Chiral Recognition ofO-Phosphoserine by Mass Spectrometry

Fago, Giovanna; Filippi, Antonello; Giardini, Anna; Laganà, Aldo; Paladini, Alessandra; Speranza, Maurizio

doi:10.1002/1521-3757(20011105)113:21<4175::aid-ange4175>3.0.co;2-n

Cited by 17 publications

(21 citation statements)

References 18 publications

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“…Observable enantioselectivity can be passed on to the ratio between daughter ions and the non-dissociated parent complex ions [25][26][27][28]. The other type of tandem experiments, so-called kinetic method (KM), was developed by Cooks and co-workers [2,[29][30][31][32][33][34][35][36][37][38][39][40][41][42]. Higher order ionized complexes (i.e.…”

Section: Chiral Recognition Based On Dissociation Of Complexesmentioning

confidence: 99%

Enantiomer assays of amino acid derivatives using tertiary amine appended trans-4-hydroxyproline derivatives as chiral selectors in the gas phase

Woolfolk

Koscho

2010

Analytica Chimica Acta

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Section: Chiral Recognition Based On Dissociation Of Complexesmentioning

confidence: 99%

Enantiomer assays of amino acid derivatives using tertiary amine appended trans-4-hydroxyproline derivatives as chiral selectors in the gas phase

Woolfolk

Koscho

2010

Analytica Chimica Acta

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“…These differences can be exploited (i.e., by comparison to data for known standards) and used to determine the enantiomeric purity of a sample. Cooks [3][4][5][6][7][8][9][10][11][12][13][14][15][16], Dearden , , Speranza [27][28][29][30][31][32][33][34][35], and others have provided useful examples of this approach to stereochemical analysis.Along with methods for analyzing the enantiomeric purity of products, there is a growing need for the development of new reaction processes that are stereoselective. In general, these processes have been probed in the condensed phase, but there is no reason why mass spectrometry could not also be used to screen gas phase reactions for stereoselectivity [35,36].…”

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confidence: 99%

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confidence: 99%

Stereoselectivity in the collision-activated reactions of gas phase salt complexes

Gronert

Fagin

Okamoto

2004

J. Am. Soc. Mass Spectrom.

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The collision-activated dissociations (CAD) of gas phase salt complexes composed of chiral ions were studied in a quadrupole ion trap mass spectrometer. Because both partners in the salt are chiral, diastereomeric complexes can be formed (e.g., RR, RS). Two general types of complexes were investigated. In the first, the complex was composed of deprotonated binaphthol and a chiral bis-tetraalkylammonium dication. CAD of these complexes leads to the transfer of a proton or an alkyl cation to the binaphtholate leading to a singly-charged tetraalkylammonium cation. During CAD, diastereomeric complexes give significantly different product distributions indicating reasonable stereoselectivity in the process. In the second system, the complexes involved a peptide dianion and a chiral tetraalkylammonium cation. These systems may be viewed as very simple models for the interactions of peptides/proteins with small chiral molecules. Again, stereoselectivity was evident during CAD, but the extent was dependent on the nature of the peptide and not observable in some cases. To better understand the structural features needed to achieve stereoselectivity in gas phase salt complexes, representative transition states were modeled computationally. The results suggest that it is critical for the asymmetry of the nucleophile (i.e., anion) to be well represented in the vicinity of its reactive center. T he high sensitivity and rapid analysis capabilities of mass spectrometry make it an attractive methodology for solving a wide range of analytical problems. However, stereochemical issues are a challenge because a mass-to-charge ratio provides no direct information with regards to the stereochemistry of a species. Nonetheless, many workers have developed novel approaches for gaining stereochemical information from mass spectrometric data [1,2]. Much of this work has focused on the development of methods that could be used to determine the enantiomeric purity of a product mixture . Like many condensed phase approaches to enantiomeric analysis, the methods rely on complexing the analyte with a substrate of known chirality. This leads to the formation of a pair of diastereomers (assuming that the analyte is not enantiomerically pure). The diastereomers are not equivalent and as a result have different stabilities, kinetic reactivities, and dissociation patterns. These differences can be exploited (i.e., by comparison to data for known standards) and used to determine the enantiomeric purity of a sample. Cooks [3][4][5][6][7][8][9][10][11][12][13][14][15][16], Dearden , , Speranza [27][28][29][30][31][32][33][34][35], and others have provided useful examples of this approach to stereochemical analysis.Along with methods for analyzing the enantiomeric purity of products, there is a growing need for the development of new reaction processes that are stereoselective. In general, these processes have been probed in the condensed phase, but there is no reason why mass spectrometry could not also be used to screen gas phase reactions for stereo...

