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Identification and Spectroscopic Characterization of Nonheme Iron(III) Hypochlorite Intermediates
Fe(III)–hypohalite complexes have been implicated in a wide range of important enzyme‐catalyzed halogenation reactions including the biosynthesis of natural products and antibiotics and post‐translational modification of proteins. The absence of spectroscopic data on such species precludes their ide...
Autores principales: | , , , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
WILEY‐VCH Verlag
2015
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4955228/ https://www.ncbi.nlm.nih.gov/pubmed/27478260 http://dx.doi.org/10.1002/ange.201411995 |
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author | Draksharapu, Apparao Angelone, Davide Quesne, Matthew G. Padamati, Sandeep K. Gómez, Laura Hage, Ronald Costas, Miquel Browne, Wesley R. de Visser, Sam P. |
author_facet | Draksharapu, Apparao Angelone, Davide Quesne, Matthew G. Padamati, Sandeep K. Gómez, Laura Hage, Ronald Costas, Miquel Browne, Wesley R. de Visser, Sam P. |
author_sort | Draksharapu, Apparao |
collection | PubMed |
description | Fe(III)–hypohalite complexes have been implicated in a wide range of important enzyme‐catalyzed halogenation reactions including the biosynthesis of natural products and antibiotics and post‐translational modification of proteins. The absence of spectroscopic data on such species precludes their identification. Herein, we report the generation and spectroscopic characterization of nonheme Fe(III)–hypohalite intermediates of possible relevance to iron halogenases. We show that Fe(III)‐OCl polypyridylamine complexes can be sufficiently stable at room temperature to be characterized by UV/Vis absorption, resonance Raman and EPR spectroscopies, and cryo‐ESIMS. DFT methods rationalize the pathways to the formation of the Fe(III)‐OCl, and ultimately Fe(IV)=O, species and provide indirect evidence for a short‐lived Fe(II)‐OCl intermediate. The species observed and the pathways involved offer insight into and, importantly, a spectroscopic database for the investigation of iron halogenases. |
format | Online Article Text |
id | pubmed-4955228 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2015 |
publisher | WILEY‐VCH Verlag |
record_format | MEDLINE/PubMed |
spelling | pubmed-49552282016-07-29 Identification and Spectroscopic Characterization of Nonheme Iron(III) Hypochlorite Intermediates Draksharapu, Apparao Angelone, Davide Quesne, Matthew G. Padamati, Sandeep K. Gómez, Laura Hage, Ronald Costas, Miquel Browne, Wesley R. de Visser, Sam P. Angew Chem Weinheim Bergstr Ger Zuschriften Fe(III)–hypohalite complexes have been implicated in a wide range of important enzyme‐catalyzed halogenation reactions including the biosynthesis of natural products and antibiotics and post‐translational modification of proteins. The absence of spectroscopic data on such species precludes their identification. Herein, we report the generation and spectroscopic characterization of nonheme Fe(III)–hypohalite intermediates of possible relevance to iron halogenases. We show that Fe(III)‐OCl polypyridylamine complexes can be sufficiently stable at room temperature to be characterized by UV/Vis absorption, resonance Raman and EPR spectroscopies, and cryo‐ESIMS. DFT methods rationalize the pathways to the formation of the Fe(III)‐OCl, and ultimately Fe(IV)=O, species and provide indirect evidence for a short‐lived Fe(II)‐OCl intermediate. The species observed and the pathways involved offer insight into and, importantly, a spectroscopic database for the investigation of iron halogenases. WILEY‐VCH Verlag 2015-03-27 2015-02-06 /pmc/articles/PMC4955228/ /pubmed/27478260 http://dx.doi.org/10.1002/ange.201411995 Text en © 2015 The Authors. Published by Wiley‐VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited. Open access. |
spellingShingle | Zuschriften Draksharapu, Apparao Angelone, Davide Quesne, Matthew G. Padamati, Sandeep K. Gómez, Laura Hage, Ronald Costas, Miquel Browne, Wesley R. de Visser, Sam P. Identification and Spectroscopic Characterization of Nonheme Iron(III) Hypochlorite Intermediates |
title | Identification and Spectroscopic Characterization of Nonheme Iron(III) Hypochlorite Intermediates
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title_full | Identification and Spectroscopic Characterization of Nonheme Iron(III) Hypochlorite Intermediates
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title_fullStr | Identification and Spectroscopic Characterization of Nonheme Iron(III) Hypochlorite Intermediates
|
title_full_unstemmed | Identification and Spectroscopic Characterization of Nonheme Iron(III) Hypochlorite Intermediates
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title_short | Identification and Spectroscopic Characterization of Nonheme Iron(III) Hypochlorite Intermediates
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title_sort | identification and spectroscopic characterization of nonheme iron(iii) hypochlorite intermediates |
topic | Zuschriften |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4955228/ https://www.ncbi.nlm.nih.gov/pubmed/27478260 http://dx.doi.org/10.1002/ange.201411995 |
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