Tracking isotopically labeled oxidants using boronate-based redox probes

Ríos, Natalia - Radi, Rafael - Kalyanaraman, Balaraman - Zielonka, Jacek

Resumen:

Reactive oxygen and nitrogen species have been implicated in many biological processes and diseases, including immune responses, cardiovascular dysfunction, neurodegeneration, and cancer. These chemical species are short-lived in biological settings, and detecting them in these conditions and diseases requires the use of molecular probes that form stable, easily detectable, products. The chemical mechanisms and limitations of many of the currently used probes are not well-understood, hampering their effective applications. Boronates have emerged as a class of probes for the detection of nucleophilic two-electron oxidants. Here, we report the results of an oxygen-18-labeling MS study to identify the origin of oxygen atoms in the oxidation products of phenylboronate targeted to mitochondria. We demonstrate that boronate oxidation by hydrogen peroxide, peroxymonocarbonate, hypochlorite, or peroxynitrite involves the incorporation of oxygen atoms from these oxidants. We therefore conclude that boronates can be used as probes to track isotopically labeled oxidants. This suggests that the detection of specific products formed from these redox probes could enable precise identification of oxidants formed in biological systems. We discuss the implications of these results for understanding the mechanism of conversion of the boronate-based redox probes to oxidant-specific products.

Detalles Bibliográficos
2020
Hydrogen peroxide
Hypochlorous acid
Isotope tracing
Isotopic tracer
Mass spectrometry (MS)
Oxygen radicals; oxygen-18
Peroxymonocarbonate
Peroxynitrite
Reaction mechanism
Reactive nitrogen species (RNS)
Reactive oxygen species (ROS)
Redox probes
Superoxide ion
Superoxide radical anion
ÁCIDOS BORÓNICOS
METABOLISMO
ENCÉFALO
MARCAJE ISOTÓPICO
SONDAS MOLECULARES
ISÓTOPOS DE OXÍGENO
OXIDANTES
Inglés
Universidad de la República
COLIBRI
https://hdl.handle.net/20.500.12008/55805
Acceso abierto
Licencia Creative Commons Atribución (CC - By 4.0)
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author Ríos, Natalia
author2 Radi, Rafael
Kalyanaraman, Balaraman
Zielonka, Jacek
author2_role author
author
author
author_facet Ríos, Natalia
Radi, Rafael
Kalyanaraman, Balaraman
Zielonka, Jacek
author_role author
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http://localhost:8080/xmlui/bitstream/20.500.12008/55805/1/Tracking+isotopically+labeled+oxidants+using+boronate+based+redox+probes.pdf
collection COLIBRI
dc.contributor.filiacion.none.fl_str_mv Ríos Natalia, Universidad de la República (Uruguay). Facultad de Medicina. Departamento de Bioquímica y Centro de Investigaciones Biomédicas
Radi Rafael, Universidad de la República (Uruguay). Facultad de Medicina. Departamento de Bioquímica y Centro de Investigaciones Biomédicas
Kalyanaraman Balaraman, Medical College of Wisconsin (E.E.U.U.). Department of Biophysics
Zielonka Jacek, Medical College of Wisconsin (E.E.U.U.). Department of Biophysics
dc.creator.none.fl_str_mv Ríos, Natalia
Radi, Rafael
Kalyanaraman, Balaraman
Zielonka, Jacek
dc.date.accessioned.none.fl_str_mv 2026-06-30T14:45:43Z
dc.date.available.none.fl_str_mv 2026-06-30T14:45:43Z
dc.date.issued.none.fl_str_mv 2020
dc.description.abstract.none.fl_txt_mv Reactive oxygen and nitrogen species have been implicated in many biological processes and diseases, including immune responses, cardiovascular dysfunction, neurodegeneration, and cancer. These chemical species are short-lived in biological settings, and detecting them in these conditions and diseases requires the use of molecular probes that form stable, easily detectable, products. The chemical mechanisms and limitations of many of the currently used probes are not well-understood, hampering their effective applications. Boronates have emerged as a class of probes for the detection of nucleophilic two-electron oxidants. Here, we report the results of an oxygen-18-labeling MS study to identify the origin of oxygen atoms in the oxidation products of phenylboronate targeted to mitochondria. We demonstrate that boronate oxidation by hydrogen peroxide, peroxymonocarbonate, hypochlorite, or peroxynitrite involves the incorporation of oxygen atoms from these oxidants. We therefore conclude that boronates can be used as probes to track isotopically labeled oxidants. This suggests that the detection of specific products formed from these redox probes could enable precise identification of oxidants formed in biological systems. We discuss the implications of these results for understanding the mechanism of conversion of the boronate-based redox probes to oxidant-specific products.
