| Differentiation of diastereomeric cyclic beta-amino acids by varying the neutral reagent in ion/molecule reactions studied by electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry. | |
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MedLine Citation:
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PMID: 18181235 Owner: NLM Status: MEDLINE |
Abstract/OtherAbstract:
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Stereochemical differentiation of diasteromeric pairs of cis- and trans-2-aminocyclohexane-, -2-amino-4-cyclohexene-, and -2-aminocyclopentanecarboxylic acids was investigated with host-guest complexes where tetraethyl resorcarene was the host molecule. Diastereoselectivity was evaluated by ion/molecule reactions and collision-induced dissociation with electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FTICRMS). The effect of varying the neutral reagent (n-propylamine, i-propylamine, diethylamine, and triethylamine) in ion/molecule reactions was evaluated. Both steric interactions and proton affinity of the neutral reagents influenced the reaction rates. High proton affinity of the neutral reagent apparently had a twofold effect. If the proton affinity of the neutral reagent was too high, the reaction tended to become too exothermic and part of the host-guest complex decomposed instead of transforming to a new host-guest complex, effecting a decrease in the reaction rate. The remaining portion of the host-guest complexes meanwhile reacted very fast with the neutral reagent due to high proton affinity causing an increase in the reaction rate. n-Propylamine and i-propylamine proved to be the best neutral reagents, providing clear diastereoselectivity for beta-amino acids in ion/molecule reactions. Interestingly, diastereoselectivity was better for flexible cyclohexane beta-amino acids (2 and 3) than for more rigid cyclopentane beta-amino acids (6 and 7). The results of ab initio and hybrid density functional theory calculations on the structures of the host-guest complexes of saturated beta-amino acids were in good agreement with the experimental results. |
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Authors:
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Anna R M Hyyryläinen; Jaana M H Pakarinen; Pirjo Vainiotalo; Ferenc Fülöp |
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Publication Detail:
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Type: Journal Article; Research Support, Non-U.S. Gov't |
Journal Detail:
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Title: Rapid communications in mass spectrometry : RCM Volume: 22 ISSN: 0951-4198 ISO Abbreviation: Rapid Commun. Mass Spectrom. Publication Date: 2008 |
Date Detail:
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Created Date: 2008-01-17 Completed Date: 2008-04-11 Revised Date: - |
Medline Journal Info:
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Nlm Unique ID: 8802365 Medline TA: Rapid Commun Mass Spectrom Country: England |
Other Details:
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Languages: eng Pagination: 337-44 Citation Subset: IM |
Copyright Information:
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Copyright (c) 2008 John Wiley & Sons, Ltd. |
Affiliation:
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Department of Chemistry, University of Joensuu, PO Box 111, 80101 Joensuu, Finland. |
Export Citation:
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APA/MLA Format Download EndNote Download BibTex |
| MeSH Terms | |
Descriptor/Qualifier:
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Amino Acids, Cyclic
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analysis*,
chemistry* Cyclotrons Hydrogen-Ion Concentration Indicators and Reagents / chemistry Ions Isomerism Spectrometry, Mass, Electrospray Ionization / methods Spectroscopy, Fourier Transform Infrared / methods* |
| Chemical | |
Reg. No./Substance:
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0/Amino Acids, Cyclic; 0/Indicators and Reagents; 0/Ions |
From MEDLINE®/PubMed®, a database of the U.S. National Library of Medicine
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