Nanografting of polymer brushes on gold substrate by RAFT-RIGP

Optical sensors based on surface plasmon resonance (SPR) have made great strides in the detection of various chemical and biological analytes. A surface plasmon is a bound, non-radiative evanescent wave generated as resonant electrons on a metal-dielectric surface absorb energy from an incident light. As analytes bind to a functionalized metal substrate, the refractometric response generated can be used for quantitation with great selectivity, sensitivity, and capacity for label-free real-time analysis. Polymer nanobrushes are ideal recognition elements because of their greater surface area and their wide range of functional versatility. Here, we introduce a simple “grafting-from” method to covalently attach nanometer-thick polymer chains on a gold surface. Nanografting on gold-coated BK-7 glass was performed in two steps: (1) self-assembly of organosulfur compounds; and (2) RAFT-mediated radiation-induced graft polymerization (RAFT-RIGP) of polyglycidyl methacrylate (PGMA). Surface modification was monitored and verified using FTIR, SPR, and SEM-EDS. Layer-by-layer thickness calculated based on Winspall 3.02 simulation fitted with experimental SPR curves showed successful self-assembly of 1-dodecanethiol (DDT) monolayer with thickness measuring 1.4 nm. These alkane chains of DDT served as the graft initiation sites for RAFT-RIGP. Nanografting was controlled by adjusting the absorbed dose in the presence of chain transfer agent, 4-cyano-4-(phenylcarbonothioylthio)pentanoic acid. The molecular weight of grafted polymers measuring 2.8 and 4.3 kDa, corresponded to a thickness increase of 3.6 and 7.9 nm respectively. These stable nanografted gold substrates may be further functionalized for sensing applications.