dc.format.extent.es.fl_str_mv 12 p.
dc.format.mimetype.es.fl_str_mv application/pdf
dc.identifier.citation.es.fl_str_mv Ríos N, Radi R, Kalyanaraman B y otros. Tracking isotopically labeled oxidants using boronate-based redox probes. Journal of Biological Chemistry [en línea]. 2020;295(19):6665-6676
dc.identifier.doi.none.fl_str_mv 10.1074/jbc.RA120.013402
dc.identifier.eissn.none.fl_str_mv 1083-351X
dc.identifier.uri.none.fl_str_mv https://hdl.handle.net/20.500.12008/55805
dc.language.iso.none.fl_str_mv en
eng
dc.publisher.es.fl_str_mv American Society for Biochemistry and Molecular Biology
dc.relation.none.fl_str_mv Journal of Biological Chemistry. 2020;295(19):6665-6676
dc.rights.license.none.fl_str_mv Licencia Creative Commons Atribución (CC - By 4.0)
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
dc.source.none.fl_str_mv reponame:COLIBRI
instname:Universidad de la República
instacron:Universidad de la República
dc.subject.es.fl_str_mv Hydrogen peroxide
Hypochlorous acid
Isotope tracing
Isotopic tracer
Mass spectrometry (MS)
Oxygen radicals; oxygen-18
Peroxymonocarbonate
Peroxynitrite
Reaction mechanism
Reactive nitrogen species (RNS)
Reactive oxygen species (ROS)
Redox probes
Superoxide ion
Superoxide radical anion
dc.subject.other.es.fl_str_mv ÁCIDOS BORÓNICOS
METABOLISMO
ENCÉFALO
MARCAJE ISOTÓPICO
SONDAS MOLECULARES
ISÓTOPOS DE OXÍGENO
OXIDANTES
dc.title.none.fl_str_mv Tracking isotopically labeled oxidants using boronate-based redox probes
dc.type.es.fl_str_mv Artículo
dc.type.none.fl_str_mv info:eu-repo/semantics/article
dc.type.version.none.fl_str_mv info:eu-repo/semantics/publishedVersion
description Reactive oxygen and nitrogen species have been implicated in many biological processes and diseases, including immune responses, cardiovascular dysfunction, neurodegeneration, and cancer. These chemical species are short-lived in biological settings, and detecting them in these conditions and diseases requires the use of molecular probes that form stable, easily detectable, products. The chemical mechanisms and limitations of many of the currently used probes are not well-understood, hampering their effective applications. Boronates have emerged as a class of probes for the detection of nucleophilic two-electron oxidants. Here, we report the results of an oxygen-18-labeling MS study to identify the origin of oxygen atoms in the oxidation products of phenylboronate targeted to mitochondria. We demonstrate that boronate oxidation by hydrogen peroxide, peroxymonocarbonate, hypochlorite, or peroxynitrite involves the incorporation of oxygen atoms from these oxidants. We therefore conclude that boronates can be used as probes to track isotopically labeled oxidants. This suggests that the detection of specific products formed from these redox probes could enable precise identification of oxidants formed in biological systems. We discuss the implications of these results for understanding the mechanism of conversion of the boronate-based redox probes to oxidant-specific products.
