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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...

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Autores principales: Draksharapu, Apparao, Angelone, Davide, Quesne, Matthew G., Padamati, Sandeep K., Gómez, Laura, Hage, Ronald, Costas, Miquel, Browne, Wesley R., de Visser, Sam P.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: WILEY‐VCH Verlag 2015
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.
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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
title_full Identification and Spectroscopic Characterization of Nonheme Iron(III) Hypochlorite Intermediates
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
title_short Identification and Spectroscopic Characterization of Nonheme Iron(III) Hypochlorite Intermediates
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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