Squid Beak Inspired Cross-Linked Cellulose Nanocrystal Composites.

Abstract

Bioinspired cross-linked polymer nanocomposites that mimic the water-enhanced mechanical gradient properties of the squid beak have been prepared by embedding either carboxylic acid- or allyl-functionalized cellulose nanocrystals (CNC) into an alkene-containing polymer matrix (poly(vinyl acetate-co-vinyl pentenoate), P(VAc-co-VP)). Cross-linking is achieved by imbibing the composite with a tetrathiol cross-linker and carrying out a photoinduced thiol-ene reaction. Central to this study was an investigation on how the placement of cross-links (i.e., within matrix only or between the matrix and filler) impacts the wet mechanical properties of these materials. Through cross-linking both the CNCs and matrix, it is possible to access larger wet mechanical contrasts (E'stiff/E'soft = ca. 20) than can be obtained by just cross-linking the matrix alone (where contrast E'stiff/E'soft of up 11 are observed). For example, in nanocomposites fabricated with 15 wt % of allyl-functionalized tunicate CNCs and P(VAc-co-VP) with about 30 mol % of the alkene-containing VP units, an increase in the modulus of the wet composite from about 14 MPa to about 289 MPa at physiological temperature (37 °C) can be observed after UV irradiation. The water swelling of the nanocomposites is greatly reduced in the cross-linked materials as a result of the thiol-ene cross-linking network, which also contributes to the wet modulus increase. Given the mechanical turnability and the relatively simple approach that also allows photopatterning the material properties, these water-activated bioinspired nanocomposites have potential uses in a broad range of biomedical applications, such as mechanically compliant intracortical microelectrodes.