Electrospray mass and tandem mass spectrometry identification of ozone oxidation products of amino acids and small peptides

Tapio Kotiaho (Corresponding Author), Risto Kostiainen, Pirjo Vainiotalo, Marcos Eberlin (Corresponding Author)

Research output: Contribution to journalArticleScientificpeer-review

94 Citations (Scopus)

Abstract

Aqueous ozonation of the 22 most common amino acids and some small peptides were studied by electrospray mass (ESI-MS) and tandem mass spectrometry. After 5 min of ozonation only His, Met, Trp, and Tyr form oxidation products clearly detectable by ESI-MS. For His, the main oxidation product is formed by the addition of three oxygen atoms, His + 3O; for Met and Tyr by the addition of one oxygen atom, Met + O and Tyr + O, and for Trp by the addition of two oxygen atoms, Trp + 2O. Ozone oxidation occurs rapidly, products are already detected after 30 s of ozonation, and the reactivity order is Met > Trp > Tyr > His. The structures of the oxygen addition products were investigated by electrospray product ion mass spectra, and by comparing these spectra to those of protonated intact amino acids, and when available, to those of model compounds. His + 3O was assigned as 2-amino-4-oxo-4-(3-formylureido)butanoic acid (1) formed by oxidation of the His imidazole ring, Met + O as methionine sulfoxide (2), Trp + 2O as N-formylkynurenine (4), and Tyr + O as a mixture of dihydroxyphenylalanines (7 and 8). Ozonation of peptides show that the same number of oxygen atoms are added as expected from the ozonation of the free amino acids. The product ion mass spectra of both the protonated intact peptides, MH+, and the main ozonation products (M + nO)H+ (n = 1–3) revealed b and y type ions as the main fragments, which allow one to assign the type and location of modified amino acid in the model peptides.
Original languageEnglish
Pages (from-to)526 - 535
Number of pages10
JournalJournal of the American Society for Mass Spectrometry
Volume11
Issue number6
DOIs
Publication statusPublished - 2000
MoE publication typeA1 Journal article-refereed

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Ozonization
Ozone
Tandem Mass Spectrometry
Mass spectrometry
Oxygen
Amino Acids
Oxidation
Peptides
Ions
Atoms
Dihydroxyphenylalanine
Butyric Acid
Electrospray Ionization Mass Spectrometry

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Kotiaho, Tapio ; Kostiainen, Risto ; Vainiotalo, Pirjo ; Eberlin, Marcos. / Electrospray mass and tandem mass spectrometry identification of ozone oxidation products of amino acids and small peptides. In: Journal of the American Society for Mass Spectrometry. 2000 ; Vol. 11, No. 6. pp. 526 - 535.
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title = "Electrospray mass and tandem mass spectrometry identification of ozone oxidation products of amino acids and small peptides",
abstract = "Aqueous ozonation of the 22 most common amino acids and some small peptides were studied by electrospray mass (ESI-MS) and tandem mass spectrometry. After 5 min of ozonation only His, Met, Trp, and Tyr form oxidation products clearly detectable by ESI-MS. For His, the main oxidation product is formed by the addition of three oxygen atoms, His + 3O; for Met and Tyr by the addition of one oxygen atom, Met + O and Tyr + O, and for Trp by the addition of two oxygen atoms, Trp + 2O. Ozone oxidation occurs rapidly, products are already detected after 30 s of ozonation, and the reactivity order is Met > Trp > Tyr > His. The structures of the oxygen addition products were investigated by electrospray product ion mass spectra, and by comparing these spectra to those of protonated intact amino acids, and when available, to those of model compounds. His + 3O was assigned as 2-amino-4-oxo-4-(3-formylureido)butanoic acid (1) formed by oxidation of the His imidazole ring, Met + O as methionine sulfoxide (2), Trp + 2O as N-formylkynurenine (4), and Tyr + O as a mixture of dihydroxyphenylalanines (7 and 8). Ozonation of peptides show that the same number of oxygen atoms are added as expected from the ozonation of the free amino acids. The product ion mass spectra of both the protonated intact peptides, MH+, and the main ozonation products (M + nO)H+ (n = 1–3) revealed b and y type ions as the main fragments, which allow one to assign the type and location of modified amino acid in the model peptides.",
author = "Tapio Kotiaho and Risto Kostiainen and Pirjo Vainiotalo and Marcos Eberlin",
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pages = "526 -- 535",
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Electrospray mass and tandem mass spectrometry identification of ozone oxidation products of amino acids and small peptides. / Kotiaho, Tapio (Corresponding Author); Kostiainen, Risto; Vainiotalo, Pirjo; Eberlin, Marcos (Corresponding Author).

