Silica-silk fibroin hybrid (bio)aerogels: two-step versus one-step hybridization.

In this study, silk fibroin as a highly promising naturally occurring biopolymer extracted from silkworm cocoon is applied to mechanically reinforce silica aerogels. To this aim, two different approaches for the incorporation of silk fibroin into the silica network are compared: (1) a one-step acid catalyzed and (2) a two-step acid-base catalyzed sol-gel reaction. The total organosilane concentration, as well as the SF to silane mass fractions, regulated the hybridization process to proceed either through a one-step or two-step sol-gel reaction. In both processes, for an efficient chemical mixing the silk fibroin components with the silane phase, a silane coupling agent, 5-(trimethoxysilyl) pentanoic acid (TMSPA), comprising carboxylic acid groups and a pentyl hydrocarbon chain has been used. For a low organosilane content (3.4 mmol) along with a high SF to silane mass ratio (15-30%), the gelation of the silane and silk fibroin phases took place in a one-pot/one-step process in the presence of an acid catalyst in an entirely aqueous system. In the two-step synthesis approach, which was applied for high initial silane contents (17 mmol), and low SF to silane mass ratios (1-4%), first, the gelation of the silk fibroin phase was triggered by addition of an acid catalyst followed by a more pronounced condensation of the silane catalyzed by the addition of the base. Both synthesis approaches led to materials with promising mechanical properties-being 1) the one-step process resulting in gels with much better compressibility (up to 70% of strain), low density (0.17-0.22 g cm