No abstract

We report a new paradigm for the rational design of chiral nanostructures that is based on the hierarchical self-assembly of a ferrocene (Fc)-modified dipeptide, ferrocene-L-Phe-L-Phe-OH (Fc-FF). Compared to other chiral self-assembling systems, Fc-FF is unique because of its smaller size, biocompatibility, multiple functions (a redox center), and environmental responsiveness. X-ray and spectroscopic analyses showed that the incorporation of counterions during the hierarchical self-assembly of Fc-FF changed the conformations of the secondary structures from flat β sheets into twisted β sheets. This approach enables chiral self-assembly and the formation of well-defined chiral nanostructures composed of helical twisted β sheets. We identified two elementary forms for the helical twist of the β sheets, which allowed us to create a rich variety of rigid chiral nanostructures over a wide range of scales. Furthermore, through subtle modulations in the counterions, temperature, and solvent, we are able to precisely control the helical pitch, diameter, and handedness of the self-assembled chiral nanostructures. This unprecedented level of control not only offers insights into how rationally designed chiral nanostructures can be formed from simple molecular building blocks but also is of significant practical value for the use in chiroptics, templates, chiral sensing, and separations.

Facile, efficient, and robust immobilization of metal nanostructures on porous bioscaffolds is an interesting topic in materials chemistry and heterogeneous catalysis. This study reports a facile in situ method for the synthesis and immobilization of small silver nanoparticles (AgNPs) at room temperature on natural eggshell membrane (ESM), which presents interwoven fibrous structure and can be used as a unique protein-based biotemplate. Procyanidin (Pro), a typical plant polyphenol extracted from grape seeds and skins, was first grafted onto ESM fibers to serve as both reductant and stabilizer during the synthesis process. As a result, the AgNPs were facilely synthesized and robustly immobilized on the ESM fibers without additional chemical reductant or physical treatments. The morphology and microstructure of the as-prepared AgNPs@Pro-ESM composites were characterized by combined microscopy and spectroscopy technologies. The results indicate that small AgNPs with mean diameter of 2.46 nm were successfully prepared on the Pro-ESM biotemplate. The composites exhibited good catalytic activity toward the reduction of 4-nitrophenol (4-NP). More importantly, these composite catalysts can be easily recovered and reused for more than eight cycles because of their high stability.