Electrospray Ionization Ion Mobility Spectrometry of Carboxylate Anions:  Ion Mobilities and a Mass−Mobility Correlation

Kim, Hugh I.; Johnson, P. V.; Beauchamp, J. L.; Kanik, I.

doi:10.1021/jp051274h

Cited by 26 publications

(19 citation statements)

References 24 publications

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“…A useful early review is that of Castleman and Keesee, but there are a number of more recent studies, including those from the Leone group[51], and others. A quantitative analysis of comparative modifier effects appears possible based on thermochemical free energy values from computational chemistry, optimized conformations considering energetics and steric hindrance, combined with computations of mobility [22, 52, 53] from predicted structures, and further investigations are in progress. The schema and thermochemistry for ion-cluster / modifier equilibria is summarized in Appendix A.…”

Section: Resultsmentioning

confidence: 99%

“…Temperature scaling leads to a reduced mobility, K 0 (corrected to 0°C, 1 atm) that still depends weakly on temperature, but that variation is dwarfed in DMS by dynamic cluster size variation. Although it is not important in low pressure IMS, or in traveling wave IMS [18, 19], the importance of clustering is well known in atmospheric pressure IMS, where a cluster-free mass-mobility correlation can only be obtained by the use of high drift tube temperatures, typically 200°C or higher [9, 20–26]. Except in special cases, low pressure IMS, and travelling wave IMS, operate with pure, non-polar drift gases and determine accurate cross-sections for a wide range of molecules, while DMS modifier effects depend on polar molecules with a long range attractive potential [27].…”

Section: Introductionmentioning

confidence: 99%

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Understanding Gas Phase Modifier Interactions in Rapid Analysis by Differential Mobility-Tandem Mass Spectrometry

Kafle

Coy

Wong

et al. 2014

J. Am. Soc. Mass Spectrom.

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A systematic study involving the use and optimization of gas phase modifiers in quantitative differential mobility- mass spectrometry (DMS-MS) analysis is presented using mucleoside-adduct biomarkers of DNA damage as an important reference point for analysis in complex matrices. Commonly used polar protic and polar aprotic modifiers have been screened for use against two deoxyguanosine adducts of DNA: N-(deoxyguanosin-8-yl)-4-aminobiphenyl (dG-C8-4-ABP) and N-(deoxyguanosin-8-y1)-2-amino-l-methyl-6-phenylimidazo[4,5-b]pyridine (dG-C8-PhIP). Particular attention was paid to compensation voltage (CoV) shifts, peak shapes and product ion signal intensities while optimizing the DMS-MS conditions. The optimized parameters were then applied to rapid quantitation of the DNA adducts in calf thymus DNA. After a protein precipitation step, adduct levels corresponding to less than one modification in 106 normal DNA bases were detected using the DMS-MS platform. Based on DMS fundamentals and ab-initio thermochemical results we interpret the complexity of DMS modifier responses in terms of thermal activation and the development of solvent shells. At very high bulk gas temperature, modifier dipole moment may be the most important factor in cluster formation and cluster geometry in mobility differences, but at lower temperatures multi-neutral clusters are important and less predictable. This work provides a useful protocol for targeted DNA adduct quantitation and a basis for future work on DMS modifier effects.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Understanding Gas Phase Modifier Interactions in Rapid Analysis by Differential Mobility-Tandem Mass Spectrometry

Kafle

Coy

Wong

et al. 2014

J. Am. Soc. Mass Spectrom.

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“…One is deprotonation of a hydroxyl group of the lactone, (26) by which the lactone is directly ionized. The other is adduction of an anion to the lactone.…”

Section: Rate Constants Of Lactonization and Hydrolysismentioning

confidence: 99%

Lactonization and Protonation of Gluconic Acid: A Thermodynamic and Kinetic Study by Potentiometry, NMR and ESI-MS

et al. 2007

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In acidic aqueous solutions, gluconate protonation is coupled with lactonization of gluconic acid. With the decrease of pC H , two lactones (δ/γ) are sequentially formed. The δ-lactone forms more readily than the γ-lactone. In 0.1 M gluconate solutions, if pC H is above 2.5, only the δ-lactone is generated. When pC H is decreased below 2.0, the formation of the γ-lactone is observable although the δ-lactone predominates. At I = 0.1 M NaClO 4 and room temperature, the deprotonation constant of the carboxylic group, using the NMR technique, was determined to be log K a = 3.30 ± 0.02; the δ-lactonization constant, by the batch potentiometric titrations, was obtained to be log K L = -(0.54 ± 0.04). Using ESI-MS, the rate constants of the δ-lactonization and the hydrolysis at pC H ~ 5.0 were estimated to be k 1 = 3.2 x 10 -5 s -1 and k -1 = 1.1 x 10 -4 s -1 , respectively.