In: Journal of the American Society for Mass Spectrometry, Vol. 11, No. 6, 2000, p. 526 - 535.

Research output: Contribution to journalArticleScientificpeer-review

TY - JOUR

T1 - Electrospray mass and tandem mass spectrometry identification of ozone oxidation products of amino acids and small peptides

AU - Kotiaho, Tapio

AU - Kostiainen, Risto

AU - Vainiotalo, Pirjo

AU - Eberlin, Marcos

PY - 2000

Y1 - 2000

N2 - Aqueous ozonation of the 22 most common amino acids and some small peptides were studied by electrospray mass (ESI-MS) and tandem mass spectrometry. After 5 min of ozonation only His, Met, Trp, and Tyr form oxidation products clearly detectable by ESI-MS. For His, the main oxidation product is formed by the addition of three oxygen atoms, His + 3O; for Met and Tyr by the addition of one oxygen atom, Met + O and Tyr + O, and for Trp by the addition of two oxygen atoms, Trp + 2O. Ozone oxidation occurs rapidly, products are already detected after 30 s of ozonation, and the reactivity order is Met > Trp > Tyr > His. The structures of the oxygen addition products were investigated by electrospray product ion mass spectra, and by comparing these spectra to those of protonated intact amino acids, and when available, to those of model compounds. His + 3O was assigned as 2-amino-4-oxo-4-(3-formylureido)butanoic acid (1) formed by oxidation of the His imidazole ring, Met + O as methionine sulfoxide (2), Trp + 2O as N-formylkynurenine (4), and Tyr + O as a mixture of dihydroxyphenylalanines (7 and 8). Ozonation of peptides show that the same number of oxygen atoms are added as expected from the ozonation of the free amino acids. The product ion mass spectra of both the protonated intact peptides, MH+, and the main ozonation products (M + nO)H+ (n = 1–3) revealed b and y type ions as the main fragments, which allow one to assign the type and location of modified amino acid in the model peptides.

AB - Aqueous ozonation of the 22 most common amino acids and some small peptides were studied by electrospray mass (ESI-MS) and tandem mass spectrometry. After 5 min of ozonation only His, Met, Trp, and Tyr form oxidation products clearly detectable by ESI-MS. For His, the main oxidation product is formed by the addition of three oxygen atoms, His + 3O; for Met and Tyr by the addition of one oxygen atom, Met + O and Tyr + O, and for Trp by the addition of two oxygen atoms, Trp + 2O. Ozone oxidation occurs rapidly, products are already detected after 30 s of ozonation, and the reactivity order is Met > Trp > Tyr > His. The structures of the oxygen addition products were investigated by electrospray product ion mass spectra, and by comparing these spectra to those of protonated intact amino acids, and when available, to those of model compounds. His + 3O was assigned as 2-amino-4-oxo-4-(3-formylureido)butanoic acid (1) formed by oxidation of the His imidazole ring, Met + O as methionine sulfoxide (2), Trp + 2O as N-formylkynurenine (4), and Tyr + O as a mixture of dihydroxyphenylalanines (7 and 8). Ozonation of peptides show that the same number of oxygen atoms are added as expected from the ozonation of the free amino acids. The product ion mass spectra of both the protonated intact peptides, MH+, and the main ozonation products (M + nO)H+ (n = 1–3) revealed b and y type ions as the main fragments, which allow one to assign the type and location of modified amino acid in the model peptides.

U2 - 10.1016/S1044-0305(00)00116-1

DO - 10.1016/S1044-0305(00)00116-1

M3 - Article

VL - 11

SP - 526

EP - 535

JO - Journal of the American Society for Mass Spectrometry

JF - Journal of the American Society for Mass Spectrometry

SN - 1044-0305

IS - 6

ER -