화학공학소재연구정보센터
Biomacromolecules, Vol.21, No.6, 2176-2186, 2020
Highly Mineralized Biomimetic Polysaccharide Nanofiber Materials Using Enzymatic Mineralization
Many biological high-performance composites, such as bone, antler, and crustacean cuticles, are composed of densely mineralized and ordered nanofiber materials. The mimicry of even simplistic bioinspired structures, i.e., of densely and homogeneously mineralized nanofibrillar materials with controllable mechanical performance, continues to be a grand challenge. Here, using alkaline phosphatase as an enzymatic catalyst, we demonstrate the dense, homogeneous, and spatially controlled mineralization of calcium phosphate nanostructures within networks of anionically charged cellulose nanofibrils (CNFs) and cationically charged chitin nanofibrils (ChNFs)-both emerging biobased nanoscale building blocks for sustainable high-performance materials design. Our study reveals that anionic CNFs lead to a more homogeneous nanoscale mineralization with very high mineral contents up to ca. 70 wt % with a transition from amorphous to crystalline deposits, while cationic ChNFs yield rod-like crystalline morphologies. The bone-inspired CNF bulk films exhibit a significantly increased stiffness, maintain good flexibility and translucency, and have a significant gain in wet state mechanical properties. The mechanical properties can be tuned both by the enzyme concentration and the mineralization time. Moreover, we also show a spatial control of the mineralization using kinetically controlled substrate uptake in a dialysis reactor, and by spatially selectively incorporating the enzyme into 2D printed filament patterns. The strategy highlights possibilities for spatial encoding of enzymes in tailored structures and patterns and programmed mineralization processes, promoting the potential application of mineralized CNF biomaterials with complex gradients for bone substitutes and tissue regeneration in general.