Document Detail


Ionization behavior of aqueous short-chain carboxylic acids: a carbon-13 NMR study.
MedLine Citation:
PMID:  7119577     Owner:  NLM     Status:  MEDLINE    
Abstract/OtherAbstract:
The 13C chemical shift of each carbon of aqueous acetic, propionic, and butyric acids has been measured as a function of pH or of added equivalents of base. A plot of chemical shifts for the carboxyl, alpha, and beta carbons as a function of pH is sigmoidal and yields pKa values that agree closely with values obtained by potentiometric titration. In contrast, a plot of chemical shift as a function of added equivalents of base is linear and has a sharp break at the equivalence point. Based on this result, we propose that the local (microscopic) ionization state of the carboxyl group can be determined directly by NMR without need for pH or pK determinations. In addition to titration curves, the effects of concentration, ionic strength, and temperature upon fatty acid chemical shifts are reported. For aqueous acids, changes in ionic strength and temperature have no effect on chemical shifts. However, changes in concentration do affect chemical shifts, probably as a result of changes in the relative degree of acid-acid and acid-water hydrogen bonding. Our results provide necessary background data for 13C NMR studies of higher fatty acids in lipid-lipid and lipid-protein systems.
Authors:
D P Cistola; D M Small; J A Hamilton
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Publication Detail:
Type:  Journal Article; Research Support, U.S. Gov't, P.H.S.    
Journal Detail:
Title:  Journal of lipid research     Volume:  23     ISSN:  0022-2275     ISO Abbreviation:  J. Lipid Res.     Publication Date:  1982 Jul 
Date Detail:
Created Date:  1982-12-02     Completed Date:  1982-12-02     Revised Date:  2007-11-14    
Medline Journal Info:
Nlm Unique ID:  0376606     Medline TA:  J Lipid Res     Country:  UNITED STATES    
Other Details:
Languages:  eng     Pagination:  795-9     Citation Subset:  IM    
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MeSH Terms
Descriptor/Qualifier:
Acetic Acid
Acetic Acids
Butyric Acid
Butyric Acids
Carboxylic Acids*
Magnetic Resonance Spectroscopy
Propionic Acids
Grant Support
ID/Acronym/Agency:
HL07291/HL/NHLBI NIH HHS; HL26335/HL/NHLBI NIH HHS
Chemical
Reg. No./Substance:
0/Acetic Acids; 0/Butyric Acids; 0/Carboxylic Acids; 0/Propionic Acids; 107-92-6/Butyric Acid; 64-19-7/Acetic Acid; 79-09-4/propionic acid

From MEDLINE®/PubMed®, a database of the U.S. National Library of Medicine


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