A Self-Assembled Plasmonic Substrate for Enhanced Fluorescence Resonance Energy Transfer

Fluorescence resonance energy transfer (FRET) has found widespread uses in biosensing, molecular imaging, and light harvesting. Plasmonic metal nanostructures offer the possibility of engineering photonic environment of specific fluorophores to enhance the FRET efficiency. However, the potential of plasmonic nanostructures to enable tailored FRET enhancement on planar substrates remains largely unrealized, which are of considerable interest for high-performance on-surface bioassays and photovoltaics. The main challenge lies in the necessitated concurrent control over the spectral properties of plasmonic substrates to match that of fluorophores and the fluorophore–substrate spacing. Here, a self-assembled plasmonic substrate based on polydopamine (PDA)-coated plasmonic nanocrystals is developed to effectively address this challenge. The PDA coating not only drives interfacial self-assembly of the nanocrystals to form closely packed arrays with customized optical properties, but also can serve as a tailored nanoscale spacer between the fluorophores and plasmonic nanocrystals, which collectively lead to optimized fluorescence enhancement. The biocompatible plasmonic substrate that allows convenient bioconjugation imparted by PDA has afforded improved FRET efficiency in DNA microarray assay and FRET imaging of live cells. It is envisioned that the self-assembled plasmonic substrates can be readily integrated into fluorescence-based platforms for diverse biomedical and photoconversion applications.     

Depolarization of surface-enhanced fluorescence: an approach to fluorescence polarization assays

Localized surface plasmons of metallic particles of subwavelength sizes strongly modify the spectral properties of nearby fluorophores. The enhanced radiative decay rate leads to high fluorescence efficiencies and decreased fluorescence lifetimes. In this report we show that metal-enhanced fluorescence generated by the presence of the silver islands on the glass substrate displays high depolarization. Intensities, lifetimes, and emission anisotropies of several fluorophore protein conjugates have been studied in the absence and presence of metallic nanostructures. Despite highly decreased lifetimes of about 10-fold and immobilization of conjugates on the solid substrate, the observed emission anisotropies for all fluorophores on the metal-enhanced substrate decreased 300-500% compared to that in solution. This observation implies a new generation of fluorescence polarization immunoassays with broad applications because of no restrictions to the lifetime of the probe and the size of labeled biomolecules. The changes in polarization are due to binding that occur on the bioactive surface localized near the metal particles.     

Tuning the Intensity of Metal‐Enhanced Fluorescence by Engineering Silver Nanoparticle Arrays

It is demonstrated that silver nanoparticle (SNP) arrays fabricated by combining nanoimprint lithography and electrochemical deposition methods can be used as substrates for metal‐enhanced fluorescence, which is widely used in optics, sensitive detection, and bioimaging. The method presented here is simple and efficient at controlling the nanoparticle density and interparticle distance within one array. Furthermore, it is found that the fluorescence intensity can be tuned by engineering the feature size of the SNP arrays. This is due to the different coupling efficiency between the emission of the fluorophores and surface plasmon resonance band of the metallic nanostructures.     

Nanowire‐Intensified Metal‐Enhanced Fluorescence in Hybrid Polymer‐Plasmonic Electrospun Filaments

Hybrid polymer‐plasmonic nanostructures might combine high enhancement of localized fields from metal nanoparticles with light confinement and long‐range transport in subwavelength dielectric structures. Here, the complex behavior of fluorophores coupling to Au nanoparticles within polymer nanowires, which features localized metal‐enhanced fluorescence (MEF) with unique characteristics compared to conventional structures, is reported. The intensification effect when the particle is placed in the organic filaments is remarkably higher with respect to thin films of comparable thickness, thus highlighting a specific, nanowire‐related enhancement of MEF effects. A dependence on the confinement volume in the dielectric nanowire is also indicated, with MEF significantly increasing upon reduction of the wire diameter. These findings are rationalized by finite element simulations, predicting a position‐dependent enhancement of the quantum yield of fluorophores embedded in the fibers. Calculation of the ensemble‐averaged fluorescence enhancement unveils the possibility of strongly enhancing the overall emission intensity for structures with size twice the diameter of the embedded metal particles. These new, hybrid fluorescent systems with localized enhanced emission, and the general nanowire‐enhanced MEF effects associated to them, are highly relevant for developing nanoscale light‐emitting devices with high efficiency and intercoupled through nanofiber networks, highly sensitive optical sensors, and novel laser architectures.     

