Tailoring Patterns of Surface-Attached Multiresponsive Polymer Networks.

A new strategy for the fabrication of micropatterns of surface-attached hydrogels with well-controlled chemistry is reported. The "grafting onto" approach is preferred to the "grafting from" approach. It consists of cross-linking and grafting preformed and functionalized polymer chains through thiol-ene click chemistry. The advantage is a very good control without adding initiators. A powerful consequence of thiol-ene click reaction by UV irradiation is the facile fabrication of micropatterned hydrogel thin films by photolithography. It is achieved either with photomasks using common UV lamp or without photomasks by direct drawing due to laser technology. Our versatile approach allows the fabrication of various chemical polymer networks on various solid substrates. It is demonstrated here with silicon wafers, glass and gold surfaces as substrates, and two responsive hydrogels, poly(N-isopropylacrylamide) for its responsiveness to temperature and poly(acrylic acid) for its pH-sensitivity. We also demonstrate the fabrication of stable hydrogel multilayers (or stacked layers) in which each elementary layer height can widely range from a few nanometers to several micrometers, providing an additional degree of freedom to the internal architecture of hydrogel patterns. This facile route for the synthesis of micrometer-resolute hydrogel patterns with tailored architecture and multiresponsive properties should have a strong impact.