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Zr IV ‐tetraphenylporphyrinates as Nuclease Mimics: Structural, Kinetic and Mechanistic Studies on Phosphate Diester Transesterification
Author(s) -
Stulz Eugen,
Bürgi HansBeat,
Leumann Christian
Publication year - 2000
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/(sici)1521-3765(20000204)6:3<523::aid-chem523>3.0.co;2-1
Subject(s) - solvolysis , chemistry , phosphodiester bond , catalysis , phosphate , substituent , transesterification , nuclease , hydrolysis , stereochemistry , cationic polymerization , medicinal chemistry , crystallography , organic chemistry , rna , enzyme , biochemistry , gene
Potent, functional nuclease mimics that can accelerate phosphodiester transesterification by 6 to 9 orders of magnitude above background can be obtained with Zr IV ‐tetraphenylporphyrinates. A structural, kinetic and mechanistic investigation on DNA and RNA model phosphodiesters as substrates suggests the catalytically active species to be a dinuclear complex (see figure). According to X‐ray analysis, electrostatic effects seem to overrule stereoelectronic effects in phosphodiester activation.