Lanznaster, Mauricio, Neves, Ademir, Bortoluzzi, Adailton J., Aires, Veronika V. E., Szpoganicz, Bruno, Terenzi, Hernan, Severino, Patricia C., Fuller, Julie M., Drew, Simon C., Gahan, Lawrence R., Hanson, Graeme R., Riley, Mark J. and Schenk, Gerhard (2005) A New Heterobinuclear FeIIICuII Complex with a Single Terminal FeIII–O(phenolate) Bond. Relevance to Purple Acid Phosphatases and Nucleases. Journal of Biological Inorganic Chemistry, 10 (4). pp. 319-332. ISSN 0949-8257
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Abstract
Abstract
A novel heterobinuclear mixed valence complex [FeIIICuII (BPBPMP)(OAc)2]ClO4, 1, with
the unsymmetrical N5O2 donor ligand 2-bis[{(2-pyridylmethyl)aminomethyl}-6-{(2-
hydroxybenzyl)(2-pyridylmethyl)}aminomethyl]-4-methylphenol (H2BPBPMP) has been
synthesized and characterized. A combination of data from mass spectrometry, potentiometric
titrations, X-ray absorption and electron paramagnetic resonance spectroscopy, as well as
kinetics measurements indicates that in ethanol/water solutions an [FeIII–(μ)OH–CuIIOH2]+
species is generated which is the likely catalyst for 2,4-bis(dinitrophenyl)phosphate and DNA
hydrolysis. Insofar as the data are consistent with the presence of an FeIII-bound hydroxide
acting as a nucleophile during catalysis, 1 presents a suitable mimic for the hydrolytic enzyme
purple acid phosphatase. Notably, 1 is significantly more reactive than its isostructural
homologues with different metal composition (FeIIIMII, where MII is ZnII, MnII, NiII, or FeII).
Of particular interest is the observation that cleavage of double-stranded plasmid DNA occurs
even at very low concentrations of 1 (2.5 μM), under physiological conditions (optimum pH
of 7.0), with a rate enhancement of 2.7×107 over the uncatalyzed reaction. Thus, 1 is one of
the most effective model complexes to date, mimicking the function of nucleases.
Item Type: | Article |
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Keywords: | heterobinuclear FeIIICuII complex; purple acid phosphatase; phosphate diester hydrolysis; DNA cleavage; EPR; XAS; |
Academic Unit: | Faculty of Science and Engineering > Chemistry |
Item ID: | 3696 |
Depositing User: | Gary Schenk |
Date Deposited: | 29 May 2012 11:45 |
Journal or Publication Title: | Journal of Biological Inorganic Chemistry |
Publisher: | Springer Verlag |
Refereed: | Yes |
Related URLs: | |
URI: | https://mu.eprints-hosting.org/id/eprint/3696 |
Use Licence: | This item is available under a Creative Commons Attribution Non Commercial Share Alike Licence (CC BY-NC-SA). Details of this licence are available here |
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