Collisionally-induced dissociation mass spectra of organic sulfate anions

Attygalle, Athula B.; García-Rubio, Silvina; Ta, Jennifer; Meinwald, Jerrold

doi:10.1039/b009019k

Cited by 60 publications

(98 citation statements)

References 40 publications

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“…Benzyl sulfate did not fragment to m/z 97, and rather had a major product ion at m/z 96, consistent with collisionally-induced dissociation mass spectra of benzyl sulfate (Attygalle et al, 2001). The product ion with m/z 97 is formed due to the transfer of a proton from the C2 position of organosulfates to SO 2− 4 moiety, as demonstrated by doing the fragmentation analysis of hexadecyl sulfate with deuterium labeling (Attygalle et al, 2001). In benzyl sulfate, there is no hydrogen atom at the C2 position, rendering proton transfer impossible and yielding the major fragment ion of m/z 96, which corresponded to the sulfate radical (SO − 4 ).…”

Section: Characterization Of Benzyl Sulfate Standardmentioning

confidence: 51%

“…1a, which were assigned as HSO Prior studies have documented that organosulfates fragment to a major product ion at m/z 97, which has been used as a means of identifying parent organosulfates Romero and Oehme, 2005). Benzyl sulfate did not fragment to m/z 97, and rather had a major product ion at m/z 96, consistent with collisionally-induced dissociation mass spectra of benzyl sulfate (Attygalle et al, 2001). The product ion with m/z 97 is formed due to the transfer of a proton from the C2 position of organosulfates to SO 2− 4 moiety, as demonstrated by doing the fragmentation analysis of hexadecyl sulfate with deuterium labeling (Attygalle et al, 2001).…”

Section: Characterization Of Benzyl Sulfate Standardmentioning

confidence: 58%

“…Additionally, it is not possible to transfer H + atom from C2 position to SO 2− 4 moiety for the formation of product ion at m/z 97. Due to a similar reason, product ion at m/z 97 was not observed in the fragmentation analysis of benzyl sulfate (Attygalle et al, 2001). Figure 3b shows the EIC of m/z 201.02 ± 0.01 for which several peaks elute in the range of 6.5-7.1 min.…”

Section: Other Aromatic Organosulfates In Atmospheric Aerosolsmentioning

confidence: 93%

“…3a inset. When the sulfate functional group is directly attached to the aromatic ring, the elimination of SO − 4 is less favorable due to electron delocalization, making SO − 3 the more abundant sulfur-containing fragment ion (Attygalle et al, 2001). Additionally, it is not possible to transfer H + atom from C2 position to SO 2− 4 moiety for the formation of product ion at m/z 97.…”

Section: Other Aromatic Organosulfates In Atmospheric Aerosolsmentioning

confidence: 99%

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Evidence and quantitation of aromatic organosulfates in ambient aerosols in Lahore, Pakistan

Kundu

Quraishi

et al. 2013

Atmos. Chem. Phys.

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Abstract. Organosulfates are important components of atmospheric organic aerosols, yet their structures, abundances, sources and formation processes are not adequately understood. This study presents the identification and quantitation of benzyl sulfate in atmospheric aerosols, which is the first confirmed atmospheric organosulfate with aromatic carbon backbone. Benzyl sulfate was identified and quantified in fine particulate matter (PM2.5) collected in Lahore, Pakistan, during 2007–2008. An authentic standard of benzyl sulfate was synthesized, standardized, and identified in atmospheric aerosols with quadrupole time-of-flight (Q-ToF) mass spectrometry (MS). Benzyl sulfate was quantified in aerosol samples using ultra performance liquid chromatography (UPLC) coupled to negative electrospray ionization triple quadrupole (TQ) MS. The highest benzyl sulfate concentrations were recorded in November and January 2007 (0.50 ± 0.11 ng m−3) whereas the lowest concentration was observed in July (0.05 ± 0.02 ng m−3). To evaluate matrix effects, benzyl sulfate concentrations were determined using external calibration and the method of standard addition; comparable concentrations were detected by the two methods, which ruled out significant matrix effects in benzyl sulfate quantitation. Three additional organosulfates with m/z 187, 201 and 215 were qualitatively identified as aromatic organosulfates with additional methyl substituents by high-resolution mass measurements and tandem MS. The observed aromatic organosulfates form a homologous series analogous to toluene, xylene, and trimethylbenzene, which are abundant anthropogenic volatile organic compounds (VOC), suggesting that aromatic organosulfates may be formed by secondary reactions. However, stronger statistical correlations of benzyl sulfate with combustion tracers (EC and levoglucosan) than with secondary tracers (SO42− and α-pinene-derived nitrooxy organosulfates) suggest that aromatic organosulfates may be emitted from the combustion sources or their subsequent atmospheric processing. Further studies are needed to elucidate the sources and formation pathways of aromatic organosulfates in the atmosphere.