eu_rights_str_mv openAccess
format article
id COLIBRI_aac7b7e95763eb4f26ddfd9cf2aad3b6
identifier_str_mv Ríos N, Radi R, Kalyanaraman B y otros. Tracking isotopically labeled oxidants using boronate-based redox probes. Journal of Biological Chemistry [en línea]. 2020;295(19):6665-6676
10.1074/jbc.RA120.013402
1083-351X
instacron_str Universidad de la República
institution Universidad de la República
instname_str Universidad de la República
language eng
language_invalid_str_mv en
network_acronym_str COLIBRI
network_name_str COLIBRI
oai_identifier_str oai:colibri.udelar.edu.uy:20.500.12008/55805
publishDate 2020
reponame_str COLIBRI
repository.mail.fl_str_mv karina.camps@seciu.edu.uy
repository.name.fl_str_mv COLIBRI - Universidad de la República
repository_id_str 4771
rights_invalid_str_mv Licencia Creative Commons Atribución (CC - By 4.0)
spelling Ríos Natalia, Universidad de la República (Uruguay). Facultad de Medicina. Departamento de Bioquímica y Centro de Investigaciones BiomédicasRadi Rafael, Universidad de la República (Uruguay). Facultad de Medicina. Departamento de Bioquímica y Centro de Investigaciones BiomédicasKalyanaraman Balaraman, Medical College of Wisconsin (E.E.U.U.). Department of BiophysicsZielonka Jacek, Medical College of Wisconsin (E.E.U.U.). Department of Biophysics2026-06-30T14:45:43Z2026-06-30T14:45:43Z2020Ríos N, Radi R, Kalyanaraman B y otros. Tracking isotopically labeled oxidants using boronate-based redox probes. Journal of Biological Chemistry [en línea]. 2020;295(19):6665-6676https://hdl.handle.net/20.500.12008/5580510.1074/jbc.RA120.0134021083-351XReactive oxygen and nitrogen species have been implicated in many biological processes and diseases, including immune responses, cardiovascular dysfunction, neurodegeneration, and cancer. These chemical species are short-lived in biological settings, and detecting them in these conditions and diseases requires the use of molecular probes that form stable, easily detectable, products. The chemical mechanisms and limitations of many of the currently used probes are not well-understood, hampering their effective applications. Boronates have emerged as a class of probes for the detection of nucleophilic two-electron oxidants. Here, we report the results of an oxygen-18-labeling MS study to identify the origin of oxygen atoms in the oxidation products of phenylboronate targeted to mitochondria. We demonstrate that boronate oxidation by hydrogen peroxide, peroxymonocarbonate, hypochlorite, or peroxynitrite involves the incorporation of oxygen atoms from these oxidants. We therefore conclude that boronates can be used as probes to track isotopically labeled oxidants. This suggests that the detection of specific products formed from these redox probes could enable precise identification of oxidants formed in biological systems. We discuss the implications of these results for understanding the mechanism of conversion of the boronate-based redox probes to oxidant-specific products.Submitted by Almiñana María Cecilia (marialminana@gmail.com) on 2026-06-29T21:46:00Z No. of bitstreams: 2 license_rdf: 25630 bytes, checksum: e7132498e7c1fe99f7096667baa99b25 (MD5) Tracking isotopically labeled oxidants using boronate based redox probes.pdf: 8006551 bytes, checksum: 950ef3eda533f6d36374a77261a12b7d (MD5)Approved for entry into archive by Almiñana María Cecilia (marialminana@gmail.com) on 2026-06-30T14:08:08Z (GMT) No. of bitstreams: 