Reversibility of strain stiffening in silk fibroin gels


INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES, vol.95, pp.24-31, 2017 (SCI-Expanded) identifier identifier


We investigate the linear and nonlinear viscoelastic properties as well as the reversibility of strain stiffening behavior of silk fibroin gels. The gels are prepared from 4.2 w/v% fibroin solution in the presence of butanediol diglycidyl ether and N,N,N',N'-tetramethylethylenediamine (TEMED) as a cross-linker and catalyst, respectively. By changing the concentration of TEMED in the gelation system, fibroin gels exhibiting a storage modulus G' between 10(-1)-10(5) Pa and a loss factor tan delta between 10(-2) and 10 degrees could be obtained. We observe a strong stiffening (up to 900%) in fibroin gels with increasing strain above 10% deformation, but reversibly if the strain is removed, the gel recovers its initial viscoelastic properties. The strain induced formation of transient intermolecular domains acting as reversible cross-links are responsible for the stiffening behavior of fibroin gels. These additional cross-links formed in the hardened fibroin gels have a temporary nature with lifetimes of the order of seconds. The nonlinear behavior of fibroin gels can be reproduced by a wormlike chain model taking into account the entropic elasticity of fibroin molecules and the strain induced increase in the cross-link density of fibroin gels. (C) 2016 Elsevier B.V. All rights reserved.