Fabrication of Submicrometer Biomolecular Patterns by Near-Field Exposure of Plasma-Polymerized Tetraglyme Films

Plasma-polymerized tetraglyme films (PP4G) have been modified by exposure to ultraviolet (UV) light from a frequency-doubled argon ion laser (244 nm) and characterized using X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). XPS data indicated that the ether component of the C 1s spectrum declined after UV exposure, while components due to carbonyl and carboxylate groups increased. The film was physically eroded by UV exposure: after 100 s the rate of erosion reached a steady state of 0.05 nm s−1. The coefficient of friction, measured by friction force microscopy (FFM), increased substantially following exposure to UV light, reaching a limiting value after 10 min exposure, in agreement with the time taken for the ether and carboxylate components in the C 1s spectrum to reach a limiting value. Samples exposed to UV light through a mask yielded excellent frictional contrast. When immersed in solutions of proteins and protein-functionalized nanoparticles labeled with fluorescent markers, selective adsorption occurred onto the exposed regions of these samples. Excellent fluorescence contrast was obtained when samples were characterized by confocal microscopy, indicating that the exposed areas become adhesive toward proteins, while the masked areas remain resistant to adsorption. Submicrometer structures have been formed by exposing PP4G films to UV light using a scanning near-field optical microscope coupled to a UV laser. Structures as small as 338 nm have been formed and used to immobilize proteins. Again, excellent contrast difference was observed when labeled proteins were adsorbed and characterized by confocal microscopy, suggesting a simple and effective route to the formation of submicrometer scale protein patterns.