Poly(N-isopropylacrylamide) (pNIPAM) microgels are soft and deformable particles, which can adsorb at liquid interfaces. In the present paper, we study the two-dimensional organization of charged and quasi-neutral microgels with different cross-linking densities, under compression at the air−water interface and the transfer of the microgel monolayer onto a solid substrate at different surface pressures. At low cross-linking densities, the microgels form highly ordered hexagonal lattices on the solid substrate over large areas, with a unique lattice parameter
that decreases continuously as the surface pressure increases. We thus prove that the microgel conformation evolves at the air−water interface. The microgels undergo a continuous transition from a highly flattened state at low surface coverage, where the maximal polymer segments are adsorbed at the interface, to entangled flattened microgels, and finally the thickening of the layer up to a dense hydrogel layer of compacted microgels. Moreover, two batches of microgels, with and without charges, are compared. The contribution of electrostatic interactions is assessed via changing the charge density of the microgels or modulating the Debye length. In both cases, electrostatics does not change the lattice parameter, meaning that, despite the microgel different swelling ratio, charges do not affect neither interactions between particles at the interface nor microgels adsorption. Conversely, the cross-linking density has a strong impact on microgel packing at the interface: increasing the cross-linking density strongly decreases the extent of microgel flattening and promotes the occurrence of coexisting hexagonally ordered domains with different lattice parameters.
C. Wattanakit, T. Yutthalekha, S. Asssavapanumat, V. Lapeyre, A. Kuhn
Asymmetric synthesis of molecules is of crucial importance to obtain pure chiral compounds, which are of primary interest in many areas including medicine, biotechnology, and chemistry. Various methods have been used very successfully to increase the enantiomeric yield of reaction pathways, but there is still room for the development of alternative highly enantioselective reaction concepts, either as a scientific challenge of tremendous fundamental
significance, or owing to the increasing demand for enantiopure products, e.g., in the pharmaceutical industry. In this context, we report here a strategy for the synthesis of chiral compounds, based on pulsed electrochemical conversion. We illustrate the approach with the stereospecific electroreduction of a prochiral model molecule at chiral mesoporous metal structures, resulting in an enantiomeric excess of over 90%. This change of paradigm opens up promising reaction schemes for the straightforward synthesis of high-added-value molecules.
V. Eßmann, S. Voci, G. Loget, N. Sojic, W. Schuhmann, A. Kuhn
Bipolar electrochemistry has been shown to enable and control various kinds of propulsion of non‑wired conducting objects: translation, rotation, and levitation. There is a very rapid development in the field of controlled motion combined with other functionalities. Here, we integrate two different concepts in one system to generate wireless electrochemical motion of a specifically designed rotor and track its polarization simultaneously by electrochemical light emission. Locally produced hydrogen bubbles at the cathodic pole of the bipolar rotor are the driving force of the motion, whereas [Ru(bpy)3]Cl2 and tripropylamine react at the anodic extremity, thus generating an electrochemiluminescence signal with an intensity directly correlated with the orientation of the rotor arms. This allows in a straightforward way the qualitative visualization of the changing interfacial potential differences during rotation, and shows for the first time that light emission can be coupled to autonomously rotating bipolar electrodes.
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 to demon-strate 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 over-expressed 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 to the unique ECL mechanism and is rationalized by considering the limited lifetimes of the electrogenerated coreactant radicals. The electrochemi-cal stimulus used for luminescence generation does not suffer from background signals, such as the typical auto-fluorescence of biological samples. The presented surface-confined ECL microscopy should find promising applications in ultrasensitive single cell imaging assays.
We design polystyrene–poly(N′-isopropylacrylamide-co-acrylic acid) core–shell particles that exhibit dynamically tunable scattering. We show that under normal solvent conditions the shell is nearly index-matched to pure water, and the particle scattering is dominated by Rayleigh scattering from the core. As the temperature or salt concentration increases, both the scattering cross-section and the forward scattering increase, characteristic of Mie scatterers. The magnitude of the change in the scattering cross-section and scattering anisotropy can be controlled through the solvent conditions and the size of the core. Such particles may find use as optical switches or optical filters with tunable opacity.
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