Recent Advances in Electrochemiluminescence Visual Biosensing and Bioimaging.

Electrochemiluminescence (ECL) is one of the most powerful techniques that meet the needs of analysis and detection in a variety of scenarios, because of its highly analytical sensitivity and excellent spatiotemporal controllability. ECL combined with microscopy (ECLM) offers a promising approach for quantifying and mapping a wide range of analytes. To date, ECLM has been widely used to image biological entities and processes, such as cells, subcellular structures, proteins and membrane transport properties. In this review, we first introduced the mechanisms of several classic ECL systems, then highlighted the progress of visual biosensing and bioimaging by ECLM in the last decade. Finally, the characteristics of ECLM were summarized, as well as some of the current challenges. The future research interests and potential directions for the application of ECLM were also outlooked.

Electrochemiluminescence Distance and Reactivity of Coreactants Determine the Sensitivity of Bead-Based Immunoassays.

Herein we report the study of electrochemiluminescence (ECL) generation by tris(2,2'-bipyridyl)ruthenium (Ru(bpy)3 2+ ) and five tertiary amine coreactants. The ECL distance and lifetime of coreactant radical cations were measured by ECL self-interference spectroscopy. And the reactivity of coreactants was quantitatively evaluated in terms of integrated ECL intensity. By statistical analysis of ECL images of single Ru(bpy)3 2+ -labeled microbeads, we propose that ECL distance and reactivity of coreactant codetermine the emission intensity and thus the sensitivity of immunoassay. 2,2-bis(hydroxymethyl)-2,2',2''-nitrilotriethanol (BIS-TRIS) can well balance ECL distance-reactivity trade-off and enhance the sensitivity by 236 % compared with tri-n-propylamine (TPrA) in the bead-based immunoassay of carcinoembryonic antigen. The study brings an insightful understanding of ECL generation in bead-based immunoassay and a way of maximizing the analytical sensitivity from the aspect of coreactant.

Nanochannel Templated Iridium Oxide Nanostructures for Wide-Range pH Sensing from Solutions to Human Skin Surface.

Herein we report the fabrication of highly sensitive solid-state pH sensors based on iridium oxide nanowires (IONWs) for a wide-range of pH measurements. IONWs were confined electrodeposits on the indium tin oxide (ITO) electrode using a highly ordered silica nanochannel membrane as the template. Subsequently removing the template produced amorphous IONWs consisting of hydrated iridium oxyhydroxides. The IONW/ITO sensor can rapidly respond to the pH of the aqueous solutions in a wide range (from 0 to 13), avoiding the acid and alkaline errors encountered by conventional pH electrodes and exhibiting a super-Nernst analytical sensitivity as high as 235.5 mV/pH in the very acidic range of ∼0-2.5 and 90.1 mV/pH beyond (pH = ∼2.5-13). The sensitivity was associated with the interconversion of oxidation states of iridium oxyhydroxides. While in the very acidic range, intercalation of Cl- was proved to be responsible for the exceptionally high pH sensitivity. Moreover, the sensor was also demonstrated to work in organic solutions too. Finally, the flexible IONW/ITO electrode was prepared and interfaced to a wireless electrochemical device for real-time epidermal pH analysis with smartphones.

Electrodeposition of nickel nanostructures using silica nanochannels as confinement for low-fouling enzyme-free glucose detection.

This work reports an enzyme-free glucose sensor based on nickel nanostructures electrodeposited on a fluorine-doped tin oxide (FTO) electrode modified with a silica nanochannel membrane (SNM). The SNM consists of a high density of nanochannels vertically oriented to the electrode surface, which can spatially confine the electrodeposition of nickel nanostructures and protect them to make Ni@SNM/FTO electrodes. In alkaline media, nickel could be converted to nickel oxyhydroxide that displayed catalytic activity toward the anodic oxidation of glucose. The electrodes could thus function as enzyme-free sensors for glucose detection. Under optimal conditions, the sensors exhibited an excellent analytical performance, with an analytical sensitivity as high as 62.3 µA mM-1 cm-2, a wide detection range from 10 µM to 12 mM and a low detection limit of 0.44 µM. Furthermore, given nickel nanostructures were embedded inside the nanochannels of the SNM (with a diameter of 2-3 nm), the sensor possessed anti-fouling ability and outstanding current stability, thus allowing the direct detection of glucose in dilute blood samples.

Confined Electrochemiluminescence Generation at Ultra-High-Density Gold Microwell Electrodes.

Electrochemiluminescence (ECL) imaging analysis based on the ultra-high-density microwell electrode array (UMEA) has been successfully used in biosensing and diagnostics, while the studies of ECL generation mechanisms with spatial resolution remain scarce. Herein we fabricate a gold-coated polydimethylsiloxane (PDMS) UMEA using electroless deposition method for the visualization of ECL reaction process at the single microwell level in conjunction with using microscopic ECL imaging technique, demonstrating that the microwell gold walls are indeed capable of enhancing the ECL generation. For the classical ECL system involving tris(2,2'-bipyridyl)ruthenium (Ru(bpy)3 2+) and tri-n-propylamine (TPrA), the ECL image of a single microwell appears as a surface-confined ring, indicating the ECL intensity generated inside the well is much stronger than that on the top surface of UMEA. Moreover, at a low concentration of Ru(bpy)3 2+, the ECL image remains to be ring-shaped with the increase of exposure time, because of the limited lifetime of TPrA radical cations TPrA+•. In combination with the theoretical simulation, the ring-shaped ECL image is resolved to originate from the superposition effect of the mass diffusion fields at both microwell wall and bottom surfaces.