On mass discrimination in high-pressure mass spectrometry: potential errors in measurements leading to absolute ion abundances

Hovey, Jamey K.; Likholyot, Alexander

doi:10.1016/s1387-3806(00)00234-7

Cited by 6 publications

(3 citation statements)

References 13 publications

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“…Therefore, enthalpy and entropy changes for halide stepwise hydration reactions calculated from the van't Hoff plots and given in Tables 1 and 2 are independent of temperature within the observed experimental errors. Errors due to mass discrimination in sampling (Hovey and Likholyot, 2000) are small compared with experimental errors and therefore, entropies were not corrected for this effect. Equilibria containing higher ligand numbers cannot be measured accurately with the present HPMS method.…”

Section: Resultsmentioning

confidence: 99%

Experimental and theoretical study of hydration of halide ions

Likholyot

Hovey

Seward

2005

Geochimica et Cosmochimica Acta

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Section: Resultsmentioning

confidence: 99%

Experimental and theoretical study of hydration of halide ions

Likholyot

Hovey

Seward

2005

Geochimica et Cosmochimica Acta

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“…Such discrimination errors would be most likely in this study for the ratio of the lowest-molecular-weight ionic species [CH 3 NH 3 + ] and its first hydration. Hovey and Likholyot showed that the actual ion intensities need to be weighted by the square root of ion clusters' mass. This correction applied to this ratio would amount to a of 0.2 kcal/mol, well within our experimental uncertainty.…”

Section: Methodsmentioning

confidence: 99%

Hydration of Alkylammonium Ions in the Gas Phase

et al. 2003

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Electrospray ionization-high-pressure mass spectrometry was used to determine the enthalpy, entropy, and Gibbs free energy for the equilibrium gas-phase ion-molecule association reactions of C m H 2m+1 NH 3 + (m ) 1-8), (CH 3 ) 2 NH 2 + , and (CH 3 ) 3 NH + with one to three water ligands. A subset of these ions has been studied previously, and the thermochemical properties determined in this investigation compare favorably with the previously published results, providing validation of our experimental technique and method. In addition, the present measurements show that the addition of a water ligand to the monohydrated alkylammonium ion results in an increased stabilization in its structure and binding.

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“…Mass dependent discrimination of signal intensities in ion transmission are a possibility in any quadrupole mass analyzer, but they are likely to be most severe for the lowest molecular weight species, the protonated diols and their first hydration states. Hovey and Likholyot [12] showed that to compensate for this, measured ion intensities should be weighted by the square root of ionic mass. Applying this correction to an ion ratio would amount to a ⌬G 298 of 0.2 kcal/mol, well within our experimental uncertainty.…”

Section: Methodsmentioning

confidence: 99%

Solvation of propanediol ions by water molecules in the gas phase

Gilligan

Vieira

Yergey

2004

J. Am. Soc. Mass Spectrom.

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The thermochemical properties of protonated hydrates of 1,2-and 1,3-propanediols have been investigated using electrospray ionization-high pressure mass spectrometry. The binding enthalpies, entropies, and free energies of the stepwise hydration of protonated propanediols with one to three waters are reported. The observed negative entropy change [⌬⌬S 1,3 o for the addition of the third water to 1,3-propanediol⅐H ϩ (H 2 O) 2 suggests a stable structure due to an increased number of hydrogen bonds and the loss of the intramolecular hydrogen bond in the water cluster ion. The thermochemical properties of two isomers of butanediol were also investigated in order to further elucidate the structures of the protonated K nowledge of the thermochemical properties of non-covalent bonds, particularly those involving water and biologically significant molecules, is fundamental in understanding the molecular interactions and changes in protein conformations. The role of ionic clusters and the thermodynamics of cluster formation is of interest to many wide ranging areas of chemistry such as stratospheric chemistry and polar stratospheric clouds [1], the chemistry in the ionosphere [2], and the elucidation of enzymatic reaction mechanisms [3].A major advancement in methods to study solvated ions came with the development of electrospray mass spectrometry. This technique provided a solution to the difficulty of solvating doubly-charged ions [4] and provided information on the sites of protonation and proton affinities of gas-phase aromatic compounds [5]. Our laboratory has recently implemented this technique for the study of hydration of organic ions [6], thereby validating our experimental technique and method and providing new insights into the thermochemical properties of alkylammonium ions.Leikin and co-workers have reported differential effects of 1,2-and 1,3-propanediol on collagen selfassembly [7]. 1,2-propanediol was found to weakly inhibit fiber assembly and did not affect the interaction between collagen helices in fibers while, at the same concentration, 1,3-propanediol strongly suppressed fibrillogenesis and eliminated the attraction between collagen helices. The ability of these two diols to inhibit fiber assembly differs by more than an order of magnitude. Leikin proposed that hydrogen-bonded water clusters bridging opposing collagen fiber helices were disrupted by competition due to the formation of crucial hydrogen bonds with 1,3-propanediol. It was suggested that the efficiency to destabilize fibers is dependent on the ability of a species to compete with water for crucial hydrogen bonds and disrupt water bridges.In the present work, we sought to gain further insight into the interactions between water and the propanediols, and to contribute to a better understanding of fibrillogenesis inhibition. Reactions of protonated propanediols and water were studied using a variable temperature high pressure source mass spectrometer. Two protonated butanediols were also investigated to further characterize the effect o...

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On mass discrimination in high-pressure mass spectrometry: potential errors in measurements leading to absolute ion abundances

Cited by 6 publications

References 13 publications

Experimental and theoretical study of hydration of halide ions

Experimental and theoretical study of hydration of halide ions

Hydration of Alkylammonium Ions in the Gas Phase

Solvation of propanediol ions by water molecules in the gas phase

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