A mass spectrometry and DFT study of pyrithione complexes with transition metals in the gas phase

2-Mercaptopyridine N-oxide (pyrithione, PTOH) along with several transition metal ions forms coordination compounds displaying notable biological activities. Gas-phase complexes formed between pyrithione and manganese (II), cobalt (II), nickel (II), copper (II), and zinc (II) were investigated by in...

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Publicado:	2017
Materias:	density functional theory electrospray ionization mass spectrometry metal complexes pyrithione redox-active ligand Cobalt compounds Complexation Density functional theory Drug products Electrospray ionization Gases Ionization of gases Ligands Mass spectrometers Mass spectrometry Metal complexes Metal ions Positive ions Redox reactions Spectrometry Transition metal compounds Transition metals Zinc compounds Coordination compounds Doubly charged ions Electrospray ionization mass spectrometry Fragmentation pathways Metal-ion complexes Quadrupole-time-of-flight mass spectrometer Redox-active ligand Metals cobalt complex copper complex manganese metal complex nickel complex pyridine transition element zinc complex Article chemical structure collisionally activated dissociation comparative study controlled study electrochemical analysis electrospray mass spectrometry gas mass spectrometer oxidation oxidation reduction state priority journal proton transport quadrupole mass spectrometry scientific literature time of flight mass spectrometry
Acceso en línea:	https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_10765174_v52_n11_p728_Butler http://hdl.handle.net/20.500.12110/paper_10765174_v52_n11_p728_Butler
Aporte de:	Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) de Universidad de Buenos Aires

