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2015 ; 109
(5
): 948-55
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Hexagonal Substructure and Hydrogen Bonding in Liquid-Ordered Phases Containing
Palmitoyl Sphingomyelin
#MMPMID26331252
Sodt AJ
; Pastor RW
; Lyman E
Biophys J
2015[Sep]; 109
(5
): 948-55
PMID26331252
show ga
All-atom simulation data are presented for ternary mixtures of palmitoyl
sphingomyelin (PSM), cholesterol, and either palmitoyl oleoyl phosphatidyl
choline or dioleoyl phosphatidyl choline (DOPC). For comparison, data for a
mixture of dipalmitoyl phosphatidyl choline (DPPC), cholesterol, and DOPC are
also presented. Compositions corresponding to the liquid-ordered phase, the
liquid-disordered phase, and coexistence of the two phases are simulated for each
mixture. Within the liquid-ordered phase, cholesterol is preferentially solvated
by DOPC if it is available, but if DOPC is replaced by POPC, cholesterol is
preferentially solvated by PSM. In the DPPC mixtures, cholesterol interacts
preferentially with the saturated chains via its smooth face, whereas in the PSM
mixtures, cholesterol interacts preferentially with PSM via its rough face.
Interactions between cholesterol and PSM have a very particular character:
hydrogen bonding between cholesterol and the amide of PSM rotates the tilt of the
amide plane, which primes it for more robust hydrogen bonding with other PSM.
Cholesterol-PSM hydrogen bonding also locally modifies the hexagonal packing of
hydrocarbon chains in the liquid-ordered phase of PSM mixtures.