2 license_rdf: 25630 bytes, checksum: e7132498e7c1fe99f7096667baa99b25 (MD5) Tracking isotopically labeled oxidants using boronate based redox probes.pdf: 8006551 bytes, checksum: 950ef3eda533f6d36374a77261a12b7d (MD5)Made available in DSpace by Luna Fabiana (fabiana.luna@seciu.edu.uy) on 2026-06-30T14:45:43Z (GMT). No. of bitstreams: 2 license_rdf: 25630 bytes, checksum: e7132498e7c1fe99f7096667baa99b25 (MD5) Tracking isotopically labeled oxidants using boronate based redox probes.pdf: 8006551 bytes, checksum: 950ef3eda533f6d36374a77261a12b7d (MD5) Previous issue date: 202012 p.application/pdfenengAmerican Society for Biochemistry and Molecular BiologyJournal of Biological Chemistry. 2020;295(19):6665-6676Las obras depositadas en el Repositorio se rigen por la Ordenanza de los Derechos de la Propiedad Intelectual de la Universidad de la República.(Res. Nº 91 de C.D.C. de 8/III/1994 – D.O. 7/IV/1994) y por la Ordenanza del Repositorio Abierto de la Universidad de la República (Res. 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charset=utf-844http://localhost:8080/xmlui/bitstream/20.500.12008/55805/2/license_urla0ebbeafb9d2ec7cbb19d7137ebc392cMD52license_textlicense_texttext/html; charset=utf-831351http://localhost:8080/xmlui/bitstream/20.500.12008/55805/3/license_textc2be1a593bc16fa3ffa80ce838a200caMD53license_rdflicense_rdfapplication/rdf+xml; charset=utf-825630http://localhost:8080/xmlui/bitstream/20.500.12008/55805/4/license_rdfe7132498e7c1fe99f7096667baa99b25MD54ORIGINALTracking isotopically labeled oxidants using boronate based redox probes.pdfTracking isotopically labeled oxidants using boronate based redox probes.pdfapplication/pdf8006551http://localhost:8080/xmlui/bitstream/20.500.12008/55805/1/Tracking+isotopically+labeled+oxidants+using+boronate+based+redox+probes.pdf950ef3eda533f6d36374a77261a12b7dMD5120.500.12008/558052026-06-30 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- Universidad de la Repúblicafalse
spellingShingle Tracking isotopically labeled oxidants using boronate-based redox probes
Ríos, Natalia
Hydrogen peroxide
Hypochlorous acid
Isotope tracing
Isotopic tracer
Mass spectrometry (MS)
Oxygen radicals; oxygen-18
Peroxymonocarbonate
Peroxynitrite
Reaction mechanism
Reactive nitrogen species (RNS)
Reactive oxygen species (ROS)
Redox probes
Superoxide ion
Superoxide radical anion
ÁCIDOS BORÓNICOS
METABOLISMO
ENCÉFALO
MARCAJE ISOTÓPICO
SONDAS MOLECULARES
ISÓTOPOS DE OXÍGENO
OXIDANTES
status_str publishedVersion
title Tracking isotopically labeled oxidants using boronate-based redox probes
title_full Tracking isotopically labeled oxidants using boronate-based redox probes
title_fullStr Tracking isotopically labeled oxidants using boronate-based redox probes
title_full_unstemmed Tracking isotopically labeled oxidants using boronate-based redox probes
title_short Tracking isotopically labeled oxidants using boronate-based redox probes
title_sort Tracking isotopically labeled oxidants using boronate-based redox probes
topic Hydrogen peroxide
Hypochlorous acid
Isotope tracing
Isotopic tracer
Mass spectrometry (MS)
Oxygen radicals; oxygen-18
Peroxymonocarbonate
Peroxynitrite
Reaction mechanism
Reactive nitrogen species (RNS)
Reactive oxygen species (ROS)
Redox probes
Superoxide ion
Superoxide radical anion
ÁCIDOS BORÓNICOS
METABOLISMO
ENCÉFALO
MARCAJE ISOTÓPICO
SONDAS MOLECULARES
ISÓTOPOS DE OXÍGENO
OXIDANTES
url https://hdl.handle.net/20.500.12008/55805