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Differentiation between two isomers of hydroxypyridine N-oxide according to the metal cation adducts generated by electrospray ionization (ESI) was investigated for different metal cations, namely Mg (II), Al (III), Ca (II), Sc (III), Fe (III), Co (II), Ni (II), Cu (II), Zn (II), Ga (III), besides the diatomic cation VO(IV). Protonated molecules of the isomeric hydroxypyridine N-oxides as well as the singly/doubly charged adducts formed from neutral or deprotonated ligands and a doubly/ triply charged cation were produced in the gas phase using ESI, recording mass spectra with different metal ions for each isomer. While complex formation was successful for 2- hydroxypyridine N-oxide with trivalent ions, in the case of 3-hydroxypyridine N-oxide, only peaks related to the protonated molecule were present. On the other hand, divalent cations formed specific species for each isomer, giving characteristic spectra in every case. Hence, differentiation was possible irrespective of the metal cation utilized. In addition, quantum chemical calculations at the B3LYP/6-31+G(d,p) level of theory were performed in order to gain insight into the different complexation of calcium(II) with the isomers of hydroxypyridine N-oxide. The relative stability in the gas phase of the neutral complexes of calcium made up of two ligands, as well as the singly charged and doubly charged complexes, was investigated. The results of these calculations improved the understanding of the differences observed in the mass spectra obtained for each isomer. © American Society for Mass Spectrometry,2011.


Documento: Artículo
Título:Differentiation of isomeric hydroxypyridine N-Oxides using metal complexation and electrospray ionization mass spectrometry
Autor:Butler, M.; Manez, P.A.; Cabrera, G.M.
Filiación:Departamento de Química Orgánica, UMyMFOR-CONICET, Universidad de Buenos Aires, 3 piso, C1428EHA, Buenos Aires, Argentina
Departamento de Química Inorgánica, INQUIMAE-CONICET, Universidad de Buenos Aires, 1 piso, Buenos Aires, C1428EHA, Argentina
Palabras clave:Electrospray; Hydroxypyridine N-oxides; Metal complexation; Charged cations; Charged complexes; Complex formations; Divalent cation; Electrospray ionization mass spectrometry; Electrosprays; Gain insight; Gasphase; Hydroxypyridine; Mass spectra; Metal cation; Metal complexation; N-Oxides; Neutral complexes; Protonated molecules; Quantum chemical calculations; Relative stabilities; Trivalent ion; Calcium; Cobalt compounds; Electrospray ionization; Gases; Ionization of gases; Iron compounds; Isomers; Ligands; Mass spectrometers; Mass spectrometry; Metal ions; Metals; Positive ions; Protonation; Quantum chemistry; Scandium; Scandium compounds; Zinc compounds; Copper; 2 hydroxypyridine oxide; 3 hydroxypyridine oxide; aluminum chloride; calcium chloride; cobalt chloride; copper sulfate; divalent cation; ferrous chloride; gallium chloride; magnesium chloride; nickel sulfate; pyridine derivative; scandium; unclassified drug; zinc chloride; article; chemical structure; complex formation; controlled study; density functional theory; electrospray mass spectrometry; proton transport; quantum chemistry
Página de inicio:545
Página de fin:556
Título revista:Journal of the American Society for Mass Spectrometry
Título revista abreviado:J. Am. Soc. Mass Spectrom.
CAS:aluminum chloride, 7446-70-0, 7784-13-6; calcium chloride, 10043-52-4; cobalt chloride, 1332-82-7, 7646-79-9; copper sulfate, 7758-98-7, 7758-99-8; ferrous chloride, 12040-57-2, 7758-94-3; gallium chloride, 13450-90-3; magnesium chloride, 7786-30-3, 7791-18-6; nickel sulfate, 7786-81-4; scandium, 10361-84-9, 7440-20-2; zinc chloride, 7646-85-7


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---------- APA ----------
Butler, M., Manez, P.A. & Cabrera, G.M. (2011) . Differentiation of isomeric hydroxypyridine N-Oxides using metal complexation and electrospray ionization mass spectrometry. Journal of the American Society for Mass Spectrometry, 22(3), 545-556.
---------- CHICAGO ----------
Butler, M., Manez, P.A., Cabrera, G.M. "Differentiation of isomeric hydroxypyridine N-Oxides using metal complexation and electrospray ionization mass spectrometry" . Journal of the American Society for Mass Spectrometry 22, no. 3 (2011) : 545-556.
---------- MLA ----------
Butler, M., Manez, P.A., Cabrera, G.M. "Differentiation of isomeric hydroxypyridine N-Oxides using metal complexation and electrospray ionization mass spectrometry" . Journal of the American Society for Mass Spectrometry, vol. 22, no. 3, 2011, pp. 545-556.
---------- VANCOUVER ----------
Butler, M., Manez, P.A., Cabrera, G.M. Differentiation of isomeric hydroxypyridine N-Oxides using metal complexation and electrospray ionization mass spectrometry. J. Am. Soc. Mass Spectrom. 2011;22(3):545-556.