Abstract
Hydrogels containing synthetic polymers and supramolecular cross-linking units are expected to exhibit unique functions and properties. The heme-heme pocket interaction in hemeproteins may be useful for development of a cross-linking unit because heme binding depends on the redox states of the iron center. In this work, hexameric tyrosine-coordinated hemoprotein (HTHP) is employed as a cross-linking unit in a polyacrylamide gel to create redox-responsive hydrogels. First, redox-dependent stability of the heme-heme pocket interaction in HTHP was evaluated, and it was found that the heme affinity dramatically decreases in the Fe(ii) state. Second, the polymerization of acrylamide and engineered HTHP possessing acryloyl group-tethering heme moieties provided a polyacrylamide gel containing HTHP as a cross-linking unit. A reduction-triggered gel-sol transition in the presence of apomyoglobin was observed. Furthermore, the mechanical properties of the gels containing the engineered HTHP and methylene bisacrylamide were evaluated by a tensile test, and the Young's modulus value was determined to be 14 kPa, which is higher than that of the control gel containing only methylene bisacrylamide (8.5 kPa). Compression tests of the gels revealed redox-responsive mechanical behavior, resulting in a decrease in the compressive modulus upon the addition of a reductant. This behavior is qualitatively consistent with the redox-responsive heme binding of HTHP in a solution state. This finding is expected to contribute to the development of redox-responsive materials for biomedical and biological applications.