Study of metal complexation of cardenolides with divalent metal ions by Electrospray Ionization Mass Spectrometry

Cardenolides are natural products with positive inotropic and cytotoxic activity that are able to interact with metals, although the possible role that these interactions may play in their biological activity is not known. Mixtures of the following cardenolides: digoxigenin (DgG), gitoxigenin (GxG),...

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Autores principales:	Siless, G.E., Butler, M., Cabrera, G.M.
Formato:	JOUR
Materias:	2(5H)-Furanone Cardenolides Metal complexation
Acceso en línea:	http://hdl.handle.net/20.500.12110/paper_13873806_v419_n_p44_Siless
Aporte de:	Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) de Universidad de Buenos Aires

id	todo:paper_13873806_v419_n_p44_Siless
record_format	dspace
spelling	todo:paper_13873806_v419_n_p44_Siless2023-10-03T16:12:30Z Study of metal complexation of cardenolides with divalent metal ions by Electrospray Ionization Mass Spectrometry Siless, G.E. Butler, M. Cabrera, G.M. 2(5H)-Furanone Cardenolides Metal complexation Cardenolides are natural products with positive inotropic and cytotoxic activity that are able to interact with metals, although the possible role that these interactions may play in their biological activity is not known. Mixtures of the following cardenolides: digoxigenin (DgG), gitoxigenin (GxG), digitoxigenin (DxG), uzarigenin (UzG) and a butenolide, 2(5H)-furanone (Fur), with different metal cations, namely Ca2+, Mg2+, Cu2+, Co2+ and Zn2+,were studied by Electrospray Ionization Mass Spectrometry in a Quadrupole-Time of Flight. The relative stability of the most important adducts was studied by threshold collision induced dissociation, E1/2. Computational modeling of the observed complexes with calcium was performed using DFT B3LYP/6-31G+(d,p) level of theory. Complexes of stoichiometry [nM+Me]2+, with n = 4 to 6 ligands and Me a metal cation, were observed for all studied compounds. The adducts [4M+Me]2+ corresponded to the most intense peaks in most of the mass spectra and showed the highest E1/2. GxG showed a higher tendency to form complexes with low coordination numbers. Calculations showed that the carbonyl oxygen of the butenolide moiety is the most important site of coordination and allowed the proposal of different binding modes to explain the differences observed in the GxG MS spectra. A direct relationship was observed between experimental and computational data, which allowed to predict the MS behavior of these or similar compounds. The analysis can be extrapolated to other compounds with a furanone ring, and used as an analytical tool to characterize furanone compounds, or for the differentiation of DgG and GxG. © 2017 Elsevier B.V. Fil:Siless, G.E. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. Fil:Butler, M. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. Fil:Cabrera, G.M. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. JOUR info:eu-repo/semantics/openAccess http://creativecommons.org/licenses/by/2.5/ar http://hdl.handle.net/20.500.12110/paper_13873806_v419_n_p44_Siless
institution	Universidad de Buenos Aires
institution_str	I-28
repository_str	R-134
collection	Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA)
topic	2(5H)-Furanone Cardenolides Metal complexation
spellingShingle	2(5H)-Furanone Cardenolides Metal complexation Siless, G.E. Butler, M. Cabrera, G.M. Study of metal complexation of cardenolides with divalent metal ions by Electrospray Ionization Mass Spectrometry
topic_facet	2(5H)-Furanone Cardenolides Metal complexation
description	Cardenolides are natural products with positive inotropic and cytotoxic activity that are able to interact with metals, although the possible role that these interactions may play in their biological activity is not known. Mixtures of the following cardenolides: digoxigenin (DgG), gitoxigenin (GxG), digitoxigenin (DxG), uzarigenin (UzG) and a butenolide, 2(5H)-furanone (Fur), with different metal cations, namely Ca2+, Mg2+, Cu2+, Co2+ and Zn2+,were studied by Electrospray Ionization Mass Spectrometry in a Quadrupole-Time of Flight. The relative stability of the most important adducts was studied by threshold collision induced dissociation, E1/2. Computational modeling of the observed complexes with calcium was performed using DFT B3LYP/6-31G+(d,p) level of theory. Complexes of stoichiometry [nM+Me]2+, with n = 4 to 6 ligands and Me a metal cation, were observed for all studied compounds. The adducts [4M+Me]2+ corresponded to the most intense peaks in most of the mass spectra and showed the highest E1/2. GxG showed a higher tendency to form complexes with low coordination numbers. Calculations showed that the carbonyl oxygen of the butenolide moiety is the most important site of coordination and allowed the proposal of different binding modes to explain the differences observed in the GxG MS spectra. A direct relationship was observed between experimental and computational data, which allowed to predict the MS behavior of these or similar compounds. The analysis can be extrapolated to other compounds with a furanone ring, and used as an analytical tool to characterize furanone compounds, or for the differentiation of DgG and GxG. © 2017 Elsevier B.V.
format	JOUR
author	Siless, G.E. Butler, M. Cabrera, G.M.
author_facet	Siless, G.E. Butler, M. Cabrera, G.M.
author_sort	Siless, G.E.
title	Study of metal complexation of cardenolides with divalent metal ions by Electrospray Ionization Mass Spectrometry
title_short	Study of metal complexation of cardenolides with divalent metal ions by Electrospray Ionization Mass Spectrometry
title_full	Study of metal complexation of cardenolides with divalent metal ions by Electrospray Ionization Mass Spectrometry
title_fullStr	Study of metal complexation of cardenolides with divalent metal ions by Electrospray Ionization Mass Spectrometry
title_full_unstemmed	Study of metal complexation of cardenolides with divalent metal ions by Electrospray Ionization Mass Spectrometry
title_sort	study of metal complexation of cardenolides with divalent metal ions by electrospray ionization mass spectrometry
url	http://hdl.handle.net/20.500.12110/paper_13873806_v419_n_p44_Siless
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Study of metal complexation of cardenolides with divalent metal ions by Electrospray Ionization Mass Spectrometry

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