UV- and Visible-Light Photopatterning of Molecular Gradients Using the Thiol-yne Click Reaction.

The rational design of chemical coatings is used to control surface interactions with small molecules, biomolecules, nanoparticles, and liquids as well as optical and other properties. Specifically, micropatterned surface coatings have been used in a wide variety of applications, including biosensing, cell growth assays, multiplexed biomolecule interaction arrays, and responsive surfaces. Here, a maskless photopatterning process is studied, using the photocatalyzed thiol-yne "click" reaction to create both binary and gradient patterns on thiolated surfaces. Nearly defect-free patterns are produced by first coating glass surfaces with mercaptopropylsilatrane, a silanizing agent that forms smoother self-assembled monolayers than the commonly used 3-mercaptopropyltrimethoxysilane. Photopatterning is then performed using UV (365 nm) or visible (405 nm) light to graft molecules onto the surface in tunable concentrations based on the local exposure. The technique is demonstrated for multiple types of molecular grafts, including fluorescent dyes, poly(ethylene glycol), and biotin, the latter allowing subsequent deposition of biomolecules via biotin-avidin binding. Patterning is demonstrated in water and dimethylformamide, and the process is repeated to combine molecules soluble in different phases. The combination of arbitrary gradient formation, broad applicability, a low defect rate, and fast prototyping thanks to the maskless nature of the process creates a particularly powerful technique for molecular surface patterning that could be used for a wide variety of micropatterned applications.