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A new heterobinuclear FeIIICuII complex with a single terminal FeIII–O(phenolate) bond. Relevance to purple acid phosphatases and nucleases

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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.

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Abbreviations

2,4-BDNPP:

2,4-Bis(dinitrophenol)phosphate

n-Bu4NPF6:

Tetrabutylammonium hexafluorophosphate

HBPMP:

2,6-Bis[(bis(2-pyridylmethyl)amino)methyl]-4-methylphenol

DMSO:

Dimethylsulfoxide

EPR:

Electron paramagnetic resonance

EXAFS:

Extended X-ray absorption fine structure

H2BPBPMP:

2-Bis[{(2-pyridylmethyl)aminomethyl}-6-{(2-hydroxylbenzyl)(2-pyridylmethyl)}aminomethyl]-4-methylphenol

MES:

2-Morpholinoethanesulfonic acid

MOPS:

3-(N-Morpholino)propanesulfonic acid

PAP:

Purple acid phosphatase

XAS:

X-ray absorption spectroscopy

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Acknowledgements

Financial support was received from CNPq, PRONEX (Brazil). M.L. and P.C.S. are grateful to CNPq (Brazil) for a scholarship. XAS data collection was performed at the Australian National Beamline Facility with support from the Australian Synchrotron Research Program, which is funded by the Commonwealth of Australia under the Major National Research Facilities Program. We would also like to thank G. Foran and J. Hester for their help in data collection. We are grateful to the Australian Research Council for funding this research and for grants to purchase the EPR facilities.

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Authors and Affiliations

  1. LABINC Laboratório de Bioinorgânica e Cristalografia, Departamento de Química, Universidade Federal de Santa Catarina, Campus Trindade, 88040-900, Florianópolis, SC, Brazil

    Mauricio Lanznaster, Ademir Neves, Adailton J. Bortoluzzi, Veronika V. E. Aires & Bruno Szpoganicz

  2. Laboratório de Expressão Gênica, Departamento de Bioquímica, Universidade Federal de Santa Catarina, Campus Trindade, 88040-900, Florianópolis, SC, Brazil

    Hernán Terenzi & Patricia Cardoso Severino

  3. Centre for Magnetic Resonance, The University of Queensland, St. Lucia, QLD, 4072, Australia

    Simon C. Drew & Graeme R. Hanson

  4. Department of Chemistry, School of Molecular and Microbial Sciences, The University of Queensland, St. Lucia, QLD, 4072, Australia

    Julie M. Fuller, Lawrence R. Gahan, Mark J. Riley & Gerhard Schenk

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  1. Mauricio Lanznaster
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Correspondence to Ademir Neves.

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Lanznaster, M., Neves, A., Bortoluzzi, A.J. et al. A new heterobinuclear FeIIICuII complex with a single terminal FeIII–O(phenolate) bond. Relevance to purple acid phosphatases and nucleases. J Biol Inorg Chem 10, 319–332 (2005). https://doi.org/10.1007/s00775-005-0635-7

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