Bulk Electrosynthesis of Patchy Particles with Highly Controlled Asymmetric Features.

Asymmetric modification of particles with various patches of different composition and size at predefined positions is an important challenge in contemporary surface chemistry, as such particles have numerous potential applications, ranging from materials science and (photo)catalysis to self-assembly and drug delivery. However, approaches allowing the synthesis of this kind of complex objects in the bulk of a solution in a straightforward way are currently lacking. In this context, bipolar electrochemistry (BE) is a powerful technique for the asymmetric modification of conducting objects. Herein, this approach is used for the highly controlled modification of particles with different metal patches, generated at specific locations of isotropic objects. The synthesis is carried out in the bulk of the solution and leads to predefined patterns of increasing complexity, including even a specific chiral arrangement of the patches.

Local reactivity of metal-insulator-semiconductor photoanodes imaged by photoinduced electrochemiluminescence microscopy.

Localized photoinduced electrochemiluminescence (PECL) is studied on photoanodes composed of Ir microbands deposited on n-Si/SiOx. We demonstrate that PECL microscopy precisely imaged the hole-driven heterogeneous photoelectrochemical reactivity. The method is promising for elucidating the local activity of photoelectrodes that are employed in solar energy conversion.

Spatial Precision Tailoring the Catalytic Activity of Graphene Monolayers for Designing Janus Swimmers.

Graphene monolayers have interesting applications in many fields due to their intrinsic physicochemical properties, especially when they can be postmodified with high precision. Herein, we describe the highly site-selective functionalization of freestanding graphene monolayers with platinum (Pt) clusters by bipolar electrochemistry. The deposition of such metal spots leads to catalytically active hybrid two-dimensional (2D) nanomaterials. Their catalytic functionality is illustrated by the spatially controlled decomposition of hydrogen peroxide, inducing motion at the water/air interface due to oxygen bubble evolution. A series of such 2D Janus structures with Pt deposition at predefined positions (corners and edges) is studied with respect to the generation of autonomous motion. The type and speed of motion can be fine-tuned by controlling the deposition time and location of the Pt clusters. These proof-of-principle experiments indicate that this type of hybrid 2D object opens up interesting perspectives in terms of applications, such as environmental detection or remediation.

Magnetic field-enhanced redox chemistry on-the-fly for enantioselective synthesis.

Chemistry on-the-fly is an interesting concept, extensively studied in recent years due to its potential use for recognition, quantification and conversion of chemical species in solution. In this context, chemistry on-the-fly for asymmetric synthesis is a promising field of investigation, since it can help to overcome mass transport limitations, present for example in conventional organic electrosynthesis. Herein, the synergy between a magnetic field-enhanced self-electrophoretic propulsion mechanism and enantioselective redox chemistry on-the-fly is proposed as an efficient method to boost stereoselective conversion. We employ Janus swimmers as redox-active elements, exhibiting a well-controlled clockwise or anticlockwise motion with a speed that can be increased by one order of magnitude in the presence of an external magnetic field. While moving, these bifunctional objects convert spontaneously on-the-fly a prochiral molecule into a specific enantiomer with high enantiomeric excess. The magnetic field-enhanced self-mixing of the swimmers, based on the formation of local magnetohydrodynamic vortices, leads to a significant improvement of the reaction yield and the conversion rate.

Responsive microgels-based colloidosomes constructed from all-aqueous pH-switchable coacervate droplets.

HYPOTHESIS: Colloidosomes made of stimuli-responsive microgels offer the opportunity to design polymeric capsules with a hierarchical and tunable pore distribution. Coacervates stabilized by a microgel monolayer represent a unique strategy to build colloidosomes from all-aqueous emulsion drops, while exploiting the sequestration and dissolution properties of the coacervates. EXPERIMENTS: Methacrylated poly(N-isopropylacrylamide) (pNIPAM) microgels are used to stabilize coacervates made of an ampholyte polymer at a pH close to its isoelectric point. They are further cross-linked under UV-irradiation. The resulting assemblies are studied by means of confocal microscopy. Their permeability towards dextrans and nanoparticles is studied before and after dissolution of the coacervate. FINDINGS: PNIPAM microgels are found to stabilize the coacervates by adsorbing at their surface. Inter cross-linking the microgels results in the formation of an elastic colloidosome that persists after the coacervate dissolution and withstands surface deformations up to about 200%. The coacervate is exploited as a sequestrating core to entrap a water-soluble payload, which can be further released upon coacervate dissolution, while the membrane exhibits a size-selecting permeability. The membrane properties can also be switched by the volume phase transition of the microgels. Coacervate-embedded colloidosomes open new perspectives in the area of encapsulation/extraction and controlled transport of water-soluble/dispersed species.

