Development of Self-Assembled Conducting Polymer Ultrathin Films and Poly(aniline) Nanowires/Sol-Gel Composite Materials as Substrates for Planar Supported Biomimetic Artificial Photosynthetic Systems

摘要

This research focuses on the development of a biomimetic photosynthetic energy transduction system which can convert the light energy into a transmembrane potential gradient. This potential gradient provides energy for transmembrane proton pumping, which can be detected potentiometrically and/or spectroscopically through the changes in the optical and electrochemical properties of conductive polymers that supports a lipid bilayer. To achieve this goal, there were two major objectives: 1) Development of a pH sensitive, conducting polymer-based thin film platform as a suitable interface to couple a planar lipid membrane to an ITO electrode and as a pH transducer to detect transmembrane proton motive force (pmf). 2) Construction of an ionophore-aided, transmembrane proton transport model system in a planar supported lipid membrane.Toward the first objective, two different approaches have been used: a) to create a conducting polymer thin film, composed of alternating layers of poly(aniline) PANI and poly(acrylic acid) PAA on an ITO-coated, planar glass substrate. The electroactivity in a neutral environment and the pH dependence of the self-assembled (SA) PANI/PAA multilayer thin films were demonstrated both electrochemically and spectroscopically. Additionally, (PANI/PAA)2 films were shown to be compatible with PSLB. The polymer cushion supported lipid bilayer was found to be highly impermeable to protons, as demonstrated by the blockage of the pH response of the PANI film underneath the lipid membrane. b) to create a PANI nanowire/sol-gel hybrid thin film on an ITO-coated, planar glass substrate. Electrochemical growth of PANI nanowires through a porous sol-gel matrix was demonstrated. The PANI nanowire/sol-gel hybrid thin film with a sol-gel capping layer was found to respond to pH both potentiometrically and spectroscopically and a uniform lipid membrane was formed on the capping layer.To achieve the second objective, a ΔpH-driven transmembrane proton transport model system supported by a PANI nanowire doped sol-gel/ITO substrate with a sol-gel capping layer was developed. Ionophore valinomycin and CCCP were incorporated into the planar supported lipid bilayer (PSLB). Driven by a transmembrane pH gradient, an enhanced rate of proton transport with a proton permeability ca. 3 orders of magnitude higher than that of the lipid membrane without ionophores was demonstrated.