Abstract
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 2 IV (OH)4]4+, showing that this is the catalytically active species. According to quantum-chemical calculation, the two Ce(IV) ions in this [Ce2 IV (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.
| Original language | English |
|---|---|
| Pages (from-to) | 523-538 |
| Number of pages | 16 |
| Journal | Nucleosides, Nucleotides and Nucleic Acids |
| Volume | 25 |
| Issue number | 4-6 |
| DOIs | |
| Publication status | Published - 2006 Jun 1 |
| Externally published | Yes |
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Keywords
- Artificial nuclease
- Cerium
- DNA cleavage
- Enzyme models
- Phosphodiester hydrolysis
ASJC Scopus subject areas
- Genetics
- Biochemistry
Cite this
Active species for Ce(IV)-induced hydrolysis of phosphodiester linkage in cAMP and DNA. / Sumaoka, Jun; Furuki, Kenichiro; Kojima, Yuki; Shibata, Masahiko; Hirao, Kimihiko; Takeda, Naoya; Komiyama, Makoto.
In: Nucleosides, Nucleotides and Nucleic Acids, Vol. 25, No. 4-6, 01.06.2006, p. 523-538.Research output: Contribution to journal › Article
}
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
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 2 IV (OH)4]4+, showing that this is the catalytically active species. According to quantum-chemical calculation, the two Ce(IV) ions in this [Ce2 IV (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 2 IV (OH)4]4+, showing that this is the catalytically active species. According to quantum-chemical calculation, the two Ce(IV) ions in this [Ce2 IV (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
UR - http://www.scopus.com/inward/record.url?scp=33747591615&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=33747591615&partnerID=8YFLogxK
U2 - 10.1080/15257770600684209
DO - 10.1080/15257770600684209
M3 - Article
C2 - 16838843
AN - SCOPUS:33747591615
VL - 25
SP - 523
EP - 538
JO - Nucleosides and Nucleotides
JF - Nucleosides and Nucleotides
SN - 0732-8311
IS - 4-6
ER -