Design of optoelectrodes for the remote imaging of cells and in situ electrochemical detection of neurosecretory events.

Optical fibers have opened avenues for remote imaging, bioanalyses and recently optogenetics. Besides, miniaturized electrochemical sensors have offered new opportunities in sensing directly redox neurotransmitters. The combination of both optical and electrochemical approaches was usually performed on the platform of microscopes or within microsystems. In this work, we developed optoelectrodes which features merge the advantages of both optical fibers and microelectrodes. Optical fiber bundles were modified at one of their extremity by a transparent ITO deposit. The electrochemical responses of these ITO-modified bundles were characterized for the detection of dopamine, epinephrine and norepinephrine. The analytical performances of the optoelectrodes were equivalent to the ones reported for carbon microelectrodes. The remote imaging of model neurosecretory PC12 cells by optoelectrodes was performed upon cell-staining with common fluorescent dyes: acridine orange and calcein-AM. An optoelectrode placed by micromanipulation at a few micrometers-distance from the cells offered remote images with single cell resolution. Finally, in situ electrochemical sensing was demonstrated by additions of K+-secretagogue solutions near PC12 cells under observation, leading to exocytotic events detected as amperometric spikes at the ITO surface. Such dual sensors should pave the way for in vivo remote imaging, optogenetic stimulation, and simultaneous detection of neurosecretory activities.

Autonomous Chiral Microswimmers with Self-mixing Capabilities for Highly Efficient Enantioselective Synthesis.

The development of chiral catalysts plays a very important role in various areas of chemical science. Heterogeneous catalysts have the general advantage of allowing a more straightforward separation from the products. One specific case of heterogeneous catalysis is electrocatalysis, being potentially a green chemistry approach. However, a typical drawback is that the redox conversion of molecules occurs only at the electrode/electrolyte interface, and not in the bulk of the electrolyte. The second limitation is that the electrodes have to be physically connected to a power supply to induce the desired reactions. To circumvent these problems, we propose here a complementary approach by replacing macroscopic electrodes with an ensemble of self-propelled redox active microswimmers. They move autonomously in solution while transforming simultaneously a prochiral starting compound into a specific enantiomer with a very high enantiomeric excess, accompanied by a significantly increased production rate of the favorite enantiomer.

Electropolymerizable Thiophene-Oligonucleotides for Electrode Functionalization.

Inserting complex biomolecules such as oligonucleotides during the synthesis of polymers remains an important challenge in the development of functionalized materials. In order to engineer such a biofunctionalized interface, a single-step method for the covalent immobilization of oligonucleotides (ONs) based on novel electropolymerizable lipid thiophene-oligonucleotide (L-ThON) conjugates was employed. Here, we report a new thiophene phosphoramidite building block for the synthesis of modified L-ThONs. The biofunctionalized material was obtained by direct electropolymerization of L-ThONs in the presence of 2,2'-bithiophene (BTh) to obtain a copolymer film on indium tin oxide electrodes. In situ electroconductance measurements and microstructural studies showed that the L-ThON was incorporated in the BTh copolymer backbone. Furthermore, the covalently immobilized L-ThON sequence showed selectivity in subsequent hybridization processes with a complementary target, demonstrating that L-ThONs can directly be used for manufacturing materials via an electropolymerization strategy. These results indicate that L-ThONs are promising candidates for the development of stable ON-based bioelectrochemical platforms.

Thermo-induced inversion of water-in-water emulsion stability by bis-hydrophilic microgels.

