DNA‐Origami‐Based Assembly of Anisotropic Plasmonic Gold Nanostructures

Precise control over the assembly of anisotropic plasmonic gold nanostructures with relative spatial directionality and sequence asymmetry remains a major challenge and offers great fundamental insight and optical application possibilities. Here, a novel strategy is developed to anisotropically functionalize gold nanorods (AuNRs) by using a DNA‐origami‐based precise machine to transfer essential DNA sequence configurations to the surface of the AuNRs through an intentionally designed toehold‐initiated displacement reaction. Different AuNR products are examined via hybridization with DNA‐AuNPs that display distinct elements of regiospecificity. These assembled anisotropic plasmonic gold nanostructures based on the DNA‐origami precise machine inherit the encoded information from the parent platform with high fidelity and show fixed orientation and bonding anisotropy, thereby generating discrete plasmonic nanostructures with enhanced Raman resonance.     

Humidity‐Responsive Single‐Nanoparticle‐Layer Plasmonic Films

2D materials possess many interesting properties, and have shown great application potentials. In this work, the development of humidity‐responsive, 2D plasmonic nanostructures with switchable chromogenic properties upon wetting–dewetting transitions is reported. By exploiting DNA hybridization‐directed anchoring of gold nanoparticles (AuNPs) on substrates, a series of single‐nanoparticle‐layer (SNL) plasmonic films is fabricated. Due to the collective plasmonic responses in SNL, these ultrathin 2D films display rapid and reversible red‐blue color change upon the wetting–dewetting transition, suggesting that hydration‐induced microscopic plasmonic coupling between AuNPs is replicated in the macroscopic, centimeter‐scale films. It is also found that hydration finely tunes the electric field distribution between AuNPs in the SNL film, based on which responsive surface‐enhanced Raman scattering substrates with spatially homogeneous hot spots are developed. Thus it is expected that DNA‐mediated 2D SNL structures open new avenues for designing miniaturized plasmonic nanodevices with various applications.     

Building plasmonic nanostructures with DNA

Plasmonic structures can be constructed from precise numbers of well-defined metal nanoparticles that are held together with molecular linkers, templates or spacers. Such structures could be used to concentrate, guide and switch light on the nanoscale in sensors and various other devices. DNA was first used to rationally design plasmonic structures in 1996, and more sophisticated motifs have since emerged as effective and versatile species for guiding the assembly of plasmonic nanoparticles into structures with useful properties. Here we review the design principles for plasmonic nanostructures, and discuss how DNA has been applied to build finite-number assemblies (plasmonic molecules), regularly spaced nanoparticle chains (plasmonic polymers) and extended two- and three-dimensional ordered arrays (plasmonic crystals).     

Spiral Patterning of Au Nanoparticles on Au Nanorod Surface to Form Chiral AuNR@AuNP Helical Superstructures Templated by DNA Origami

Plasmonic motifs with precise surface recognition sites are crucial for assembling defined nanostructures with novel functionalities and properties. In this work, a unique and effective strategy is successfully developed to pattern DNA recognition sites in a helical arrangement around a gold nanorod (AuNR), and a new set of heterogeneous AuNR@AuNP plasmonic helices is fabricated by attaching complementary‐DNA‐modified gold nanoparticles (AuNPs) to the predesigned sites on the AuNR surface. AuNR is first assembled to one side of a bifacial rectangular DNA origami, where eight groups of capture strands are selectively patterned on the other side. The subsequently added link strands make the rectangular DNA origami roll up around the AuNR into a tubular shape, therefore giving birth to a chiral patterning of DNA recognition sites on the surface of AuNR. Following the hybridization with the AuNPs capped with the complementary strands to the capture strands on the DNA origami, left‐handed and right‐handed AuNR@AuNP helical superstructures are precisely formed by tuning the pattern of the recognition sites on the AuNR surface. Our strategy of nanoparticle surface patterning innovatively realizes hierarchical self‐assembly of plasmonic superstructures with tunable chiroptical responses, and will certainly broaden the horizon of bottom‐up construction of other functional nanoarchitectures with growing complexity.     

