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Avoidable hospitalizations among nursing home residents result in poorer health outcomes and excess costs. Consequently, efforts to reduce avoidable hospitalizations have been a priority over the recent decade. However, many potential interventions are time-intensive, require dedicated clinical staff, and nursing homes are chronically understaffed. The Optimizing Patient Transfers, Impacting Medical Quality, and Improving Symptoms: Transforming Institutional Care (OPTIMISTIC) project was one of seven sites selected by CMS as "enhanced care & coordination providers" and was implemented from 2012 to 2020. A virtual program based on the principles of OPTIMISTIC was developed in the spring of 2020 with the goal of expanding the reach of the program’s services. This qualitative study explores the perceptions and experiences of the nurses that piloted a virtual care support project in 11 nursing homes in a midwestern state, and identified the nurses’ perceived facilitators of, and barriers to, the effectiveness of delivering a novel virtual care support program. A key finding from this analysis is that relationships, communication, and access to information were identified as common themes facilitating or impeding the perceived effectiveness of implementation of virtual care support programs within nursing homes, from the perspective of the nurses delivering the services. The experiences and recommendations of the program nurses provide insights into crucial elements important to the implementation of similar virtual care support models, and the role of telehealth in bridging healthcare workforce gaps.

Natural cellulose-based

Surface-attached hydrogel films with well-controlled chemistry are a new approach of polymer thin layers and an actual alternative to polymer brushes and layer-by-layer assemblies. The advantage is that the thickness of hydrogel films can widely range from a few nanometers to several micrometers. Hydrogel films can also remarkably respond to stimuli such as temperature: (i) the thickness change is of great amplitude, fourfold and more, which could not be reached with the geometry of polymer brushes or layer-by-layer assemblies, (ii) the time response is very short (less than 1 s), and (iii) the swelling-to-collapse transition is narrow (a small temperature change of a few degrees may be enough). Poly(N-isopropylacrylamide) (PNIPAM) is the most temperature-responsive polymer investigated with a lower critical solution temperature (LCST) of around 32 °C. However, it is relevant to have the available polymers responding to various transition temperatures with the advantage of keeping the same chemistry. Poly[oligo(ethylene glycol) methacrylate] (PEGMA) meets these specifications since its transition temperature can be finely tuned with the number of oligo ethylene glycol units, while it attractively combines biocompatibility with PEG side chains. Here, we report the synthesis and the temperature-responsive properties of poly(PEGMA) hydrogel thin films. We used a simple, versatile, and well-controlled approach through thiol-ene click reaction, the so-called cross-linking and grafting, to synthesize surface-attached poly(PEGMA) hydrogel films with various thickness. We show that the transition temperature of poly(PEGMA) hydrogel films ranges from 15 to 60 °C if the number of PEG units is from 2 to 5. This transition temperature can also be finely adjusted for hydrogel films containing copolymers or mixing homopolymers of PEGMA with a suitable ratio. Moreover, the LCST properties, swelling-to-collapse amplitude and transition temperature, are not sensitive to salt. In particular, there is no effect on the LCST properties of surface-attached poly(PEGMA) hydrogel films in phosphate saline buffer, which is promising for applications in biology such as injectable hydrogels, drug delivery systems, hydrogel-based microfluidic valves, and flow switches for biotechnologies.

International audience; We report on the transient frictional response of contacts between a rigid spherical glass probe and a micrometer-thick poly(dimethylacrylamide) hydrogel film grafted onto a glass substrate when a lateral relative motion is applied to the contact initially at rest. From dedicated experiments with in situ contact visualization, both the friction force and the contact size are observed to vary well beyond the occurrence of a full sliding condition at the contact interface. Depending on the imposed velocity and on the static contact time before the motion is initiated, either an overshoot or an undershoot in the friction force is observed. These observations are rationalized by considering that the transient is predominantly driven by the flow of water within the stressed hydrogel networks. From the development of a poroelastic contact model using a thin film approximation, we provide a theoretical description of the main features of the transient. We especially justify the experimental observation that the relaxation of friction force Ft(t) toward steady state is uniquely dictated by the time-dependence of the contact radius a(t), independently on the sliding velocity and on the applied normal load.

International audience; Driven by the growing concern about the release of untreated emerging pollutants and the need for determining small amounts of these pollutants present in the environment, novel biosensors dedicated to molecular recognition are developed. We have designed biosensors using a novel class of grafted polymers, surface-attached hydrogel thin films, on conductive transducers as a biocompatible matrix for biomolecule immobilization. We showed that they can be dedicated to the molecular recognition of diclofenac (DCL). The immobilization of the aptamer onto surface-attached hydrogel thin films by covalent attachment provides a biodegradable shelter, providing the aptamer with excellent environments to preserve its active and functional structure while allowing the detection of DCL. The grafting of the aptamer is obtained using the formation of amide bonds via the activation of carboxylic acid groups of the poly(acrylic acid) hydrogel thin film. For improved sensitivity and higher stability of the sensor, a high density of the immobilized aptamer is enabled. The aptamer-modified electrode was then incubated with DCL solutions at different concentrations. The performances of the aptasensor were investigated by electrochemical impedance spectroscopy. The change in charge-transfer resistance was found to be linear with DCL concentration in the 30 pM to 1 μM range. The detection limit was calculated to be 0.02 nM. The improvement of the limit of detection can be mainly attributed to the three-dimensional environment of the hydrogel matrix which improves the grafting density of the aptamer and the affinity of the aptamer to DCL.