HYPOTHESIS: Stabilization of water-in-water (W/W) emulsions resulting from the separation of polymeric phases such as dextran (DEX) and poly(ethyleneoxide) (PEO) is highly challenging, because of the very low interfacial tensions between the two phases and because of the interface thickness extending over several nanometers. In the present work, we present a new type of stabilizers, based on bis-hydrophilic, thermoresponsive microgels, incorporating in the same structure poly(N-isopropylacrylamide) (pNIPAM) chains having an affinity for the PEO phase and dextran moieties. We hypothesize that these particles allow better control of the stability of the W/W emulsions. EXPERIMENTS: The microgels were synthesized by copolymerizing the NIPAM monomer with a multifunctional methacrylated dextran. They were characterized by dynamic light scattering, zeta potential measurements and nuclear magnetic resonance as a function of temperature. Microgels with different compositions were tested as stabilizers of droplets of the PEO phase dispersed in the DEX phase (P/D) or vice-versa (D/P), at different concentrations and temperatures. FINDINGS: Only microgels with the highest DEX content revealed excellent stabilizing properties for the emulsions by adsorbing at the droplet surface, thus demonstrating the fundamental role of bis-hydrophilicity. At room temperature, both pNIPAM and DEX chains were swollen by water and stabilized better D/P emulsions. However, above the volume phase transition temperature (VPTT ≈ 32 °C) of pNIPAM the microgels shrunk and stabilized better P/D emulsions. At all temperatures, excess microgels partitioned more to the PEO phase. The change in structure and interparticle interaction induced by heating can be exploited to control the W/W emulsion stability.

Direct dynamic read-out of molecular chirality with autonomous enzyme-driven swimmers.

A key approach for designing bioinspired machines is to transfer concepts from nature to man-made structures by integrating biomolecules into artificial mechanical systems. This strategy allows the conversion of molecular information into macroscopic action. Here, we describe the design and dynamic behaviour of hybrid bioelectrochemical swimmers that move spontaneously at the air-water interface. Their motion is governed by the diastereomeric interactions between immobilized enantiopure oligomers and the enantiomers of a chiral probe molecule present in solution. These dynamic bipolar systems are able to convert chiral information present at the molecular level into enantiospecific macroscopic trajectories. Depending on the enantiomer in solution, the swimmers will move clockwise or anticlockwise; the concept can also be used for the direct visualization of the degree of enantiomeric excess by analysing the curvature of the trajectories. Deciphering in such a straightforward way the enantiomeric ratio could be useful for biomedical applications, for the read-out of food quality or as a more general analogue of polarimetric measurements.

Lorentz Force-Driven Autonomous Janus Swimmers.

Autonomous swimmers have been intensively studied in recent years due to their numerous potential applications in many areas ranging from biomedicine to environmental remediation. Their motion is based either on different self-propulsion mechanisms or on the use of various external stimuli. Herein, the synergy between the ion flux around self-electrophoretic Mg/Pt Janus swimmers and an external magnetic field is proposed as an efficient alternative mechanism to power swimmers on the basis of the resulting Lorentz force. A strong magnetohydrodynamic effect is observed due to the orthogonal combination of magnetic field and spontaneous ionic currents, leading to an increase of the swimmer speed by up to 2 orders of magnitude. Furthermore, the trajectory of the self-propelled swimmers can be controlled by the orientation of the magnetic field, due to the presence of an additional torque force caused by a horizontal cation flux along the swimmer edges, resulting in predictable clockwise or anticlockwise motion. In addition, this effect is independent of the swimmer size, since a similar type of rotational motion is observed for macro- and microscale objects.

Cooperative Chemotaxis of Magnesium Microswimmers for Corrosion Spotting.

Numerous artificial micro- and nanomotors, as well as various swimmers have been inspired by living organisms that are able to move in a coordinated manner. Their cooperation has also gained a lot of attention because the resulting clusters are able to adapt to changes in their environment and to perform complex tasks. However, mimicking such a collective behavior remains a challenge. In the present work, magnesium microparticles are used as chemotactic swimmers with pronounced collective features, allowing the gradual formation of macroscopic agglomerates. The formed clusters act like a single swimmer able to follow pH gradients. This dynamic behavior can be used to spot localized corrosion events in a straightforward way. The autonomous docking of the swimmers to the corrosion site leads to the formation of a local protection layer, thus increasing corrosion resistance and triggering partial self-healing.

Pickering emulsions stabilized by thermoresponsive oligo(ethylene glycol)-based microgels: Effect of temperature-sensitivity on emulsion stability.

