Affiliation:
1. Section of Organic Chemistry and Biochemistry, Department of Chemistry, University of Ioannina, 45110 Ioannina, Greece
Abstract
Molecular structures, in chloroform and DMSO solution, of the free fatty acids (FFAs) caproleic acid, oleic acid, α-linolenic acid, eicosapentanoic acid (EPA) and docosahexaenoic acid (DHA) are reported with the combined use of NMR and DFT calculations. Variable temperature and concentration chemical shifts of the COOH protons, transient 1D NOE experiments and DFT calculations demonstrate the major contribution of low molecular weight aggregates of dimerized fatty acids through intermolecular hydrogen bond interactions of the carboxylic groups, with parallel and antiparallel interdigitated structures even at the low concentration of 20 mM in CDCl3. For the dimeric DHA, a structural model of an intermolecular hydrogen bond through carboxylic groups and an intermolecular hydrogen bond between the carboxylic group of one molecule and the ω-3 double bond of a second molecule is shown to play a role. In DMSO-d6 solution, NMR and DFT studies show that the carboxylic groups form strong intermolecular hydrogen bond interactions with a single discrete solvation molecule of DMSO. These solvation species form parallel and antiparallel interdigitated structures of low molecular weight, as in chloroform solution. This structural motif, therefore, is an intrinsic property of the FFAs, which is not strongly affected by the length and degree of unsaturation of the chain and the hydrogen bond ability of the solvent.
Funder
Hellenic Foundation for Research and Innovation
Subject
Chemistry (miscellaneous),Analytical Chemistry,Organic Chemistry,Physical and Theoretical Chemistry,Molecular Medicine,Drug Discovery,Pharmaceutical Science
Reference67 articles.
1. Gunstone, F.D. (1996). Fatty Acid and Lipid Chemistry, Springer. [1st ed.].
2. Vance, D.E., and Vance, J.E. (2008). Biochemistry of Lipids, Lipoproteins and Membranes (New Comprehensive Biochemistry), Elsevier. [5th ed.].
3. Akoh, C.C. (2002). Min. D.B. Food Lipids, Chemistry, Nutrition and Biochemistry, Marcel Dekker Inc.. [2nd ed.].
4. Leray, C. (2021). Dietary Lipids for Healthy Brain Function, CRC Press.
5. Modulation of immune function by dietary fatty acids;Miles;Proc. Nutr. Soc.,1998
Cited by
2 articles.
订阅此论文施引文献
订阅此论文施引文献,注册后可以免费订阅5篇论文的施引文献,订阅后可以查看论文全部施引文献