Rich Ground State Chemical Ordering in Nanoparticles: Exact Solution of a Model for Ag-Au Clusters

We show that nanoparticles can have very rich ground state chemical order. This is illustrated by determining the chemical ordering of Ag-Au 309-atom Mackay icosahedral nanoparticles. The energy of the nanoparticles is described using a cluster expansion model, and a Mixed Integer Programming (MIP) approach is used to find the exact ground state configurations for all stoichiometries. The chemical ordering varies widely between the different stoichiometries, and display a rich zoo of structures with non-trivial ordering.Comment: Revised version. New figure added, discussion expanded, some material moved into supplementary fil

Gap-Dependent Coupling of Ag-Au Nanoparticle Heterodimers Using DNA Origami-Based Self-Assembly

© 2016 American Chemical Society. We fabricate heterocomponent dimers built from a single 40 nm gold and a single 40 nm silver nanoparticle separated by sub-5 nm gaps. Successful assembly mediated by a specialized DNA origami platform is verified by scanning electron microscopy and energy-dispersive X-ray characterization. Dark-field optical scattering on individual dimers is consistent with computational simulations. Direct plasmonic coupling between each nanoparticle is observed in both experiment and theory only for these small gap sizes, as it requires the silver dipolar mode energy to drop below the energy of the gold interband transitions. A new interparticle-spacing-dependent coupling model for heterodimers is thus required. Such Janus-like nanoparticle constructs available from DNA-mediated assembly provide an effective tool for controlling symmetry breaking in collective plasmon modes

Exploiting Combinatorics to Investigate Plasmonic Properties in Heterogeneous Ag-Au Nanosphere Chain Assemblies

Chains of coupled metallic nanoparticles are of special interest for plasmonic applications because they can sustain highly dispersive plasmon bands, allowing strong ballistic plasmon wave transport. Whereas early studies focused on homogeneous particle chains exhibiting only one dominant band, heterogeneous assemblies consisting of different nanoparticle species came into the spotlight recently. Their increased configuration space principally allows engineering multiple bands, bandgaps, or topological states. Simultaneously, the challenge of the precise arrangement of nanoparticles, including their distances and geometric patterns, as well as the precise characterization of the plasmonics in these systems, persists. Here, the surface plasmon resonances in heterogeneous Ag-Au nanoparticle chains are reported. Wrinkled templates are used for directed self-assembly of monodisperse gold and silver nanospheres as chains, which allows assembling statistical combinations of more than 109 particles. To reveal the spatial and spectral distribution of the plasmonic response, state-of-the-art scanning transmission electron microscopy coupled with electron energy loss spectroscopy accompanied by boundary element simulations is used. A variety of modes in the heterogeneous chains are found, ranging from localized surface plasmon modes occurring in single gold or silver spheres, respectively, to modes that result from the hybridization of the single particles. This approach opens a novel avenue toward combinatorial studies of plasmonic properties in heterosystems. © 2021 The Authors. Advanced Optical Materials published by Wiley-VCH Gmb

Unambiguous Observation of Single-Molecule Raman Spectroscopy Enabled by Synergic Electromagnetic and Chemical Enhancement