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spelling	paper:paper_10765174_v52_n11_p728_Butler2023-06-08T16:05:24Z A mass spectrometry and DFT study of pyrithione complexes with transition metals in the gas phase density functional theory electrospray ionization mass spectrometry metal complexes pyrithione redox-active ligand Cobalt compounds Complexation Density functional theory Drug products Electrospray ionization Gases Ionization of gases Ligands Mass spectrometers Mass spectrometry Metal complexes Metal ions Positive ions Redox reactions Spectrometry Transition metal compounds Transition metals Zinc compounds Coordination compounds Doubly charged ions Electrospray ionization mass spectrometry Fragmentation pathways Metal-ion complexes pyrithione Quadrupole-time-of-flight mass spectrometer Redox-active ligand Metals cobalt complex copper complex manganese metal complex nickel complex pyridine pyrithione transition element zinc complex Article chemical structure collisionally activated dissociation comparative study controlled study density functional theory electrochemical analysis electrospray mass spectrometry gas mass spectrometer oxidation oxidation reduction state priority journal proton transport quadrupole mass spectrometry scientific literature time of flight mass spectrometry 2-Mercaptopyridine N-oxide (pyrithione, PTOH) along with several transition metal ions forms coordination compounds displaying notable biological activities. Gas-phase complexes formed between pyrithione and manganese (II), cobalt (II), nickel (II), copper (II), and zinc (II) were investigated by infusion in the electrospray source of a quadrupole-time of flight mass spectrometer. Remarkably, positive ion mode spectra displayed the singly charged metal adduct ion [C10H8MN2O2S2]2+ ([M(PTO)2]+• or [M(DPTO)]+•), where DPTO is dipyrithione, 2,2′-dithiobis(pyridine N-oxide), among the most abundant peaks, implying a change in the oxidation state of whether the metal ion or the ligands. In addition, doubly charged ions were recognized as metal adduct ions containing DPTO ligands, [M(DPTO)n]2+. Generation of [M(PTO)2]+• / [M(DPTO)]+• could be traced by CID of [M(DPTO)2]2+, by observation of the sequential losses of a charged (PTO+) and a radical (PTO•) deprotonated pyrithione ligand. The fragmentation pathways of [M(PTO)2]+• / [M(DPTO)]+• were compared among the different metal ions, and some common features were noticed. Density functional theory (DFT) calculations were employed to study the structures of the observed adduct ions, and especially, to decide in the adduct ion [M(PTO)2]+• / [M(DPTO)]+• whether the ligands are 2 deprotonated pyrithiones or a single dipyrithione as well as the oxidation state of the metal ion in the complex. Characterization of gas-phase pyrithione metal ion complexes becomes important, especially taking into account the presence of a redox-active ligand in the complexes, because redox state changes that produce new species can have a marked effect on the overall toxicological/biological response elicited by the metal system. Copyright © 2017 John Wiley & Sons, Ltd. 2017 https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_10765174_v52_n11_p728_Butler http://hdl.handle.net/20.500.12110/paper_10765174_v52_n11_p728_Butler
institution	Universidad de Buenos Aires
institution_str	I-28
repository_str	R-134
collection	Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA)
topic	density functional theory electrospray ionization mass spectrometry metal complexes pyrithione redox-active ligand Cobalt compounds Complexation Density functional theory Drug products Electrospray ionization Gases Ionization of gases Ligands Mass spectrometers Mass spectrometry Metal complexes Metal ions Positive ions Redox reactions Spectrometry Transition metal compounds Transition metals Zinc compounds Coordination compounds Doubly charged ions Electrospray ionization mass spectrometry Fragmentation pathways Metal-ion complexes pyrithione Quadrupole-time-of-flight mass spectrometer Redox-active ligand Metals cobalt complex copper complex manganese metal complex nickel complex pyridine pyrithione transition element zinc complex Article chemical structure collisionally activated dissociation comparative study controlled study density functional theory electrochemical analysis electrospray mass spectrometry gas mass spectrometer oxidation oxidation reduction state priority journal proton transport quadrupole mass spectrometry scientific literature time of flight mass spectrometry
spellingShingle	density functional theory electrospray ionization mass spectrometry metal complexes pyrithione redox-active ligand Cobalt compounds Complexation Density functional theory Drug products Electrospray ionization Gases Ionization of gases Ligands Mass spectrometers Mass spectrometry Metal complexes Metal ions Positive ions Redox reactions Spectrometry Transition metal compounds Transition metals Zinc compounds Coordination compounds Doubly charged ions Electrospray ionization mass spectrometry Fragmentation pathways Metal-ion complexes pyrithione Quadrupole-time-of-flight mass spectrometer Redox-active ligand Metals cobalt complex copper complex manganese metal complex nickel complex pyridine pyrithione transition element zinc complex Article chemical structure collisionally activated dissociation comparative study controlled study density functional theory electrochemical analysis electrospray mass spectrometry gas mass spectrometer oxidation oxidation reduction state priority journal proton transport quadrupole mass spectrometry scientific literature time of flight mass spectrometry A mass spectrometry and DFT study of pyrithione complexes with transition metals in the gas phase
topic_facet	density functional theory electrospray ionization mass spectrometry metal complexes pyrithione redox-active ligand Cobalt compounds Complexation Density functional theory Drug products Electrospray ionization Gases Ionization of gases Ligands Mass spectrometers Mass spectrometry Metal complexes Metal ions Positive ions Redox reactions Spectrometry Transition metal compounds Transition metals Zinc compounds Coordination compounds Doubly charged ions Electrospray ionization mass spectrometry Fragmentation pathways Metal-ion complexes pyrithione Quadrupole-time-of-flight mass spectrometer Redox-active ligand Metals cobalt complex copper complex manganese metal complex nickel complex pyridine pyrithione transition element zinc complex Article chemical structure collisionally activated dissociation comparative study controlled study density functional theory electrochemical analysis electrospray mass spectrometry gas mass spectrometer oxidation oxidation reduction state priority journal proton transport quadrupole mass spectrometry scientific literature time of flight mass spectrometry
description	2-Mercaptopyridine N-oxide (pyrithione, PTOH) along with several transition metal ions forms coordination compounds displaying notable biological activities. Gas-phase complexes formed between pyrithione and manganese (II), cobalt (II), nickel (II), copper (II), and zinc (II) were investigated by infusion in the electrospray source of a quadrupole-time of flight mass spectrometer. Remarkably, positive ion mode spectra displayed the singly charged metal adduct ion [C10H8MN2O2S2]2+ ([M(PTO)2]+• or [M(DPTO)]+•), where DPTO is dipyrithione, 2,2′-dithiobis(pyridine N-oxide), among the most abundant peaks, implying a change in the oxidation state of whether the metal ion or the ligands. In addition, doubly charged ions were recognized as metal adduct ions containing DPTO ligands, [M(DPTO)n]2+. Generation of [M(PTO)2]+• / [M(DPTO)]+• could be traced by CID of [M(DPTO)2]2+, by observation of the sequential losses of a charged (PTO+) and a radical (PTO•) deprotonated pyrithione ligand. The fragmentation pathways of [M(PTO)2]+• / [M(DPTO)]+• were compared among the different metal ions, and some common features were noticed. Density functional theory (DFT) calculations were employed to study the structures of the observed adduct ions, and especially, to decide in the adduct ion [M(PTO)2]+• / [M(DPTO)]+• whether the ligands are 2 deprotonated pyrithiones or a single dipyrithione as well as the oxidation state of the metal ion in the complex. Characterization of gas-phase pyrithione metal ion complexes becomes important, especially taking into account the presence of a redox-active ligand in the complexes, because redox state changes that produce new species can have a marked effect on the overall toxicological/biological response elicited by the metal system. Copyright © 2017 John Wiley & Sons, Ltd.
title	A mass spectrometry and DFT study of pyrithione complexes with transition metals in the gas phase
title_short	A mass spectrometry and DFT study of pyrithione complexes with transition metals in the gas phase
title_full	A mass spectrometry and DFT study of pyrithione complexes with transition metals in the gas phase
title_fullStr	A mass spectrometry and DFT study of pyrithione complexes with transition metals in the gas phase
title_full_unstemmed	A mass spectrometry and DFT study of pyrithione complexes with transition metals in the gas phase
title_sort	mass spectrometry and dft study of pyrithione complexes with transition metals in the gas phase
publishDate	2017
url	https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_10765174_v52_n11_p728_Butler http://hdl.handle.net/20.500.12110/paper_10765174_v52_n11_p728_Butler
_version_	1768543668888666112

A mass spectrometry and DFT study of pyrithione complexes with transition metals in the gas phase

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