Gas-phase acidities of carboxylic acids and alcohols from collision-induced dissociation of dimer cluster ions

Graul, Susan T.; Schnute, Mark E.; Squires, Robert R.

doi:10.1016/0168-1176(90)87028-f

Cited by 84 publications

(58 citation statements)

References 19 publications

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“…The Ðrst point has been made repeatedly in the literature of the kinetic method, from very early experiments. 45,46 The second point is emphasized by Drahos and Ve key,44 but also appears in the early experiments by McLuckey et al 45 Evidence for the third point has been discussed qualitatively in various recent experimental studies. 28,47 The elegant work of Drahos and Ve key44 enhances the understanding of e †ective temperature provided by Brauman and co-workers.…”

Section: Temperatures and Internal Energy Distributionsmentioning

confidence: 89%

The kinetic method of making thermochemical determinations

1999

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Section: Temperatures and Internal Energy Distributionsmentioning

confidence: 89%

The kinetic method of making thermochemical determinations

1999

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“…Graul and Squires (37) have examined this effect in the dissociation of proton-bound alkoxide dimer ions. The results of that study showed no significant effects when comparing constant laboratory and constant center-ofmass (cm) energies (see Section VA).…”

Section: Practical Considerationsmentioning

confidence: 97%

“…The use of the ion trap is exemplified by the study of Brodbelt et al on the PA of adamantamine (41), and of Nourse et al on the PAS of various carboxylic acids as well as the measurement of secondary isotope effects on the PAS of benzoic acid, acetophenone, and 2-pentanone (42). Studies using flowing afterglow are represented by the work of Squires and co-workers (19,23,37) and of Depuy and co-workers (43). The studies of Freiser and co-workers (44) provide several examples of the use of an FT-ICR to perform kinetic method measurements.…”

Section: Practical Considerationsmentioning

confidence: 98%

“…As discussed above (25,37,52, 56), the stereochemistry of small organic compounds can be investigated using relative extents of dissociation of ionbound cluster ions. The dependence of affinities on the orientation of functional groups in various compounds has implications in guest-host studies (58).…”

Section: Affinities For Noble Alkali and Transition Metal Ionsmentioning

confidence: 99%

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Thermochemical determinations by the kinetic method

Cooks

Patrick

Kotiaho

et al. 1994

Mass Spectrometry Reviews

476

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“…Used methods: ion/molecule reaction equilibrium [69,71], collision induced dissociation and kinetic methods [70]. *From NIST webbook [68].…”

Section: Gas-phase Acidity Of the Steroidsmentioning

confidence: 99%

Stereochemical effects during [M-H]⁻ dissociations of epimeric 11-OH-17β-estradiols and distant electronic effects of substituents at C₍₁₁₎ position on gas phase acidity

Bourgoin-Voillard

Zins

Fournier

et al. 2009

J. Am. Soc. Mass Spectrom.

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The affinity of estradiol derivatives for the estrogen receptor (ER) depends strongly on nature and stereochemistry of substituents in C (11) position of the 17␤-estradiol (I). In this work, the stereochemistry effects of the 11␣-OH-17␤-estradiol (III ␣ ) and 11␤-OH-17␤-estradiol (III ␤ ) were investigated using CID experiments and gas-phase acidity (⌬H°a cid ) determination. The CID experiments showed that the steroids decompose via different pathways involving competitive dissociations with rate constants depending upon the ␣/␤ C (11) stereochemistry. It was shown that the fragmentations of both deprotonated [III ␣ -H] Ϫ and [III ␤ -H] Ϫ epimers were initiated by the deprotonation of the most acidic site, i.e. the phenolic hydroxyl at C (3) . This view was confirmed by H/D exchange and double resonance experiments. Furthermore, the ⌬H°a cid of both epimers (III ␣ and III ␤ ), 17␤-estradiol (I), and 17-desoxyestradiol (II) was determined using the extended Cooks' kinetic method. The resulting values allowed us to classify steroids as a function of their gas-phase acidity as follows:Interestingly, the ␣/␤ C (11) stereochemistry appeared to influence strongly the gas-phase acidity. This phenomenon could be explained through stereospecific proton interaction with -orbital cloud of A ring, which was confirmed by theoretical calculation. . The E 2 /ER␣ complex is stabilized by hydrogen contacts occurring between, on the one hand, the hydroxyl group of phenolic A ring (E 2 ) and Glu-353 as well as Arg-394 of the hormone binding pocket (HBP), and on the other hand, between the 17␤-hydroxyl of D-ring and His-524 (Scheme 1a) [5][6][7]. Moreover, position around the functionalized site at the C (11) position (C ring) seems to contribute to the anchorage of the hormone within this pocket of the receptor [7][8][9][10][11][12][13], suggesting that steric effects at this position are important for binding affinity. Accordingly, we may consider that the proton donor character efficiency could be reinforced through electrostatic effects mediated by the nature and the stereochemistry of substituent in position 11 [14].Mass spectrometry is widely used to characterize diastereoisomeric compound through stereochemical effects [15,16]. Many reviews have described stereochemistry differentiation of the hydroxyl group in gas phase on rigid rings [17][18][19][20][21][22]. The stereochemical effects could provide evidence that the chemical pathways for ion-molecule reaction as well as the dissociation mechanisms promoted by negative charge from stereoisomeric ion species prepared in chemical ionization and electrospray [23]. For instance, the differentiation of alkoxides of trans and cis-cyclohexanediols has been widely described in negative chemical ionization [24 -26]. This technique turned out to be also appropriate to distinguish more complex polycyclic molecules, such as mono-or polyhydroxyl norborneols, saccharides, and steroids [27][28][29][30]. The origin of stereochemical effects in these systems has been described in terms of...

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Gas-phase acidities of carboxylic acids and alcohols from collision-induced dissociation of dimer cluster ions

Cited by 84 publications

References 19 publications

The kinetic method of making thermochemical determinations

The kinetic method of making thermochemical determinations

Thermochemical determinations by the kinetic method

Stereochemical effects during [M-H]⁻ dissociations of epimeric 11-OH-17β-estradiols and distant electronic effects of substituents at C₍₁₁₎ position on gas phase acidity

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Gas-phase acidities of carboxylic acids and alcohols from collision-induced dissociation of dimer cluster ions

Cited by 84 publications

References 19 publications

The kinetic method of making thermochemical determinations

The kinetic method of making thermochemical determinations

Thermochemical determinations by the kinetic method

Stereochemical effects during [M-H]− dissociations of epimeric 11-OH-17β-estradiols and distant electronic effects of substituents at C(11) position on gas phase acidity

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Stereochemical effects during [M-H]⁻ dissociations of epimeric 11-OH-17β-estradiols and distant electronic effects of substituents at C₍₁₁₎ position on gas phase acidity