Poly(3-hydroxybuyrate) production from industrial hemp waste pretreated with a chemical-free hydrothermal process.

In this study, a mild two-stage hydrothermal pretreatment was employed to optimally valorize industrial hemp (Cannabis sativa sp.) fibrous waste into sugars for Poly(3-hydroxybuyrate) (PHB) production using recombinant Escherichia coli LSBJ. Biomass was pretreated using hot water at 160, 180, and 200 °C for 5 and 10 min (15% solids), followed by disk refining. The sugar yields during enzymatic hydrolysis were found to improve with increasing temperature and the yields for hot water-disk refining pretreatment (HWDM) were higher compared to only hot water pretreatment at all conditions. The maximum glucose (56 g/L) and cellulose conversion (92%) were achieved for HWDM at 200 °C for 10 min. The hydrolysate obtained was fermented at a sugar concentration of 20 g/L. The PHB inclusion and concentration of 48% and 1.8 g/L, respectively, were similar to those from pure sugars. A pH-controlled fermentation resulted in a near bi-fold increase in PHB yield (3.46 g/L).

Surface topography and free energy regulate osteogenesis of stem cells: effects of shape-controlled gold nanoparticles.

The surface free energy of a biomaterial plays an important role in the early stages of cell-biomaterial interactions, profoundly influencing protein adsorption, interfacial water accessibility, and cell attachment on the biomaterial surface. Although multiple approaches have been developed to engineer the surface free energy of biomaterials, systematically tuning their surface free energy without altering other physicochemical properties remains challenging. In this study, we constructed an array of chemically-equivalent surfaces with comparable apparent roughness through assembly of gold nanoparticles adopting various geometrically-distinct shapes but all capped with the same surface ligand, (1-hexadecyl)trimethylammonium chloride, on cell culture substrates. We found that bone marrow stem cells exhibited distinct osteogenic differentiation behaviours when interacting with different types of substrates comprising shape-controlled gold nanoparticles. Our results reveal that bone marrow stem cells are capable of sensing differences in the nanoscale topographical features, which underscores the role of the surface free energy of nanostructured biomaterials in regulating cell responses. The study was approved by Institutional Animal Care and Use Committee, School of Medicine, University of South Carolina.

Plasmonic Nanozymes: Engineered Gold Nanoparticles Exhibit Tunable Plasmon-Enhanced Peroxidase-Mimicking Activity.

Enzyme-mimicking inorganic nanoparticles, also known as nanozymes, have emerged as a rapidly expanding family of artificial enzymes that exhibit superior structural robustness and catalytic durability when serving as the surrogates of natural enzymes for widespread applications. However, the performance optimization of inorganic nanozymes has been pursued in a largely empirical fashion due to lack of generic design principles guiding the rational tuning of the nanozyme activities. Here we choose Au surface-roughened nanoparticles as a model plasmonic nanozyme that combines peroxidase-mimicking behaviors with tunable plasmonic characteristics to demonstrate the feasibility of fine-tuning nanozyme activities through plasmonic excitations using visible and near-infrared light sources. Taking full advantage of the unique plasmonic tunability offered by Au surface-roughened nanoparticles, we were able to unravel the detailed relationship between plasmonic excitations and nanozyme activities that underpins the hot electron-mediated working mechanism of peroxidase-mimicking plasmonic nanozymes.

Nanoscale surface curvature modulates nanoparticle-protein interactions.

Rational optimization of nanoparticle (NP) surfaces is essential for successful conjugation of proteins to NPs for numerous applications. Using surface-roughened NPs (SRNPs) and quasi-spherical NPs (QSNPs) as two model nanostructures, we examined the effects of local surface curvature on protein conformation and interfacial behaviors by circular dichroism (CD) spectroscopy, fluorescence emission spectroscopy (FES), and isothermal titration calorimetry (ITC). The surface of SRNPs consisted of a mixture of undercoordinated and close-packed surface atoms at the highly curved and locally flat surface regions, respectively, whereas QSNPs were primarily enclosed by {100} and {111} facets covered with close-packed surface atoms. Our findings demonstrated that: 1) SRNPs possess higher tendency to denature BSA and accommodate a higher number of BSA molecules on the surface and 2) the aggregation of AuNP-BSA complexes, likely induced by either denatured BSA or reduced electrostatic repulsion between complexes, is dependent on both the BSA concentration and the NP surface curvature. This study also indicated that NP local surface curvature could potentially be used as a design strategy to preserve the biological function of proteins.

Hot carriers in action: multimodal photocatalysis on Au@SnO2 core-shell nanoparticles.

