Negative ion electrospray ionization mass spectral study of dicarboxylic acids in the presence of halide ions

Kumar, M. Ravi; Prabhakar, S.; Kumar, Mithilesh; Reddy, T. Jagadeshwar; Vairamani, M.

doi:10.1002/rcm.1451

Cited by 19 publications

(10 citation statements)

References 28 publications

(46 reference statements)

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“…32 In electrospray chemical ionization techniques using iodide salt solutions as the reagent ionization source, only I − and I 3 − are observed. 111,112 Application to Cl 2 and Br 2 . As proof of concept, the PDG ionization technique using the iodine tincture reagent source was applied to gaseous Cl 2 and liquid Br 2 .…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Role of Gas-Phase Halogen Bonding in Ambient Chemical Ionization Mass Spectrometry Utilizing Iodine

Ganske

Wingen

Perraud

et al. 2019

ACS Earth Space Chem.

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Ambient ionization processes are becoming more widely used for the measurement of atmospherically relevant particles and gases. We report here ambient ionization mass spectra utilizing a commercial tincture of iodine and a piezoelectric discharge gun (PDG) to generate the ionizing reagents. Analytes include Cl 2 , Br 2 , HNO 3 , the C 1 −C 9 series of saturated monocarboxylic acids, benzoic acid, 2,2-dimethylpropanoic acid, 9-decenoic acid, and trichloroacetic acid. While Cl 2 and Br 2 form the [M + I] − iodide adducts, HNO 3 and the organic acids show unexpected peaks corresponding to [2M − 2H + I] −. For HNO 3 , the new ion formed is interpreted as the [NO 3 − •••IONO 2 ] complex, where IONO 2 is likely formed upon reaction of HOI with gaseous NO 3 −. Similarly, for the organic acids, the [2M − 2H + I] − peaks are interpreted as [RC(O)O − •••IOC(O)R] complexes formed by association of RC(O)O − with acyl hypoiodites [RC(O)OI]. It is proposed that the association of (1) Cl 2 and Br 2 with I − , (2) IONO 2 with NO 3 − ions, and (3) RC(O)OI with carboxylate ions occurs via non-covalent halogen bonding. The results suggest the possibility that halogen bonding may play a role in chemical transformations in the atmosphere, particularly in particles where concentrations of iodinated species may be significant.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Role of Gas-Phase Halogen Bonding in Ambient Chemical Ionization Mass Spectrometry Utilizing Iodine

Ganske

Wingen

Perraud

et al. 2019

ACS Earth Space Chem.

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“…Formation of clusters with the chlorine anion has been reported for a number of individual organic compounds under negative ion electrospray conditions,24–29 but no data on non‐covalent complexes of polyether oligomers with Cl − have been reported in the literature on the mass spectrometry of polymers. As the existence of gas‐phase PEG–anion clusters has not been shown experimentally, it is understandable that no attempt has been made to model such structures.…”

mentioning

confidence: 99%

Observation of poly(ethylene glycol) clusters with the chlorine anion in the gas phase under electrospray conditions

Kosevich¹,

Zobnina²,

Chagovets³

et al. 2011

Rapid Comm Mass Spectrometry

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It is demonstrated herein that poly(ethylene glycol) (PEG) oligomers can form stable complexes with the chlorine anion in the gas phase as evidenced by results from electrospray ionization mass spectrometry (ESI-MS) and molecular dynamics simulation. While the formation of crown-ether-like structures by acyclic polyethers in their complexes with alkali metal cations coordinated by the ether oxygen atoms has been extensively studied, the possibility of forming 'inversed' quasi-cyclic structures able to bind a monoatomic anion has not been proved till now. We have observed the formation of stable gas-phase complexes of oligomers of PEG-400 with the Cl(-) anion experimentally by ESI-MS for the first time. It is suggested that a necessary precondition for obtaining the polyether-chlorine anion clusters is the prevention of the formation of neutral ion pairs. Molecular dynamics simulation has demonstrated the wrapping of the Cl(-) anion by the PEG chain, to stabilize the PEG(n)•Cl(-) clusters in the gas phase. The conformation of the polyether chain in such quasi-cyclic or quasi-helical complexes is 'inversed' compared with that in the complexes with cations: that is its hydrogen atoms are turned towards the central anion. Awareness of the possibility of the Cl(-) anion being trapped in quasi-cyclic PEG structures may be of practical importance when considering the intermolecular interactions of PEGs.

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“…In such cases, attachment of small inorganic anions can be an important ionisation mechanism. For example, halide ion attachment was recently used to generate [M–H] − ions for such compounds 16–18. When these compounds are in a complex mixture, the interferences from background compounds might be reduced in the negative ion mode relative to positive ion mode.…”

Section: Resultsmentioning

confidence: 99%

Electrospray ionisation mass spectral studies on hydrolysed products of sulfur mustards

Lakshmi

Murty

Reddy

et al. 2006

Rapid Comm Mass Spectrometry

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Off-site detection of the hydrolysed products of sulfur mustards in aqueous samples is an important task in the verification of Chemical Weapons Convention (CWC)-related chemicals. The hydrolysed products of sulfur mustards are studied under positive and negative electrospray ionisation (ESI) conditions using an additive with a view to detecting them at trace levels. In the presence of cations (Li(+), Na(+), K(+) and NH(4) (+)), the positive ion ESI mass spectra of all the compounds include the corresponding cationised species; however, only the [M+NH(4)](+) ions form [M+H](+) ions upon decomposition. The tandem mass (MS/MS) spectra of [M+H](+) ions from all the hydrolysed products of the sulfur mustard homologues were distinct and allowed these compounds to be characterised unambiguously. Similarly, the negative ion ESI mass spectra of all the compounds show prominent adducts with added anions (F(-), Cl(-), Br(-), and I(-)), but the [M-H](-) ion can only be generated by decomposition of an [M+F](-) ion. The MS/MS spectra of the [M-H](-) ions from all the compounds result in a common product ion at m/z 77. A precursor ion scan of m/z 77 is shown to be useful in the rapid screening of these compounds in aqueous samples at trace levels, even in the presence of complex masking agents, without the use of time-consuming sample preparation and chromatography steps. An MS/MS method developed to measure the detection limits of the hydrolysed products of sulfur mustards found these to be in the range of 10-500 ppb.

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Negative ion electrospray ionization mass spectral study of dicarboxylic acids in the presence of halide ions

Cited by 19 publications

References 28 publications

Role of Gas-Phase Halogen Bonding in Ambient Chemical Ionization Mass Spectrometry Utilizing Iodine

Role of Gas-Phase Halogen Bonding in Ambient Chemical Ionization Mass Spectrometry Utilizing Iodine

Observation of poly(ethylene glycol) clusters with the chlorine anion in the gas phase under electrospray conditions

Electrospray ionisation mass spectral studies on hydrolysed products of sulfur mustards

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