Miniaturized Control of Acidity in Multiplexed Microreactors

The control of acidity drives the assembly of biopolymers that are essential for a wide range of applications. Its miniaturization can increase the speed and the possibilities of combinatorial throughput for their manipulation, similar to the way that the miniaturization of transistors allows logical operations in microelectronics with a high throughput. Here, we present a device containing multiplexed microreactors, each one enabling independent electrochemical control of acidity in ∼2.5 nL volumes, with a large acidity range from pH 3 to 7 and an accuracy of at least 0.4 pH units. The attained pH within each microreactor (with footprints of ∼0.3 mm2 for each spot) was kept constant for long retention times (∼10 min) and over repeated cycles of >100. The acidity is driven by redox proton exchange reactions, which can be driven at different rates influencing the efficiency of the device in order to achieve more charge exchange (larger acidity range) or better reversibility. The achieved performance in acidity control, miniaturization, and the possibility to multiplex paves the way for the control of combinatorial chemistry through pH- and acidity controlled reactions

Superhydrophobic surfaces with low and high adhesion made from mixed (hydrocarbon and fluorocarbon) 3,4-propylenedioxythiophene monomers

International audienceThis work concerns new superhydrophobic surfaces, generated by replacing long fluorocarbon chains, which bioaccumulate, with short chains whilst at the same time retaining oleophobic properties. Here, is described the synthesis of novel original 3,4-propylenedioxythiophene derivatives containing both a short fluorocarbon chain (perfluorobutyl) and a hydrocarbon chain of various lengths (ethyl, butyl and hexyl). Superhydrophobic (contact angle water > 150° ) surfaces with good oleophobic properties (60° > contact angle hexadecane > 80° ) have been obtained by electrodeposition using cyclic voltammetry. Surprisingly, the lowest hystereses and sliding angles (Lotus effect) are obtained with the shortest alkyl chains due to the presence of microstructures made of nanofibers on the surfaces, whereas, the longest alkyl chains leads to nanosheets with high adhesion (Petal effect). Such materials are potential candidates for biomedical applications

Discovery of amphoteric fingerprints of amino acids with field-effect transistors

When working with a few molecules, the existing protein sequencing technologies lack the single-site amino acid (AA) precision required to detect abnormalities that escape genome analysis.We offer a new method for identifying AAs and short polypeptides using the signal from the surface potential and capacitance obtained from Field Effect Transistor (FET) sensors. Using a combination of the Site-binding and Gouy-Chapman-Stern (GCS) models, we found the signatures of every single AA and polypeptides. These fingerprints are based on orthogonal features such as the proton dissociation constants of each AA’s charging sites, the dielectric constant, and the effective length

Rational design of a planar junctionless field-effect transistor for sensing biomolecular interactions

In the ElectroMed project, we are interested in screening certain peptide sequences for their ability to selectively interact with antibodies or MHC proteins. This poses a combinatorial challenge that requires a highly multiplexed setup of label-free immunosensors. Label-free FET-based immunosensors are good candidates due to their high multiplexing capability and fast response time. Nanowire-based FET sensors have shown high sensitivity but are unreliable for clinical applications due to drift and gate stability issues. To address this, a label-free immuno-FET architecture based on planar junctionless FET devices is proposed. This geometry can improve the signal-to-noise ratio due to its larger planar structure, which is less prone to defects that cause noise and is better suited to the functionalization of different receptor molecules

Conception of low surface energy materials : a novel step towards sustainable products

