Electrochemical impedance spectroscopy of single Au nanorods.
ABSTRACT: We propose monochromatic dark-field imaging microscopy (DFM) to measure the non-faradaic electrochemical impedance spectroscopy (EIS) of single Au nanorods (AuNRs). DFM was utilized to monitor the plasmonic scattering of monochromatic incident light by surface-immobilized individual AuNRs. When modulating the surface potential at a certain frequency, non-faradaic charging and discharging of AuNRs altered their electron density, leading to periodical fluctuations in the scattering intensity. Analysis of the amplitude and phase of the optical intensity fluctuation as a function of modulation frequency resulted in the EIS of single AuNRs. High-frequency (>100 Hz) modulation allowed us to differentiate the intrinsic charging effect from other contributions such as the periodic migration and accumulation of counterions in the surrounding medium, because the latter occurred at a longer timescale. As a result, single nanoparticle EIS led to the surface capacitance of single AuNRs being closer to the theoretical value. Since interfacial capacitance has been proven sensitive to molecular interactions, the present work also offers a new platform for single nanoparticle sensing by measuring the single nanoparticle capacitance.
Project description:A novel label-free method is presented to detect and quantify cell-derived microparticles (MPs) by the electrochemical potential-modulated electrochemical impedance spectroscopy (EIS). MPs are present in elevated concentrations during pathological conditions and play a major role in the establishment and pathogenesis of many diseases. Considering this, accurate detection and quantification of MPs is very important in clinical diagnostics and therapeutics. A combination of bulk solution electrokinetic sorting and interfacial impedance responses allows achieving detection limits as low as several MPs per ?L. By fitting resulting EIS spectra with an equivalent electrical circuit, the bulk solution electrokinetic and interfacial impedance responses were characterized. In the bulk solution two major relaxations were prominent-?-relaxation in low MHz region due to the MP capacitive membrane bridging, and ?-relaxation at ?10 kHz due to counter ions diffusion. At low frequencies (10-0.1 Hz) at electrochemical potentials exceeding -100 mV, a facile interfacial Faradaic process of oxidation in MPs coupled with diffusion and non-Faradaic double layer charging dominate, probably due to oxidation of phospholipids and/or proteins on the MP surface and MP lysis. Buffer influence on the MP detection demonstrated that a relatively low conductivity Tyrode's buffer background solution is preferential for the MP electrokinetic separation and characterization. This study also demonstrated that standard laboratory methods such as flow cytometry underestimate MP concentrations, especially those with smaller average sizes, by as much as a factor of 2-40.
Project description:Dark-field microscope (DFM) analysis of nanoparticle binding signal is highly useful for a variety of research and biomedical applications, but current applications for nanoparticle quantification rely on expensive DFM systems. The cost, size, limited robustness of these DFMs limits their utility for non-laboratory settings. Most nanoparticle analyses use high-magnification DFM images, which are labor intensive to acquire and subject to operator bias. Low-magnification DFM image capture is faster, but is subject to background from surface artifacts and debris, although image processing can partially compensate for background signal. We thus mated an LED light source, a dark-field condenser and a 20× objective lens with a mobile phone camera to create an inexpensive, portable and robust DFM system suitable for use in non-laboratory conditions. This proof-of-concept mobile DFM device weighs less than 400g and costs less than $2000, but analysis of images captured with this device reveal similar nanoparticle quantitation results to those acquired with a much larger and more expensive desktop DFMM system. Our results suggest that similar devices may be useful for quantification of stable, nanoparticle-based activity and quantitation assays in resource-limited areas where conventional assay approaches are not practical.
Project description:Nanoparticles have become a powerful tool for cell imaging and biomolecule, cell and protein interaction studies, but are difficult to rapidly and accurately measure in most assays. Dark-field microscope (DFM) image analysis approaches used to quantify nanoparticles require high-magnification near-field (HN) images that are labor intensive due to a requirement for manual image selection and focal adjustments needed when identifying and capturing new regions of interest. Low-magnification far-field (LF) DFM imagery is technically simpler to perform but cannot be used as an alternate to HN-DFM quantification, since it is highly sensitive to surface artifacts and debris that can easily mask nanoparticle signal. We now describe a new noise reduction approach that markedly reduces LF-DFM image artifacts to allow sensitive and accurate nanoparticle signal quantification from LF-DFM images. We have used this approach to develop a "Dark Scatter Master" (DSM) algorithm for the popular NIH image analysis program ImageJ, which can be readily adapted for use with automated high-throughput assay analyses. This method demonstrated robust performance quantifying nanoparticles in different assay formats, including a novel method that quantified extracellular vesicles in patient blood sample to detect pancreatic cancer cases. Based on these results, we believe our LF-DFM quantification method can markedly decrease the analysis time of most nanoparticle-based assays to impact both basic research and clinical analyses.
