Plasmonic Heterodimers with Binding Site‐Dependent Hot Spot for Surface‐Enhanced Raman Scattering

A novel plasmonic heterodimer nanostructure with a controllable self‐assembled hot spot is fabricated by the conjugation of individual Au@Ag core–shell nanocubes (Au@Ag NCs) and varisized gold nanospheres (GNSs) via the biotin–streptavidin interaction from the ensemble to the single‐assembly level. Due to their featured configurations, three types of heterogeneous nanostructures referred to as Vertice, Vicinity, and Middle are proposed and a single hot spot forms between the nanocube and nanosphere, which exhibits distinct diversity in surface plasmon resonance effect. Herein, the calculated surface‐enhanced Raman scattering enhancement factors of the three types of heterodimers show a narrow distribution and can be tuned in orders of magnitude by controlling the size of GNSs onto individual Au@Ag NCs. Particularly, the Vertice heterodimer with unique configuration can provide extraordinary enhancement of the electric field for the single hot spot region due to the collaborative interaction of lightning rod effect and interparticle plasmon coupling effect. This established relationship between the architecture and the corresponding optical properties of the heterodimers provides the basis for creating controllable platforms which can be exploited in the applications of plasmonic devices, electronics, and biodetection.     

Mechanisms of Self‐Assembly and Energy Harvesting in Tuneable Conjugates of Quantum Dots and Engineered Photovoltaic Proteins

Photoreaction centers facilitate the solar energy transduction at the heart of photosynthesis and there is increasing interest in their incorporation into biohybrid devices for solar energy conversion, sensing, and other applications. In this work, the self‐assembly of conjugates between engineered bacterial reaction centers (RCs) and quantum dots (QDs) that act as a synthetic light harvesting system is described. The interface between protein and QD is provided by a polyhistidine tag that confers a tight and specific binding and defines the geometry of the interaction. Protein engineering that changes the pigment composition of the RC is used to identify Förster resonance energy transfer as the mechanism through which QDs can drive RC photochemistry with a high energy transfer efficiency. A thermodynamic explanation of RC/QD conjugation based on a multiple/independent binding model is provided. It is also demonstrated that the presence of multiple binding sites affects energy coupling not only between RCs and QDs but also among the bound RCs themselves, effects which likely stem from restricted RC dynamics at the QD surface in denser conjugates. These findings are readily transferrable to many other conjugate systems between proteins or combinations of proteins and other nanomaterials.     

Carbon Nanotube‐Quantum Dot Nanohybrids: Coupling with Single‐Particle Control in Aqueous Solution

A strategy is reported for the controlled assembly of organic‐inorganic heterostructures consisting of individual single‐walled carbon nanotubes (SWCNTs) selectively coupled to single semiconductor quantum dots (QDs). The assembly in aqueous solution was controlled towards the formation of monofunctionalized SWCNT‐QD structures. Photoluminescence studies in solution, and on surfaces at the single nanohybrid level, showed evidence of electronic coupling between the two nanostructures. The ability to covalently couple heterostructures with single particle control is crucial for the design of novel QD‐based optoelectronic and light‐energy conversion devices.     

Tunable Fluorescence from Dye‐Modified DNA‐Assembled Plasmonic Nanocube Arrays

Colloidal crystal engineering with DNA on template‐confined surfaces is used to prepare arrays of nanocube‐based plasmonic antennas and deliberately place dyes with sub‐nm precision into their hotspots, on the DNA bonds that confine the cubes to the underlying gold substrate. This combined top‐down and bottom‐up approach provides independent control over both the plasmonic gap and photonic lattice modes of the surface‐confined particle assemblies and allows for the tuning of the interactions between the excited dyes and plasmonically active antennas. Furthermore, the gap mode of the antennas can be modified in situ by utilizing the solvent‐dependent structure of the DNA bonds. This is studied by placing two dyes, with different emission wavelengths, under the nanocubes and recording their solvent‐dependent emission. It is shown that dye emission not only depends upon the in‐plane structure of the antennas but also the size of the gap, which is regulated with solvent. Importantly, this approach allows for the systematic understanding of the relationship between nanoscale architecture and plasmonically coupled dye emission, and points toward the use of colloidal crystal engineering with DNA to create stimuli responsive architectures, which can find use in chemical sensing and tunable light sources.     

