Microscale Tattooing of Hydrogels and Cells: Benzoxaborole-Driven Microcontact Printing (µCP) of Glycosylated Surfaces

Microcontact printing (µCP) is a widely used technique for microscale surface patterning. In this study, we present a polymer-supported µCP method for the patterning of (bioactive) glycosylated surfaces. This method was applied to three distinct surfaces: (1) monosaccharide-modified hydrogel surfaces prepared via a "grafting from" approach; (2) glycolsylated surfaces of polymeric microspheres; and (3) the membranes of human primary gastric cells. Specifically, we pattern aldose- (glucose, fucose, galactose) or ketose- (fructose, sorbose) functionalized surfaces. Patterning was achieved by direct contact with a patterned polydimethylsiloxane (PDMS) stamp, whose surface was grafted with a dopamine-containing polymer. The polymer brushes offer an anchor for the boronic acid derivative 6-aminobenzo[c][1,2]oxaborol-1(3H)-ol (ABOB), used as an ink for surface functionalization. During µCP, ABOB patterns transferred to the target surface through the formation of carbohydrate-ABOB complexes at neutral pH conditions. Fluorescence microscopy confirmed the successful transfer of ABOB patterns to glycosylated surfaces, with clear "tattoo-like" signatures observed on hydrogel and cell surfaces.