Surface-initiated vapor deposition polymerization of poly(gamma-benzyl-L-glutamate): optimization and mechanistic studies.

Surface-initiated vapor deposition polymerization (SI-VDP) is a very effective approach to synthesize grafted poly(amino acids). In this study, we developed an SI-VDP system with pressure and temperature control and demonstrated highly efficient surface-grafting of poly(gamma-benzyl-L-glutamate) (PBLG) on a silicon wafer at pressure 1000 times larger than those in prior reports. More importantly, we developed new methods to quantitatively investigate mechanistic details of the SI-VDP process. First, we monitored the amount of vaporized monomer and developed a VDP reaction profile (VDPRP) method to study the major monomer reservoir processes. Next, we developed a quantitative Fourier transform infrared analysis of both as-deposited PBLG and chemisorbed PBLG films in addition to ellipsometric data to evaluate the major substrate surface processes. We observed two classes of characteristic features (pulses or two peaks) of VDPRPs, which depended upon the monomer temperature, and proposed possible mechanisms. We also found that the two peaks of VDPRPs can selectively track different reservoir processes in real time. For surface processes, we proposed possible mechanisms to obtain the surface-grafted PBLG that are expected to have either high packing density with mostly alpha-helix segments or low packing density with both random coil and alpha-helix segments.