Nanoporous Gold Electrodes and Their Applications in Analytical Chemistry

Nanoporous gold prepared by dealloying Au:Ag alloys has recently become an attractive material in the field of analytical chemistry. This conductive material has an open, 3D porous framework consisting of nanosized pores and ligaments with surface areas that are 10s to 100s of times larger than planar gold of an equivalent geometric area. The high surface area coupled with an open pore network makes nanoporous gold an ideal support for the development of chemical sensors. Important attributes include conductivity, high surface area, ease of preparation and modification, tunable pore size, and a bicontinuous open pore network. In this paper, the fabrication, characterization, and applications of nanoporous gold in chemical sensing are reviewed specifically as they relate to the development of immunosensors, enzyme-based biosensors, DNA sensors, Raman sensors, and small molecule sensors

Size and Shape Control of Gold Nanodeposits in an Array of Silica Nanowells on a Gold Electrode

Ordered arrays of hemispherical nanowells were formed in a sol-gel-derived silica film on a gold electrode using 500 nm diameter polystyrene latex spheres as templates. The conductive domain located at the bottom of each nanowell upon template removal was enlarged via electroless deposition from a gold plating solution. The structured electrodes thus formed were characterized using scanning electron microscopy and atomic force microscopy. Depending on the method used to make the films, the extent of the long-range packing and the size of the conductive domain changed. Electroless deposition in the nanowells produced (near) sphere-like nanostructures of gold, the size of which depended on the incubation time in the plating solution and the size of the conductive domain. Longer exposure times yielded nanostructures that filled the nanowell, whereas smaller exposure time yielded much smaller structures. Significantly larger, rougher deposits were formed in nanowells with large conductive domains. The electrochemical response observed at these electrodes was strongly dependent on the extent of long-range packing, the presence of defect sites in the film and their relative spacing, and the redox species in solution

Potentiometric Biosensing of Ascorbic Acid, Uric Acid, and Cysteine in Microliter Volumes Using Miniaturized Nanoporous Gold Electrodes

Potentiometric redox sensing is a relatively inexpensive and passive approach to evaluate the overall redox state of complex biological and environmental solutions. The ability to make such measurements in ultra-small volumes using high surface area, nanoporous electrodes is of particular importance as such electrodes can improve the rates of electron transfer and reduce the effects of biofouling on the electrochemical signal. This work focuses on the fabrication of miniaturized nanoporous gold (NPG) electrodes with a high surface area and a small footprint for the potentiometric redox sensing of three biologically relevant redox molecules (ascorbic acid, uric acid, and cysteine) in microliter volumes. The NPG electrodes were inexpensively made by attaching a nanoporous gold leaf prepared by dealloying 12K gold in nitric acid to a modified glass capillary (1.5 mm id) and establishing an electrode connection with copper tape. The surface area of the electrodes was ~1.5 cm2, providing a roughness factor of ~16 relative to the geometric area of 0.09 cm2. Scanning electron microscopy confirmed the nanoporous framework. A linear dependence between the open-circuit potential (OCP) and the logarithm of concentration (e.g., Nernstian-like behavior) was obtained for all three redox molecules in 100 μL buffered solutions. As a first step towards understanding a real system, the response associated with changing the concentration of one redox species in the presence of the other two was examined. These results show that at NPG, the redox potential of a solution containing biologically relevant concentrations of ascorbic acid, uric acid, and cysteine is strongly influenced by ascorbic acid. Such information is important for the measurement of redox potentials in complex biological solutions

Recent Advances in Bimetallic Nanoporous Gold Electrodes for Electrochemical Sensing

Bimetallic nanocomposites and nanoparticles have received tremendous interest recently because they often exhibit better properties than single-component materials. Improved electron transfer rates and the synergistic interactions between individual metals are two of the most beneficial attributes of these materials. In this review, we focus on bimetallic nanoporous gold (NPG) because of its importance in the field of electrochemical sensing coupled with the ease with which it can be made. NPG is a particularly important scaffold because of its unique properties, including biofouling resistance and ease of modification. In this review, several different methods to synthesize NPG, along with varying modification approaches are described. These include the use of ternary alloys, immersion–reduction (chemical, electrochemical, hybrid), co-electrodeposition–annealing, and under-potential deposition coupled with surface-limited redox replacement of NPG with different metal nanoparticles (e.g., Pt, Cu, Pd, Ni, Co, Fe, etc.). The review also describes the importance of fully characterizing these bimetallic nanocomposites and critically analyzing their structure, surface morphology, surface composition, and application in electrochemical sensing of chemical and biochemical species. The authors attempt to highlight the most recent and advanced techniques for designing non-enzymatic bimetallic electrochemical nanosensors. The review opens up a window for readers to obtain detailed knowledge about the formation and structure of bimetallic electrodes and their applications in electrochemical sensing