Table 2. Thermodynamics and kinetics associated with cholesterol/cholestenone flip-flop and desorption.
Model system | ΔGdesorb a (kJ/mol) | ΔGbarrier b (kJ/mol) | ΔGcenter c (kJ/mol) | td (ns) | kd (S−1) | kf (S−1) | kflip (S−1) | |
chol | IFE (POPC/PSM/chol/cnone 2∶1∶1∶0) | 76.0±2.7 | 26.0±1.2 | 25.0±1.0 | 1–80 | 1.3×107 to 109 | 7.8×102 to 6.0×104 | 4.0×102 to 3×104 |
IIFE (POPC/PSM/chol/cnone 2∶1∶0.75∶0.25) | 70.6±1.6 | 23.5±0.9 | 22.5±0.6 | 1–80 | 1.3×107 to 109 | 2.2×103 to 1.7×105 | 1.1×103 to 0.9×105 | |
IVFE (127 POPCs and 1 chol) | 62±2.4 | 19.0±1.3 | 18.0±0.9 | 1–80 | 1.3×107 to 109 | 1.2×104 to 9.1×105 | 0.6×104 to 4.6×105 | |
cnone | IIFE (POPC/PSM/chol/cnone 2∶1∶0.75∶0.25) | 65.4±1.5 | 8.0±0.6 | 6.4±0.3 | 1–40 | 2.5×107 to 109 | 2.1×106 to 8.2×107 | 1.1×106 to 4.1×107 |
IIIFE (POPC/PSM/chol/cnone 2∶1∶0∶1) | 61.3±2.3 | 5.8±0.9 | 4.1±0.7 | 1–40 | 2.5×107 to 109 | 5.0×106 to 2.0×108 | 2.5×106 to 108 | |
VFE (127 POPCs and 1 cnone) | 57.8±1.7 | 4.9±0.9 | 3.5±0.6 | 1–40 | 2.5×107 to 109 | 6.3×106 to 2.5×108 | 3.2×106 to 1.3×108 |
ΔGdesorb is the free energy barrier for desorption from membrane to water phase.
ΔGbarrier is the free energy barrier for flip-flop.
ΔGcenter is the difference in free energy between the bilayer center (Zcenter) and the equilibrium position (Zeq).
The parameters kd, kf, kflip, and td are defined and discussed in Materials and Methods.