Target‐Triggered Assembly of Nanogap Antennas to Enhance the Fluorescence of Single Molecules and Their Application in MicroRNA Detection

Nanogap antennas are plasmonic nanostructures with a strong electromagnetic field generated at the gap region of two neighboring particles owing to the coupling of the collective surface plasmon resonance. They have great potential for improving the optical properties of fluorophores. Herein, nanogap antennas are constructed using an aqueous solution‐based method to overcome the defects of weak fluorescence and photobleaching associated with traditional organic dyes, and a highly sensitive nanogap antenna‐based sensing strategy is presented for the detection of low‐abundance nucleic acid biomarkers via a target‐triggered strand displacement amplification (SDA) reaction between two DNA hairpins that are tagged to the tips of gold nanorods (Au NRs). In the presence of targets, end‐to‐end Au NR dimers gradually form, and the fluorophores quenched by the Au NRs exhibit a dramatic fluorescence enhancement due to the plasmon‐enhanced fluorescence effect of nanogap antennas. Meanwhile, the SDA reaction results in secondary amplification of fluorescence signals. Combined with single‐molecule counting, this method applied in miRNA‐21 detection can achieve a low detection limit of 97.2 × 10^?18 m . Moreover, accurate discrimination between different cells through miRNA‐21 imaging demonstrates the potential of this method in monitoring the expression level of low‐abundance nucleic acid biomarkers.     

Plasmonically controlled lasing resonance with metallic-dielectric core-shell nanoparticles

We experimentally demonstrate the capability of tailoring lasing resonance properties by manipulating the coupling between surface plasmons and photons in random lasing media composed of metallic-dielectric core-shell nanoparticles and organic dyes. It is revealed that core-shell nanoparticle-based systems exhibit optical feedback features distinctive from those containing pure metallic nanoparticles, provided that the scattering strength is weak enough. The pump threshold increases with an increment in the shell thickness, which can provide a direct proof that the local field enhancement plays a central role in the emergence of coherent feedback. The anomalous behavior in both threshold and optical feedback is discussed in terms of the modification of fluorescent properties of fluorophores close to metallic surface.     

Controlling Plasmon‐Enhanced Fluorescence via Intersystem Crossing in Photoswitchable Molecules

By harnessing photoswitchable intersystem crossing (ISC) in spiropyran (SP) molecules, active control of plasmon‐enhanced fluorescence in the hybrid systems of SP molecules and plasmonic nanostructures is achieved. Specifically, SP‐derived merocyanine (MC) molecules formed by photochemical ring‐opening reaction display efficient ISC due to their zwitterionic character. In contrast, ISC in quinoidal MC molecules formed by thermal ring‐opening reaction is negligible. The high ISC rate can improve fluorescence quantum yield of the plasmon‐modified spontaneous emission, only when the plasmonic electromagnetic field enhancement is sufficiently high. Along this line, extensive photomodulation of fluorescence is demonstrated by switching the ISC in MC molecules at Au nanoparticle aggregates, where strongly enhanced plasmonic hot spots exist. The ISC‐mediated plasmon‐enhanced fluorescence represents a new approach toward controlling the spontaneous emission of fluorophores near plasmonic nanostructures, which expands the applications of active molecular plasmonics in information processing, biosensing, and bioimaging.     