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Section: Characterization Of Benzyl Sulfate Standardmentioning

confidence: 51%

Section: Characterization Of Benzyl Sulfate Standardmentioning

confidence: 58%

Section: Other Aromatic Organosulfates In Atmospheric Aerosolsmentioning

confidence: 93%

Section: Other Aromatic Organosulfates In Atmospheric Aerosolsmentioning

confidence: 99%

See 2 more Smart Citations

Evidence and quantitation of aromatic organosulfates in ambient aerosols in Lahore, Pakistan

Kundu

Quraishi

et al. 2013

Atmos. Chem. Phys.

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“…However, the m/z 97 product ion is not specific for glucosinolates because most organic sulfate anions form this anion via a six-membered, cyclic syn-elimination mechanism as depicted in Scheme 1. [28] However, a six-membered transition state for a similar hydrogen transfer (from R substituent) cannot be attained from glucosinolates because the N-sulfated thiohydroximate moiety of glucosinolates bears a (Z)-configuration. [29] For some molecules, particularly for those without a hydrogen atom at the C-2 position, an alternative mechanism in which two neutral molecules are eliminated via an eight-membered transition state has been proposed.…”

Section: Resultsmentioning

confidence: 99%

Collision‐induced dissociation mass spectra of glucosinolate anions

Bialecki¹,

Růžička²,

Weisbecker³

et al. 2009

J. Mass Spectrom.

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Collision-induced dissociation (CID) mass spectra of differently substituted glucosinolates were investigated under negative-ion mode. Data obtained from several glucosinolates and their isotopologues ((34)S and (2)H) revealed that many peaks observed are independent of the nature of the substituent group. For example, all investigated glucosinolate anions fragment to produce a product ion observed at m/z 195 for the thioglucose anion, which further dissociates via an ion/neutral complex to give two peaks at m/z 75 and 119. The other product ions observed at m/z 80, 96 and 97 are characteristic for the sulfate moiety. The peaks at m/z 259 and 275 have been attributed previously to glucose 1-sulfate anion and 1-thioglucose 2-sulfate anion, respectively. However, based on our tandem mass spectrometric experiments, we propose that the peak at m/z 275 represents the glucose 1-thiosulfate anion. In addition to the common peaks, the spectrum of phenyl glucosinolate (beta-D-Glucopyranose, 1-thio-, 1-[N-(sulfooxy)benzenecarboximidate] shows a substituent-group-specific peak at m/z 152 for C(6)H(5)-C(=NOH)S(-), the CID spectrum of which was indistinguishable from that of the anion of synthetic benzothiohydroxamic acid. Similarly, the m/z 201 peak in the spectrum of phenyl glucosinolate was attributed to C(6)H(5)-C(=S)OSO(2)(-).

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Low‐energy collision‐induced fragmentation of negative ions derived from ortho‐, meta‐, and para‐hydroxyphenyl carbaldehydes, ketones, and related compounds

Attygalle¹,

Růžička²,

Varughese³

et al. 2007

J. Mass Spectrom.

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Collision-induced dissociation (CID) mass spectra of anions derived from several hydroxyphenyl carbaldehydes and ketones were recorded and mechanistically rationalized. For example, the spectrum of m/z 121 ion of deprotonated ortho-hydroxybenzaldehyde shows an intense peak at m/z 93 for a loss of carbon monoxide attributable to an ortho-effect mediated by a charge-directed heterolytic fragmentation mechanism. In contrast, the m/z 121 ion derived from meta and para isomers undergoes a charge-remote homolytic cleavage to eliminate an žH and form a distonic anion radical, which eventually loses CO to produce a peak at m/z 92. In fact, for the para isomer, this two-step homolytic mechanism is the most dominant fragmentation pathway. The spectrum of the meta isomer on the other hand, shows two predominant peaks at m/z 92 and 93 representing both homolytic and heterolytic fragmentations, respectively.18 O-isotope-labeling studies confirmed that the oxygen in the CO molecule that is eliminated from the anion of meta-hydroxybenzaldehyde originates from either the aldehydic or the phenolic group. In contrast, anions of ortho-hydroxybenzaldehyde and 2-hydroxy-1-naphthaldehyde, both of which show two consecutive CO eliminations, specifically lose the carbonyl oxygen first, followed by that of the phenolic group. Anions from 2-hydroxyphenyl alkyl ketones lose a ketene by a hydrogen transfer predominantly from the a position. Interestingly, a very significant charge-remote 1,4-elimination of a H 2 molecule was observed from the anion derived from 2,4-dihydroxybenzaldehyde. For this mechanism to operate, a labile hydrogen atom should be available on the hydroxyl group adjacent to the carbaldehyde functionality.

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Collisionally-induced dissociation mass spectra of organic sulfate anions

Cited by 60 publications

References 40 publications

Evidence and quantitation of aromatic organosulfates in ambient aerosols in Lahore, Pakistan

Evidence and quantitation of aromatic organosulfates in ambient aerosols in Lahore, Pakistan

Collision‐induced dissociation mass spectra of glucosinolate anions

Low‐energy collision‐induced fragmentation of negative ions derived from ortho‐, meta‐, and para‐hydroxyphenyl carbaldehydes, ketones, and related compounds

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