Construction of Gold/Rhodium Freestanding Superstructures as Antenna-Reactor Photocatalysts for Plasmon-Driven Nitrogen Fixation.

Precisely controlling the architecture and spatial arrangement of plasmonic heterostructures offers unique opportunities to tailor the catalytic property, whereas the lack of a wet-chemistry synthetic approach to fabricating nanostructures with high-index facets limits their practical applications. Herein, we describe a universal synthetic strategy to construct Au/Rh freestanding superstructures (SSs) through the selective growth of ordered Rh nanoarrays on high-index-faceted Au nanobipyramids (NBPs). This synthetic strategy works on various metal nanocrystal substrates and can yield diverse Au/Rh and Pd/Rh SSs. Especially, the obtained Au NBP/Rh SSs exhibit high photocatalytic activity toward N2 fixation as a result of the spatially separated architecture, local electric field enhancement, and the antenna-reactor mechanism. Both theoretical and experimental results reveal that the Au NBPs can function as nanoantennas for light-harvesting to generate hot charge carriers for driving N2 fixation, while the Rh nanoarrays can serve as the active sites for N2 adsorption and activation to synergistically promote the overall catalytic activity in the Au NBP/Rh SSs. This work offers new avenues to rationally designing and constructing spatially separated plasmonic photocatalysts for high-efficiency catalytic applications.

Observation of Enantiomeric Switching of Individual Plasmonic Metamolecules.

Active plasmonic metamolecules under microscopic observation are promising for optical reporters in single molecule sensing applications. While self-assembled reconfigurable chiral plasmonic metamolecules can be conveniently engineered with sensing functionalities, their observation is usually based on ensemble measurements, where the chiroptical response of enantiomers tend to cancel each other in ensemble circular dichroism. Herein, we demonstrate microscopic observation of enantiomeric switching of individual active DNA origami-assembled plasmonic metamolecules. The metamolecules are immobilized on a glass substrate in a microfluidic chamber, in which the plasmonic metamolecule can maintain their activities upon certain local stimuli as in solution. In circular differential scattering, two enantiomeric states controlled by the strand-displacement reaction display opposite spectral signals to each other, representing successful enantiomeric switching of the chirality. Moreover, in a close-to-racemic mixture of chiral metamolecules controlled by pH-sensitive strands, the coexistence of enantiomeric individuals, which is concealed in ensemble measurements, is clearly identified.

Engineering a Hollow Carbon Sphere-Based Triphase Microenvironment for Enhanced Enzymatic Reaction Kinetics and Bioassay Performance.

Electrochemical bioassays based on oxidase reactions are frequently used in biological sciences and medical industries. However, the enzymatic reaction kinetics are severely restricted by the poor solubility and slow diffusion rate of oxygen in conventional solid-liquid diphase reaction systems, which inevitably compromises the detection accuracy, linearity, and reliability of the oxidase-based bioassay. Herein, an effective solid-liquid-air triphase bioassay system is provided that uses hydrophobic hollow carbon spheres (HCSs) as oxygen nanocarriers. The oxygen stored in the cavity of HCS can rapidly diffuse to the oxidase active sites through the mesoporous carbon shell, providing sufficient oxygen for oxidase-based enzymatic reactions. As a result, the triphase system can significantly improve the enzymatic reaction kinetics and obtain a 20-fold higher linear detection range than the normal diphase system. Other biomolecules can also be determined using this triphase technique, and the triphase design strategy offers a new route to address the gas deficiency problem in catalytic reactions that involve gas consumption.

DNA-Assembled Chiral Satellite-Core Nanoparticle Superstructures: Two-State Chiral Interactions from Dynamic and Static Conformations.

A significant challenge exists in obtaining chiral nanostructures that are amenable to both solution-phase self-assembly and solid-phase preservation, which enable the observation of unveiled optical responses impacted by the dynamic or static conformation and the incident excitations. Here, to meet this demand, we employed DNA origami technology to create quasi-planar chiral satellite-core nanoparticle superstructures with an intermediate geometry between the monolayer and the double layer. We disentangled the complex chiral mechanisms, which include planar chirality, 3D chirality, and induced chirality transfer, through combined theoretical studies and thorough experimental measurements of both solution- and solid-phase samples. Two distinct states of optical responses were demonstrated by the dynamic and static conformations, involving a split or nonsplit circular dichroism (CD) line shape. More importantly, our study on chiral nanoparticle superstructures on a substrate featuring both a dominant 2D geometry and a defined 3D represents a great leap toward the realization of colloidal chiral metasurfaces.