Self‐Aligned Anisotropic Plasmonic Nanostructures

Great opportunities emerge not only in the generation of anisotropic plasmonic nanostructures but also in controlling their orientation relative to incident light. Herein, a stepwise seeded growth method is reported for the synthesis of rod‐shaped plasmon nanostructures which are vertically self‐aligned with respect to the surface of colloidal substrates. Anisotropic growth of metal nanostructure is achieved by depositing metal seeds onto the surface of colloidal substrates and then selectively passivating the seed surface to induce symmetry breaking in the subsequent seed‐mediated growth process. The versatility of this method is demonstrated by producing nanoparticle dimers and linear trimers of Au, Au–Ag, Au–Pd, and Au–Cu₂O. Further, this unique method enables the automatic vertical alignment of the resulting plasmonic nanostructures to the surface of the colloidal substrate, thereby making it possible to design magnetic/plasmonic nanocomposites that allow the dynamic tuning of the plasmon excitation by controlling their orientation using an external magnetic field. The controlled anisotropic growth of colloidal plasmonic nanostructures and their dynamic modulation of plasmon excitation further allow them to be conveniently fixed in a thin polymer film with a well‐controlled orientation to display polarization‐dependent patterns that may find important applications in information encryption.     

Plasmonic ZnO/Ag Embedded Structures as Collecting Layers for Photogenerating Electrons in Solar Hydrogen Generation Photoelectrodes

A new fabrication strategy in which Ag plasmonics are embedded in the interface between ZnO nanorods and a conducting substrate is experimentally demonstrated using a femtosecond‐laser (fs‐laser)‐induced plasmonic ZnO/Ag photoelectrodes. This fs‐laser fabrication technique can be applied to generate patternable plasmonic nanostructures for improving their effectiveness in hydrogen generation. Plasmonic ZnO/Ag nanostructure photoelectrodes show an increase in the photocurrent of a ZnO nanorod photoelectrodes by higher than 85% at 0.5 V. Both localized surface plasmon resonance in metal nanoparticles and plasmon polaritons propagating at the metal/semiconductor interface are available for improving the capture of sunlight and collecting charge carriers. Furthermore, in‐situ X‐ray absorption spectroscopy is performed to monitor the plasmonic‐generating electromagnetic field upon the interface between ZnO/Ag nanostructures. This can reveal induced vacancies on the conduction band of ZnO, which allow effective separation of charge carriers and improves the efficiency of hydrogen generation. Plasmon‐induced effects enhance the photoresponse simultaneously, by improving optical absorbance and facilitating the separation of charge carriers.     

Circular Dichroism Studies on Plasmonic Nanostructures

In recent years, optical chirality of plasmonic nanostructures has aroused great interest because of innovative fundamental understanding as well as promising potential applications in optics, catalysis and sensing. Herein, state‐of‐the‐art studies on circular dichroism (CD) characteristics of plasmonic nanostructures are summarized. The hybrid of achiral plasmonic nanoparticles (NPs) and chiral molecules is explored to generate a new CD response at the plasmon resonance as well as the enhanced CD intensity of chiral molecules in the UV region, owing to the Coulomb static and dynamic dipole interactions between plasmonic NPs and chiral molecules. As for chiral assembly of plasmonic NPs, plasmon–plasmon interactions between the building blocks are found to induce generation of intense CD response at the plasmon resonance. Three‐dimensional periodical arrangement of plasmonic NPs into macroscale chiral metamaterials is further introduced from the perspective of negative refraction and photonic bandgap. A strong CD signal is also discerned in achiral planar plasmonic nanostructures under illumination of circular polarized plane wave at oblique incidence or input vortex beam at normal incidence. Finally perspectives, especially on future investigation of time‐resolved CD responses, are presented.     

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.     

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.     

Plasmonic‐Enhanced Organic Photovoltaics: Breaking the 10% Efficiency Barrier

Recent advances in molecular organic photovoltaics (OPVs) have shown 10% power conversion efficiency (PCE) for single‐junction cells, which put them in direct competition with PVs based on amorphous silicon. Incorporation of plasmonic nanostructures for light trapping in these thin‐film devices offers an attractive solution to realize higher‐efficiency OPVs with PCE?10%. This article reviews recent progress on plasmonic‐enhanced OPV devices using metallic nanoparticles, and one‐dimensional (1D) and two‐dimensional (2D) patterned periodic nanostructures. We discuss the benefits of using various plasmonic nanostructures for broad‐band, polarization‐insensitive and angle‐independent absorption enhancement, and their integration with one or two electrode(s) of an OPV device.     