Imaging Viral Behavior in Mammalian Cells with Self‐Assembled Capsid–Quantum‐Dot Hybrid Particles

Unique spectral properties of quantum dots (QDs) enable ultrasensitive and long‐term biolabeling. Aiming to trace the infection, movement, and localization of viruses in living cells, QD‐containing virus‐like particles (VLPs) of simian virus 40 (SV40), termed SVLP‐QDs, are constructed by in vitro self‐assembly of the major capsid protein of SV40. SVLP‐QDs show homogeneity in size (≈24 nm), similarity in spectral properties to unencapsidated QDs, and considerable stability. When incubated with living cells, SVLP‐QDs are shown to enter the cells by caveolar endocytosis, travel along the microtubules, and accumulate in the endoplasmic reticulum. This process mimics the early infection steps of SV40. This is the first paradigm of imaging viral behaviors with encapsidated QDs in living cells. The method may provide a new alternative for various purposes, such as tracing viruses or viral components, targeted nanoparticle delivery, and probing of drug delivery.     

Interfacial Capillary‐Force‐Driven Self‐Assembly of Monolayer Colloidal Crystals for Supersensitive Plasmonic Sensors

Colloidal lithography technology based on monolayer colloidal crystals (MCCs) is considered as an outstanding candidate for fabricating large‐area patterned functional nanostructures and devices. Although many efforts have been devoted to achieve various novel applicatons, the quality of MCCs, a key factor for the controllability and reproducibility of the patterned nanostructures, is often overlooked. In this work, an interfacial capillary‐force‐driven self‐assembly strategy (ICFDS) is designed to realize a high‐quality and highly‐ordered hexagonal monolayer MCCs array by resorting the capillary effect of the interfacial water film at substrate surface as well as controlling the zeta potential of the polystyrene particles. Compared with the conventional self‐assembly method, this approach can realize the reself‐assembly process on the substrate surface with few colloidal aggregates, vacancy, and crystal boundary defects. Furthermore, various typical large‐scale nanostructure arrays are achieved by combining reactive ion etching, metal‐assisted chemical etching, and so forth. Specifically, benefiting from the as‐fabricated high‐quality 2D hexagonal colloidal crystals, the surface plasmon resonance (SPR) sensors achieve an excellent refractive index sensitivity value of 3497 nm RIU^?1, which is competent for detecting bovine serum albumin with an ultralow concentration of 10^?8 m . This work opens a window to prepare high‐quality MCCs for more potential applications.     

Self‐Assembled Large Au Nanoparticle Arrays with Regular Hot Spots for SERS

The cost‐effective self‐assembly of 80 nm Au nanoparticles (NPs) into large‐domain, hexagonally close‐packed arrays for high‐sensitivity and high‐fidelity surface‐enhanced Raman spectroscopy (SERS) is demonstrated. These arrays exhibit specific optical resonances due to strong interparticle coupling, which are well reproduced by finite‐difference time‐domain (FDTD) simulations. The gaps between NPs form a regular lattice of hot spots that enable a large amplification of both photoluminescence and Raman signals. At smaller wavelengths the hot spots are extended away from the minimum‐gap positions, which allows SERS of larger analytes that do not fit into small gaps. Using CdSe quantum dots (QDs) a 3–5 times larger photoluminescence enhancement than previously reported is experimentally demonstrated and an unambiguous estimate of the electromagnetic SERS enhancement factor of ≈10⁴ is obtained by direct scanning electron microscopy imaging of QDs responsible for the Raman signal. Much stronger enhancement of ≈10⁸ is obtained at larger wavelengths for benzenethiol molecules penetrating the NP gaps.     

