Cleavage and isomerization of UpU promoted by dinuclear metal ion complexes

被引:58
作者
Linjalahti, Heidi [1 ]
Feng, Guoqiang [2 ]
Mareque-Rivas, Juan C. [3 ]
Mikkola, Satu [1 ]
Williams, Nicholas H. [2 ]
机构
[1] Univ Turku, Dept Chem, FI-20014 Turku, Finland
[2] Univ Sheffield, Dept Chem, Ctr Chem Biol, Sheffield S3 7HF, S Yorkshire, England
[3] Univ Edinburgh, Sch Chem, Edinburgh EH9 3JJ, Midlothian, Scotland
基金
英国工程与自然科学研究理事会;
关键词
D O I
10.1021/ja711347w
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
The catalysis of phosphoryl transfer by metal ions has been intensively studied in both biological and artificial systems, but the status of the transient pentacoordinate phosphoryl species (as transition state or intermediate) is the subject of considerable debate. We report that dinuclear metal ion complexes that incorporate second sphere hydrogen bond donors not only promote the cleavage of RNA fragments just as efficiently as the activated analogue HPNPP but also provide the first examples of metal ion catalyzed phosphate diester isomerization close to neutral pH. This observation implies that the reaction catalyzed by these complexes involves the formation of a phosphorane intermediate that is sufficiently long-lived to pseudorotate.
引用
收藏
页码:4232 / +
页数:3
相关论文
共 24 条
[1]  
BECKMANN C, 1997, J CHEM SOC PERK T, V2, P573
[2]   Artificial dinuclear phosphoesterases [J].
Chin, J .
CURRENT OPINION IN CHEMICAL BIOLOGY, 1997, 1 (04) :514-521
[3]   A highly reactive mononuclear Zn(II) complex for phosphodiester cleavage [J].
Feng, GQ ;
Mareque-Rivas, JC ;
de Rosales, RTM ;
Williams, NH .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2005, 127 (39) :13470-13471
[4]   Efficient phosphodiester binding and cleavage by a ZnII complex combining hydrogen-bonding interactions and double lewis acid activation [J].
Feng, Guoqiang ;
Natale, Daniela ;
Prabaharan, Ravi ;
Mareque-Rivas, Juan C. ;
Williams, Nicholas H. .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2006, 45 (42) :7056-7059
[5]   The reactivity of phosphodiester bonds within linear single-stranded oligoribonucleotides is strongly dependent on the base sequence [J].
Kaukinen, U ;
Lyytikäinen, S ;
Mikkola, S ;
Lönnberg, H .
NUCLEIC ACIDS RESEARCH, 2002, 30 (02) :468-474
[6]   ENDOCYCLIC CLEAVAGE IN THE ALKALINE-HYDROLYSIS OF THE CYCLIC PHOSPHONATE METHYL PROPYLPHOSTONATE - DIANIONIC INTERMEDIATES AND BARRIERS TO PSEUDOROTATION [J].
KLUGER, R ;
TAYLOR, SD .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1991, 113 (15) :5714-5719
[7]   GENERAL AND SPECIFIC ACID-BASE CATALYSIS OF THE HYDROLYSIS AND INTERCONVERSION OF RIBONUCLEOSIDE 2'-PHOSPHOTRIESTERS AND 3'-PHOSPHOTRIESTERS - KINETICS AND MECHANISMS OF THE REACTIONS OF 5'-O-PIVALOYLURIDINE 2'-DIMETHYLPHOSPHATES AND 3'-DIMETHYLPHOSPHATES [J].
KOSONEN, M ;
LONNBERG, H .
JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2, 1995, (06) :1203-1209
[8]   METAL-IONS THAT PROMOTE THE HYDROLYSIS OF NUCLEOSIDE PHOSPHOESTERS DO NOT ENHANCE INTRAMOLECULAR PHOSPHATE MIGRATION [J].
KUUSELA, S ;
LONNBERG, H .
JOURNAL OF PHYSICAL ORGANIC CHEMISTRY, 1993, 6 (06) :347-356
[9]   Kinetics of RNA degradation by specific base catalysis of transesterification involving the 2′-hydroxyl group [J].
Li, YF ;
Breaker, RR .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1999, 121 (23) :5364-5372
[10]   Kinetics and mechanisms for the isomerization of internucleosidic 3′-O-P-CH2-5′ and 3′-O-P-CH(OH)-5′ linkages to their 2′,5′-counterparts [J].
Lonnberg, Tuomas ;
Kralikova, Sarka ;
Rosenberg, Ivan ;
Lonnberg, Harri .
COLLECTION OF CZECHOSLOVAK CHEMICAL COMMUNICATIONS, 2006, 71 (06) :859-870