Plasmonic Nickel Nanoantennas

The fundamental optical properties of pure nickel nanostructures are studied by far‐field extinction spectroscopy and optical near‐field microscopy, providing direct experimental evidence of the existence of particle plasmon resonances predicted by theory. Experimental and calculated near‐field maps allow for unambiguous identification of dipolar plasmon modes. By comparing calculated near‐field and far‐field spectra, dramatic shifts are found between the near‐field and far‐field plasmon resonances, which are much stronger than in gold nanoantennas. Based on a simple damped harmonic oscillator model to describe plasmonic resonances, it is possible to explain these shifts as due to plasmon damping.     

Lateral Magnetic Near‐Field Imaging of Plasmonic Nanoantennas With Increasing Complexity

The design of many promising, newly emerging classes of photonic metamaterials and subwavelength confinement structures requires detailed knowledge and understanding of the electromagnetic near‐field interactions between their building blocks. While the electric field distributions and, respectively, the electric interactions of different nanostructures can be routinely measured, for example, by scattering near‐field microscopy, only recently experimental methods for imaging the magnetic field distributions became available. In this paper, we provide direct experimental maps of the lateral magnetic near‐field distributions of variously shaped plasmonic nanoantennas by using hollow‐pyramid aperture scanning near‐field optical microscopy (SNOM). We study both simple plasmonic nanoresonators, such as bars, disks, rings and more complex antennas. For the studied structures, the magnetic near‐field distributions of the complex resonators have been found to be a superposition of the magnetic near‐fields of the individual constituting elements. These experimental results, explained and validated by numerical simulations, open new possibilities for engineering and characterization of complex plasmonic antennas with increased functionality.     

Hybrid Structures for Surface‐Enhanced Raman Scattering: DNA Origami/Gold Nanoparticle Dimer/Graphene

A combination of three innovative materials within one hybrid structure to explore the synergistic interaction of their individual properties is presented. The unique electronic, mechanical, and thermal properties of graphene are combined with the plasmonic properties of gold nanoparticle (AuNP) dimers, which are assembled using DNA origami nanostructures. This novel hybrid structure is characterized by means of correlated atomic force microscopy and surface‐enhanced Raman scattering (SERS). It is demonstrated that strong interactions between graphene and AuNPs result in superior SERS performance of the hybrid structure compared to their individual components. This is particularly evident in efficient fluorescence quenching, reduced background, and a decrease of the photobleaching rate up to one order of magnitude. The versatility of DNA origami structures to serve as interface for complex and precise arrangements of nanoparticles and other functional entities provides the basis to further exploit the potential of the here presented DNA origami–AuNP dimer–graphene hybrid structures.     

Engineering Plasmonic Gold Nanostructures and Metamaterials for Biosensing and Nanomedicine

The fields of biosensing and nanomedicine have recently witnessed an explosion of interest and progress in the design and study of plasmonic Au nanostructures (p‐AuNSs) or metamaterials geared towards a broad range of biological and biomedical applications. Due to their tunable and versatile plasmonic properties, such artificially engineered p‐AuNSs and materials have the potential to push biosensor sensitivity towards the single‐molecule detection limit, enabling new bioimaging modalities and new analytical techniques and tools capable of single‐molecule detection, analysis and manipulation, and to revolutionize the diagnosis and treatment of many diseases, including cancers. This report summarizes and highlights recent major advances in the emerging field of bioapplication‐oriented engineering of p‐AuNSs and hybrids, focusing on design considerations and ways to carry them out. A brief overview of the optical properties of p‐AuNSs is introduced, and then the importance of plasmonic engineering and future promising research directions and challenges in the field are discussed.     

Dynamically Switchable Multicolor Electrochromic Films

The dynamic optical switch of plasmonic nanostructures is highly desirable due to its promising applications in many smart optical devices. To address the challenges in the reversibility and transmittance contrast of the plasmonic electrochromic devices, here, a strategy is reported to fabricate color switchable electrochromic films through electro‐responsive dissolution and deposition of Ag on predefined hollow shells of Au/Ag alloy. Using the hollow Au/Ag alloy nanostructures as stable seeds for site‐specific deposition of Ag, elimination of the random self‐nucleation events is enabled and optimal reversibility in color switching is allowed. The hollow structure further enables excellent transmittance contrast between the bleached and colored states. With its additional advantages such as the convenience for preparation, high sensitivity, and field‐tunable optical property, it is believed that this new electrochromic film represents a unique platform for designing novel smart optical devices.     