Graphene Oxide Quantum Dots Exfoliated From Carbon Fibers by Microwave Irradiation: Two Photoluminescence Centers and Self‐Assembly Behavior

Graphene oxide quantum dots (GOQDs) attract great attention for their unique properties and promising application potential. The difficulty in the formation of a confined structure, and the numerous and diverse oxygen‐containing functional groups results in a low emission yield to GOQDs. Here, GOQDs with a size of about 5 nm, exfoliated from carbon fibers by microwave irradiation, are detected and analyzed. The exfoliated GOQDs are deeply oxidized and induce large numbers of epoxy groups and ether bonds, but only a small amount of carbonyl groups and hydroxyl groups. The subdomains of sp² clusters, involving epoxy groups and ether bonds, are responsible for the two strong photoluminescence emissions of GOQDs under different excitation wavelengths. Moreover, GOQDs tend to self‐assemble at the edges of their planes to form self‐assembly films (SAFs) with the evaporation of water. SAFs can further assemble into different 3D patterns with unique microstructures such as sponge bulk, sponge ball, microsheet, sisal, and schistose coral, which are what applications such as supercapacitors, cells, catalysts, and electrochemical sensors need. This method for preparation of GOQDs is easy, quick, and environmentally friendly, and this work may open up new research interests about GOQDs.     

Peptidic Ligands to Control the Three‐Dimensional Self‐Assembly of Quantum Rods in Aqueous Media

The use of peptidic ligands is validated as a generic chemical platform allowing one to finely control the organization in solid phase of semiconductor nanorods originally dispersed in an aqueous media. An original method to generate, on a macroscopic scale and with the desired geometry, three‐dimensional supracrystals composed of quantum rods is introduced. In a first step, nanorods are transferred in an aqueous phase thanks to the substitution of the original capping layer by peptidic ligands. Infrared and nuclear magnetic resonance spectroscopy data prove that the exchange is complete; fluorescence spectroscopy demonstrates that the emitter optical properties are not significantly altered; electrophoresis and dynamic light scattering experiments assess the good colloidal stability of the resulting aqueous suspension. In a second step, water evaporation in a microstructured environment yields superstructures with a chosen geometry and in which nanorods obey a smectic B arrangement, as shown by electron microscopy. Incidentally, bulk drying in a capillary tube generates a similar local order, as evidenced by small angle X‐ray scattering.     

Virus‐Templated Plasmonic Nanoclusters with Icosahedral Symmetry via Directed Self‐Assembly

The assembly of plasmonic nanoparticles with precise spatial and orientational order may lead to structures with new electromagnetic properties at optical frequencies. The directed self‐assembly method presented controls the interparticle‐spacing and symmetry of the resulting nanometer‐sized elements in solution. The self‐assembly of three‐dimensional (3D), icosahedral plasmonic nanosclusters (NCs) with resonances at visible wavelengths is demonstrated experimentally. The ideal NCs consist of twelve gold (Au) nanospheres (NSs) attached to thiol groups at predefined locations on the surface of a genetically engineered cowpea mosaic virus with icosahedral symmetry. In situ dynamic light scattering (DLS) measurements confirm the NSs assembly on the virus. Transmission electron micrographs (TEM) demonstrate the ability of the self‐assembly method to control the nanoscopic symmetry of the bound NSs, which reflects the icosahedral symmetry of the virus. Both, TEM and DLS show that the NCs comprise of a distribution of capsids mostly covered (i.e., 6–12 NS/capsid) with NSs. 3D finite‐element simulations of aqueous suspensions of NCs reproduce the experimental bulk absorbance measurements and major features of the spectra. Simulations results show that the fully assembled NCs give rise to a 10‐fold surface‐averaged enhancement of the local electromagnetic field.