Hydration‐Induced β‐Sheet Crosslinking of α‐Helical‐Rich Spider Prey‐Wrapping Silk

Stengel, Dillan; Addison, J. Bennett; Onofrei, David; Huynh, Nha Uyen; Youssef, George; Holland, Gregory P.

doi:10.1002/adfm.202007161

Title: Hydration‐Induced β‐Sheet Crosslinking of α‐Helical‐Rich Spider Prey‐Wrapping Silk

Journal Article · Mon Jan 04 00:00:00 UTC 2021 · Advanced Functional Materials

DOI: https://doi.org/10.1002/adfm.202007161 · OSTI ID:1804210

Stengel, Dillan ^[1]; Addison, J. Bennett ^[2]; Onofrei, David ^[1]; Huynh, Nha Uyen ^[3]; Youssef, George ^[3];

^[1]

Department of Chemistry and Biochemistry San Diego State University San Diego CA 92182‐1030 USA
Renewable Resources and Enabling Sciences Center 15013 Denver West Parkway Golden CO 80401 USA
Experimental Mechanics Laboratory Mechanical Engineering Department San Diego State University San Diego CA 92182 USA

Abstract Due to its moderate strength (≈700 MPa) and impressive extensibility before breaking (≈60–80%), orb‐weaving spider aciniform (AC) prey‐wrapping silks are actually the toughest of the spider silks but are remarkably understudied. The previous results indicate that native AC silk fibers are an α‐helix rich coiled‐coil/β‐sheet hybrid nanofiber, and that conversion of disordered or helical domains to β‐sheet aggregates is surprisingly minimal and overall β‐sheet content is low (≈15%). In this work, it is demonstrated through scanning electron microscopy that native AC silk fibers undergo matted cross‐linking upon exposure to moisture that increases silk stiffness. The unique molecular mechanism of water‐induced cross‐linking is revealed with solid‐state NMR (SSNMR) methods; water‐induced morphological changes are correlated with an increase in AC silk protein β‐sheet content, and additionally a minor unfolding of coiled‐coil regions is observed. Continued and increased β‐sheet cross‐linking is observed upon application of mechanical shear. The size of these β‐sheet domains to be 4–6 nm using Wide‐Line Separation SSNMR is determined. The observation that merely water treatment can be used to convert a protein‐based material from a flexible/extensible α‐helix‐rich fiber to a rigid crossed‐linked β‐sheet mat is a novel observation that should provide new avenues in bioinspired materials design.

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Sponsoring Organization:: USDOE

Grant/Contract Number:: AC36-08GO28308

OSTI ID:: 1804210

Journal Information:: Advanced Functional Materials, Journal Name: Advanced Functional Materials Journal Issue: 13 Vol. 31; ISSN 1616-301X

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

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