Differential Membrane Packing of Stereoisomers of Bis(monoacylglycero)phosphate
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文摘
Bis(monoacylglycero)phosphate (BMP) reveals an unusual sn-1,sn-1' stereoconfiguration ofglycerophosphate. We synthesized sn-(3-myristoyl-2-hydroxy)glycerol-1-phospho-sn-1'-(3'-myristoyl-2'-hydroxy)glycerol (1,1'-DMBMP) and characterized the thermotropic phase behavior and membranestructure, in comparison with those of the corresponding sn-3:sn-1' stereoisomer (3,1'-DMBMP), by meansof differential scanning calorimetry (DSC), small- and wide-angle X-ray scattering (SAXS and WAXS,respectively), pressure-area (-A) isotherms, epifluorescence microscopy of monolayers, and moleculardynamics (MD) simulations. In DSC, these lipids exhibited weakly energetic broad peaks with an onsettemperature of 9 C for 1,1'-DMBMP and 18 C for 3,1'-DMBMP. In addition, a highly cooperative,strongly energetic transition peak was observed at ~40 C for 1,1'-DMBMP and ~42 C for 3,1'-DMBMP.These results are supported by the observation that 1,1'-DMBMP exhibited a larger phase transition pressure(c) than 3,1'-DMBMP. Small- and wide-angle X-ray scattering measurements identified these small andlarge energetic transitions as a quasi-crystalline (Lc1)-quasi-crystalline with different tilt angle (Lc2) phasetransition and an Lc2-L main phase transition, respectively. X-ray measurements also revealed that theseDMBMPs undergo an unbinding at the main phase transition temperature. The MD simulations estimatedstronger hydrogen bonding formation in the 3,1'-DMBMP membrane than in 1,1'-DMBMP, supportingthe experimental data.

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