Rearrangement of aromatic sulfonate anions in the gas phase

Binkley, Roger W.; Flechtner, Thomas W.; Tevesz, Michael J. S.; Winnik, Witold; Zhong, Buqing

doi:10.1002/oms.1210280708

Cited by 27 publications

(36 citation statements)

References 17 publications

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“…The observed unimolecular reactivity is reminiscent of the formation of phenoxide ions by loss of SO 2 that is observed upon CID of aromatic sulfonate ions . Forthcoming efforts will be aimed to unravel the rearrangement/fragmentation mechanism of [cysS−SO 3 ] − ions.…”

Section: Resultsmentioning

confidence: 99%

Amino Acid Oxidation: A Combined Study of Cysteine Oxo Forms by IRMPD Spectroscopy and Simulations

Scuderi

Bodo

Chiavarino

et al. 2016

Chemistry A European J

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The redox activity of cysteine sulfur allows numerous post-translational protein modifications involved in the oxidative regulation of metabolism, in metal binding, and in signal transduction. A combined approach based on infrared multiple photon dissociation spectroscopy at the Centre Laser Infrarouge d'Orsay (CLIO) free electron laser facility, calculations of IR frequencies, and finite temperature ab initio molecular dynamics simulations has been employed to characterize the gas-phase structures of deprotonated cysteine sulfenic, sulfinic, and sulfonic acids, [cysSO ] (x=1, 2, 3, representing the number of S-bound oxygen atoms), which are key intermediates in the redox-switching chemistry of proteins. The ions show different structural motifs owing to preferential binding of the proton to either the carboxylate or sulfur-containing group. Due to the decreasing basicity of the sulfenic, sulfinic, and sulfonic terminals, the proton bound to SO in [cysSO] migrates to the carboxylate in [cysSO ] , whereas it turns out to be shared in [cysSO ] . Evidence is gathered that a mixture of close-lying low-energy conformers is sampled for each cysteine oxo form in a Paul ion trap at room temperature.

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Section: Resultsmentioning

confidence: 99%

Amino Acid Oxidation: A Combined Study of Cysteine Oxo Forms by IRMPD Spectroscopy and Simulations

Scuderi

Bodo

Chiavarino

et al. 2016

Chemistry A European J

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“…It was proposed that an initial intramolecular nucleophilic addition of the sulfonamide nitrogen atom to the aromatic ring was followed by a heterolytic cleavage of the C-S bond to rearomatize the ring. 16 This generates an intermediate sulfurous acid half-ester which loses SO 2 to afford the phenoxide ion, analogous to the mechanism proposed for the aromatic nitro compound which loses NO with the migration of an oxygen atom. 17 This NO elimination can be enhanced by the presence of an ortho-substituted functional group.…”

Section: So 2 Elimination-rearrangement Mechanismsmentioning

confidence: 91%

Fragmentation of aromatic sulfonamides in electrospray ionization mass spectrometry: elimination of SO₂ via rearrangement

2007

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Arylsulfonamides are attractive pharmacophores for drug candidates. Fragmentation behaviors of selected aromatic sulfonamides were investigated using electrospray ionization mass spectrometry in the positive ion mode. Some of the sulfonamides afforded unique loss of 64 (loss of SO(2)) ions upon collision-induced dissociation followed by intramolecular rearrangements in the gas phase. This SO(2) elimination-rearrangement pathway leading to the generation of [M + H - SO(2)](+) ions appeared to be susceptible to substitutions on the aromatic (Ar) ring that would affect the Ar--sulfur bond strength and the stability of the partially positive charge developed at the ipso position upon bond dissociation. Electron withdrawing groups such as chlorine attached to the aromatic ring at ortho position seem to promote the SO(2) extrusion. Although this fragmentation pathway in atmospheric pressure ionization MS is less predictable than in electron impact MS, it is a frequently encountered reaction. The absence of this fragmentation pathway in some of the arylsulfonamides indicates that other factors such as nucleophilicity of the nitrogen may also play a role in the process. With respect to the site of attachment of the migrating NR'R'', ipso-substitution on the aromatic ring is evident since this fragmentation mechanism is operative in the fully ortho-substituted arylsulfonamides.

