(115g) Activation Thermodynamics For Phospholipid Flip-Flop In Planar Supported Lipid Bilayers Measured By Sum-Frequency Vibrational Spectroscopy

Basic transition state theory is used to describe the activation thermodynamics for phospholipid flip-flop in planar supported lipid bilayers prepared by the Langmuir-Blodgett / Langmuir Schaeffer method. Kinetics of flip-flop are determined as a function of varying temperature and lateral surface pressure for model bilayers of 1,2-distearoyl-sn-glycero-3-phosphocholine (DSPC) using sum-frequency vibrational spectroscopy (SFVS). The temperature and pressure dependence of the kinetics of DSPC flip-fop provide a complete description of the activation thermodynamics for flip-flop in the gel state, including free energy of activation, area of activation, and entropy of activation. This is the first description of phospholipid flip-flop according to basic transition state theory with explicit treatment of the free-energy dependence of the process and determination of the entropic contribution to the transition state.