Identification of Toxicity Effects of Cu2O Materials on C. elegans as a Function of Environmental Ionic Composition.

Previous work has shown that spherical CuO nanomaterials show negative effects on cell and animal physiology. The biological effects of Cu2O materials, which posess unique chemical features compared to CuO nanomaterials and can be synthesized in a similarly large variety of shapes and sizes, are comparatively less studied. Here, we synthesized truncated octahedral Cu2O particles and characterized their structure, stability, and physiological effects in the nematode worm animal model, Caenorhabditis elegans. Cu2O particles were found to be generally stable in aqueous media, although the particles did show signs of oxidation and leaching of Cu2+ within hours in worm growth media. The particles were found to be especially sensitive to inorganic phosphate (PO4 3-) found in standard NGM nematode growth medium. Cu2O particles were observed being taken up into the nematode pharynx and detected in the lumen of the gut. Toxicity experiments revealed that treatment with Cu2O particles caused a significant reduction in animal size and lifespan. These toxic effects resembled treatment with Cu2+, but measurements of Cu leaching, worm size, and long-term behavior experiments show the particles are more toxic than expected from Cu ion leaching alone. These results suggest worm ingestion of intact Cu2O particles enhances their toxicity and behavior effects while particle exposure to environmental phosphate precipitates leached Cu2+ into biounavailable phosphate salts. Interestingly, the worms showed an acute avoidance of bacterial food with Cu2O particles, suggesting that animals can detect chemical features of the particles and/or their breakdown products and actively avoid areas with them. These results will help to understand how specific, chemically-defined particles proposed for use in polluted soil and wastewater remediation affect animal toxicity and behaviors in their natural environment.

Biomimetic strategies to produce catalytically reactive CuS nanodisks.

Copper sulfide materials have diverse applications from cancer therapy to environmental remediation due to their narrow bandgap and easily tuned plasmon. The synthesis of these materials often involves toxic reagents and harsh conditions where biomimetic methods may provide opportunities to produce these structures under sustainable conditions. To explore this capability, simple amino acids were exploited as biological ligands for the ambient synthesis of CuS materials. Using an aqueous-based approach, CuS nanodisks were prepared using acid-containing amino acid molecules that stabilize the materials against bulk aggregation. These structures were fully characterized by UV-vis analysis, transmission electron microscopy, dynamic light scattering, atomic force microscopy, selected area electron diffraction, and X-ray diffraction, which confirmed the formation of CuS. The materials possessed a vibrant plasmon band in the near IR region and demonstrated enhanced photocatalytic reactivity for the advanced oxidation of organic dyes in water. These results demonstrate a room temperature synthetic route to optically important materials, which could have important application in catalysis, optics, nanomedicine, etc.

Solution Effects on Peptide-Mediated Reduction and Stabilization of Au Nanoparticles.

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 NaBH4, leading to nanoparticle nucleation and growth. In biological systems, strong reductants such as NaBH4 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 Au3+ 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.

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.

Carbohydrate nanotechnology: hierarchical assembly using nature's other information carrying biopolymers.

Despite their central role in directing some of the most complex biological processes, carbohydrates--nature's other information carrying biopolymer--have been largely ignored as building blocks for synthetic hierarchical assemblies. The non-stoichiometric binding and astronomical diversity characteristic of carbohydrates could lead to tantalizingly complex assembly algorithms, but these attributes simultaneously increase the difficulty of preparing carbohydrate assemblies and anticipating their behavior. Convergences in biotechnology, nanotechnology, polymer chemistry, surface science, and supramolecular chemistry have led to many recent important breakthroughs in glycan microarrays and synthetic carbohydrate receptors, where the idiosyncrasies of carbohydrate structure and binding are increasingly considered. We hope to inspire more researchers to consider carbohydrate structure, diversity, and binding as attractive tools for constructing synthetic hierarchical assemblies.