Titania Binding Peptides as Templates in the Biomimetic Synthesis of Stable Titania Nanosols: Insight into the Role of Buffers in Peptide-Mediated Mineralization

In this Article, we report the unusual behavior of two peptides (Ti-1 (QPYLFATDSLIK) and Ti-2 (GHTHYHAVRTQT)) with high affinity for titania that efficiently promote titania mineralization from an aqueous titanium bisammonium lactatodihydroxide (TiBALDH) solution, yielding small (ca. 4 nm) titania nanoparticles. As a result, we were able to produce for the first time using a biomimetic approach highly stable sub-10-nm titania sols. Both sequences show a high titania mineralization activity per unit peptide concentration and a capacity to control particle size and stabilize nanoparticles through specific surface interactions. We also show that phosphate ions disrupt the controlled particle formation and stabilization achieved in the presence of the two peptides. The products obtained from phosphate buffered solutions are titanium-containing materials (not pure oxide) with poor morphological control similar to those previously reported by others. Our results provide important insights into understanding the mechanism of titania mineralization in a range of different aqueous media (water, Tris, and phosphate buffer)

Biologically Tunable Reactivity of Energetic Nanomaterials Using Protein Cages

The performance of aluminum nanomaterial based energetic formulations is dependent on the mass transport, diffusion distance, and stability of reactive components. Here we use a biologically inspired approach to direct the assembly of oxidizer loaded protein cages onto the surface of aluminum nanoparticles to improve reaction kinetics by reducing the diffusion distance between the reactants. Ferritin protein cages were loaded with ammonium perchlorate (AP) or iron oxide and assembled with nAl to create an oxidation–reduction based energetic reaction and the first demonstration of a nanoscale biobased thermite material. Both materials showed enhanced exothermic behavior in comparison to nanothermite mixtures of bulk free AP or synthesized iron oxide nanopowders prepared without the use of ferritin. In addition, by utilizing a layer-by-layer (LbL) process to build multiple layers of protein cages containing iron oxide and iron oxide/AP on nAl, stoichiometric conditions and energetic performance can be optimized

Biotic–Abiotic Interactions: Factors that Influence Peptide–Graphene Interactions

Understanding the factors that influence the interaction between biomolecules and abiotic surfaces is of utmost interest in biosensing and biomedical research. Through phage display technology, several peptides have been identified as specific binders to abiotic material surfaces, such as gold, graphene, silver, and so forth. Using graphene–peptide as our model abiotic–biotic pair, we investigate the effect of graphene quality, number of layers, and the underlying support substrate effect on graphene–peptide interactions using both experiments and computation. Our results indicate that graphene quality plays a significant role in graphene–peptide interactions. The graphene–biomolecule interaction appears to show no significant dependency on the number of graphene layers or the underlying support substrate

Multifunctional Analytical Platform on a Paper Strip: Separation, Preconcentration, and Subattomolar Detection

We report a plasmonic paper-based analytical platform with functional versatility and subattomolar (<10^–18 M) detection limit using surface-enhanced Raman scattering as a transduction method. The microfluidic paper-based analytical device (μPAD) is made with a lithography-free process by a simple cut and drop method. Complex samples are separated by a surface chemical gradient created by differential polyelectrolyte coating of the paper. The μPAD with a starlike shape is designed to enable liquid handling by lateral flow without microchannel patterning. This design generates a rapid capillary-driven flow capable of dragging liquid samples as well as gold nanorods into a single cellulose microfiber, thereby providing an extremely preconcentrated and optically active detection spot

Adsorption Behavior of Silk Fibroin on Amphiphilic Graphene Oxide

Graphene oxide-silk composites have gained a significant interest in the recent times because of the unique mechanical properties of both GO and silk and their ability to form layered structures that exhibit a striking resemblance to the layered (brick-mortar) composites found in nature. However, various aspects of the interaction between silk and graphene oxide (e.g., conformation and distribution of the silk chains on chemically heterogeneous GO surface) are not completely understood. In this study, we demonstrate that the interaction between the silk fibroin chains and GO can be modulated by altering the pH of the silk fibroin solution. We employed atomic force microscopy (AFM) and Fourier transform infrared (FTIR) spectroscopy to probe the distribution and the secondary structure of silk fibroin adsorbed on GO. In acidic pH conditions (i.e., pH < pI), a high density of silk chains were found to adsorb on the GO surface, whereas an increase in pH resulted in a progressive decrease in the density of the adsorbed silk chains. This pH-dependent adsorption is ascribed to the electrostatic interactions between the negatively charged GO surface and the tunable ionization of the silk molecules. The secondary structure of silk fibroin chains adsorbed on GO was also found to be highly dependent on the pH. This study provides a deeper understanding of the interaction between GO and silk fibroin that is critical for the design and fabrication of bioinspired nanocomposites with tailored mechanical properties

Determining Peptide Sequence Effects That Control the Size, Structure, and Function of Nanoparticles