Project description:Nanoparticles have shown great potential as vehicles for the delivery of drugs, nucleic acids, and therapeutic proteins; an efficient, high-throughput screening method to analyze nanoparticle interaction with the cytomembrane would substantially improve the efficiency and accuracy of the delivery. Here, we developed a capacitance sensor array that monitored the capacitance values of nanoparticle-treated cells in a real-time manner, without the need for labeling. Upon cellular uptake of the nanoparticles, a capacitance peak was observed at a low frequency (e.g., 100?Hz) as a function of time based on zeta potential changes. In the high frequency region (e.g., 15-20?kHz), the rate of decreasing capacitance slowed as a function of time compared to the cell growth control group, due to increased cytoplasm resistance and decreased membrane capacitance and resistance. The information provided by our capacitance sensor array will be a powerful tool for scientists designing nanoparticles for specific purposes.
Project description:Single nanoparticle imaging is a significant technique to help reveal the reaction mechanism and provides insight into the nanoparticle transformation. Here, we monitor the in situ morphological transformation of Au nanostars (GNSs) induced by iodide (I<sup>-</sup>) in real time using dark-field microscopy (DFM) with 638 nm red (R) and 534 nm green (G) laser coillumination. The two lasers are selected because the longitudinal localized surface plasmon resonance of GNSs is located at 638 nm and that for GNSs after transformation is at 534 nm. Interestingly, I<sup>-</sup> can interact with GNSs directly without the engagement of other reagents, and upon increasing I<sup>-</sup> concentrations, GNSs undergo color changes from red to orange, yellow, and green under DFM. Accordingly, green/red channel intensities (G/R ratios) are extracted by obtaining red and green channel intensities of single nanoparticles to weigh the morphological changes and quantify I<sup>-</sup>. A single nanoparticle sensor is constructed for I<sup>-</sup> detection with a detection limit of 6.9 nM. Finally, a novel mechanism is proposed to elucidate this shape transformation. I<sup>-</sup> absorbed onto the surface of GNSs binds with Au atoms to form AuI<sup>-</sup>, lowering the energy of its bond with other Au atoms, which facilitates the diffusion of this atom across the nanoparticle surface to low-energy sites at the concaves, thus deforming to spherical Au nanoparticles.
Project description:The acceleration of Faradaic reactions by oscillating electric potentials has emerged as a viable tool to enhance electrocatalysis, but the non-Faradaic dynamic promotion of thermal catalytic processes remains to be proven. Here, we present experimental evidence showing that oscillating potentials are capable of enhancing the rate of ethylene hydrogenation despite no promotion effect being observed under static potentials. The non-Faradaic dynamic enhancement reaches up to 553% on a Pd/C electrode when cycling between -0.25 and 0.55 V<sub>NHE</sub> under optimized conditions with a frequency of around 0.1 Hz and a duty cycle of 99%. Under those conditions, the catalytic reaction rates were promoted beyond the rate of charge transfer to the electrode surface, confirming the non-Faradaic nature of the process. Experiments in different electrolytes reveal a good correlation between the catalytic enhancement and the double-layer capacitance, a measure for the interfacial electric field strength. Preliminary kinetic data is consistent with cyclic removal of adsorbates from the surface at negative potential and the subsequent adsorption of H<sub>2</sub> and C<sub>2</sub>H<sub>4</sub> and hydrogenation reaction at the positively polarized surface.
Project description:Supercapacitors based on activated carbon electrodes and ionic liquids as electrolytes are capable of storing charge through the electrosorption of ions on porous carbons and represent important energy storage devices with high power delivery/uptake. Various computational and instrumental methods have been developed to understand the ion storage behavior, however, techniques that can probe various cations and anions of ionic liquids separately remain lacking. Here, we report an approach to monitoring cations and anions independently by using silica nanoparticle-grafted ionic liquids, in which ions attaching to silica nanoparticle cannot access activated carbon pores upon charging, whereas free counter-ions can. Aided by this strategy, conventional electrochemical characterizations allow the direct measurement of the respective capacitance contributions and acting potential windows of different ions. Moreover, coupled with electrochemical quartz crystal microbalance, this method can provide unprecedented insight into the underlying electrochemistry.
