Transnitrosylation products of the dipeptide cysteinyl-cysteine: An examination by tandem mass spectrometry and density functional theory

The fragmentation pathways of protonated mono-and di-nitrosylated derivatives from the dipeptide Cys-Cys obtained by electrospray were examined. Protonated mononitrosylated dipeptide upon loss of NO formed a radical cation, which in turn shows two fragment ions, one from the loss of HS and the other...

Descripción completa

Guardado en:

Detalles Bibliográficos
Autor principal:	Butler, Matìas
Publicado:	2016
Materias:	cysteine cysteinylcysteine dipeptide chemistry electrospray mass spectrometry tandem mass spectrometry thermodynamics Cysteine Dipeptides Spectrometry, Mass, Electrospray Ionization Tandem Mass Spectrometry Thermodynamics
Acceso en línea:	https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_14639076_v18_n8_p6047_Butler http://hdl.handle.net/20.500.12110/paper_14639076_v18_n8_p6047_Butler
Aporte de:	Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) de Universidad de Buenos Aires

id	paper:paper_14639076_v18_n8_p6047_Butler
record_format	dspace
spelling	paper:paper_14639076_v18_n8_p6047_Butler2023-06-08T16:16:30Z Transnitrosylation products of the dipeptide cysteinyl-cysteine: An examination by tandem mass spectrometry and density functional theory Butler, Matìas cysteine cysteinylcysteine dipeptide chemistry electrospray mass spectrometry tandem mass spectrometry thermodynamics Cysteine Dipeptides Spectrometry, Mass, Electrospray Ionization Tandem Mass Spectrometry Thermodynamics The fragmentation pathways of protonated mono-and di-nitrosylated derivatives from the dipeptide Cys-Cys obtained by electrospray were examined. Protonated mononitrosylated dipeptide upon loss of NO formed a radical cation, which in turn shows two fragment ions, one from the loss of HS and the other from a neutral loss giving a radical cation of formula C2H5NS+. Protonated dinitrosylated dipeptide dissociated by losing both NO molecules, forming a cyclic structure with a vicinal disulfide bridge whose major dissociation channel was the loss of CO. After CO loss, two pathways were observed (loss of NH3 and C2H3NS) which were preceded by proton exchange occurring between one β-carbon and the nitrogen atom. DFT calculations did not show significant differences in the energies involved for the loss of the NO radical from either of the cysteine residues of the protonated di-nitrosylated dipeptide. Upon loss of the first NO radical, the thiyl radical afforded the vicinal disulfide product with a small barrier through radical substitution of the remaining NO moiety. The calculated relative energy barriers for the different channels are in good agreement with experimental observations. Structures of the ions obtained after dissociation are suggested on the basis of the proposed mechanisms. © 2016 the Owner Societies. Fil:Butler, M. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. 2016 https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_14639076_v18_n8_p6047_Butler http://hdl.handle.net/20.500.12110/paper_14639076_v18_n8_p6047_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	cysteine cysteinylcysteine dipeptide chemistry electrospray mass spectrometry tandem mass spectrometry thermodynamics Cysteine Dipeptides Spectrometry, Mass, Electrospray Ionization Tandem Mass Spectrometry Thermodynamics
spellingShingle	cysteine cysteinylcysteine dipeptide chemistry electrospray mass spectrometry tandem mass spectrometry thermodynamics Cysteine Dipeptides Spectrometry, Mass, Electrospray Ionization Tandem Mass Spectrometry Thermodynamics Butler, Matìas Transnitrosylation products of the dipeptide cysteinyl-cysteine: An examination by tandem mass spectrometry and density functional theory
topic_facet	cysteine cysteinylcysteine dipeptide chemistry electrospray mass spectrometry tandem mass spectrometry thermodynamics Cysteine Dipeptides Spectrometry, Mass, Electrospray Ionization Tandem Mass Spectrometry Thermodynamics
description	The fragmentation pathways of protonated mono-and di-nitrosylated derivatives from the dipeptide Cys-Cys obtained by electrospray were examined. Protonated mononitrosylated dipeptide upon loss of NO formed a radical cation, which in turn shows two fragment ions, one from the loss of HS and the other from a neutral loss giving a radical cation of formula C2H5NS+. Protonated dinitrosylated dipeptide dissociated by losing both NO molecules, forming a cyclic structure with a vicinal disulfide bridge whose major dissociation channel was the loss of CO. After CO loss, two pathways were observed (loss of NH3 and C2H3NS) which were preceded by proton exchange occurring between one β-carbon and the nitrogen atom. DFT calculations did not show significant differences in the energies involved for the loss of the NO radical from either of the cysteine residues of the protonated di-nitrosylated dipeptide. Upon loss of the first NO radical, the thiyl radical afforded the vicinal disulfide product with a small barrier through radical substitution of the remaining NO moiety. The calculated relative energy barriers for the different channels are in good agreement with experimental observations. Structures of the ions obtained after dissociation are suggested on the basis of the proposed mechanisms. © 2016 the Owner Societies.
author	Butler, Matìas
author_facet	Butler, Matìas
author_sort	Butler, Matìas
title	Transnitrosylation products of the dipeptide cysteinyl-cysteine: An examination by tandem mass spectrometry and density functional theory
title_short	Transnitrosylation products of the dipeptide cysteinyl-cysteine: An examination by tandem mass spectrometry and density functional theory
title_full	Transnitrosylation products of the dipeptide cysteinyl-cysteine: An examination by tandem mass spectrometry and density functional theory
title_fullStr	Transnitrosylation products of the dipeptide cysteinyl-cysteine: An examination by tandem mass spectrometry and density functional theory
title_full_unstemmed	Transnitrosylation products of the dipeptide cysteinyl-cysteine: An examination by tandem mass spectrometry and density functional theory
title_sort	transnitrosylation products of the dipeptide cysteinyl-cysteine: an examination by tandem mass spectrometry and density functional theory
publishDate	2016
url	https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_14639076_v18_n8_p6047_Butler http://hdl.handle.net/20.500.12110/paper_14639076_v18_n8_p6047_Butler
work_keys_str_mv	AT butlermatias transnitrosylationproductsofthedipeptidecysteinylcysteineanexaminationbytandemmassspectrometryanddensityfunctionaltheory
_version_	1768544242193399808

Transnitrosylation products of the dipeptide cysteinyl-cysteine: An examination by tandem mass spectrometry and density functional theory

Ejemplares similares