Protein Micropatterns Using a pH-Responsive Polymer and Light

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Abstract
Protein and peptide microarrays are popular candidates for medical diagnostics because of the possibility for high sensitivity and simultaneous marker screening. To realize the potential of these arrays, new strategies for ligand patterning are needed. We report a method for patterning proteins that utilizes a pH-responsive polymer, deep ultraviolet (DUV) light, and a photoacid generator (PAG). Poly(3,3‘-diethoxypropyl methacrylate) (PDEPMA) contains reactive acetal side chains which are converted to aldehydes following treatment with acid. PDEPMA was spin-coated onto Si−SiO2 substrates and was either chemically deprotected with 1 M HCl or photochemically deprotected by exposure to DUV in the presence of triphenylsulfonium triflate. Conversion to aldehyde groups was confirmed with Purpald and by reaction with a green fluorescent hydroxylamine. Protein microarrays were demonstrated by incubating photochemically patterned surfaces with an aldehyde-reactive biotin followed by red fluorescent streptavidin. This methodology provides a new substrate for the precise patterning of both peptides and proteins for various biological applications including medical sensors.