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“…[43,44] In the case of aromatic sulfonates, the neutral loss of an SO 2 (Fig. 2(A-E)) has been studied in detail by Binkley et al [24] Furthermore, the m/z 81 peak is also observed in the mass spectra of aromatic sulfonates, such as benzenesulfonate ([5 -H] -, Fig. 2(A) Fig.…”

Section: Resultsmentioning

confidence: 97%

“…[20][21][22][23][24][25][26][27][28] Negative-ion mass spectra of alkyl and aryl sulfonates indicate that the major product ion produced by collision-induced fragmentation is the sulfur trioxide radical anion (SO 3 -Á , m/z 80). [20][21][22][23][24][25][26][27][28] On the other hand, some sulfonates are known to give the bisulfite anion (HSO 3 -, m/z 81). [20,28] For example, in the collision-induced dissociation (CID) mass spectra of fluorotelomer sulfonates, the base peak is observed at m/z 81 indicating the formation of the bisulfite anion.…”

Section: Introductionmentioning

confidence: 99%

Formation of the bisulfite anion (HSO₃^–, m/z 81) upon collision‐induced dissociation of anions derived from organic sulfonic acids

et al. 2012

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In the negative-ion collision-induced dissociation mass spectra of most organic sulfonates, the base peak is observed at m/z 80 for the sulfur trioxide radical anion (SO(3) (-·) ). In contrast, the product-ion spectra of a few sulfonates, such as cysteic acid, aminomethanesulfonate, and 2-phenylethanesulfonate, show the base peak at m/z 81 for the bisulfite anion (HSO(3) (-) ). An investigation with an extensive variety of sulfonates revealed that the presence of a hydrogen atom at the β-position relative to the sulfur atom is a prerequisite for the formation of the bisulfite anion. The formation of HSO(3) (-) is highly favored when the atom at the β-position is nitrogen, or the leaving neutral species is a highly conjugated molecule such as styrene or acrylic acid. Deuterium-exchange experiments with aminomethanesulfonate demonstrated that the hydrogen for HSO(3) (-) formation is transferred from the β-position. The presence of a peak at m/z 80 in the spectrum of 2-sulfoacetic acid, in contrast to a peak at m/z 81 in that of 3-sulfopropanoic acid, corroborated the proposed hydrogen transfer mechanism. For diacidic compounds, such as 4-sulfobutanoic acid and cysteic acid, the m/z 81 ion can be formed by an alternative mechanism, in which the negative charge of the carboxylate moiety attacks the α-carbon relative to the sulfur atom. Experiments conducted with deuterium-exchanged and deuterium-labeled analogs of sulfocarboxylic acids demonstrated that the formation of the bisulfite anion resulted either from a hydrogen transfer from the β-carbon, or from a direct attack by the carboxylate moiety on the α-carbon.

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Rearrangement of aromatic sulfonate anions in the gas phase

Cited by 27 publications

References 17 publications

Amino Acid Oxidation: A Combined Study of Cysteine Oxo Forms by IRMPD Spectroscopy and Simulations

Amino Acid Oxidation: A Combined Study of Cysteine Oxo Forms by IRMPD Spectroscopy and Simulations

Fragmentation of aromatic sulfonamides in electrospray ionization mass spectrometry: elimination of SO₂ via rearrangement

Formation of the bisulfite anion (HSO₃^–, m/z 81) upon collision‐induced dissociation of anions derived from organic sulfonic acids

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Rearrangement of aromatic sulfonate anions in the gas phase

Cited by 27 publications

References 17 publications

Amino Acid Oxidation: A Combined Study of Cysteine Oxo Forms by IRMPD Spectroscopy and Simulations

Amino Acid Oxidation: A Combined Study of Cysteine Oxo Forms by IRMPD Spectroscopy and Simulations

Fragmentation of aromatic sulfonamides in electrospray ionization mass spectrometry: elimination of SO2 via rearrangement

Formation of the bisulfite anion (HSO3–, m/z 81) upon collision‐induced dissociation of anions derived from organic sulfonic acids

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Fragmentation of aromatic sulfonamides in electrospray ionization mass spectrometry: elimination of SO₂ via rearrangement

Formation of the bisulfite anion (HSO₃^–, m/z 81) upon collision‐induced dissociation of anions derived from organic sulfonic acids