Please release me: Electrochemically activated cell release is achieved using a redox‐active supramolecular complex (see picture). Host molecule CB[8] (green) links surface‐bound viologen (purple) with solution‐exposed RGD peptides (red). Electrochemical reduction dissociates the complex, releases the peptides, and thus releases the cells from the substrates. This supramolecular strategy is also applicable to microelectrodes.
The treatment of a suspension of graphite oxide (GO) with sodium azide leads to a material that, after reduction, features amino groups at the top and bottom of the sheets. These groups react through microcontact printing with an isothiocyanate monolayer on a silicon oxide substrate to form covalent bonds that strongly attach to the particles on the surface. With ultrasonication it is possible to obtain exfoliation of the sheets that are not covalently bound to the surface leaving single-layer platelets attached to the substrate. The azido derivative can be also used to functionalize the graphene oxide with long alkylic chains through a click chemistry approach. This functionalization results in the exfoliation of this material in dimethylformamide. The novel materials were fully characterized by different techniques including IR spectroscopy, thermogravimetric analysis (TGA), scanning and transmission electron microscopy (SEM and TEM), X-Ray photoelectron spectroscopy (XPS), and solid state NMR spectroscopy. The material with amino groups, after the reduction step, is conductive with a resistivity only approximately seven times larger than that of unprocessed graphite. This implies that after reduction of the GO, the conjugated sp2 network is largely restored. We consider this to be an important step towards a chemical approach for forming conducting large-area platelet films of single-layer graphene.
This review surveys recent developments in the field of electrochemically generated gradients. The gradual variation of properties, which is a key characteristic of gradients, is of eminent importance in technology, for example, directional wetting, as well as biology, for example, chemotaxis. Electrochemical techniques offer many benefits, such as the generation of dynamic solution and surface gradients, integration with electronics, and compatibility with automation. An overview is given of newly developed methods, from purely electrochemical techniques to the combination of electrochemistry with other methods. Electrochemically fabricated gradients are employed extensively for biological and technological applications, such as high-throughput screening, high-throughput deposition, and device development, all of which are covered herein. Especially promising are developments towards the study and control of dynamic phenomena, such as the directional motion of molecules, droplets, and cells.
Studying and controlling reactions at surfaces is of great fundamental and applied interest in, among others, biology, electronics and catalysis. Because reaction kinetics is different at surfaces compared with solution, frequently, solution-characterization techniques cannot be used. Here we report solution gradients, prepared by electrochemical means, for controlling and monitoring reactivity at surfaces in space and time. As a proof of principle, electrochemically derived gradients of a reaction parameter (pH) and of a catalyst (Cu(I)) have been employed to make surface gradients on the micron scale and to study the kinetics of the (surface-confined) imine hydrolysis and the copper(I)-catalysed azide-alkyne 1,3-dipolar cycloaddition, respectively. For both systems, the kinetic data were spatially visualized in a two-dimensional reactivity map. In the case of the copper(I)-catalysed azide-alkyne 1,3-dipolar cycloaddition, the reaction order (2) was deduced from it.
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