Nanostructural metallic materials: Structures and mechanical properties

The trade-off of strength and ductility of metals has long plagued materials scientists. To resolve this issue, great efforts have been devoted over the past decades to developing a variety of technological pathways for effectively tailoring the microstructure of metallic materials. Here, we review the recent advanced nanostructure design strategies for purposely fabricating heterogeneous nanostructures in crystalline and non-crystalline metallic materials. Several representative structural approaches are introduced, including (1) hierarchical nanotwinned (HNT) structures, extreme grain refinement and dislocation architectures etc. for crystalline metals; (2) nanoglass structure for non-crystalline alloys, i.e. metallic glasses (MGs); and (3) a series of supra-nano-dual-phase (SNDP) nanostructures for composite alloys. The mechanical properties are further optimized by manipulating these nanostructures, especially coupling multiple advanced nanostructures into one material. Particularly, the newly developed SNDP nanostructures greatly enrich the nanostructure design strategies by utilizing supra-nano sized crystals and MGs, which exhibit unique size and synergistic effects. The origins of these gratifying properties are discussed in this review. Furthermore, based on a comprehensive understanding of microscopic mechanisms, a broad vision of strategies towards high strength and high ductility are proposed to promote future innovations.     

DNA‐Directed Gold Nanodimers with Tunable Sizes and Interparticle Distances and Their Surface Plasmonic Properties

A quantitative understanding of the localized surface plasmon resonances (LSPRs) of metallic nanostructures has received tremendous interest. However, most of the current studies are concentrated on theoretical calculation due to the difficulty in experimentally obtaining monodisperse discrete metallic nanostructures with high purity. In this work, endeavors to assemble symmetric and asymmetric gold nanoparticle (AuNP) dimer structures with exceptional purity are reported using a DNA self‐assembly strategy through a one‐step gel electrophoresis, which greatly facilitates the preparation process and improves the final purity. In the obtained Au nanodimers, the sizes of AuNPs (13, 20, and 40 nm) and the interparticle distances (5, 10, and 15 nm) are tunable. The size‐ and distance‐dependent plasmon coupling of ensembles of single, isolated dimers in solution are subsequently investigated. The experimental measurements are correlated with the modeled plasmon optical properties of Au nanodimers, showing an expected resonance shift with changing particle sizes and interparticle distances. This new strategy of constructing monodisperse metallic nanodimers will be helpful for building more complicated nanostructures, and our theoretical and experimental understanding of the intrinsic dependence of plasmon property of metallic nanodimer on the sizes and interparticle distances will benefit the future investigation and exploitation of near‐field plasmonic properties.     

Synthesis, assembly, and characterization of Si nanocrystals and Si nanocrystal-carbon nanotube hybrid structures

Silicon nanocrystals of a few nanometers in size are of great interest for optoelectronic applications. Here we present a mini-arc plasma method to produce silicon nanocrystals at atmospheric pressure directly from solid silicon precursors. The product silicon nanocrystals are then assembled onto the external surface of carbon nanotubes (CNTs) to form hybrid nanostructures. The absorption properties of both the silicon nanocrystals and the Si-CNT hybrid structures have been characterized. Quantum size effects have been observed for as-produced silicon nanocrystals. The resulting silicon nanocrystals and hybrid nanostructures are promising for optoelectronic applications.     

Coupling Solar Energy into Reactions: Materials Design for Surface Plasmon‐Mediated Catalysis

Enabled by surface plasmons, noble metal nanostructures can interact with and harvest incident light. As such, they may serve as unique media to generate heat, supply energetic electrons, and provide strong local electromagnetic fields for chemical reactions through different mechanisms. This solar‐to‐chemical pathway provides a new approach to solar energy utilization, alternative to conventional semiconductor‐based photocatalysis. To provide readers with a clear picture of this newly recognized process, this review presents coupling solar energy into chemical reactions through plasmonic nanostructures. It starts with a brief introduction of surface plasmons in metallic nanostructures, followed by a demonstration of tuning plasmonic features by tailoring their physical parameters. Owing to their tunable plasmonic properties, metallic materials offer a platform to trigger and drive chemical reactions at the nanoscale, as systematically overviewed in this article. The design rules for plasmonic materials for catalytic applications are further outlined based on existing examples. At the end of this article, the challenges and opportunities for further development of plasmonic‐mediated catalysis toward energy and environmental applications are discussed.     

