Designing sequence-defined peptoids for fibrillar self-assembly and silicification

Wenchao Yang; Yicheng Zhou; Biao Jin; Xin Qi; Bin Cai; Qiuxiang Yin; Jim Pfaendtner; James J De Yoreo; Chun-Long Chen

doi:10.1016/j.jcis.2022.11.136

Designing sequence-defined peptoids for fibrillar self-assembly and silicification

J Colloid Interface Sci. 2023 Mar 15:634:450-459. doi: 10.1016/j.jcis.2022.11.136. Epub 2022 Nov 28.

Authors

Wenchao Yang¹, Yicheng Zhou², Biao Jin², Xin Qi³, Bin Cai⁴, Qiuxiang Yin⁵, Jim Pfaendtner⁶, James J De Yoreo⁷, Chun-Long Chen⁸

Affiliations

¹ Physical Sciences Division, Pacific Northwest National Laboratory, Richland, WA 99352, United States; School of Chemical Engineering and Technology, State Key Laboratory of Chemical Engineering, Tianjin University, Tianjin 300072, China.
² Physical Sciences Division, Pacific Northwest National Laboratory, Richland, WA 99352, United States.
³ Department of Chemical Engineering, University of Washington, Seattle, WA 98195, United States.
⁴ Physical Sciences Division, Pacific Northwest National Laboratory, Richland, WA 99352, United States; School of Chemistry and Chemical Engineering, Shandong University, Shandong 250100, China.
⁵ School of Chemical Engineering and Technology, State Key Laboratory of Chemical Engineering, Tianjin University, Tianjin 300072, China; The Co-Innovation Center of Chemistry and Chemical Engineering of Tianjin, Tianjin University, Tianjin 300072, China.
⁶ Physical Sciences Division, Pacific Northwest National Laboratory, Richland, WA 99352, United States; Department of Chemical Engineering, University of Washington, Seattle, WA 98195, United States.
⁷ Physical Sciences Division, Pacific Northwest National Laboratory, Richland, WA 99352, United States; Materials Science and Engineering, University of Washington, Seattle, WA 98105, United States.
⁸ Physical Sciences Division, Pacific Northwest National Laboratory, Richland, WA 99352, United States; Department of Chemical Engineering, University of Washington, Seattle, WA 98195, United States. Electronic address: Chunlong.Chen@pnnl.gov.

PMID: 36542974
DOI: 10.1016/j.jcis.2022.11.136

Abstract

In the biological environment, mineral crystals exquisitely controlled by biomacromolecules often show intricate hierarchical structures and superior mechanical properties. Among these biominerals, spicules, hybrid silica/protein superstructures serving as skeletal elements in demosponges, represent an excellent example for motivating the synthesis of silica materials. Herein, by designing sequence-defined peptoids containing side chains with a strong binding to silica, we demonstrated that self-assembly of these peptoids into fiber structures enables the mimicking of both biocatalytic and templating functions of silicatein filaments for the formation of silica fibers at near-neutral pH and ambient temperature. We further showed that the presence of amino groups is significant for the nucleation of silica on self-assembled peptoid nanofibers. Molecular dynamics simulation further confirmed that having silica-binding of amino side chains is critical for self-assembled peptoid fibers in triggering silica formation. We demonstrated that tuning inter-peptoid interactions by varying carboxyl and amino side chains significantly influences the assembly kinetics and final morphologies of peptoid assemblies as scaffolds for directing silica mineralization to form silica spheres, fibers, and sheets. The formation of silica shell on peptoid fibers increased the mechanical property of peptoid hydrogel materials by nearly 1000-fold, highlighting the great potential of using silicification to enhance the mechanical property of hydrogel materials for applications including tissue engineering. Since peptoids are highly robust and programmable, we expect that self-assembly of peptoids containing solid-binding side chains into hierarchical materials opens new opportunities in the design and synthesis of highly tunable scaffolds that direct the formation of composite nanomaterials.

Keywords: Dynamic template; Fibrillar self-assembly; Peptoids; Silicification; Surface modification; near-neutral pH.

MeSH terms

Hydrogels
Nanostructures*
Peptoids* / chemistry
Silicon Dioxide

Substances

Peptoids
Hydrogels
Silicon Dioxide