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| Azevedo, Nuno Monteiro |
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Fossati, Stefan
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article
Microstructuring of Thermoresponsive Biofunctional Hydrogels by Multiphoton Photocrosslinking
Abstract
A pioneering method is introduced for creating thermoresponsive biofunctional hydrogel microstructures using maskless multiphoton lithography. Departing from conventional polymerization-based techniques, this approach relies on simultaneous photocrosslinking and attachment of pre-synthesized polymer chains onto solid substrates. The method enhances control over polymer network characteristics and allows facile integration of additional functionalities through postmodification with biomolecules at specific sites. Exploring two distinct benzophenone- and anthraquinone-based photocrosslinkers incorporated into specially designed poly(N-isopropyl acrylamide)-based co- and terpolymers, the photocrosslinking efficacy is scrutinized. Utilizing a custom femtosecond near-infrared laser lithographer, photocrosslinking conditions are precisely controlled. Comprehensive characterization via surface plasmon resonance imaging, atomic force microscopy, and optical fluorescence microscopy reveals swelling behavior and demonstrates postmodification feasibility. Notably, within specific multiphoton photocrosslinking parameters, the surface-attached microstructures exhibit quasiperiodic topography akin to wrinkle-pattern formation. Leveraging the capabilities of established multiphoton lithographer systems offering fast pattern writing with high resolution, this approach holds great promise for fabricating multifunctional 3D micro- and nanostructures. Such tailored responsive biofunctional materials with control over composition, swelling behavior, and spatially controlled postmodification are particularly attractive in the areas of bioanalytical and biomedical technologies.