Synthesis of hollow silver nanostructures by a simple strategy

Various silver nanostructures with hollow interiors, including nanoscaled cubic or quasi-cubic boxes, tubes, triangular rings, trapeziform rings and hybrid structures composed of tubes and cubic boxes, were synthesized via an extremely simple route. The method involved the modification of the solid silver nanocrystals by dithiol, and subsequent dissolving of the interior metal and assembly of the outer surface. In the whole process, only one simple step of pretreatment was needed before the transformation from Ag solid nanostructures to their corresponding hollow nanostructures. According to the morphological, spectral and structural changes in the evolution from silver solid nanostructures to their corresponding hollow nanostructures, a layer-by-layer assembly mechanism was proposed. The method is believed to open up a simple and versatile route to the fabrication of metallic hollow nanostructures with various morphologies according to the starting templates.     

Femtosecond Photon‐Mediated Plasma Enhances Photosynthesis of Plasmonic Nanostructures and Their SERS Applications

Laser ablation in liquid has proven to be a universal and green method to synthesize nanocrystals and fabricate functional nanostructures. This study demonstrates the superiority of femtosecond laser‐mediated plasma in enhancing photoredox of metal cations for controllable fabrication of plasmonic nanostructures in liquid. Through employing upstream high energetic plasma during laser‐induced microexplosions, single/three‐electron photoreduction of metallic cations can readily occur without chemical reductants or capping agents. Experimental evidences demonstrate that this process exhibits higher photon utilization efficiency in yield of colloidal metal nanoparticles than direct irradiation of metallic precursors. Photogenerated hydrated electrons derived from strong ionization of silicon and water are responsible for this enhanced consequences. Furthermore, these metallic nanoparticles are accessible to self‐assemble into nanoplates for silver and nanospheres for gold, favored by surface‐tension gradients between laser irradiated and unirradiated regions. These metallic nanostructures exhibit excellent surface‐enhanced Raman spectroscopy performance in trace detection of Rhodamine 6G (R6G), 4‐mercaptobenzoic acid (4‐MBA), and mercapto‐5‐nitrobenzimidazole molecules with high sensitivity (down to 10^?12 mol L^?1, 30 × 10^?15 m for R6G), good reproducibility (relative standard deviation < 7%), and good dual‐analyte detection ability with mixture ratios of R6G to 4‐MBA ranging from 20 to 0.025. The conceptual importance of this plasma‐enhanced‐photochemical process may provide exciting opportunities in photochemical reactions, plasmofluidics, and material synthesis.     

Plasmon dynamics in colloidal Cu₂-xSe nanocrystals

The optical response of metallic nanostructures after intense excitation with femtosecond-laser pulses has recently attracted increasing attention: such response is dominated by ultrafast electron-phonon coupling and offers the possibility to achieve optical modulation with unprecedented terahertz bandwidth. In addition to noble metal nanoparticles, efforts have been made in recent years to synthesize heavily doped semiconductor nanocrystals so as to achieve a plasmonic behavior with spectrally tunable features. In this work, we studied the dynamics of the localized plasmon resonance exhibited by colloidal Cu(2-x)Se nanocrystals of 13 nm in diameter and with x around 0.15, upon excitation by ultrafast laser pulses via pump-probe experiments in the near-infrared, with ～200 fs resolution time. The experimental results were interpreted according to the two-temperature model and revealed the existence of strong nonlinearities in the plasmonic absorption due to the much lower carrier density of Cu(2-x)Se compared to noble metals, which led to ultrafast control of the probe signal with modulation depth exceeding 40% in transmission.     

Hybrid Frenkel-Wannier-Mott excitons at interfaces and in microcavities

We discuss the linear and nonlinear optical properties of organic-inorganic nanostructures (quantum wells and superlattices) brought about by resonance interactions between Frenkel excitons in organic QWs and Wannier-Mott excitons in semiconductor QWs. We show that such a coupling (Coulomb dipole-dipole at an interface and through the cavity photons in a microcavity) is responsible for the appearance of mixed Frenkel-Wannier excitations. We demonstrate that the new hybrid states and their dispersion curves can be tailored to engineer the enhancement of resonant optical nonlinearity, fluorescence efficiency and relaxation processes.     

