Dilong Liu

Black Gold: Plasmonic Colloidosomes with Broadband Absorption Self-Assembled from Monodispersed Gold Nanospheres by Using a Reverse Emulsion System†

A facile approach for the fabrication of novel black plasmonic colloidosomes assembled from Au nanospheres is developed by an emulsion-templating strategy. This self-assembly process is based on a new reverse water-in-1-butanol emulsion system, in which the water emulsion droplets can dissolve into 1-butanol (oil) phase at an appropriate rate. These Au colloidosomes possess hexagonal close-packed multilayer shells and show a low reflectivity and intense broadband absorption owing to the strong interparticle plasmonic coupling, which is further investigated by a finite-difference time-domain method. This method is universal and is suitable for self-assembly of different noble-metal nanoparticles into different colloidosomes. These colloidosomes have important applications in photothermal therapy, biosensors, and drug delivery.

Physical Deposition Improved SERS Stability of Morphology Controlled Periodic Micro/Nanostructured Arrays Based on Colloidal Templates

An effective and inexpensive method is developed to fabricate periodic arrays by sacrificial colloidal monolayer template route by chemical deposition and further physical deposition. By a colloidal template induced precursor solution dipping strategy, different periodic arrays of semi-hollow sphere array, inverse opal with monolayer pore arrays and hole arrays are obtained under different conditions. After magnetron sputtering deposition, their morphologies are changed to novel micro/nanostructured arrays of honeycomb-shaped arrays, hollow cavity arrays, and regular network arrays due to multiple direction deposition of sputtering deposition and shadow effect. After coating a gold thin layer, these periodic micro/nanostructured arrays are used as SERS active substrates and demonstrate a very stable SERS performance compared with periodic arrays achieved by direct colloidal template-induced chemical deposition. Additionally, a honeycomb-shaped array displays better SERS enhancement than that of a hollow cavity array or a regular network array. After optimization of honeycomb-shaped arrays with different periodicities, an array with periodicity of 350 nm demonstrates much stronger SERS enhancement and possesses a low detection limit of 10(-11) M R6G. Such stable SERS performance is useful for practical application in portable Raman detecting devices to detect organic molecules.

Rapid synthesis of monodisperse Au nanospheres through a laser irradiation-induced shape conversion, self-assembly and their electromagnetic coupling SERS enhancement.

We develop a facile and effective strategy to prepare monodispersed Au spherical nanoparticles by two steps. Large-scale monocrystalline Au nanooctahedra with uniform size were synthesized by a polyol-route and subsequently Au nanoparticles were transformed from octahedron to spherical shape in a liquid under ambient atmosphere by non-focused laser irradiation in very short time. High monodipersed, ultra-smooth gold nanospheres can be obtained by simply optimizing the laser fluence and irradiation time. Photothermal melting-evaporation model was employed to get a better understanding of the morphology transformation for the system of nanosecond pulsed-laser excitation. These Au nanoparticles were fabricated into periodic monolayer arrays by self-assembly utilizing their high monodispersity and perfect spherical shape. Importantly, such Au nanospheres arrays demonstrated very good SERS enhancement related to their periodic structure due to existence of many SERS hot spots between neighboring Au nanospheres caused by the electromagnetic coupling in an array. These gold nanospheres and their self-assembled arrays possess distinct physical and chemical properties. It will make them as an excellent and promising candidate for applying in sensing and spectroscopic enhancement, catalysis, energy, and biology.

Optical sensor based on hydrogel films with 2D colloidal arrays attached on both the surfaces: anti-curling performance and enhanced optical diffraction intensity

An interesting strategy to create free standing hydrogel composite films with colloidal monolayers attached on both the surfaces, which could act as visualizing sensors with high diffraction intensity, is developed. Owing to the balanced stress on both the surfaces, the colloidal monolayer–hydrogel composite films overcome the curling problem of traditional hydrogel films loaded with a colloidal monolayer on one side. They also display enhanced diffraction intensity compared to those with the attachment of only a single 2D colloidal monolayer due to a multi-diffraction effect. Such sensing hydrogel composite films with anti-curling performance and enhanced optical diffraction intensity are very helpful to improve their practical applications in visual and quantitative detection. In addition, this strategy is universal and could be suitable for fabricating various functional hydrogel films loaded with different nanosphere arrays for novel optical sensors.

Periodic nanostructured Au arrays on an Si electrode for high-performance electrochemical detection of hydrogen peroxide without an enzyme

Periodic gold nanosphere arrays were prepared on a planar silicon substrate, which could be directly developed as an electrode to sensitively and selectively detect H2O2 without an enzyme via an electrochemical method. The arrays of Au nanospheres were fabricated on a large scale (∼cm2) on the Si substrate using polystyrene (PS) colloidal monolayers as the template, after Au deposition and subsequent annealing. The developed biosensor based on the Au nanosphere arrays on the Si substrate demonstrated excellent catalytic activity towards H2O2 over a wide linear range of 0.2 μM–5 mM with a very low detection limit of 0.1 μM. Importantly, the electrochemical biosensor possessed good stability and high reproducibility. The catalytic activity can be enhanced by reducing the gold nanoparticle size and periodic length in the array. The biosensors based on periodic Au nanosphere arrays used to determine the concentration of H2O2 have the advantages of non-enzymatic detection and non-Pt electrode strategy when compared to the conventional method, which may open up new horizons in the production of outstanding biosensors and can be used as a platform for the preparation of various electrochemical biosensors.