HYPOTHESIS: The stability of emulsions stabilized by soft and responsive microgels and their macroscopic properties are governed by the microstructure of microgels, in particular their deformability. However, little is known about the role of the microgel chemistry, though it is expected that polymeric backbone with an amphiphilic structure is a requirement for their adsorption at the oil-water interface. EXPERIMENTS: A series of biocompatible, thermoresponsive and amphiphilic poly(oligoethylene glycol)methacrylate (pOEMA) microgels is synthesized, with varying hydrophobic-hydrophilic balance, or equivalent varying volume phase transition temperature (VPTT). Their behavior in the bulk phase and at solid interfaces is compared to their behavior at liquid interfaces, studied on flat and model interfaces by the pendant drop method, and on drops, in microgel-stabilized emulsions. FINDINGS: Controlling the composition of microgels by simply changing the number of ethylene oxide groups in the hydrophilic side chain allows a precise tuning of their VPTT in the range of 20-60 °C. Simultaneously, the swelling ratio and the deformability of the microgels increase by increasing the hydrophilicity, as a result of the polymerization process. Regardless of their hydrophilicity, all the swollen pOEMA microgels adsorb at the liquid interface and stabilize emulsions, whose flocculation state and mechanical stability depends on the microgel deformability. Unexpectedly, most emulsions remain stable upon heating above the VPTT of the microgels. Such feature highlights their extreme robustness, whose origin is discussed. This study opens new opportunities for the use of biocompatible Pickering emulsifiers.

Enhancing the sensitivity of plasmonic optical fiber sensors by analyzing the distribution of the optical modes intensity.

Improving the sensitivity of plasmonic optical fiber sensors constitutes a major challenge as it could significantly enhance their sensing capabilities for the label-free detection of biomolecular interactions or chemical compounds. While many efforts focus on developing more sensitive structures, we present here how the sensitivity of a sensor can be significantly enhanced by improving the light analysis. Contrary to the common approach where the global intensity of the light coming from the core is averaged, our approach is based on the full analysis of the retro-reflected intensity distribution that evolves with the refractive index of the medium being analyzed. Thanks to this original and simple approach, the refractive index sensitivity of a plasmonic optical fiber sensor used in reflection mode was enhanced by a factor of 25 compared to the standard method. The reported approach opens exciting perspectives for improving the remote detection as well as for developing new sensing strategies.

Light and electric field induced unusual large-scale charge separation in hybrid semiconductor objects.

Separation of electric charges is the most crucial phenomenon in natural photosynthesis, and is also extremely important for many artificial energy conversion systems based on semiconductors. The usual roadblock in this context is the fast recombination of electrons and holes. Here we demonstrate that the synergy of light and electric fields allows separating very efficiently electric charges over an unusually large distance in TiO2. The generated internal electric field can also be used to shuttle electrons simultaneously to the two opposite sides of a hybrid TiO2-polyaniline object. This counterintuitive behavior is based on the combination of the principles of bipolar electrochemistry and semi-conductor physics.

Asymmetric Modification of Carbon Nanotube Arrays with Thermoresponsive Hydrogel for Controlled Delivery.

In this work, bipolar electrochemistry is used to perform wireless indirect electrodeposition of two different polymer coatings on both sides of carbon nanotube arrays. Using a thermoresponsive hydrogel on one side and an inert insoluble polymer on the other side, it is possible to generate, in a single step, a nanoporous reservoir with Janus character closed on one side by a thermoresponsive membrane. The thermoresponsive polymer, poly(N-isopropylacrylamide) (pNIPAM), is generated by the local reduction of persulfate ions, which initiates radical polymerization of NIPAM. Electrophoretic paint (EP) is chosen as an inert polymer. It is deposited by precipitation because of a local decrease in pH during water oxidation. Both polymers can be deposited simultaneously on opposite sides of the bipolar electrode during the application of the electric field, yielding a double-modified Janus object. Moreover, the length and thickness of the polymer layers can be controlled by varying the electric field and the deposition time. This concept is applied to vertically aligned carbon nanotube arrays (VACNTs), trapped inside an anodic aluminum oxide membrane, which can further be used as a smart reservoir for chemical storage and release. A fluorescent dye is loaded in the VACNTs and its release is studied as a function of temperature. Low temperature, when the hydrogel layer is in the swollen state, allows diffusion of the molecule. Dye release occurs on the hydrogel-modified side of the VACNTs. At high temperatures, when the hydrogel layer is in the collapsed state, dye release is blocked because of the impermeability of the pNIPAM layer. This concept paves the way toward the design of advanced devices in the fields of drug storage and directed delivery.

Multiplexed Remote SPR Detection of Biological Interactions through Optical Fiber Bundles.

