Nešo Šojić

Bipolar electrochemistry, a phenomenon which generates an asymmetric reactivity on the surface of conductive objects in a wireless manner, is an important concept for many purposes, from analysis to materials science as well as for the generation of motion. Chemists have known the basic concept for a long time, but it has recently attracted additional attention, especially in the context of micro- and nanoscience. In this Account, we introduce the fundamentals of bipolar electrochemistry and illustrate its recent applications, with a particular focus on the fields of materials science and dynamic systems. Janus particles, named after the Roman god depicted with two faces, are currently in the heart of many original investigations. These objects exhibit different physicochemical properties on two opposite sides. This makes them a unique class of materials, showing interesting features. They have received increasing attention from the materials science community, since they can be used for a large variety of applications, ranging from sensing to photosplitting of water. So far the great majority of methods developed for the generation of Janus particles breaks the symmetry by using interfaces or surfaces. The consequence is often a low time-space yield, which limits their large scale production. In this context, chemists have successfully used bipolar electrodeposition to break the symmetry. This provides a single-step technique for the bulk production of Janus particles with a high control over the deposit structure and morphology, as well as a significantly improved yield. In this context, researchers have used the bipolar electrodeposition of molecular layers, metals, semiconductors, and insulators at one or both reactive poles of bipolar electrodes to generate a wide range of Janus particles with different size, composition and shape. In using bipolar electrochemistry as a driving force for generating motion, its intrinsic asymmetric reactivity is again the crucial aspect, as there is no directed motion without symmetry breaking. Controlling the motion of objects at the micro- and nanoscale is of primary importance for many potential applications, ranging from medical diagnosis to nanosurgery, and has generated huge interest in the scientific community in recent years. Several original approaches to design micro- and nanomotors have been explored, with propulsion strategies based on chemical fuelling or on external fields. The first strategy is using the asymmetric particles generated by bipolar electrodeposition and employing them directly as micromotors. We have demonstrated this by using the catalytic and magnetic properties of Janus objects. The second strategy is utilizing bipolar electrochemistry as a direct trigger of motion of isotropic particles. We developed mechanisms based on a simultaneous dissolution and deposition, or on a localized asymmetric production of bubbles. We then used these for the translation, the rotation and the levitation of conducting objects. These examples give insight into two interesting fields of applications of the concept of bipolar electrochemistry, and open perspectives for future developments in materials science and for generating motion at different scales.

We report here the development of coreactant-based electrogenerated chemiluminescence (ECL) as a surface-confined microscopy to image single cells and their membrane proteins. Labeling the entire cell membrane allows one to demonstrate that, by contrast with fluorescence, ECL emission is only detected from fluorophores located in the immediate vicinity of the electrode surface (i.e., 1-2 μm). Then, to present the potential diagnostic applications of our approach, we selected carbon nanotubes (CNT)-based inkjet-printed disposable electrodes for the direct ECL imaging of a labeled plasma receptor overexpressed on tumor cells. The ECL fluorophore was linked to an antibody and enabled to localize the ECL generation on the cancer cell membrane in close proximity to the electrode surface. Such a result is intrinsically associated with the unique ECL mechanism and is rationalized by considering the limited lifetimes of the electrogenerated coreactant radicals. The electrochemical stimulus used for luminescence generation does not suffer from background signals, such as the typical autofluorescence of biological samples. The presented surface-confined ECL microscopy should find promising applications in ultrasensitive single cell imaging assays.

Herein is reported a surface-confined microscopy based on electrochemiluminescence (ECL) that allows to image the plasma membrane of single cells at the interface with an electrode. By analyzing photoluminescence (PL), ECL and AFM images of mammalian CHO cells, we demonstrate that, in contrast to the wide-field fluorescence, ECL emission is confined to the immediate vicinity of the electrode surface and only the basal membrane of the cell becomes luminescent. The resulting ECL microscopy reveals details that are not resolved by classic fluorescence microscopy, without any light irradiation and specific setup. The thickness of the ECL-emitting regions is ∼500 nm due to the unique ECL mechanism that involves short-lifetime electrogenerated radicals. In addition, the reported ECL microscopy is a dynamic technique that reflects the transport properties through the cell membranes and not only the specific labeling of the membranes. Finally, disposable transparent carbon nanotube (CNT)-based electrodes inkjet-printed on classic microscope glass coverslips were used to image cells in both reflection and transmission configurations. Therefore, our approach opens new avenues for ECL as a surface-confined microscopy to develop single cell assays and to image the dynamics of biological entities in cells or in membranes.

-doped silica/Au nanoparticles (RuDSNs/AuNPs) as the ECL nanoemitters. The ECL emission is confined to the local surface of RuDSNs leading to a significant enhancement in the intensity. To prove the concept, a single protein molecule at the electrode is initially visualized using the as-prepared RuDSN/AuNPs nanoemitters. Furthermore, the nanoemitter-labeled antibody is linked at the cellular membrane to image a single membrane protein at one cell, without the interference of current and optical background. The success in single-biomolecule ECL imaging solves the long-lasting task in the ultrasensitive ECL analysis, which should be able to provide more elegant information about the protein in cellular biology.

A new class of bead-based microarray that uses electrogenerated chemiluminescence (ECL) as a readout mechanism to detect multiple antigens simultaneously is presented. This platform demonstrates the possibility of performing highly multiplexed assays using ECL because all the individual sensing beads in the array are simultaneously imaged and individually resolved by ECL. Duplex and triplex assay results are demonstrated as well as a cross reactivity study.