In Situ STM and Vibrational Study of Nanometer-Scale Reorganization of a Phospholipid Monolayer Accompanied by Potential-Driven Headgroup Digestion

In situ dynamic observation of model biological cell membranes, formed on a water/gold substrate interface, has been performed by the combination of electrochemical scanning tunneling microscopy and reflection infrared absorption vibrational spectroscopy. Monolayers of 1,2-dihexanoyl-sn-glycero-3-phosphocholine (DHPC) were formed on alkanethiol-modified gold surfaces in a buffer solution, and the microscopic phase transitions driven by electrochemical potential control were observed more in detail than our previous study on the same system [Electrochem. Commun. 2007, 9, 645-650]. This time the transitions were associated with the chemistry of DHPC by the aid of vibrational spectroscopy and the utilization of deuterium-labeled DHPC molecules. A negative potential shift solidifies the fluidic lipid layers into static striped or grainy features without notable chemical reactions. The first positive potential shift over the virginal DHPC monolayer breaks DHPC into choline and the corresponding phosphatidic acid (DHPA). This is the first case of a phospholipid electrochemical reaction microscopically detected at the solid surface.