Rationally Designed DNA‐Origami Nanomaterials for Drug Delivery In Vivo

The recent decades have seen a surge of new nanomaterials designed for efficient drug delivery. DNA nanotechnology has been developed to construct sophisticated 3D nanostructures and artificial molecular devices that can be operated at the nanoscale, giving rise to a variety of programmable functions and fascinating applications. In particular, DNA‐origami nanostructures feature rationally designed geometries and precise spatial addressability, as well as marked biocompatibility, thus providing a promising candidate for drug delivery. Here, the recent successful efforts to employ self‐assembled DNA‐origami nanostructures as drug‐delivery vehicles are summarized. The remaining challenges and open opportunities are also discussed.     

Fluorescence Enhancement on Large Area Self‐Assembled Plasmonic‐3D Photonic Crystals

Discontinuous plasmonic‐3D photonic crystal hybrid structures are fabricated in order to evaluate the coupling effect of surface plasmon resonance and the photonic stop band. The nanostructures are prepared by silver sputtering deposition on top of hydrophobic 3D photonic crystals. The localized surface plasmon resonance of the nanostructure has a symbiotic relationship with the 3D photonic stop band, leading to highly tunable characteristics. Fluorescence enhancements of conjugated polymer and quantum dot based on these hybrid structures are studied. The maximum fluorescence enhancement for the conjugated polymer of poly(5‐methoxy‐2‐(3‐sulfopropoxy)‐1,4‐phenylenevinylene) potassium salt by a factor of 87 is achieved as compared with that on a glass substrate due to the enhanced near‐field from the discontinuous plasmonic structures, strong scattering effects from rough metal surface with photonic stop band, and accelerated decay rates from metal‐coupled excited state of the fluorophore. It is demonstrated that the enhancement induced by the hybrid structures has a larger effective distance (optimum thickness ≈130 nm) than conventional plasmonic systems. It is expected that this approach has tremendous potential in the field of sensors, fluorescence‐imaging, and optoelectronic applications.     

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.     

Plasmonic Metallic Heteromeric Nanostructures

Binary, ternary, and other high‐order plasmonic heteromers possess remarkable physical and chemical properties, enabling them to be used in numerous applications. The seed‐mediated approach is one of the most promising and versatile routes to produce plasmonic heteromers. Selective growth of one or multiple domains on desired sites of noble metal, semiconductor, or magnetic seeds would form desired heteromeric nanostructures with multiple functionalities and synergistic effects. In this work, the challenges for the synthetic approaches are discussed with respect to tuning the thermodynamics, as well as the kinetic properties (e.g., pH, temperature, injection rate, among others). Then, plasmonic heteromers with their structure advantages displaying unique activities compared to other hybrid nanostructures (e.g., core–shell, alloy) are highlighted. Some of the main most recent applications of plasmonic heteromers are also presented. Finally, perspectives for further exploitation of plasmonic heteromers are demonstrated. The goal of this work is to provide the current know‐how on the synthesis routes of plasmonic heteromers in a summarized manner, so as to achieve a better understanding of the resulting properties and to gain an improved control of their performances and extend their breadth of applications.     

Smart Drug Delivery Nanocarriers with Self‐Assembled DNA Nanostructures

Self‐assembled DNA nanostructures have emerged as a type of nano‐biomaterials with precise structures, versatile functions and numerous applications. One particularly promising application of these DNA nanostructures is to develop universal nanocarriers for smart and targeted drug delivery. DNA is the genetic material in nature, and inherently biocompatible. Nevertheless, cell membranes are barely permeable to naked DNA molecules, either single‐ or double‐ stranded; transport across the cell membrane is only possible with the assistance of transfection agents. Interestingly, recent studies revealed that many DNA nanostructures could readily go into cells with high cell uptake efficiency. In this Progress Report, we will review recent advances on using various DNA nanostructures, e.g., DNA nanotubes, DNA tetrahedra, and DNA origami nanorobot, as drug delivery nanocarriers, and demonstrate several examples aiming at therapeutic applications with CpG‐based immunostimulatory and siRNA‐based gene silencing oligonucleotides.