Plasmonic-Based Imaging of Local Square Wave Voltammetry

Square wave voltammetry (SWV) is widely used in electrochemical analysis and sensors because of its high sensitivity and efficient rejection of background current, but SWV by the conventional electrochemical detection method does not provide spatial resolution. We report here a plasmonic method to image local SWV, which opens the door for analyzing heterogeneous electrochemical reactions and for high-throughput detections of microarrays. We describe the basic principle, validate the principle by comparing the plasmonic-based SWV with those obtained with the conventional method, and demonstrate imaging capability for local electrochemical analysis

Plasmonic-Based Imaging of Local Square Wave Voltammetry

Square wave voltammetry (SWV) is widely used in electrochemical analysis and sensors because of its high sensitivity and efficient rejection of background current, but SWV by the conventional electrochemical detection method does not provide spatial resolution. We report here a plasmonic method to image local SWV, which opens the door for analyzing heterogeneous electrochemical reactions and for high-throughput detections of microarrays. We describe the basic principle, validate the principle by comparing the plasmonic-based SWV with those obtained with the conventional method, and demonstrate imaging capability for local electrochemical analysis

Quantifying Ligand–Protein Binding Kinetics with Self-Assembled Nano-oscillators

Measuring ligand–protein interactions is critical for unveiling molecular-scale biological processes in living systems and for screening drugs. Various detection technologies have been developed, but quantifying the binding kinetics of small molecules to the proteins remains challenging because the sensitivities of the mainstream technologies decrease with the size of the ligand. Here, we report a method to measure and quantify the binding kinetics of both large and small molecules with self-assembled nano-oscillators, each consisting of a nanoparticle tethered to a surface via long polymer molecules. By applying an oscillating electric field normal to the surface, the nanoparticle oscillates, and the oscillation amplitude is proportional to the number of charges on the nano-oscillator. Upon the binding of ligands onto the nano-oscillator, the oscillation amplitude will change. Using a plasmonic imaging approach, the oscillation amplitude is measured with subnanometer precision, allowing us to accurately quantify the binding kinetics of ligands, including small molecules, to their protein receptors. This work demonstrates the capability of nano-oscillators as an useful tool for measuring the binding kinetics of both large and small molecules

Plasmonic Measurement of Electron Transfer between a Single Metal Nanoparticle and an Electrode through a Molecular Layer

We study electron transfer associated with electrocatalytic reduction of hydrogen on single platinum nanoparticles separated from an electrode surface with an alkanethiol monolayer using a plasmonic imaging technique. By varying the monolayer thickness, we show that the reaction rate depends on electron tunneling from the electrode to the nanoparticle. The tunneling decay constant is ∼4.3 nm–1, which is small compared to those in literature for alkanethiols. We attribute it to a reduced tunneling barrier resulting from biasing the electrode potential negatively to the hydrogen reduction regime. In addition to allowing study of electron transfer of single nanoparticles, the work demonstrates an optical method to measure charge transport in molecules electrically wired to two electrodes

Pauli Repulsion-Induced Expansion and Electromechanical Properties of Graphene

Because graphene has nearly zero density of states at the Dirac point, charging it must overcome Pauli repulsion. We show here that this repulsion causes graphene to expand, which is measurable with an optical edge-tracking method despite that graphene is the strongest material. The expansion increases quadratically with applied voltage as predicted by theory and has a coefficient of ∼10^–4 per V at 1 V. Graphene has many attractive properties, but it lacks piezoelectricity, which limits its electromechanical applications. The observed Pauli repulsion-induced expansion provides an alternative way to electrically control graphene dimension. It also provides a simple and direct method to measure the elastic properties of graphene and other low dimensional materials

Plasmonic Imaging and Detection of Single DNA Molecules

The capability of imaging and detecting single DNA molecules is critical in the study, analysis, and applications of DNA. Fluorescence imaging is a widely used method, but it suffers from blinking and photobleaching, and fluorescence tags may block or affect binding sites on DNA. We report on label-free imaging of single DNA molecules with a differential plasmonic imaging technique. The technique produces high contrast images due to the scattering of surface plasmonic waves by the molecules and the removal of background noises and interference patterns, allowing for quantitative analysis of individual DNA molecules. Simulation of the images based on a scattering model shows good agreement with the experiment. We further demonstrate optical mapping of single DNA molecules

Molecular Scale Origin of Surface Plasmon Resonance Biosensors

Surface plasmon resonance (SPR) has become an indispensable tool for label-free detection and quantification of molecular binding. Traditionally, the principle of SPR biosensors is described with a stratified medium model, in which discrete molecules are approximated with a uniform thin film. With the recent technical advances, SPR can now detect extremely low coverage of molecules, which raises the question of the validity of the traditional model. Here, we present combined theoretical, numerical and experimental analysis of SPR detection principle by considering the discrete nature of the molecules (particles). Our results show that the stratified medium model can provide reasonable description of SPR biosensors for relatively high coverage and weakly scattering samples. However, interference between the SPR images of individual particles needs to be considered for high spatial resolution images and for strong scattering samples at certain incident angles of light

Plasmonic Imaging of Surface Electrochemical Reactions of Single Gold Nanowires

Nanomaterials have been widely used in energy and sensing applications because of their unique chemical and physical properties, especially their surface reactions. Measuring the local reactions of individual nanomaterials, however, has been an experimental challenge. Here we report on plasmonic imaging of surface electrochemical reactions of individual gold nanowires (AuNWs). We coated a gold thin film (plasmonic sensing layer) with a dielectric layer (Cytop) with refractive index close to that of water, and then a graphene layer for electrical contact. This design removed the interference from the sensing layer while preserving sharp surface plasmon resonance, which allowed us to obtain cyclic voltammograms of surface electrochemistry of individual AuNWs for the first time. We also investigated the difference in the electrochemical reactions of AuNWs and Au surfaces, and local distribution of electrochemical activities within a single AuNW