Metamorphic Proteins to Achieve Conformationally Selective Material Surface Binding.

The controlled binding of proteins on nanoparticle surfaces remains a grand challenge required for many applications ranging from biomedical to energy storage. The difficulty in achieving this ability arises from the different functional groups of the biomolecule that can adsorb on the nanoparticle surface. While most proteins can only adopt a single structure, metamorphic proteins can access at least two different conformations, which presents intriguing opportunities to exploit such structural variations for binding to nanoparticles.

Exploiting Materials Binding Peptides for the Organization of Resilient Biomolecular Constructs.

Elastomers based on the resilin protein confer exceptional mechanical resilience in nature, but it remains elusive to recover the remarkable properties of these materials when they are made in the laboratory. This is possibly due to preorganized conformations of resilin in its natural setting, facilitating Tyr-based cross-linking. Here, resilin-like peptides (RLPs) are conjugated with a graphene-binding peptide, P1, to produce P1/RLP conjugates, in which the P1 domain may provide favorable preorganization on a graphene surface.

Graphene exfoliation using multidomain peptides.

Liquid-phase exfoliation using biomolecules in aqueous solution is a promising approach to obtain high quality 2D nanosheets. For example, the well-studied graphene-binding peptide, P1 (sequence HSSYWYAFNNKT), has been previously investigated and shown to have a good ability to exfoliate graphene sheets in aqueous conditions under sonication, maintaining colloidal stability. Building on this, the biomolecular exfoliant and assembly motif (BEAM) peptide, that features a graphene-binding domain at one end and a hexagonal boron nitride (h-BN) binding domain at the other, separated by a 10-carbon fatty acid chain in the centre, is shown to exfoliate graphene sheets from bulk graphite in aqueous media.

Biomimetic Control over Bimetallic Nanoparticle Structure and Activity via Peptide Capping Ligand Sequence.

The controlled design of bimetallic nanoparticles (BNPs) is a key goal in tailoring their catalytic properties. Recently, biomimetic pathways demonstrated potent control over the distribution of different metals within BNPs, but a direct understanding of the peptide effect on the compositional distribution at the interparticle and intraparticle levels remains lacking. We synthesized two sets of PtAu systems with two peptides and correlated their structure, composition, and distributions with the catalytic activity.

Peptide/Nanoparticle Biointerfaces for Multistep Tandem Catalysis.

The realization of multifunctional nanoparticle systems is essential to achieve highly efficient catalytic materials for specific applications; however, their production remains quite challenging. They are typically achieved through the incorporation of multiple inorganic components; however, incorporation of functionality could also be achieved at the organic ligand layer. In this work, we demonstrate the generation of multifunctional nanoparticle catalysts using peptide-based ligands for tandem catalytic functionality.

Achieving regioselective materials binding using multidomain peptides.

The ability to integrate two disparate materials-binding domains into a single ligand to achieve regiospecific binding would be powerful to direct material assembly; however, this has proven challenging to achieve due to cross-materials binding. Accomplishing this goal might be achieved by harnessing the precision of biology to exploit the recognition between peptides and specific nanomaterials. Here, a designed bifunctional molecule termed Biomolecular Exfoliant and Assembly Motifs (BEAM) is introduced, featuring two different materials-binding peptide domains, one for graphene and one for hexagonal boron nitride (-BN), at each end of the molecule, separated by a fatty acid spacer.

Manipulation of peptide-fatty acid bioconjugates on graphene: effects of fatty acid chain length and attachment point.

The non-destructive functionalisation of graphene in aqueous media is a critical process with the potential to enhance the versatility of the 2D nanosheet material as a technological enabler. This could also unlock strategies for a wider uptake of graphene in bio-related applications. Graphene functionalisation can be achieved using peptides that specifically recognise the carbon-based material, resulting in persistent non-covalent adsorption without damaging the nanosheet.

Tuning Materials-Binding Peptide Sequences toward Gold- and Silver-Binding Selectivity with Bayesian Optimization.

Peptide sequence engineering can potentially deliver materials-selective binding capabilities, which would be highly attractive in numerous biotic and abiotic nanomaterials applications. However, the number of known materials-selective peptide sequences is small, and identification of new sequences is laborious and haphazard. Previous attempts have sought to use machine learning and other informatics approaches that rely on existing data sets to accelerate the discovery of materials-selective peptides, but too few materials-selective sequences are known to enable reliable prediction.

Design of Pd-Decorated SrTiO/BiOBr Heterojunction Materials for Enhanced Visible-Light-Based Photocatalytic Reactivity.

The development of photocatalytic materials that exploit visible light is imperative for their sustainable application in environmental remediation. While a variety of approaches have been attempted, facile routes to achieve such structures remain limited. In this contribution, a direct route for the production of a SrTiO/BiOBr/Pd heterojunction is presented that employs a low temperature, sustainable production method.