The ability to tune the size, shape, and composition of nanomaterials at length scales <10 nm remains a challenging task. Such capabilities are required to fully realize the application of nanotechnology for catalysis, energy storage, and biomedical technologies. Conversely, nature employs biomacromolecules such as proteins and peptides as highly specific nanoparticle ligands that demonstrate exacting precision over the particle morphology through controlling the biotic/abiotic interface. Here we demonstrate the ability to finely tune the size, surface structure, and functionality of single-crystal Pd nanoparticles between 2 and 3 nm using materials directing peptides. This was achieved by selectively altering the peptide sequence to change the binding motif, which in turn modifies the surface structure of the particles. The materials were fully characterized before and after reduction using atomically resolved spectroscopic and microscopic analyses, which indicated that the coordination environment prior to reduction significantly affects the structure of the final nanoparticles. Additionally, changes to the particle surface structure, as a function of peptide sequence, can allow for chloride ion coordination that alters the catalytic abilities of the materials for the C–C coupling Stille reaction. These results suggest that peptide-based approaches may be able to achieve control over the structure/function relationship of nanomaterials where the peptide sequence could be used to selectivity tune such capabilities

Peptide-Modified Dendrimers as Templates for the Production of Highly Reactive Catalytic Nanomaterials

Peptide-driven nanomaterials synthesis and assembly has become a significant research thrust due to the capability to generate a range of multifunctional materials with high spatial precision and tunable properties. Despite the extensive amount of available literature, the majority of studies report the use of free peptides to drive synthesis and assembly. Such strategies are not an entirely accurate representation of nature, as many materials binding peptides found in biological systems are sterically constrained to a larger biological motif. Herein we report the synthesis of catalytic Pd nanomaterials using constrained peptides covalently attached to the surface of small, water-soluble dendrimers. Using the R5 peptide conjugated to polyamidoamine dendrimer as a bioconjugate, Pd nanomaterials were generated that displayed altered morphologies compared to nanomaterials templated with free R5. It was discovered that the peptide surface density on the dendrimer affected the resulting nanoscale morphology. Furthermore, the catalytic activities of Pd materials templated with R5/dendrimer are higher as compared to the R5-templated Pd materials for the hydrogenation of allyl alcohol, with an average increase in turnover frequency of ∼1500 mol product (mol Pd × h)⁻¹. Small angle X-ray scattering analysis and dynamic light scattering indicate that Pd derived from R5/dendrimer templates remained less aggregated in solution and displayed more available reactive Pd surface area. Such morphological changes in solution are attributed to the constrained peptide binding motifs, which altered the Pd morphology and subsequent properties. Moreover, the results of this study suggest that constrained materials binding peptide systems can be employed as a means to alter morphology and improve resulting properties

Wood–Graphene Oxide Composite for Highly Efficient Solar Steam Generation and Desalination

Solar steam generation is a highly promising technology for harvesting solar energy, desalination and water purification. We introduce a novel bilayered structure composed of wood and graphene oxide (GO) for highly efficient solar steam generation. The GO layer deposited on the microporous wood provides broad optical absorption and high photothermal conversion resulting in rapid increase in the temperature at the liquid surface. On the other hand, wood serves as a thermal insulator to confine the photothermal heat to the evaporative surface and to facilitate the efficient transport of water from the bulk to the photothermally active space. Owing to the tailored bilayer structure and the optimal thermo-optical properties of the individual components, the wood–GO composite structure exhibited a solar thermal efficiency of ∼83% under simulated solar excitation at a power density of 12 kW/m². The novel composite structure demonstrated here is highly scalable and cost-efficient, making it an attractive material for various applications involving large light absorption, photothermal conversion and heat localization

Sporicidal/Bactericidal Textiles via the Chlorination of Silk

Bacterial spores, such as those of the <i>Bacillus</i> genus, are extremely resilient, being able to germinate into metabolically active cells after withstanding harsh environmental conditions or aggressive chemical treatments. The toughness of the bacterial spore in combination with the use of spores, such as those of <i>Bacillus anthracis</i>, as a biological warfare agent necessitates the development of new antimicrobial textiles. In this work, a route to the production of fabrics that kill bacterial spores and cells within minutes of exposure is described. Utilizing this facile process, unmodified silk cloth is reacted with a diluted bleach solution, rinsed with water, and dried. The chlorination of silk was explored under basic (pH 11) and slightly acidic (pH 5) conditions. Chloramine-silk textiles prepared in acidified bleach solutions were found to have superior breaking strength and higher oxidative Cl contents than those prepared under caustic conditions. Silk cloth chlorinated for ≥1 h at pH 5 was determined to induce >99.99996% reduction in the colony forming units of <i>Escherichia coli</i>, as well as <i>Bacillus thuringiensis</i> Al Hakam (<i>B. anthracis</i> simulant) spores and cells within 10 min of contact. The processing conditions presented for silk fabric in this study are highly expeditionary, allowing for the on-site production of protein-based antimicrobial materials from a variety of agriculturally produced feed-stocks

Influence of Surface Charge of the Nanostructures on the Biocatalytic Activity

The physicochemical properties of abiotic nanostructures determine the structure and function of biological counterparts in biotic–abiotic nanohybrids. A comprehensive understanding of the interfacial interactions and the predictive capability of their structure and function is paramount for virtually all fields of bionanotechnology. In this study, using plasmonic nanostructures as a model abiotic system, we investigate the effect of the surface charge of nanostructures on the biocatalytic reaction kinetics of a bound enzyme. We found that the surface charge of nanostructures profoundly influences the structure, orientation, and activity of the bound enzyme. Furthermore, the interactions of the enzyme with nanoparticles result in stable conjugates that retain their functionality at elevated temperatures, unlike their free counterparts that lose their secondary structure and biocatalytic activity