title: Reversibility of strain stiffening in silk fibroin gels.
abstract: 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 4.2w/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 10-1-105Pa and a loss factor tan δ between 10-2and 10° 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.
authors.affiliation: Istanbul Technical University, Department of Chemistry, 34469 Maslak, Istanbul, Turkey.
authors.forename: Zeynep
authors.initials: Z
authors.lastname: Oztoprak
authors.affiliation: Istanbul Technical University, Department of Chemistry, 34469 Maslak, Istanbul, Turkey. Electronic address: okayo@itu.edu.tr.
authors.forename: Oguz
authors.initials: O
authors.lastname: Okay
mesh_terms: D005349:Fibroins / Q000737:chemistry*; D005782:Gels; D012212:Rheology; D013314:Stress, Mechanical
chemical_list: D005782:Gels; D005349:Fibroins
keywords: Hydrogels; Silk fibroin; Strain stiffening