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Iron(III) Complexes of Metal‐Binding Copolymers as Proficient Catalysts for Acid Hydrolysis of Phosphodiesters and Oxidative DNA Cleavage – Insight into the Rational Design of Functional Metallopolymers
Author(s) -
Lykourinou Vasiliki,
Hanafy Ahmed I.,
Bisht Kirpal S.,
Angerhofer Alexander,
Ming LiJune
Publication year - 2009
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.200800644
Subject(s) - phosphodiester bond , chemistry , catalysis , hydrolysis , pyridine , nucleophile , selectivity , kinetics , cleavage (geology) , metal , rational design , polymer chemistry , medicinal chemistry , organic chemistry , biochemistry , nanotechnology , rna , physics , geotechnical engineering , quantum mechanics , fracture (geology) , engineering , gene , materials science
Fe 3+ complexes of pyridine‐containing copolymers were found to be efficient and selective catalysts toward phosphodiester hydrolysis and show significant activity toward oxidative DNA cleavage. The catalysis toward bis( p ‐nitrophenyl)phosphate (BNPP) hydrolysis exhibits enzyme‐like pre‐equilibrium kinetics with maximum activities in the range of ca. pH 6–8 and a first‐order catalytic proficiency ( k cat / k o ) of 4.2 × 10 7 ‐fold at the acidic pH value of 5.3 (i.e., p K a of the coordinated nucleophilic water) and 25 °C, entitling this Fe 3+ copolymer an acid phosphodiester catalyst. This catalyst also shows significant selectivity toward BNPP hydrolysis relative to the hydrolyses of p ‐nitrophenyl phenylphosphonate and p ‐nitrophenylphosphate monoester, with a ratio of 4250:16:1 in terms of their first‐order catalytic proficiencies at pH 8.0 and 25 °C. Fe 3+ complexes of a few pyridine‐containing copolymers show different hydrolytic activities, which points a direction for rational design of catalytic metallopolymers. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)