Patterning of light-emitting conjugated polymer nanofibres

Organic materials have revolutionized optoelectronics by their processability, flexibility and low cost, with application to light-emitting devices for full-colour screens, solar cells and lasers. Some low-dimensional organic semiconductor structures exhibit properties resembling those of inorganics, such as polarized emission and enhanced electroluminescence. One-dimensional metallic, III-V and II-VI nanostructures have also been the subject of intense investigation as building blocks for nanoelectronics and photonics. Given that one-dimensional polymer nanostructures, such as polymer nanofibres, are compatible with sub-micrometre patterning capability and electromagnetic confinement within subwavelength volumes, they can offer the benefits of organic light sources to nanoscale optics. Here we report on the optical properties of fully conjugated, electrospun polymer nanofibres. We assess their waveguiding performance and emission tuneability in the whole visible range. We demonstrate the enhancement of the fibre forward emission through imprinting periodic nanostructures using room-temperature nanoimprint lithography, and investigate the angular dispersion of differently polarized emitted light.     

Octopods versus concave nanocrystals: control of morphology by manipulating the kinetics of seeded growth via co-reduction

Au/Pd octopods and concave core@shell Au@Pd nanocrystals have been prepared by coupling for the first time a seed-mediated synthetic method with co-reduction. The integration of these two methods is central to the formation of these binary Au/Pd nanocrystals wherein the kinetics of seeded growth are manipulated via the co-reduction technique to control the final morphology of the nanocrystals. Significantly, the synthesis of these structures under similar reaction conditions illustrates that they are structurally related kinetic products. Detailed characterization by STEM-EDX analysis highlights the unique structural features of these nanocrystals and indicates that Pd localizes on the higher-energy features of the nanocrystals. Optical and electrocatalytic characterization also demonstrates their promise as a new class of multifunctional nanostructures.     

The Microemulsion Synthesis of Hydrophobic and Hydrophilic Silicon Nanocrystals

Silicon nanocrystals, also called quantum dots, have unique optical properties when in the quantum‐confinement regime. These optical properties make silicon nanocrystals promising materials for a wide variety of applications ranging from optoelectronic devices to fluorophores in biological imaging. A liquid‐phase synthetic approach is reported using surfactant molecules to control particle growth, producing highly monodisperse silicon particles. The surface of the nanocrystals are capped by functional organic molecules that passivate and protect the silicon particles from oxidation, enabling the particles to be used in hydrophobic and hydrophilic applications. The use of hydrophilic silicon quantum dots as optical probes is illustrated by the imaging of Vero cells.     

Selective binding of dye molecules and CdSe nanocrystals on nanostructures generated by AFM lithography of silicon surfaces

Anchoring optically active molecules or semiconductor nanocrystals on nanostructured surfaces is one of the first steps for building complex structures with variable properties and functions. Electrostatic interactions have been used for selective binding of cationic molecular species on lithographically generated and negatively charged nanostructures. Semiconductor nanocrystals, covered by amphiphilic molecules, have been bound via hydrophobic interactions. Selective binding of cationic Rhodamin 6G molecules to freshly prepared silicon oxide nanostructures as well as the CdSe/ZnS nanocrystals to the surrounding hydrophobic alkyl monolayer could be identified both by optical methods and by atomic force microscopy. The adsorption of CdSe/ZnS nanoparticles was accompanied by self-organization phenomena of the surfactant tri octyl phosphine oxide (TOPO).     

Mn-doped ZnO nanocrystals embedded in Al2O3: structural and electrical properties

We report on the structural and electrical properties of Mn-doped ZnO/Al(2)O(3) nanostructures produced by the pulsed laser deposition technique. Grazing incidence small angle x-ray scattering (GISAXS) and Rutherford backscattering spectrometry revealed the multilayered structure in as-deposited samples. Annealing of the nanostructures was shown to promote the formation of nanocrystals embedded in the Al(2)O(3) matrix, as was evidenced by GISAXS and high resolution transmission microscopy. Particle-induced x-ray emission analysis showed a doping of 8 at.% Mn in ZnO. Grazing incidence x-ray diffraction and Raman spectroscopy demonstrated that the nanocrystals have the pure wurtzite ZnMnO crystalline phase. Resonant Raman scattering displayed an increase of intensity of the 1LO mode as well as broadening of the 2LO mode related to the size effect. Capacitance-voltage measurements showed carrier retention with a voltage shift higher than those reported for similar systems.