Structure and Stability of Carbohydrate–Lipid Interactions. Methylmannose Polysaccharide–Fatty Acid Complexes. (13th July 2016)

• Record Type: Journal Article
• Authors: Liu, Lan; Siuda, Iwona; Richards, Michele R.; Renaud, Justin; Kitova, Elena N.; Mayer, Paul M.; Tieleman, D. Peter; Lowary, Todd L.; Klassen, John S.
• Is Part Of: Chembiochem. Volume 17:Number 16(2016)
• Page Start: 1571
• Page End: 1578
• Publication Date: 2016-07-13
• Subjects: carbohydrates -- lipids -- mass spectrometry -- molecular dynamics -- NMR spectroscopy; Biochemistry -- Periodicals; Molecular biology -- Periodicals; Pharmaceutical chemistry -- Periodicals; 572
• DOI: 10.1002/cbic.201600123
• Languages: English
• ISSNs: 1439-4227

Abstract

Abstract: We report a detailed study of the structure and stability of carbohydrate–lipid interactions. Complexes of a methylmannose polysaccharide (MMP) derivative and fatty acids (FAs) served as model systems. The dependence of solution affinities and gas‐phase dissociation activation energies ( E a ) on FA length indicates a dominant role of carbohydrate–lipid interactions in stabilizing (MMP+FA) complexes. Solution 1 H NMR results reveal weak interactions between MMP methyl groups and FA acyl chain; MD simulations suggest the complexes are disordered. The contribution of FA methylene groups to the E a is similar to that of heats of transfer of n ‐alkanes from the gas phase to polar solvents, thus suggesting that MMP binds lipids through dipole‐induced dipole interactions. The MD results point to hydrophobic interactions and H‐bonds with the FA carboxyl group. Comparison of collision cross sections of deprotonated (MMP+FA) ions with MD structures suggests that the gaseous complexes are disordered. Abstract : We report the first detailed study of the structure and stability of carbohydrate–lipid interactions with a series of fatty acids (FAs). The dependency of the solution affinities and gas‐phase dissociation activation energies on the length of the FA acyl chain conclusively establishes the role of carbohydrate–lipid interactions in complex stabilization.