Sumaoka, Jun
AU - Furuki, Kenichiro
AU - Kojima, Yuki
AU - Shibata, Masahiko
AU - Hirao, Kimihiko
AU - Takeda, Naoya
AU - Komiyama, Makoto
N1 - Funding Information:
Received 29 December 2005; accepted 9 February 2006. This work was partially supported by the Bio-oriented Technology Research Advancement Institution. The support by a Grant-in-Aid for Scientific Research from the Ministry of Education, Culture, Sports, Science and Technology, Japan is also acknowledged. This article is dedicated to Professor Eiko Ohtsuka on the occasion of her 70th birthday. Current address for Naoya Takeda: Consolidated Research Institute for Advanced Science and Medical Care, Waseda University, Shinjuku-ku, Tokyo 162-0041, Japan. Address correspondence to Makoto Komiyama, Research Center for Advanced Science and Technology, The University of Tokyo, Komaba, Tokyo 153-8904, Japan. E-mail: komiyama@mkomi.rcast. u-tokyo.ac.jp
PY - 2006/6/1
Y1 - 2006/6/1
N2 - The hydrolysis of cyclic adenosine 3′,5′-monophosphate and 2′-deoxythymidylyl(3′-5′)2′-deoxythymidine by Ce(NH 4)2(NO3)6 was kinetically studied. The rate of hydrolysis was fairly proportional to the concentration of [Ce 2IV (OH)4]4+, showing that this is the catalytically active species. According to quantum-chemical calculation, the two Ce(IV) ions in this [Ce2IV (OH)4] 4+ cluster are bridged by two OH residues. Upon the complex formation with H2PO4- (a model compound for the phosphodiesters), these two Ce(IV) ions bind the two oxygen atoms of the substrate and enhance the electrophilicity of the phosphorus atom. The catalytic mechanism of Ce(IV)-induced hydrolysis of phosphodiesters has been proposed on the basis these results.
AB - The hydrolysis of cyclic adenosine 3′,5′-monophosphate and 2′-deoxythymidylyl(3′-5′)2′-deoxythymidine by Ce(NH 4)2(NO3)6 was kinetically studied. The rate of hydrolysis was fairly proportional to the concentration of [Ce 2IV (OH)4]4+, showing that this is the catalytically active species. According to quantum-chemical calculation, the two Ce(IV) ions in this [Ce2IV (OH)4] 4+ cluster are bridged by two OH residues. Upon the complex formation with H2PO4- (a model compound for the phosphodiesters), these two Ce(IV) ions bind the two oxygen atoms of the substrate and enhance the electrophilicity of the phosphorus atom. The catalytic mechanism of Ce(IV)-induced hydrolysis of phosphodiesters has been proposed on the basis these results.
KW - Artificial nuclease
KW - Cerium
KW - DNA cleavage
KW - Enzyme models
KW - Phosphodiester hydrolysis
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U2 - 10.1080/15257770600684209
DO - 10.1080/15257770600684209
M3 - Article
C2 - 16838843
AN - SCOPUS:33747591615
VL - 25
SP - 523
EP - 538
JO - Nucleosides, Nucleotides and Nucleic Acids
JF - Nucleosides, Nucleotides and Nucleic Acids
SN - 1525-7770
IS - 4-6
ER -