Raman spectroscopy is a powerful tool to detect, analyze and identify molecules. It has been a long-history pursuit to push the detection limit of Raman spectroscopy down to the fundamental single-molecule (SM) level. Due to the tiny cross section of intrinsic Raman scattering of molecule, some enhancement mechanisms of light-matter interaction must be implemented to levitate the Raman scattering intensity by a huge number of ~14-15 orders of magnitude, to the level comparable with the molecule fluorescence intensity. In this work we report unambiguous observation of single-molecule Raman spectroscopy via synergic action of electromagnetic and chemical enhancement for rhodamine B (RhB) molecule absorbed within the plasmonic nanogap formed by gold nanoparticle sitting on the two-dimensional (2D) monolayer WS2 and 2 nm SiO2 coated gold thin film. Raman spectroscopy down to an extremely dilute value of 10-18 mol/L can still be clearly visible, and the statistical enhancement factor could reach 16 orders of magnitude compared with the reference detection sample of silicon plate with a detection limit of 10-2 mol/L. The electromagnetic enhancement comes from local surface plasmon resonance induced at the nanogap, which could reach ~10-11 orders of magnitude, while the chemical enhancement comes from monolayer WS2 2D material, which could reach 4-5 orders of magnitudes. The synergic implementation and action of these two prestigious Raman scattering enhancement mechanisms in this specially designed 2D material-plasmon nanogap composite nanoscale system enables unambiguous experimental observation of single-molecule Raman spectroscopy of RhB molecule. This route of Raman enhancement devices could open up a new frontier of single molecule science, allowing detection, identification, and monitor of single molecules and their spatial-temporal evolution under various internal and external stimuli

Surface-Enhanced Raman Scattering with Gold Core Silver Shell Nanoparticles

Nanotechnology is becoming increasingly important and has many different applications; understanding the chemical and physical properties of matter in this size regime is therefore important. Gold and silver nanoparticles are particularly interesting because they are relatively simple to make and they provide a substrate for surface-enhanced Raman scattering (SERS). SERS can be used to characterize how molecules adsorbed to silver or gold nanoparticles are orientated and if they react on the surfaces. When making silver nanoparticles, batch to batch variability of particle size and shape is high even though silver gives the best enhancement for SERS. This results in low reproducibility in SERS with silver. Gold nanoparticles are more consistent in shape from one batch to the next, but they do not give the enhancement that silver nanoparticles do. We are trying to address this limitation by making gold core silver shell nanoparticles that have the batch consistency of gold and enhancement close to silver. We are testing the gold core silver shell nanoparticles with p-(dimethyamino) cinnamic acid (DMACA) and p-aminocinnamic acid (ACA) to the surface of the nanoparticles

Preparation of a Polypyrrole-Polyvinylsulphonate Composite Film Biosensor for Determination of Cholesterol Based on Entrapment of Cholesterol Oxidase

In this paper, a novel amperometric cholesterol biosensor with immobilization of cholesterol oxidase on electrochemically polymerized polypyrrole–polyvinylsulphonate (PPy–PVS) films has been accomplished via the entrapment technique on the surface of a platinum electrode. Electropolymerization of pyrrole and polyvinylsulphonate on the Pt surface was carried out by cyclic voltammetry between −1.0 and +2.0 V (vs. Ag/AgCl) at a scan rate of 100 mV upon the Pt electrode with an electrochemical cell containing pyrrole and polyvinylsulphonate. The amperometric determination is based on the electrochemical detection of H2O2 generated in the enzymatic reaction of cholesterol. Determination of cholesterol was carried out by the oxidation of enzymatically produced H2O2 at 0.4 V vs. Ag/AgCl. The effects of pH and temperature were investigated and optimum parameters were found to be 7.25 and 35 °C, respectively. The storage stability and operational stability of the enzyme electrode were also studied. The results show that 32% of the response current was retained after 19 activity assays. The prepared cholesterol biosensor retained 43% of initial activity after 45 days when stored in 0.1 M phosphate buffer solution at 4 °C

Synthesis of Ag-Au Nanoparticles by Galvanic Replacement and Their Morphological Studies by HRTEM and Computational Modeling

Bimetallic nanoparticles are important because they possess catalytic and electronic properties with potential applications in medicine, electronics, and chemical industries. A galvanic replacement reaction synthesis has been used in this research to form bimetallic nanoparticles. The complete description of the synthesis consists of using the chemical reduction of metallic silver nitrite (AgNO3) and gold-III chloride hydrate (HAuCl) salt precursors. The nanoparticles display round shapes, as revealed by high-resolution transmission electron microscope (HRTEM). In order to better understand the colloidal structure, it was necessary to employ computational models which involved the simulations of HRTEM images