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“…The oxalate anion is an excellent bidentate ligand for metal complexes producing five membered rings of which potassium ferrioxalate is a good example [14]. In the gas phase, metal oxalate clusters can be readily generated and detected with both negative and positive electrospray mass spectrometry [15][16][17]. In 2008, Tian and coworkers generated the lithium oxalate anion and reported the loss of CO 2 and CO by CID mass spectrometry, producing the strongest base known to date, LiO Ϫ [18].…”

mentioning

confidence: 99%

Old acid, new chemistry. Negative metal anions generated from alkali metal oxalates and others

Curtis

Renaud

Holmes

et al. 2010

J. Am. Soc. Mass Spectrom.

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A brief search in Sci Finder for oxalic acid and oxalates will reward the researcher with a staggering 129,280 hits. However, the generation of alkali metal and silver anions via collision-induced dissociation of the metal oxalate anion has not been previously been reported, though Tian and coworkers recently investigated the dissociation of lithium oxalate [18]. The exothermic decomposition of alkali metal oxalate anion to carbon dioxide in the collision cell of a triple quadrupole mass spectrometer leaves no place for the electron to reside, resulting in a double electron-transfer reaction to produce an alkali metal anion. This reaction is facilitated by the negative electron affinity of carbon dioxide and, as such, the authors believe that metal oxalates are potentially unique in this respect. The observed dissociation reactions for collision with argon gas (1.7-1.8 ϫ 10 Ϫ3 mbar) for oxalic acid and various alkali metal oxalates are discussed and summarized. Silver oxalate is also included to demonstrate the propensity of this system to generate transition-metal anions, as well. (J Am Soc Mass Spectrom 2010, 21, 1944 -1946) © 2010 American Society for Mass Spectrometry T he chemical concept of metals producing positive ions (cations) and non-metals negative ions (anions) is a fundamental precept taught as early as in high school and reinforced throughout a person's university career. However, under certain conditions, metal anions can be created and, as such, their electron affinities are well characterized and calculated both experimentally and theoretically [1]. In solution, alkali metal anions (except lithium) in 'supra molecule complexes' have been prepared in THF and crown ethers. These characteristically blue solutions are now fabricated to control the amount of metal ions, including metal anions. Such solutions have been extensively studied for use in organic synthesis and elucidation of charge-transfer to solvent dynamics (CTTS) [2][3][4][5][6][7][8][9]. In the gas phase, a beam of positively charged alkali cations created from metal vapor can undergo double electron capture to generate a low density negative ion beam [10]. Other means of negative ion generation include discharge and sputter ion sources, namely Cs ϩ ions with a suitable metal cathode [11]. Studies in ion traps utilize dissociative electron attachment to create metal anions [12]. Thus, metal anions are created only via complex experimental procedures or specific experimental apparatus. This paper outlines a method for the production of metal anions requiring a simple oxalate salt solution and a commercially available triple quadrupole mass spectrometer.Oxalic acid is one of the oldest known acids, first isolated from wood sorrel (Oxalis acetosella). It is often found as salt oxalates in many biological systems; particular well known is calcium oxalate found in rhubarb root, known for both its medicinal properties and as a potential poison. Ammonium oxalate is found in guano and there is evidence for the sodium and potassium salts pres...

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Electrospray Ionization Ion Mobility Spectrometry of Carboxylate Anions: Ion Mobilities and a Mass−Mobility Correlation

Cited by 26 publications

References 24 publications

Understanding Gas Phase Modifier Interactions in Rapid Analysis by Differential Mobility-Tandem Mass Spectrometry

Understanding Gas Phase Modifier Interactions in Rapid Analysis by Differential Mobility-Tandem Mass Spectrometry

Lactonization and Protonation of Gluconic Acid: A Thermodynamic and Kinetic Study by Potentiometry, NMR and ESI-MS

Old acid, new chemistry. Negative metal anions generated from alkali metal oxalates and others

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