Sum frequency generation studies of membrane transport phenomena

This is the final report of a three-year, Laboratory Directed Research and Development (LDRD) project at the Los Alamos National Laboratory (LANL). The objective of this work is to study the transport of protons and ions across biological membranes, one of the most fundamental processes in living organisms, critical for energy transduction in respiration and photosynthesis and for a wide variety of cellular signal transduction events. Membrane protein structure and function, in particular proton and ion pumping are poorly understood. The authors have developed sum frequency generation (SFG) spectroscopy for the study of membrane phenomena, a nonlinear spectroscopic technique that is uniquely sensitive to interfaces and with demonstrated structural specificity. They have used SFG and conventional vibrational spectroscopic approaches to study proton transport processes in cytochrome c oxidase. A key finding has been the identification of vibrational modes associated with proton labile groups, including a glutamic acid near the redox active binuclear center and structural waters. These groups are sensitive to the ligation and redox states of the metal centers and hence are ideal candidates for coupling redox energy to proton transport processes