Metal-semiconductor hybrid heteronanostructures exhibit intriguing multimodal photocatalytic behaviors dictated by multiple types of photoexcited charge carriers with distinct energy distribution profiles, excited-state lifetimes, and interfacial transfer dynamics. Here we take full advantage of the optical tunability offered by Au@SnO2 core-shell nanoparticles to systematically tune the frequencies of plasmonic electron oscillations in the visible and near-infrared over a broad spectral range well-below the energy thresholds for the interband transitions of Au and the excitonic excitations of SnO2. Employing Au@SnO2 core-shell nanoparticles as an optically tunable photocatalyst, we have been able to create energetic hot carriers exploitable for photocatalysis by selectively exciting the plasmonic intraband transitions and the d → sp interband transitions in the Au cores at energies below the band gap of the SnO2 shells. Using photocatalytic mineralization of organic dye molecules as model reactions, we show that the interband and plasmonic intraband hot carriers exhibit drastically distinct photocatalytic behaviors in terms of charge transfer pathways, excitation power dependence, and apparent photonic efficiencies. The insights gained from this work form an important knowledge foundation guiding the rational optimization of hot carrier-driven chemical transformations on nanostructured metal-semiconductor hybrid photocatalysts.

Carving growing nanocrystals: coupling seed-mediated growth with oxidative etching.

This work presents multiple experimental evidences coherently showing that the versatile structural evolution of Au nanocrystals during seed-mediated growth under the guidance of foreign metal ions and halide-containing surfactants is essentially dictated by the dynamic interplay between oxidative etching and nanocrystal growth. Coupling nanocrystal growth with oxidative etching under kinetically controlled conditions enables the in situ surface carving of the growing nanocrystals, through which the surface topography of shape-controlled nanocrystals can be deliberately tailored on the nanometer length-scale.

Galvanic Replacement-Driven Transformations of Atomically Intermixed Bimetallic Colloidal Nanocrystals: Effects of Compositional Stoichiometry and Structural Ordering.

Galvanic replacement reactions dictated by deliberately designed nanoparticulate templates have emerged as a robust and versatile approach that controllably transforms solid monometallic nanocrystals into a diverse set of architecturally more sophisticated multimetallic hollow nanostructures. The galvanic atomic exchange at the nanoparticle/liquid interfaces induces a series of intriguing structure-transforming processes that interplay over multiple time and length scales. Using colloidal Au-Cu alloy and intermetallic nanoparticles as structurally and compositionally fine-tunable bimetallic sacrificial templates, we show that atomically intermixed bimetallic nanocrystals undergo galvanic replacement-driven structural transformations remarkably more complicated than those of their monometallic counterparts. We interpret the versatile structure-transforming behaviors of the bimetallic nanocrystals in the context of a unified mechanistic picture that rigorously interprets the interplay of three key structure-evolutionary pathways: dealloying, Kirkendall diffusion, and Ostwald ripening. By deliberately tuning the compositional stoichiometry and atomic-level structural ordering of the Au-Cu bimetallic nanocrystals, we have been able to fine-maneuver the relative rates of dealloying and Kirkendall diffusion with respect to that of Ostwald ripening through which an entire family of architecturally distinct complex nanostructures are created in a selective and controllable manner upon galvanic replacement reactions. The insights gained from our systematic comparative studies form a central knowledge framework that allows us to fully understand how multiple classic effects and processes interplay within the confinement by a colloidal nanocrystal to synergistically guide the structural transformations of complex nanostructures at both the atomic and nanoparticulate levels.

Nanoscale Surface Curvature Effects on Ligand-Nanoparticle Interactions: A Plasmon-Enhanced Spectroscopic Study of Thiolated Ligand Adsorption, Desorption, and Exchange on Gold Nanoparticles.

The interfacial adsorption, desorption, and exchange behaviors of thiolated ligands on nanotextured Au nanoparticle surfaces exhibit phenomenal site-to-site variations essentially dictated by the local surface curvatures, resulting in heterogeneous thermodynamic and kinetic profiles remarkably more sophisticated than those associated with the self-assembly of organothiol ligand monolayers on atomically flat Au surfaces. Here we use plasmon-enhanced Raman scattering as a spectroscopic tool combining time-resolving and molecular fingerprinting capabilities to quantitatively correlate the ligand dynamics with detailed molecular structures in real time under a diverse set of ligand adsorption, desorption, and exchange conditions at both equilibrium and nonequilibrium states, which enables us to delineate the effects of nanoscale surface curvature on the binding affinity, cooperativity, structural ordering, and the adsorption/desorption/exchange kinetics of organothiol ligands on colloidal Au nanoparticles. This work provides mechanistic insights on the key thermodynamic, kinetic, and geometric factors underpinning the surface curvature-dependent interfacial ligand behaviors, which serve as a central knowledge framework guiding the site-selective incorporation of desired surface functionalities into individual metallic nanoparticles for specific applications.

Multifaceted Gold-Palladium Bimetallic Nanorods and Their Geometric, Compositional, and Catalytic Tunabilities.