Single-particle spectroscopic investigation on the scattering spectrum of Au@MoS2 core-shell nanosphere heterostructure.

Owing to the uniform shape of the nanospheres, the Au@MoS2 core-shell nanosphere heterostructure enables us to design nano-optoelectronic devices and nanosensors with highly tunable and reproducible optical properties. However, until now, at the single-particle level, there is still uncertainty as to how much the scattering characteristics depend on the particle size and the local environment. In this letter, we performed an in situ single-particle study of the scattering spectrum of the Au@MoS2 core-shell nanosphere heterostructure before and after coating with the MoS2 layer. Single-particle characterization confirms that the classic quasi-static approximation (QSA) theory can be used to predict the scattering spectra of Au@MoS2 core-shell nanoparticles. Moreover, we have found that the A and B-exciton absorption peaks do not rely on the local refractive index change, while the position of the particle plasmon resonances does. Such features can be used as an internal reference for sensing applications against measurement errors, such as defocusing the imaging. Our results show that Au@MoS2 core-shell nanoparticles have the potential to become one of the promising nanosensors in the field of single-particle sensing.

Mapping Hot Electron Response of Individual Gold Nanocrystals on a TiO2 Photoanode.

Incorporating metal nanocrystals with semiconductor photoanodes significantly enhances the efficiency of the energy conversion in the visible range during water splitting due to the excitation of hot electrons. While extensively studied on ensemble samples, hot electron response of metal nanocrystals in a photoelectrochemical cell remains unexploited at the single-particle level. Herein, we systematically investigate hot electron response of individual single-crystalline gold nanocrystals (AuNCs) on a TiO2 photoanode during water splitting. We directly correlate the morphology of the AuNC and its plasmonic property to the efficiencies involving hot electrons with the help of single-particle dark-field microscopy and photocurrent mapping. Our results show that the efficiencies of individual AuNCs are dependent on a variety of factors including interface condition, applied bias, excitation power, incident angle, and AuNC size. Our research may shed light on optimizing the light-harvesting capability of metal/semiconductor photoanodes by providing insights into the photocatalytic processes.

In situ monitoring of silver adsorption on assembled gold nanorods by surface-enhanced Raman scattering.

Self-assembly of metal nanocrystals is able to create a gap of sub-nanometer distance for concentrating incoming light by the strong coupling of surface plasmon resonance, known as a 'hot spot'. Although the plasmonic property of silver is better than other metals in the visible range, the superior Raman enhancement of silver compared to gold is still under debate. To provide direct evidence, in this work, we studied the silver adsorption on assembled gold nanorods (AuNRs) using in situ surface-enhanced Raman scattering (SERS) measurements. The self-assembled AuNR multimers were used as the SERS substrate, where the 4-mercaptophenol (MPh) molecules in our experiment played dual roles as both probe molecules for the Raman scattering and linking molecules for the AuNR assembly in a basic environment. Silver atoms were adsorbed on the surface of gold nanorod assemblies by reduction of Ag+ anions. The stability of the adsorbed silver was guaranteed by the basic environment. We monitored the SERS signal during the silver adsorption with a home-built in situ Raman spectroscope, which was synchronized by recording the UV-vis absorption spectra of the reaction solution to instantly quantify the plasmonic effect of the silver adsorption. Although a minor change was found in the plasmonic resonance wavelength or intensity, the measured SERS signal at specific modes faced a sudden increase by 2.1 folds during the silver adsorption. The finite element method (FEM) simulation confirmed that the silver adsorption corresponding to the plasmonic resonance variation gave little change to the electric field enhancement. We attributed the mode-specific enhancement mechanism of the adsorption of silver to the chemical enhancement from charge transfer (CT) for targeting molecules with a specific orientation. Our findings provided new insights to construct SERS substrates with higher enhancement factor (EF), which hopefully would encourage new applications in the field of surface-enhanced optical spectroscopies.

Fano-like chiroptical response in plasmonic heterodimer nanostructures.

Plasmonic chirality has attracted more and more attention recently due to the enhanced chiroptical response and its potential applications in biosensing. Plasmonic Fano resonance arises from the interference between a dark narrow resonance and a bright broad resonance, and it provides a new paradigm to control the plasmon mode interactions. Even though a strong circular dichroism (CD) effect has been predicted in chiral nanostructures with a Fano resonance, there are few experimental studies, and the correlation between the two effects is unclear. In this research, we investigate these two effects in plasmonic heterodimer nanorods in the same spectral range. We find that the heterodimer nanostructure exhibits a Fano-like resonance and Fano-like chiroptical response, both of which are correlated with the coupling between a super-radiant electric dipole and a sub-radiant magnetic dipole mode. Due to the interference nature of the Fano resonance, the Fano-like chiroptical response exhibits distinctively sharp features in a narrow spectral range. This Fano-like chiroptical response can be explained by a modified chiral molecule theory and a simplified coupled electric-magnetic dipole model. This research may provide new insight into the physics picture of plasmonic chirality and paves the way for the development of sensitive plasmonic sensors.

