Tunable assembly of biomimetic peptoids as templates to control nanostructure catalytic activity.

Nanostructured materials present new opportunities to achieve sustainable catalytic reactivity. Fabrication and organization of these catalytic particles for enhanced reactivity remain challenging due to limited synthetic and organization strategies. Biomimetic approaches represent new avenues to address such challenges. Here we report the tunable assembly of sequence-defined peptoids as templates to control the formation of highly reactive Pd nanostructures of different arrangements. In this regard, peptoid 2D membranes and 1D fibers were assembled and used to template Pd nanoparticles in specific orientations. Catalytic analysis of the resulting materials demonstrated enhanced reactivity from the fiber-based system due to changes in inorganic material display. These results suggest that the morphology of peptoid-based templates plays an important role in controlling material properties, which could open a new direction of using peptoid assemblies for applications in optics, plasmonics, sensing, etc.

Effects of Metal Composition and Ratio on Peptide-Templated Multimetallic PdPt Nanomaterials.

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.

Identifying the Atomic-Level Effects of Metal Composition on the Structure and Catalytic Activity of Peptide-Templated Materials.

Bioinspired approaches for the formation of metallic nanomaterials have been extensively employed for a diverse range of applications including diagnostics and catalysis. These materials can often be used under sustainable conditions; however, it is challenging to control the material size, morphology, and composition simultaneously. Here we have employed the R5 peptide, which forms a 3D scaffold to direct the size and linear shape of bimetallic PdAu nanomaterials for catalysis. The materials were prepared at varying Pd:Au ratios to probe optimal compositions to achieve maximal catalytic efficiency. These materials were extensively characterized at the atomic level using transmission electron microscopy, extended X-ray absorption fine structure spectroscopy, and atomic pair distribution function analysis derived from high-energy X-ray diffraction patterns to provide highly resolved structural information. The results confirmed PdAu alloy formation, but also demonstrated that significant surface structural disorder was present. The catalytic activity of the materials was studied for olefin hydrogenation, which demonstrated enhanced reactivity from the bimetallic structures. These results present a pathway to the bioinspired production of multimetallic materials with enhanced properties, which can be assessed via a suite of characterization methods to fully ascertain structure/function relationships.

Structure of arginine overlayers at the aqueous gold interface: implications for nanoparticle assembly.

Adsorption of small biomolecules onto the surface of nanoparticles offers a novel route to generation of nanoparticle assemblies with predictable architectures. Previously, ligand-exchange experiments on citrate-capped gold nanoparticles with the amino acid arginine were reported to support linear nanoparticle assemblies. Here, we use a combination of atomistic modeling with experimental characterization to explore aspects of the assembly hypothesis for these systems. Using molecular simulation, we probe the structural and energetic characteristics of arginine overlayers on the Au(111) surface under aqueous conditions at both low- and high-coverage regimes. In the low-density regime, the arginines lie flat on the surface. At constant composition, these overlayers are found to be lower in energy than the densely packed films, although the latter case appears kinetically stable when arginine is adsorbed via the zwitterion group, exposing the charged guanidinium group to the solvent. Our findings suggest that zwitterion-zwitterion hydrogen bonding at the gold surface and minimization of the electrostatic repulsion between adjacent guanidinium groups play key roles in determining arginine overlayer stability at the aqueous gold interface. Ligand-exchange experiments of citrate-capped gold nanoparticles with arginine derivatives agmatine and N-methyl-l-arginine reveal that modification at the guanidinium group significantly diminishes the propensity for linear assembly of the nanoparticles.

Structural and equilibrium effects of the surface passivant on the stability of Au nanorods.

Au nanomaterials are well-known for their optical properties, where Au nanorods have demonstrated unique capabilities because of their readily tunable size and shape. Unfortunately, functionalization of the material surface is challenging because of their lack of stability after only a few purification cycles. Here, we demonstrate that enhanced Au-nanorod stability can be achieved by purifying the materials using dilute cetyltrimethylammonium bromide (CTAB) wash solutions. To this end, purifying the materials in such a manner shifts the passivant on/off equilibrium to maintain surfactant adsorption to the metal surface, leading to enhanced stability. Interestingly, from this study, a bimodal distribution of Au nanorods was evident, where one species was prone to bulk aggregation, whereas the second population remained stable in solution. This likely arose from defects within the CTAB bilayer at the nanorod surface, resulting in selective material aggregation. For this, those structures with high numbers of defects aggregated, whereas nanorods with a more pristine bilayer remained stable. Coating of the Au nanorods using polyelectrolytes was also explored for enhanced stability, where the composition of the anionic polymer played an important role in controlling materials stability. Taken together, these results demonstrate that the stability of Au nanorods can be directly tuned by the solvent-exposed surface structure, which could be manipulated to allow for the extensive material functionalization that is required for the generation of nanoplatforms with multiple applications.