Kinetically controlled, seed-mediated co-reduction provides a robust and versatile synthetic approach to multimetallic nanoparticles with precisely controlled geometries and compositions. Here, we demonstrate that single-crystalline cylindrical Au nanorods selectively transform into a series of structurally distinct Au@Au-Pd alloy core-shell bimetallic nanorods with exotic multifaceted geometries enclosed by specific types of facets upon seed-mediated Au-Pd co-reduction under diffusion-controlled conditions. By adjusting several key synthetic parameters, such as the Pd/Au precursor ratio, the reducing agent concentration, the capping surfactant concentration, and foreign metal ion additives, we have been able to simultaneously fine-tailor the atomic-level surface structures and fine-tune the compositional stoichiometries of the multifaceted Au-Pd bimetallic nanorods. Using the catalytic hydrogenation of 4-nitrophenol by ammonia borane as a model reaction obeying the Langmuir-Hinshelwood kinetics, we further show that the relative surface binding affinities of the reactants and the rates of interfacial charge transfers, both of which play key roles in determining the overall reaction kinetics, strongly depend upon the surface atomic coordinations and the compositional stoichiometries of the colloidal Au-Pd alloy nanocatalysts. The insights gained from this work not only shed light on the underlying mechanisms dictating the intriguing geometric evolution of multimetallic nanocrystals during seed-mediated co-reduction but also provide an important knowledge framework that guides the rational design of architecturally sophisticated multimetallic nanostructures toward optimization of catalytic molecular transformations.

Controlled Dealloying of Alloy Nanoparticles toward Optimization of Electrocatalysis on Spongy Metallic Nanoframes.

Atomic-level understanding of the structural transformations of multimetallic nanoparticles triggered by external stimuli is of vital importance to the enhancement of our capabilities to fine-tailor the key structural parameters and thereby to precisely tune the properties of the nanoparticles. Here, we show that, upon thermal annealing in a reducing atmosphere, Au@Cu2O core-shell nanoparticles transform into Au-Cu alloy nanoparticles with tunable compositional stoichiometries that are predetermined by the relative core and shell dimensions of their parental core-shell nanoparticle precursors. The Au-Cu alloy nanoparticles exhibit distinct dealloying behaviors that are dependent upon their Cu/Au stoichiometric ratios. For Au-Cu alloy nanoparticles with Cu atomic fractions above the parting limit, nanoporosity-evolving percolation dealloying occurs upon exposure of the alloy nanoparticles to appropriate chemical etchants, resulting in the formation of particulate spongy nanoframes with solid/void bicontinuous morphology composed of hierarchically interconnected nanoligaments. The nanoporosity evolution during percolation dealloying is synergistically guided by two intertwining structural rearrangement processes, ligament domain coarsening driven by thermodynamics and framework expansion driven by Kirkendall effects, both of which can be maneuvered by controlling the Cu leaching rates during the percolation dealloying. The dealloyed nanoframes possess large open surface areas accessible by the reactant molecules and high abundance of catalytically active undercoordinated atoms on the ligament surfaces, two unique structural features highly desirable for high-performance electrocatalysis. Using the room temperature electro-oxidation of methanol as a model reaction, we further demonstrate that, through controlled percolation dealloying of Au-Cu alloy nanoparticles, both the electrochemically active surface areas and the specific activity of the dealloyed metallic nanoframes can be systematically tuned to achieve the optimal electrocatalytic activities.

Faceted Gold Nanorods: Nanocuboids, Convex Nanocuboids, and Concave Nanocuboids.

Au nanorods are optically tunable anisotropic nanoparticles with built-in catalytic activities. The state-of-the-art seed-mediated nanorod synthesis offers excellent control over the aspect ratios of cylindrical Au nanorods, which enables fine-tuning of plasmon resonances over a broad spectral range. However, facet control of Au nanorods with atomic-level precision remains significantly more challenging. The coexistence of various types of low-index and high-index facets on the highly curved nanorod surfaces makes it extremely challenging to quantitatively elucidate the atomic-level structure-property relationships that underpin the catalytic competence of Au nanorods. Here we demonstrate that cylindrical Au nanorods undergo controlled facet evolution during their overgrowth in the presence of Cu(2+) and cationic surfactants, resulting in the formation of anisotropic nanostructures enclosed by well-defined facets, such as low-index faceting nanocuboids and high-index faceting convex nanocuboids and concave nanocuboids. These faceted Au nanorods exhibit enriched optical extinction spectral features, broader plasmonic tuning range, and enhanced catalytic tunability in comparison to the conventional cylindrical Au nanorods. The capabilities to both fine-tailor the facets and fine-tune the plasmon resonances of anisotropic Au nanoparticles open up unique opportunities for us to study, in great detail, the facet-dependent interfacial molecular transformations on Au nanocatalysts using surface-enhanced Raman scattering as a time-resolved spectroscopic tool.