Monoesterase activity of a purple acid phosphatase mimic with a cyclam platform
The synthesis and characterization of a novel dinucleating ligand L (L=4,11-dimethyl-1,8-bis2-[N-(di-2-pyridylmethyl)amino]ethylcyclam) and its μ-oxo-bridged diferric complex [(H2L)FeIII2(O)(Cl)4]2+ are reported. This diiron(III) complex is the first example of a truly functional purple acid phospha...
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| Main Authors: | , |
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| Format: | Article (Journal) |
| Language: | English |
| Published: |
10 January 2012
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| In: |
Chemistry - a European journal
Year: 2012, Volume: 18, Issue: 6, Pages: 1700-1710 |
| ISSN: | 1521-3765 |
| DOI: | 10.1002/chem.201100229 |
| Online Access: | Verlag, Volltext: http://dx.doi.org/10.1002/chem.201100229 Verlag, Volltext: https://onlinelibrary.wiley.com/doi/abs/10.1002/chem.201100229 
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| Author Notes: | Peter Comba, Lawrence R. Gahan, Graeme R. Hanson, Valeriu Mereacre, Christopher J. Noble, Annie K. Powell, Ion Prisecaru, Gerhard Schenk and Marta Zajaczkowski‐Fischer |
| Summary: | The synthesis and characterization of a novel dinucleating ligand L (L=4,11-dimethyl-1,8-bis2-[N-(di-2-pyridylmethyl)amino]ethylcyclam) and its μ-oxo-bridged diferric complex [(H2L)FeIII2(O)(Cl)4]2+ are reported. This diiron(III) complex is the first example of a truly functional purple acid phosphatase (PAP) mimic as it accelerates the hydrolysis of the activated phosphomonoester 2,4-dinitrophenyl phosphate (DNPP). The spectroscopic and kinetic data indicate that only substrates that are monodentately bound to one of the two ferric ions can be attacked by a suitable nucleophile. This is, most probably, a terminal iron(III)-bound hydroxide. DFT calculations support this assumption and also highlight the importance of secondary interactions, exerted by the protonated cyclam platform, for the positioning and activation of the iron(III)-bound substrate. Similar effects are postulated in the native enzyme but addressed in PAP mimics for the first time. |
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| Item Description: | Gesehen am 22.08.2018 |
| Physical Description: | Online Resource |
| ISSN: | 1521-3765 |
| DOI: | 10.1002/chem.201100229 |