Project description:We present a comprehensive study of the electrochemical capacitance between a one-dimensional electronic material and an electrolyte. In contrast to a conventional, planar electrode, the nanoscale dimension of the electrode (with diameter smaller than the Debye length and approaching the size of the ions in solution) qualitatively changes the capacitance, which we measure and model herein. Furthermore, the finite density of states in these low dimensional electronic systems results in a quantum capacitance, which is comparable to the electrochemical capacitance. Using electrochemical impedance spectroscopy (EIS), we measure the ensemble average, complex, frequency dependent impedance (from 0.1 Hz to 1 MHz) between a purified (99.9%) semiconducting nanotube network and an aqueous electrolyte (KCl) at different concentrations between 10 mM and 1 M. The potential dependence of the capacitance is convoluted with the potential dependence of the in-plane conductance of the nanotube network, which we model using a transmission-line model to account for the frequency dependent in-plane impedance as well as the total interfacial impedance between the network and the electrolyte. The ionic strength dependence of the capacitance is expected to have a root cause from the double layer capacitance, which we model using a modified Poisson-Boltzmann equation. The relative contributions from those two capacitances can be quantitatively decoupled. We find a total capacitance per tube of 0.67-1.13 fF/?m according to liquid gate potential varying from -0.5 to -0.7 V.
Project description:Label-free and sensitive detection of PSA (Prostate Specific Antigen) is still a big challenge in the arena of prostate cancer diagnosis in males. We present a comparative study for label-free PSA aptasensor and PSA immunosensor for the PSA-specific monoclonal antibody, based on graphene quantum dots-gold nanorods (GQDs-AuNRs) modified screen-printed electrodes. GQDs-AuNRs composite has been synthesized and used as an electro-active material, which shows fast electron transfer and catalytic property. Aptamer or anti-PSA has immobilized onto the surface of modified screen printed electrodes. Three techniques are used simultaneously, viz. cyclic voltammetry (CV), differential pulse voltammetry (DPV) and electrochemical impedence spectroscopy (EIS) to investigate the analytical performance of both PSA aptasensor and PSA immunosensor with its corresponding PSA antigen. Under optimum conditions, both sensors show comparable results with an almost same limit of detection (LOD) of 0.14 ng mL-1. The results developed with aptasensor and anti-PSA is also checked through the detection of PSA in real samples with acceptable results. Our study suggests some advantages of aptasensor in terms of better stability, simplicity and cost effectiveness. Further our present work shows enormous potential of our developed sensors for real application using voltammetric and EIS techniques simultaneous to get reliable detection of the disease.
Project description:We report molecular-fluorescence enhancement via the blue-shifted plasmon-induced resonance energy transfer (PIRET) from single Au nanorods (AuNRs) to merocyanine (MC) dye molecules. The blue-shifted PIRET occurs when there is a proper spectral overlap between the scattering of AuNRs and the absorption of MC molecules. Along with the quenching of scattering from AuNRs, the blue-shifted PIRET enhances the fluorescence of nearby molecules. On the basis of the fluorescence enhancement, we conclude that AuNRs can be used as donors with clear advantages to excite the fluorescence of molecules as acceptors in AuNR-molecule hybrids. On the one hand, compared to conventional molecular donors in Förster resonance energy transfer (FRET), AuNRs have much larger absorption cross sections at the plasmon resonance frequencies. On the other hand, energy-transfer efficiency of PIRET decreases at a lower rate than that of FRET when the donor-acceptor distance is increased. Besides, the blue-shifted PIRET allows excitation with incident light of lower energy than the acceptor's absorption, which is difficult to achieve in FRET because of the Stokes shift. With the capability of enhancing molecular fluorescence with excitation light of low intensity and long wavelength, the blue-shifted PIRET will expand the applications of nanoparticle- molecule hybrids in biosensing and bioimaging by increasing signal-to-noise ratio and by reducing photodamage to biological cells and organelles at the targeted areas.