The development of sensitive methods for in situ detection of biomarkers is a real challenge to bring medical diagnosis a step forward. The proof-of-concept of a remote multiplexed biomolecular interaction detection through a plasmonic optical fiber bundle is demonstrated here. The strategy relies on a fiber optic biosensor designed from a 300 µm diameter bundle composed of 6000 individual optical fibers. When appropriately etched and metallized, each optical fiber exhibits specific plasmonic properties. The surface plasmon resonance phenomenon occurring at the surface of each fiber enables to measure biomolecular interactions, through the changes of the retro-reflected light intensity due to light/plasmon coupling variations. The functionalization of the microstructured bundle by multiple protein probes was performed using new polymeric 3D-printed microcantilevers. Such soft cantilevers allow for immobilizing the probes in micro spots, without damaging the optical microstructures nor the gold layer. We show here the potential of this device to perform the multiplexed detection of two different antibodies with limits of detection down to a few tenths of nanomoles per liter. This tool, adapted for multiparametric, real-time, and label free monitoring is minimally invasive and could then provide a useful platform for in vivo targeted molecular analysis.

Sugar-responsive Pickering emulsions mediated by switching hydrophobicity in microgels.

HYPOTHESIS: Pickering emulsions stabilized by soft and responsive microgels can demulsify on demand upon microgel collapse. The concept has been explored with simple model microgels such as poly(N-isopropylacrylamide) (pNIPAM) and their derivatives, but the role of functionalization is largely unexplored. EXPERIMENTS: Saccharide-responsive phenylboronic-modified microgels are used as Pickering emulsion stabilizers. Emulsion stability and microgel organization at drop surface are studied as a function of saccharide concentration. Better insight into their behavior at interfaces is gained through adsorption kinetics and Langmuir film studies at air-water interface. FINDINGS: The functionalization of water-swollen microgels by phenylboronic functions imparts some hydrophobicity to the structure, at the origin of additional internal cross-links analogous which rigidify the structure compared to non-functionalized microgels, as proved by their slow adsorption kinetics and poor interfacial compressibility. Upon boronate ester formation with diol groups of the saccharide, the hydrophobic character of the phenylboronic acid decreases, increasing the adsorption kinetics and their interfacial compressibility. Emulsions are stable in the presence of saccharide, given the high deformability of the yet-hydrophilic microgels, and mechanically unstable with less deformable particles in low saccharide concentration. The hydrophobic-hydrophilic switch acts as a trigger to tune the microgel stabilizing properties.

Wireless Coupling of Conducting Polymer Actuators with Light Emission.

Combining the actuation of conducting polymers with additional functionalities is an interesting fundamental scientific challenge and increases their application potential. Herein we demonstrate the possibility of direct integration of a miniaturized light emitting diode (LED) in a polypyrrole (PPy) matrix in order to achieve simultaneous wireless actuation and light emission. A light emitting diode is used as a part of an electroactive surface on which electrochemical polymerization allows direct incorporation of the electronic device into the polymer. The resulting free-standing polymer/LED hybrid can be addressed by bipolar electrochemistry to trigger simultaneously oxidation and reduction reactions at its opposite extremities, leading to a controlled deformation and an electron flow through the integrated LED. Such a dual response in the form of actuation and light emission opens up interesting perspectives in the field of microrobotics.

Highly parallel remote SPR detection of DNA hybridization by micropillar optical arrays.

Remote detection by surface plasmon resonance (SPR) is demonstrated through microstructured optical arrays of conical nanotips or micropillars. Both geometries were fabricated by controlled wet chemical etching of bundles comprising several thousands of individual optical fibers. Their surface was coated by a thin gold layer in order to confer SPR properties. The sensitivity and resolution of both shapes were evaluated as a function of global optical index changes in remote detection mode performed by imaging through the etched optical fiber bundle itself. With optimized geometry of micropillar arrays, resolution was increased up to 10-4 refractive index units. The gold-coated micropillar arrays were functionalized with DNA and were able to monitor remotely the kinetics of DNA hybridization with complementary strands. We demonstrate for the first time highly parallel remote SPR detection of DNA via microstructured optical arrays. The obtained SPR sensitivity combined with the remote intrinsic properties of the optical fiber bundles should find promising applications in biosensing, remote SPR imaging, a lab-on-fiber platform dedicated to biomolecular analysis, and in vivo endoscopic diagnosis. Graphical abstract We present a single fabrication step to structure simultaneously all the individual cores of an optical fiber bundle composed of thousands of fibers. The resulting sensor is optimized for reflection mode (compatible with in vivo applications) and is used to perform for the first time highly parallel remote SPR detection of DNA via several thousands of individual optical fiber SPR sensors paving the way for multiplexed biological detection.