title: An interfacial oxime reaction to immobilize ligands and cells in patterns and gradients to photoactive surfaces.
abstract: We report a molecularly controlled interfacial chemoselective methodology to immobilize ligands and cells in patterns and gradients to self-assembled monolayers on gold. This strategy is based on reacting soluble ketone or aldehyde tethered ligands to surface-bound oxyamine alkeanethiols to generate a covalent oxime linkage to the surface. We characterize the kinetic behavior of the reaction on the surface with ferrocenecarboxaldehyde (FcCHO) as a model ligand. The precise extent of immobilization and therefore surface density of FcCHO on the SAM is monitored and determined by cyclic voltammetry, which shows a peudo-first-order rate constant of 0.13 min(-1). In order to generate complex surface patterns and gradients of ligands on the surface, we photoprotected the oxyamine group with nitroveratryloxycarbonyl (NVOC). We show that ultraviolet light irradiation through a patterned microfiche film reveals the oxyamine group and we characterize the rate of deprotection by immobilization of ketone containing redox active groups. Finally, we extend this strategy to show biospecific cell attachment of fibroblast cells by immobilizing ketone-GRGDS peptides in patterns. The interfacial oxime reaction is chemoselective and stable at physiological conditions (pH 7.0, 37 degrees C) and may potentially be used to install ligands on the surface in the presence of attached cells to modulate the cell microenvironment to generate dynamic surfaces for monitoring changes in cell behavior in real time.
authors.affiliation: Department of Chemistry and Carolina Center for Genome Science, University of North Carolina at Chapel Hill, Chapel Hill, North Carolina 27599-3290, USA.
authors.forename: Sungjin
authors.initials: S
authors.lastname: Park
authors.forename: Muhammad N
authors.initials: MN
authors.lastname: Yousaf
mesh_terms: D000447:Aldehydes / Q000737:chemistry; D001547:Benzaldehydes / Q000737:chemistry; D006863:Hydrogen-Ion Concentration; D007659:Ketones / Q000737:chemistry; D007700:Kinetics; D008024:Ligands; D008027:Light; D008856:Microscopy, Fluorescence; D008956:Models, Chemical; D008968:Molecular Conformation; D010091:Oximes / Q000737:chemistry*; D010777:Photochemistry / Q000379:methods*; D013499:Surface Properties; D013696:Temperature; D014466:Ultraviolet Rays
chemical_list: D000447:Aldehydes; D001547:Benzaldehydes; D007659:Ketones; D008024:Ligands; C402308:NVOC-chloride; D010091:Oximes