Controlling the Orientation and Viscoelasticity of Materials-Binding Peptides on Hexagonal Boron Nitride Using Fatty Acids.

The adsorption of materials-binding peptides to technologically relevant 2D nanosheets of -BN could be transformative for both property modulation and materials applications. To enhance binding, integration of non-natural functionalities into the biomolecule could prove to be important. However, very little is understood regarding the impact of these biomolecular structural alterations on the binding, which could influence the affinity and surface-adsorbed structures.

Atomically Resolved Characterization of Optically Driven Ligand Reconfiguration on Nanoparticle Catalyst Surfaces.

Dynamic ligand layers on nanoparticle surfaces could prove to be critically important to enhance the functionality of individual materials. Such capabilities could complement the properties of the inorganic component to provide multifunctionality or the ability to be remotely actuated. Peptide-based ligands have demonstrated the ability to be remotely responsive to structural changes when adsorbed to nanoparticle surfaces via incorporation of photoswitches into their molecular structure.

Selective manipulation of peptide orientation on hexagonal boron nitride nanosheets.

The bio-recognition capabilities of materials-specific peptides offer a promising route to obtaining and organizing 2D nanosheet materials in aqueous media. Although significant advances have been made for graphene, little is currently understood regarding how to apply this strategy to hexagonal boron nitride (h-BN) due to a lack of knowledge regarding peptide/h-BN interactions. Here, one of the few peptide sequences known with affinity for h-BN, BP7, is the focus of mutation studies and bio-conjugation.

Identification of Parameters Controlling Peptide-Driven Graphene Exfoliation in Aqueous Media.

Bio-inspired approaches represent potentially transformational methods to fabricate and activate non-natural materials for applications ranging from biomedical diagnostics to energy harvesting platforms. Recently, bio-based methods for the exfoliation of graphene in water have been developed, resulting in peptide-capped nanosheets; however, a clear understanding of the reaction system and peptide ligand structure remains unclear, limiting the advance of such approaches. Here the effects of reaction solution conditions and peptide ligand structure were systematically examined for graphene exfoliation, identifying key parameters to optimize material production.

Material composition and peptide sequence affects biomolecule affinity to and selectivity for h-boron nitride and graphene.

Nanosheet heterostructures offer emergent optical/electronic properties. These could be achieved using selective materials binding peptides, but lack of understanding of selectivity impedes advancement. Here we examine peptides with affinity for graphene or h-BN using quantitative experiments and molecular simulation to identify traits for design of 2D nanosheet selective peptides.

Identification of Toxicity Effects of CuO Materials on 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 CuO 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 CuO particles and characterized their structure, stability, and physiological effects in the nematode worm animal model, .

Biomolecular Material Recognition in Two Dimensions: Peptide Binding to Graphene, -BN, and MoS Nanosheets as Unique Bioconjugates.

Two-dimensional nanosheet-based materials such as graphene, hexagonal boron nitride, and MoS represent intriguing structures for a variety of biological applications ranging from biosensing to nanomedicine. Recent advances have demonstrated that peptides can be identified with affinity for these three materials, thus generating a highly unique bioconjugate interfacial system. This Review focuses on recent advances in the formation of bioconjugates of these types, paying particular attention to the structure/function relationship of the peptide overlayer.

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.

Optical Control of Nanoparticle Catalysis Influenced by Photoswitch Positioning in Hybrid Peptide Capping Ligands.

Here, we present an in-depth analysis of structural factors that modulate peptide-capped nanoparticle catalytic activity via optically driven structural reconfiguration of the biointerface present at the particle surface. Six different sets of peptide-capped Au nanoparticles were prepared, in which an azobenzene photoswitch was incorporated into one of two well-studied peptide sequences with known affinity for Au, each at one of three different positions: the N- or C-terminus or mid-sequence. Changes in the photoswitch isomerization state induce a reversible structural change in the surface-bound peptide, which modulates the catalytic activity of the material.

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.

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 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.

Biointerface Structural Effects on the Properties and Applications of Bioinspired Peptide-Based Nanomaterials.

Peptide sequences are known to recognize and bind different nanomaterial surfaces, which has resulted in the screening and identification of hundreds of peptides with the ability to bind to a wide range of metallic, metal oxide, mineral, and polymer substrates. These biomolecules are able to bind to materials with relatively high affinity, resulting in the generation of a complex biointerface between the biotic and abiotic components. While the number of material-binding sequences is large, at present, quantitative materials-binding characterization of these peptides has been accomplished only for a relatively small number of sequences.

Nature of peptide wrapping onto metal nanoparticle catalysts and driving forces for size control.

Colloidal metal nanocrystals find many applications in catalysis, energy conversion devices, and therapeutics. However, the nature of ligand interactions and implications on shape control have remained uncertain at the atomic scale. Large differences in peptide adsorption strength and facet specificity were found on flat palladium surfaces versus surfaces of nanoparticles of 2 to 3 nm size using accurate atomistic simulations with the Interface force field.

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.