Site-Specific Surface Functionalization of Gold Nanorods Using DNA Origami Clamps.

Precise control over surface functionalities of nanomaterials offers great opportunities for fabricating complex functional nanoarchitectures but still remains challenging. In this work, we successfully developed a novel strategy to modify a gold nanorod (AuNR) with specific surface recognition sites using a DNA origami clamp. AuNRs were encapsulated by the DNA origami through hybridization of single-stranded DNA on the AuNRs and complementary capture strands inside the clamp. Another set of capture strands on the outside of the clamp create the specific recognition sites on the AuNR surface. By means of this strategy, AuNRs were site-specifically modified with gold nanoparticles at the top, middle, and bottom of the surface, respectively, to construct a series of well-defined heterostructures with controlled "chemical valence". Our study greatly expands the utility of DNA origami as a tool for building complex nanoarchitectures and represents a new approach for precise tailoring of nanomaterial surfaces.

Massively Screening the Temporal Spectra of Single Nanoparticles to Uncover the Mechanism of Nanosynthesis.

Nanosynthesis is the basis of nanotechnology and its applications. It is necessary to understand the growth mechanism of nanoparticles and the functions of growth factors. An effective way to study the synthesis is at the single nanoparticle level. This study reports a single nanoparticle spectrometer, which is based on a commercial dark-field microscopy and a group of narrowband filters. This spectrometer has many advantages, such as high light transparency (35%-75%), low cost (<$1500), massive screening (≈200 nanoplates at a time), and a high time resolution (<5 s). By using this spectrometer, the galvanic replacement reaction (GRR) is studied on single Ag nanoplates in situ and in real time. The research reveals that GRR on single Ag nanoplates has three different types according to the change of peak wavelength during reaction. Such diverse reaction types can be attributed to the different relative reaction rates of GRR on the faces and edges of Ag nanoplate with different facets. Further research shows that the relative reaction rates of different facets vary a lot under different concentrations of tri-sodium citrate. This research successfully demonstrates that the new single nanoparticle spectrometer can study the growth of single nanoparticles and the effect of growth factors.

Dispersive Plasmon Damping in Single Gold Nanorods by Platinum Adsorbates.

Surface modifications of plasmonic nanoparticles with metal adsorbates are essential in applications such as plasmonic sensing, plasmon-enhanced photocatalysis, etc., where spectral broadening is usually observed. A single particle study is presented on plasmon damping by adsorption of platinum (Pt) clusters. Single particle dark-field spectroscopy is employed to measure exactly the same gold nanorod before and after the Pt adsorption. The Pt-induced plasmon damping in terms of linewidth increase is found dependent on the resonance wavelength of the measured nanorod, which is dispersive in nature. The measured dispersion generally matches the theoretical prediction, and it basically exhibits a gradual increase with decreasing resonance energy. This increase can be attributed to the fact that the nanorod as a better resonator is more susceptible to the Pt adsorption than the spherical particles. Moreover, simulated results based on discrete dipole approximation method further indicate that the damping is mainly contributed from the adsorbates on the ends of the nanorod and independent on the type of the metal adsorbed. Knowledge and insights gained in this study can be very important for the design and fabrication of plasmonic heterostructures as functional nanomaterials.

2D Confined-Space Assisted Growth of Molecular-Level-Thick Polypyrrole Sheets with High Conductivity and Transparency.

Herein, the use of a 2D soft template system composed of hundred-nanometer-thick water/ethanol mixed layers sandwiched by lamellar bilayer membranes of a self-assembled amphiphilic molecule to produce ultrathin polyprrole (PPy) with a uniform thickness as thin as 3.8 nm and with large dimensions (>2 µm(2)) is presented. The obtained PPy nanosheets exhibit regioregularity with ordered chain alignment where the polymer chains in the nanosheets produced are well aligned with a clear interchain spacing as confirmed by small-angle X-ray scattering measurement. The molecular-level-thick PPy nanosheets exhibit extremely high conductivity up to 1330 S m(-1), thanks to the ordered alignment of polymer chains in the nanosheets, and a high transparency in both the visible region (transmittance >99%) and near-infrared region (transmittance >93%).

