Glycopolymer Microarrays with Sub-Femtomolar Avidity for Glycan Binding Proteins Prepared by Grafted-To/Grafted-From Photopolymerizations.

We report a novel glycan array architecture that binds the mannose-specific glycan binding protein, concanavalin A (ConA), with sub-femtomolar avidity. A new radical photopolymerization developed specifically for this application combines the grafted-from thiol-(meth)acrylate polymerization with thiol-ene chemistry to graft glycans to the growing polymer brushes. The propagation of the brushes was studied by carrying out this grafted-to/grafted-from radical photopolymerization (GTGFRP) at >400 different conditions using hypersurface photolithography, a printing strategy that substantially accelerates reaction discovery and optimization on surfaces.

Orthogonal Images Concealed Within a Responsive 6-Dimensional Hypersurface.

A photochemical printer, equipped with a digital micromirror device (DMD), leads to the rapid elucidation of the kinetics of the surface-initiated atom-transfer radical photopolymerization of N,N-dimethylacrylamide (DMA) and N-isopropylacrylamide (NIPAM) monomers. This effort reveals conditions where polymer brushes of identical heights can be grown from each monomer. With these data, hidden images are created that appear upon heating the substrate above the lower critical solution temperature (LCST) of polyNIPAM.