Amine-Reactive Azlactone-Containing Nanofibers for the Immobilization and Patterning of New Functionality on Nanofiber-Based Scaffolds

We report the design of amine-reactive polymer nanofibers and nonwoven reactive nanofiber mats fabricated by the electrospinning of azlactone-functionalized polymers. We demonstrate that randomly oriented nanofibers fabricated using a random copolymer of methyl methacrylate and 2-vinyl-4,4-dimethylazlactone contain intact and reactive azlactone groups that can be used to introduce new chemical functionality and modulate important interfacial properties of these materials (e.g., wetting behaviors), by postfabrication treatment with primary amine-based nucleophiles. The facile and "click-like" nature of these reactions permits functionalization under mild conditions without substantial changes to nanofiber or mat morphologies. This approach also enables the patterning of new functionality on mat-coated surfaces by treatment with bulk solutions of primary amines or by using methods such as microcontact printing. Further, these reactive mats can also, themselves, be contact transferred or "printed" onto secondary surfaces by pressing them into contact with other amine-functionalized objects. Finally, we demonstrate that functionalization with hydrophobic amines can increase the stability of these materials in aqueous environments and yield hydrophobic nanofiber scaffolds useful for the design of "slippery" liquid-infused materials. The approaches reported here enable the introduction of new properties to reactive polymer mats after fabrication and, thus, reduce the need to synthesize individual functional polymers prior to electrospinning to achieve new properties. The azlactone chemistry used here broadens the scope of reactions that can be used to functionalize polymer nanofibers and is likely to prove general. We anticipate that this approach can be used with a range of amines or other nucleophiles (e.g., alcohols or thiols) to design nanofibers and reactive nanofiber-based materials with new physical properties, surface features, and behaviors that may be difficult to achieve by the direct electrospinning of conventional materials or other functional polymers.