Au nanorod helical superstructures with designed chirality.

A great challenge for nanotechnology is to controllably organize anisotropic nanomaterials into well-defined three-dimensional superstructures with customized properties. Here we successfully constructed anisotropic Au nanorod (AuNR) helical superstructures (helices) with tailored chirality in a programmable manner. By designing the 'X' pattern of the arrangement of DNA capturing strands (15nt) on both sides of a two-dimensional DNA origami template, AuNRs functionalized with the complementary DNA sequences were positioned on the origami and were assembled into AuNR helices with the origami intercalated between neighboring AuNRs. Left-handed (LH) and right-handed (RH) AuNR helices were conveniently accomplished by solely tuning the mirrored-symmetric 'X' patterns of capturing strands on the origami. The inter-rod distance was precisely defined as 14 nm and inter-rod angle as 45°, thus a full helix contains 9 AuNRs with its length up to about 220 nm. By changing the AuNR/origami molar ratio in the assembly system, the average number of AuNR in the helices was tuned from 2 to 4 and 9. Intense chiroptical activities arose from the longest AuNR helices with a maximum anisotropy factor of ∼0.02, which is highly comparable to the reported macroscopic AuNR assemblies. We expect that our strategy of origami templated assembly of anisotropic chiral superstructures would inspire the bottom-up fabrication of optically active nanostructures and shed light on a variety of applications, such as chiral fluids, chiral signal amplification, and fluorescence combined chiral spectroscopy.

Role of bromide in hydrogen peroxide oxidation of CTAB-stabilized gold nanorods in aqueous solutions.

In recent years hydrogen peroxide has often been used as the oxidizing agent to tune the resonance wavelength of gold nanorods (AuNRs) through anisotropic shortening in the presence of cetyltrimethylammonium bromide (CTAB). However, a complete picture of the reaction mechanism remains elusive. In this work, we present a systematic study on the mechanism of the AuNR oxidation by revealing the important role of bromide. Hydrogen peroxide slowly oxidizes bromide into elemental bromine. The latter two form tribromide, which exhibits a characteristic 272 nm absorption peak. The peak intensity, representing the concentration of tribromide, is found to have a linear correlation with the oxidation rate of AuNRs. Tribromide approaches AuNRs through conjugating strongly with CTA cationic micelles, which leads to the oxidation occurring on the surface of AuNRs. In contrast, the CTA micelles protect AuNRs from the direct oxidation by hydrogen peroxide. Our findings are believed to provide new insights into the reaction mechanism occurring in the relevant CTAB-AuNR systems, which can be important for understanding the principles governing the reaction dynamics.

Circular Differential Photocurrent Mapping of Hot Electron Response from Individual Plasmonic Nanohelicoids.

Chiral plasmonic nanocrystals have recently attracted increasing attention in circular polarization-dependent photocatalysis driven by hot carriers. While being concealed in traditional ensemble measurements, the individual chiral photocatalytic activity of nanocrystals can exclusively be revealed by directly correlating the circular differential photocurrent response to helical morphologies using single-particle techniques. Herein, we develop a method named circular differential photocurrent mapping (CDPM) and demonstrate that CDPM can be used to characterize the circular differential hot electron (CDHE) response from individual Au nanohelicoids (AuNHs) on a TiO2 photoanode in a photoelectrochemical cell. The single-particle circular differential scattering and CDHE measurements were interpreted with calculations performed on a model in direct correlation to the helical morphologies of the nanocrystal. While CDHE response was found inactive at a dipolar resonance of 750 nm, helicity-convoluted sites of HE generation were identified on the AuNH at a specific higher-order mode of 550 nm, resulting in a significant response of CDHE in association with the handedness of the AuNH. Details of circular differential contributions were further resolved by examining the efficiencies of individual AuNHs in terms of g-factors. Our study provides a powerful microscopic method at the single-particle level for the photocatalytic characterization of chiral nanocrystals, gaining fundamental insights into the photocatalysis of chirality, especially toward plasmon-induced asymmetrical photochemistry or photoelectrochemistry.

Bifacial DNA origami-directed discrete, three-dimensional, anisotropic plasmonic nanoarchitectures with tailored optical chirality.