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“…(3) Discriminating the intensities of product or reactant complexes in second stage mass spectra, based on the different ion/ molecule reaction rates of formation of a pair of diastereomeric host-guest complexes or that of exchange of the complexes with a new guest [26 -36]. (4) Comparing the dissociation kinetics of diastereomeric complexes based on two competitive dissociation pathways in a collisional induced dissociation experiment, which is popularly known as the kinetic method [37][38][39][40][41][42][43][44][45][46][47]. All these methods mentioned above need a chiral host molecule or an optically pure reagent to associate with the target compound forming an enantioselective intermolecular interaction system.…”

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confidence: 99%

“…It is also possible to discriminate the enantiomer in a host-guest system applying chiral crown ether [26 -30], cyclodextrin [31][32][33][34][35][36], and some kinds of antibiotic drug with macrocyclic structure [50]. Recently, the metal binding complexes of natural chiral amino acids have commonly been utilized as chiral selectors [37][38][39][40][41][43][44][45][46][47]. It has been shown that these chiral amino acids with an aromatic side chain provide the greatest chiral distinction [24,25,37,38].…”

mentioning

confidence: 99%

Chiral recognition of zinc(II) ion complexes composed of bicyclo[3.3.0] octane-2,6-diol and s-Naproxen probed by collisional-induced dissociation

Guo

Chen

et al. 2004

J. Am. Soc. Mass Spectrom.

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Chiral recognition of racemic bicyclo[3.3.0] octane-2,6-diol(B) was achieved in the gas phase using s-Naproxen(A) as reference, using the kinetics of competitive unimolecule dissociation of tetrameric zinc(II)-bound complexes by electrospray ionization Fourier transform ion cyclotron resonance mass spectrometer(ESI-FTMS). As undergoing a mild competitive collision-induced dissociation(CID) experiment with a constant pressure argon gas introduced by leak valve, the tetrameric cluster ion [A(2)B(2)Z(n)(II)-H](+) forms only two trimeric ions and R(chiral) is subsequently obtained in the kinetic method. Further studies obtained the difference of Gibbs free energy of [ABZ(n)(II)-H](+)(Delta Delta G(ABZn(II)-H](+))) by dissociating [A(2)BZ(n)(II)-H](+), resulting two fragment ions [ABZ(n)(II)-H](+) and [A(2)Z(n)(II)-H](+), which can be established to a linear relationship between Delta Delta G([ABZn(II)-H](+)) and R(chiral)' basing on the kinetic method. The value of R(chiral)' suggested that Delta Delta G([ABZn(II)-H](+)) could be regarded as zero. Meanwhile, dissociation of [AB(2)Z(n)(II)-H](+) generated only one daughter ion [ABZ(n)(II)-H](+) in a stable pressure. Thus, a linear relationship was established between the difference of Gibbs free energy of [AB(2)Z(n)(II)-H](+)(Delta Delta G([AB(2)Zn(II)-H](+))) and R(chiral)" if the Delta Delta G([ABZn(II)-H](+)) can be negligible. Because there is also a linear relationship of R(chiral) in the tetrameric ion [A(2)B(2)Z(n)(II)-H](+) and the Gibbs energy difference of trimeric cluster ion [A(2)BZ(n)(+)(II)-H](Delta Delta G([A(2)BZn(II)-H](+))) plus that of [AB(2)Z(n)(II)-H](+), Delta Delta G([A(2)BZ(n)(II)-H]+]) is easy to be calculated in the dissociation process of tetrameric ion. Stable of R(chiral), R(chiral)' and R(chiral)" under different pressures show T(eff) does not affect the chiral recognition of cluster ions in the condition selected. If an only-one-daughter-ion fragment process of [A(2)BZ(n)(II)-H](+) was existed, R(chiral)''' relating to this dissociation would be calculated just like R(chiral)" of [AB(2)Z(n)(II)-H](+) does. Conclusion was obtained that [A(2)BZ(n)(II)-H](+) makes more contribution to chiral recognition of tetrameric ion measured by kinetic method than [AB(2)Z(n)(II)-H](+) does as R(chiral)''' and R(chiral)" were applied as index to evaluate the Gibbs free energy difference of these two trimeric cluster ions. Further discussion shows that steric interactions and pi-pi stacking interactions are the major factors responsible for the observed efficient chiral recognition in this system.

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Chiral Recognition ofO-Phosphoserine by Mass Spectrometry

Cited by 17 publications

References 18 publications

Enantiomer assays of amino acid derivatives using tertiary amine appended trans-4-hydroxyproline derivatives as chiral selectors in the gas phase

Enantiomer assays of amino acid derivatives using tertiary amine appended trans-4-hydroxyproline derivatives as chiral selectors in the gas phase

Stereoselectivity in the collision-activated reactions of gas phase salt complexes

Chiral recognition of zinc(II) ion complexes composed of bicyclo[3.3.0] octane-2,6-diol and s-Naproxen probed by collisional-induced dissociation

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