Peptides have demonstrated unique capabilities to fabricate inorganic nanomaterials of numerous compositions through non-covalent binding of the growing surface in solution. In this contribution, we demonstrate that these biomolecules can control all facets of Au nanoparticle fabrication, including Au 3+ reduction, without the use of secondary reagents. In this regard using the AuBP1 peptide, the N-terminal tryptophan residue is responsible for driving Au 3+ reduction to generate Au nanoparticles passivated by the oxidized peptide in solution, where localized residue context effects control the reducing strength of the biomolecule. The process was fully monitored by both timeresolved monitoring of the growth of the localized surface plasmon resonance and transmission electron microscopy. Nanoparticle growth occurs by a unique disaggregation of nanoparticle aggregates in solution. Computational modeling demonstrated that the oxidized residue of the peptide sequence does not impact the biomolecule's ability to bind the inorganic surface, as compared to the parent peptide, confirming that the biomolecule can be exploited for all steps in the nanoparticle fabrication process. Overall, these results expand the utility of peptides for the fabrication of inorganic nanomaterials, more strongly mimicking their use in nature via biomineralization processes. Furthermore, these capabilities enhance the simplicity of nanoparticle production and could find rapid use in the generation of complex multicomponent materials or nanoparticle assembly.

It can be difficult to simultaneously control the size, composition, and morphology of metal nanomaterials under benign aqueous conditions. For this, bioinspired approaches have become increasingly popular due to their ability to stabilize a wide array of metal catalysts under ambient conditions. In this regard, we used the R5 peptide as a three-dimensional template for formation of PdPt bimetallic nanomaterials. Monometallic Pd and Pt nanomaterials have been shown to be highly reactive toward a variety of catalytic processes, but by forming bimetallic species, increased catalytic activity may be realized. The optimal metal-to-metal ratio was determined by varying the Pd:Pt ratio to obtain the largest increase in catalytic activity. To better understand the morphology and the local atomic structure of the materials, the bimetallic PdPt nanomaterials were extensively studied by transmission electron microscopy, extended X-ray absorption fine structure spectroscopy, X-ray photoelectron spectroscopy, and pair distribution function analysis. The resulting PdPt materials were determined to form multicomponent nanostructures where the Pt component demonstrated varying degrees of oxidation based upon the Pd:Pt ratio. To test the catalytic reactivity of the materials, olefin hydrogenation was conducted, which indicated a slight catalytic enhancement for the multicomponent materials. These results suggest a strong correlation between the metal ratio and the stabilizing biotemplate in controlling the final materials morphology, composition, and the interactions between the two metal species.

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Biomimetic methods for the preparation and application of inorganic nanomaterials represent a unique avenue to sustainably generating functional materials with long-term activity. Typically, for the fabrication of these structures, the peptide is mixed with metal ions in solution prior to the addition of an exogenous reductant such as NaBH, leading to nanoparticle nucleation and growth. In biological systems, strong reductants such as NaBH are not available, thus different metal ion reduction methods must be exploited. Recent work has shown that the AuBP1 peptide (WAGAKRLVLRRE), a Au binding peptide with an N-terminal tryptophan, can spontaneously reduce Au without an exogenous reductant. Remarkably, this system initially demonstrated the formation of large Au aggregates that disassemble to form individual Au nanoparticles, stabilized by the peptide bound to the inorganic surface. In this contribution, we demonstrate the significant effects of aqueous solvent-processing conditions (pH, ionic strength, and ion composition) on the rate of particle evolution. Understanding how such effects alter the metal ion reduction process and subsequent nanoparticle fabrication is important in controlling the final structure/function relationship of the resultant peptide-capped materials. This work identifies conditions that may enhance nanoparticle synthesis using biomimetic approaches where the peptide has complete control over the complexation, reduction, nucleation, and growth of nanomaterials.

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