A multinuclear solid-state NMR study of phospholipid-cholesterol interactions. Dipalmitoylphosphatidylcholine-cholesterol binary system.
Multinuclear (1H, 13C, 31P) MASNMR and static solid-state 31P NMR were used to study the molecular interactions between dipalmitoylphosphatidylcholine (DPPC) and free cholesterol (CHOL) in multilayers of DPPC containing 0-65 mol % CHOL with respect to total lipid at temperatures between 25 and 55 degrees C. 13C chemical shifts and line shapes for DPPC and CHOL resonances were measured in 13C MASNMR spectra. The apparent chemical shift anisotropy (CSA) of the DPPC acyl methylene resonances [(CH2)n] was calculated from the 1H MASNMR spectra. CSA and line shape changes were recorded as a function of CHOL content by 31P static solids and MASNMR. The presence of CHOL significantly changed the 13C chemical shifts and line shapes of DPPC carbonyl carbons below or above the main transition temperature of pure DPPC. Chemical shift changes were also observed for CHOL carbons as a function of the mixing ratio, signifying a changing local environment of CHOL. For mixtures with CHOL > 50 mol %, 13C MASNMR detected crystalline CHOL in the monohydrate form. When the excess CHOL was in a submicroscopic crystalline form that was not readily detected by differential scanning calorimetry, or optical microscopy (but readily observed by 13C MASNMR), the 31P powder pattern was affected, suggesting interaction of the excess CHOL with the aqueous interface of the bilayer. These results suggest the potential of 13C MASNMR for detection of crystalline CHOL in biological samples.
Guo
W
W
Department of Biophysics, Boston University School of Medicine, Massachusetts 02118, USA.
Hamilton
J A
JA
D015060:1,2-Dipalmitoylphosphatidylcholine / Q000737:chemistry*; D002152:Calorimetry, Differential Scanning; D002247:Carbon Isotopes; D002784:Cholesterol / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D010759:Phosphorus Isotopes; D011522:Protons
D002247:Carbon Isotopes; D010759:Phosphorus Isotopes; D011522:Protons; D015060:1,2-Dipalmitoylphosphatidylcholine; D002784:Cholesterol