Les matériaux à faible énergie de surface (LSEMs) sont conçus pour différentes applications. Parmi celle-ci, les applications sur un support solide pour l’élaboration de surfaces superhydro/oléophobes ainsi qu’à l'interface de 2 milieux distincts pour la synthèse de nouveaux tensioactifs éco-responsables. Actuellement, ces matériaux sont constitués essentiellement de composés fluorés pour leurs propriétés uniques leur conférant à la fois l’hydro- et oléo-phobie ainsi que pour leur stabilité thermique et chimique dans des milieux corrosifs. Ce projet montre que l’élaboration des surfaces superhydro/oléophobes peut être réalisée sans utiliser nécessairement des chaînes perfluorées. Deux approches sont adoptées dans ce processus. La première stratégie est d'étudier l'influence de la longueur de la chaîne fluorée sur la structuration et la mouillabilité de la surface des dérivés du ProDOT. La seconde est d'explorer l'influence d'une chaine hydrocarbonée incorporée au coeur des monomères et d'étudier l'effet du type et de la longueur de ces chaînes sur les propriétés de surface. Dans le cadre de l'application des LSEMs sur les ‘matériaux mous’, deux études ont été réalisées : la première se focalisant sur l'effet de la longueur des chaînes hydrocarbonées sur les tensioactifs hybrides à courte chaine fluorée et la deuxième étudiant l'effet de la tête polaire. Deux séries de sulfates et bisulfates hybrides ont donc été synthétisées et leurs propriétés physico-chimiques étudiées. Ce travail a abouti à des résultats intéressants.Two types of Low surface energy materials LSEMs can be recognized; those which are firstly applied on solid surfaces to elaborate superhydro/oleophobic surfaces that are micro and nano structured, and secondly at the water/air interface to synthesize new ecofriendly surfactants. LSEMs are essentially made from fluorinated compounds due to their unique properties of being both hydro and oleophobic as well as, their thermal and chemical stability in corrosive media. This project shows that the creation of superhydrophobic materials with high oleophobic properties does not necessarily require the utilization of long and bioaccumulative perfluorocarbon chains. Two approaches were adopted in this field. The first strategy was to develop ProDOT derivatives bearing short fluorinated chains to study the influence of the fluorinated chain length on the surface wettability. The proceeding part was to explore the effect of the introduction of a hydrocarbon tail and study the effect of their type and chain length on the surface properties. Another important aspect of this research involves the application of LSEMs on soft materials like surfactants as alternatives to toxic perfluorinated homologues. This study was done to explore the effect of the variant hydrocarbon chains with a short fluorinated tail of hybrid surfactants as well as the effect of the polar head. In this area, two families of hybrid sulfate and bisulfates were synthesized. Their physico-chemical properties were investigated and interesting results were obtained

Controlling electrodeposited conducting polymer nanostructures with the number and the length of fluorinated chains for adjusting superhydrophobic properties and adhesion

International audienceControlling the formation of surface nanostructures is highly important for various applications, and in particular for superhydrophobic properties. Here, taking 3,4-propylenedioxythiophene (ProDOT) as a model molecule, we study the influence of the decrease in the perfluorocarbon chain length or the use of two shorter perfluorocarbon chains on the formation of surface nanostructures and superhydrophobic by electropolymerization. Moreover, perfluorinated compounds, especially those with long perfluorocarbon chains, are extremely used in industry but the discovery of their persistence, bioaccumulation potential and toxicity alternatives have to be found. Hopefully, it seems that their effect is dependent on the perfluorinated chain length and that alternatives with shorter perfluorinated chains can be envisaged. Here, we show in the fabrication of superhydrophobic surfaces that the use of shorter perfluorocarbon chains can even, in certain conditions, lead to better properties. Superhydrophobic properties with extremely low hysteresis are obtained with long perfluorocarbon chains (C8F17) but very close properties are also obtained with short perfluorobutyl (C4F9) and even perfluoroethyl (C2F5) chains. Superoleophilic properties are obtained with C2F5 chains, whereas the highest oleophobic properties were elaborated with the C4F9 chains. This is due to a change in the surface morphology from cauliflower structures to nanofibers as the perfluorocarbon chain decreases. By contrast, the use of two shorter perfluorocarbon chains induces very high steric hindrance during the electropolymerization and as a consequence smoother surfaces with lower surface hydrophobicity. Hence, it is possible to form structured or smooth surfaces using one or two fluorinated chains, respectively

Universal control of protons concentration using electrochemically generated acid compatible with miniaturization

Controlling locally produced acidity in miniaturized spaces is of high importance yielding to manage simultaneous chemical reactions. Here we present a platform that hosts miniaturized micro reactors, each one enabling electrochemical control of the acidity in ~nL volumes. We demonstrated the local control of chemical reactions with the deprotection of strong acid labile groups in a region of 150 μm of diameter of an upstanding glass using high proton concentrations (~10-1M) and the acidity contrasts between the cell region and the outside. We demonstrated an accurate control of the proton concentration in aqueous and organic solvents and the control of chemical reactions in organic electrolytes achieved with a sulfonated tetrafluoroethylene-based membrane, that isolates the acid generating electrodes from the reagents in the solution. The quantitative control of the acidity by the Faradaic currents was demonstrated by the calibration of carboxyfluorescein adjusted with external titrations, and with a tautomer transition occurring at pH 4.2. To the best of our knowledge, this platform shows the best control of acidity in the smallest volume reported so far

Surfactants with low fluorine content

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