Local pH-Responsive Diazoketo-Functionalized Photoresist for Multicomponent Protein Patterning

Selective surface immobilization of multiple biomolecule components, under mild conditions where they do not denature, is attractive for applications in biosensors and biotechnology. Here, we report on a biocompatible and pH-responsive photoresist containing diazoketo-functionalized methacrylate, methacrylic acid, and poly(ethylene glycol) methacrylate monomers, where the photolithographic process may be carried out in a local pH range to minimize biomolecular denaturation. The polymer is insoluble or sparsely soluble in pH 6.4 or more acidic solution or deionized water, but soluble in a basic solution, pH 7.9 or more. After UV exposure, however, carboxylic acid groups are generated by Wolff rearrangement and photodissociation of the diazoketo groups in the polymer chain, leading to dissolution of UV-exposed polymer at pH 6.4. Using the property of the pH-solubility switching, we demonstrate dual streptavidin patterning using only biological buffers, pH 6.4 and 7.9 solutions, and double exposure patterning to confirm the sustainability of the diazoketo groups in unexposed regions despite carrying out several wet processes.