Discrete three-dimensional (3D) plasmonic nanoarchitectures with well-defined spatial configuration and geometry have aroused increasing interest, as new optical properties may originate from plasmon resonance coupling within the nanoarchitectures. Although spherical building blocks have been successfully employed in constructing 3D plasmonic nanoarchitectures because their isotropic nature facilitates unoriented localization, it still remains challenging to assemble anisotropic building blocks into discrete and rationally tailored 3D plasmonic nanoarchitectures. Here we report the first example of discrete 3D anisotropic gold nanorod (AuNR) dimer nanoarchitectures formed using bifacial DNA origami as a template, in which the 3D spatial configuration is precisely tuned by rationally shifting the location of AuNRs on the origami template. A distinct plasmonic chiral response was experimentally observed from the discrete 3D AuNR dimer nanoarchitectures and appeared in a spatial-configuration-dependent manner. This study represents great progress in the fabrication of 3D plasmonic nanoarchitectures with tailored optical chirality.

Enhancing single-nanoparticle surface-chemistry by plasmonic overheating in an optical trap.

Surface-chemistry of individual, optically trapped plasmonic nanoparticles is modified and accelerated by plasmonic overheating. Depending on the optical trapping power, gold nanorods can exhibit red shifts of their plasmon resonance (i.e., increasing aspect ratio) under oxidative conditions. In contrast, in bulk exclusively blue shifts (decreasing aspect ratios) are observed. Supported by calculations, we explain this finding by local temperatures in the trap exceeding the boiling point of the solvent that cannot be achieved in bulk.

Trace detection of chiral J-aggregated molecules adsorbed on single Au nanorods.

Trace detection of chiral molecules, which is of great significance in chemical, biological, medical and pharmaceutical sciences, requires microscopic techniques at the single-particle or single-molecule level. Although ensemble experiments show that the circular dichroism of chiral molecules can be amplified by plasmonic nanocrystals, trace detection of small chiral molecules remains challenging due to weak signals that are far below the detection limit. Herein, we demonstrate trace detection of chiral J-aggregated molecules adsorbed on individual Au nanorods (NRs) using single-particle circular differential scattering (CDS) spectroscopy. Through measuring the single-particle CDS spectra, we identified dip-peak bisignatures and further determined the chirality by matching them with calculations modelled with chiral media. We therefore find that plasmonic nanocrystals can dramatically amplify the circular dichroism of strongly coupled molecules to a detectable level so that the detection limit is as low as 3.9 × 103 molecules on an individual plasmonic nanoparticle, whereas 2.5 × 1012 molecules free in solution are barely detectable using a commercial circular dichroism instrument, suggesting a significant amplification factor of 108. Our method provides a promising strategy with a high amplification factor, shedding light on the trace detection of chiral molecules using optical microscopic methods.

Antibonding plasmon modes in colloidal gold nanorod clusters.

The optical response of nanoplasmonic colloids in disperse phase is strictly related to their shape. However, upon self-assembly, new optical features, for example, bonding or antibonding modes, emerge as a result of the mutual orientations of nanoparticles. The geometry of the final assemblies often determines which mode is dominating in the overall optical response. These new plasmon modes, however, are mostly observed in silico, as self-assembly in the liquid phase leads to cluster formation with a broad range of particle units. Here we show that low-symmetry clustering of gold nanorods (AuNRs) in solution can also reveal antibonding modes. We found that UV-light irradiation of colloidal dispersions of AuNRs in N-methyl-2-pyrrolidone (NMP), stabilized by poly(vinylpyrrolidone) (PVP) results in the creation of AuNRs clusters with ladderlike morphology, where antibonding modes can be identified. We propose that UV irradiation induces formation of radicals in solvent molecules, which then promote cross-linking of PVP chains on the surface of adjacent particles. This picture opens up a number of relevant questions in nanoscience and is expected to find application in light induced self-assembly of particles with various compositions and morphologies.

Observing plasmonic-molecular resonance coupling on single gold nanorods.

Strong plasmonic-molecular resonance coupling occurs between noble metal nanocrystals and organic adsorbates when the plasmonic resonance is degenerate with the molecular one. This interaction forms the basis for many fundamental studies and practical applications. We describe here the first direct measurement of the resonance coupling on single gold nanorods. The dark-field scattering technique is employed. The nanorods are embedded in hydrogel to facilitate uniform dye adsorption. The adsorbed dye molecules exhibit both monomer and H-aggregate absorption bands. The same gold nanorods are measured before and after the dye adsorption. Both strong and weak coupling are investigated by selecting nanorods with different longitudinal plasmon bands. Excellent agreement between the experiments and an analytic theory is obtained. The resonance coupling reveals a unique three-band structure. The tunability of the coupling on individual nanorods is further demonstrated by photodecomposing the adsorbed dye molecules.