Incorporation of medium chain triacylglycerols into phospholipid bilayers: effect of long chain triacylglycerols, cholesterol, and cholesteryl esters.
The ability of water-insoluble molecules such as triacylglycerols to partition from oil phases into phospholipid interfaces may be crucial to their hydrolysis by lipases in the aqueous environment of plasma and cells. This study uses high resolution and magic angle spinning 13C NMR spectros-copy to measure the solubility of the 8-carbon medium chain triacylglycerol, trioctanoin, in the lamellar structure of phospholipids (vesicles and multilayers) in the presence of other neutral lipids that may compete for an interfacial location (long chain triacylglycerol, cholesteryl ester, and cholesterol). In the presence of a saturating concentration of triolein (approximately 3 mole%), the solubility of trioctanoin in egg phosphatidylcholine vesicles decreased from 10 mole% to 7 mole%. The presence of a saturating concentration of trioctanoin (approximately 10 mole%) decreased the interfacial solubility of long chain triolein to approximately 1 mole%. Cholesteryl oleate in phospholipid vesicles slightly diminished the incorporation of trioctanoin into the surface. The presence of cholesterol reduced the interfacial solubility of trioctanoin, but at a high level of cholesterol (30 mole%), trioctanoin had a solubility of 3 mole%. Thus, even in the presence of other competing neutral lipids, medium chain triacylglycerol retains a favorable location and surface concentration for efficient hydrolysis. 13C NMR analysis thus provides an explanation for preferential hydrolysis of medium, compared to long chain triacylglycerol, in a physical blend of medium and long chain triacylglycerol in a single emulsion particle, and in general, a valuable approach to determine substrate availability at phospholipid surfaces.
Hamilton
J A
JA
Department of Biophysics, Boston University School of Medicine, MA 02118-2394, USA.
Vural
J M
JM
Carpentier
Y A
YA
Deckelbaum
R J
RJ
D002210:Caprylates / Q000737:chemistry; D002784:Cholesterol / Q000737:chemistry; D002788:Cholesterol Esters / Q000737:chemistry; D004655:Emulsions; D006868:Hydrolysis; D066298:In Vitro Techniques; D008049:Lipase / Q000378:metabolism; D008051:Lipid Bilayers / Q000737:chemistry*; D008081:Liposomes / Q000737:chemistry; D009682:Magnetic Resonance Spectroscopy; D010743:Phospholipids / Q000737:chemistry*; D012995:Solubility; D014280:Triglycerides / Q000737:chemistry*; D014304:Triolein / Q000737:chemistry; D014867:Water
D002210:Caprylates; D002788:Cholesterol Esters; D004655:Emulsions; D008051:Lipid Bilayers; D008081:Liposomes; D010743:Phospholipids; D014280:Triglycerides; D014867:Water; D014304:Triolein; C014409:cholesteryl oleate; C003637:tricaprylin; D002784:Cholesterol; D008049:Lipase