Effective SERS-active substrates composed of hierarchical micro/nanostructured arrays based on reactive ion etching and colloidal masks

A facile route has been proposed for the fabrication of morphology-controlled periodic SiO2 hierarchical micro/nanostructured arrays by reactive ion etching (RIE) using monolayer colloidal crystals as masks. By effectively controlling the experimental conditions of RIE, the morphology of a periodic SiO2 hierarchical micro/nanostructured array could be tuned from a dome-shaped one to a circular truncated cone, and finally to a circular cone. After coating a silver thin layer, these periodic micro/nanostructured arrays were used as surface-enhanced Raman scattering (SERS)-active substrates and demonstrated obvious SERS signals of 4-Aminothiophenol (4-ATP). In addition, the circular cone arrays displayed better SERS enhancement than those of the dome-shaped and circular truncated cone arrays due to the rougher surface caused by physical bombardment. After optimization of the circular cone arrays with different periodicities, an array with the periodicity of 350 nm exhibits much stronger SERS enhancement and possesses a low detection limit of 10(-10) M 4-ATP. This offers a practical platform to conveniently prepare SERS-active substrates.

Controlled synthesis of sponge-like porous Au–Ag alloy nanocubes for surface-enhanced Raman scattering properties

We develop an interesting route to prepare new sponge-like Au–Ag alloy nanocubes (NCs) with controlled porosity and atomic percentage through an interparticle alloying and dealloying process. Au@Ag NCs were first synthesized using Au nanooctahedra as initial seeds. Then, the Au@Ag NCs were covered with SiO2 and thermally annealed, forming solid Au–Ag alloy NCs with a SiO2 layer. After removing the majority of the SiO2 layer and leaching less-stable Ag from solid Au–Ag alloy NCs, uniform sponge-like porous Au–Ag alloy NCs were obtained. In this process, SiO2 not only prevents fusion between adjacent Au@Ag NPs under thermal annealing, but also directs the final shape of sponge-like Au–Ag alloy NPs with a cubic shape as a template. Thanks to the high-density “hotspots” in nanopores, sharp corners and edges, and a synergistic effect between Au and Ag species, such sponge-like Au–Ag alloy NCs showed excellent SERS performance with an enhancement factor of ∼108, which can effectively detect 4-aminothiophenol (4-ATP) at a concentration as low as 1 × 10−10 M. This strategy is universal and it can be extended to prepare sponge-like Au–Ag alloy NPs with different accurate shapes. Such sponge-like nanoporous alloy NPs have many potential applications such as in plasmonics, SERS, drug delivery, photothermal therapy, and catalysis systems.

Optical sensing properties of Au nanoparticle/hydrogel composite microbeads using droplet microfluidics

Uniform Au nanoparticle (NP)/poly (acrylamide-co-acrylic acid) [P(AAm-co-AA)] hydrogel microbeads were successfully prepared using droplet microfluidics technology. The microbeads exhibited a good stimuli-responsive behavior to pH value. Particularly in the pH value ranging from pH 2-pH 9, the composite microbead sizes gradually increased along with the increase of pH value. The homogeneous Au NPs, which were encapsulated in the P(AAm-co-AA) hydrogel microbeads, could transform the volume changes of hydrogel into optical signals by a tested single microbead with a microspectrometre system. The glucose was translated into gluconic acid by glucose oxidase. Thus, the Au NP/P(AAm-co-AA) hydrogel microbeads were used for detecting glucose based on pH effects on the composite microbeads. For this, the single Au NP/P(AAm-co-AA) hydrogel microbead could act as a good pH- or glucose-visualizing sensor.

Surface enhanced Raman scattering properties of dynamically tunable nanogaps between Au nanoparticles self-assembled on hydrogel microspheres controlled by pH

We developed an interesting route for preparing a poly (acrylamide-co-acrylic acid) (P(AAm-co-AA)) hydrogel microsphere with a coating of Au nanospheres (hydrogel microsphere @ Au nanospheres) through self-assembly based on electrostatic interaction. The fabricated composites could be used as highly sensitive enhanced Raman scattering substrates. The nanogaps between adjacent Au nanospheres were dynamically tuned by volume changes in the hydrogel microspheres in the semiwet state under different pH conditions. At pH 6, the hydrogel microsphere @ Au nanospheres demonstrated highly sensitive SERS with an enhancement factor of 109. The product could detect very low concentrations of analytes up to 10-12M 4-aminothiophenol (4-ATP) molecules. This paper proposes a new method for detecting trace amounts of environmental organic pollutants by dynamically tuning the SERS enhancement in the semiwet testing state.

Nanosecond-Laser-Based Charge Transfer Plasmon Engineering of Solution-Assembled Nanodimers

The ability to re-engineer self-assembled functional structures with nanometer accuracy through solution-processing techniques represents a big challenge in nanotechnology. Herein we demonstrate that Ag+-soldered nanodimers with a steric confinement coating of silica can be harnessed to realize an in-solution nanosecond laser reshaping to form interparticle conductive pathway with finely controlled conductance. The high structural purity of the nanodimers, the rigid silica coating, and the uniform (but still adjustable) sub-1-nm interparticle gap together determine the success of the laser reshaping process. This method is applicable to DNA-assembled nanodimers, and thus promises DNA-based programming toward higher structural complexity. The resulting structures exhibit highly tunable charge transfer plasmons at visible and near-infrared frequencies dictated by the fluence of the laser pulses. Our work provides an in-solution, rapid, and nonperturbative route to realize charge transfer plasmonic coupling along prescribed paths defined by self-assembly, conferring great opportunities for functional metamaterials in the context of chemical, biological, and nanophotonic applications. The ability to continuously control a subnm interparticle gap and the nanomeric width of a conductive junction also provides a platform to investigate modern plasmonic theories involving quantum and nonlocal effects.