We investigate the adsorption of pH- or temperature-responsive polymer systems by ellipsometry and neutron reflectivity. To this end, temperature-responsive poly (N-isopropylacrylamide) (PNIPAM) brushes and pH-responsive poly (acrylic acid) (PAA) brushes have been prepared using the &ldquo, grafting onto&rdquo, method to investigate the adsorption process of polymers and its reversibility under controlled environment. To that purpose, macromolecular brushes were designed with various chain lengths and a wide range of grafting density. Below the transition temperature (LCST), the characterization of PNIPAM brushes by neutron reflectivity shows that the swelling behavior of brushes is in good agreement with the scaling models before they collapse above the LCST. The reversible adsorption on PNIPAM brushes was carried out with linear copolymers of N-isopropylacrylamide and acrylic acid, P(NIPAM-co-AA). While these copolymers remain fully soluble in water over the whole range of temperature investigated, a quantitative adsorption driven by solvophobic interactions was shown to proceed only above the LCST of the brush and to be totally reversible upon cooling. Similarly, the pH-responsive adsorption driven by electrostatic interactions on PAA brushes was studied with copolymers of NIPAM and N,N-dimethylaminopropylmethacrylamide, P(NIPAM-co-MADAP). In this case, the adsorption of weak polycations was shown to increase with the ionization of the PAA brush with interactions mainly located in the upper part of the brush at pH 7 and more deeply adsorbed within the brush at pH 9.

We investigate the adsorption of pH- or temperature-responsive polymer systems by ellipsometry and neutron reflectivity. To this end, temperature-responsive poly (N-isopropylacrylamide) (PNIPAM) brushes and pH-responsive poly (acrylic acid) (PAA) brushes have been prepared using the “grafting onto” method to investigate the adsorption process of polymers and its reversibility under controlled environment. To that purpose, macromolecular brushes were designed with various chain lengths and a wide range of grafting density. Below the transition temperature (LCST), the characterization of PNIPAM brushes by neutron reflectivity shows that the swelling behavior of brushes is in good agreement with the scaling models before they collapse above the LCST. The reversible adsorption on PNIPAM brushes was carried out with linear copolymers of N-isopropylacrylamide and acrylic acid, P(NIPAM-co-AA). While these copolymers remain fully soluble in water over the whole range of temperature investigated, a quantitative adsorption driven by solvophobic interactions was shown to proceed only above the LCST of the brush and to be totally reversible upon cooling. Similarly, the pH-responsive adsorption driven by electrostatic interactions on PAA brushes was studied with copolymers of NIPAM and N,N-dimethylaminopropylmethacrylamide, P(NIPAM-co-MADAP). In this case, the adsorption of weak polycations was shown to increase with the ionization of the PAA brush with interactions mainly located in the upper part of the brush at pH 7 and more deeply adsorbed within the brush at pH 9.

International audience; A new strategy for the fabrication of micropatterns of surfaceattached hydrogels with well-controlled chemistry is reported. The “grafting onto” approach is preferred to the “grafting from” approach. It consists of cross-linking and grafting preformed and functionalized polymer chains through thiol−ene click chemistry. The advantage is a very good control without adding initiators. A powerful consequence of thiol−ene click reaction by UV irradiation is the facile fabrication of micropatterned hydrogel thin films by photolithography. It is achieved either with photomasks using common UV lamp or without photomasks by direct drawing due to laser technology. Our versatile approach allows the fabrication of various chemical polymer networks on various solid substrates. It is demonstrated here with silicon wafers, glass and gold surfaces as substrates, and two responsive hydrogels, poly(N-isopropylacrylamide) for its responsiveness to temperature and poly(acrylic acid) for its pH-sensitivity. We also demonstrate the fabrication of stable hydrogel multilayers (or stacked layers) in which each elementary layer height can widely range from a few nanometers to several micrometers, providing an additional degree of freedom to the internal architecture of hydrogel patterns. This facile route for the synthesis of micrometer-resolute hydrogel patterns with tailored architecture and multiresponsive properties should have a strong impact

International audience; A facile route for the fabrication of surface-attached hydrogel thin films with well-controlled chemistry and tailored architecture on wide range of thickness from nanometers to micrometers is reported. The synthesis, which consists in cross-linking and grafting the preformed and ene-reactive polymer chains through thiol−ene click chemistry, has the main advantage of being well-controlled without the addition of initiators. As thiol−ene click reaction can be selectively activated by UV-irradiation (in addition to thermal heating), micropatterned hydrogel films are easily synthesized. The versatility of our approach is illustrated by the possibility to fabricate various chemical polymer networks, like stimuli-responsive hydrogels, on various solid substrates, such as silicon wafers, glass, and gold surfaces. Another attractive feature is the development of new complex hydrogel films with targeted architecture. The fabrication of various architectures for polymer films is demonstrated: multilayer hydrogel films in which single-networks are stacked one onto the other, interpenetrating networks films with mixture of two networks in the same layer, and nanocomposite hydrogel films where nanoparticles are stably trapped inside the mesh of the network. Thanks to its simplicity and its versatility this novel approach to surface-attached hydrogel films should have a strong impact in the area of polymer coatings

Hydrogel coatings absorb water vapor - or other solvents - and, as such, are good candidates for antifog applications. In the present study, the transfer of vapor from the atmosphere to hydrogel thin films is measured in a situation where water vapor flows alongside the coating which is set to a temperature lower that the ambient temperature. The effect of the physico-chemistry of the hydrogel film on the swelling kinetics is particularly investigated. By using model thin films of surface-grafted polymer networks with controlled thickness, varied crosslinks density, and varied affinity for water, we were able to determine the effect of the film hygroscopy on the dynamics of swelling of the film. These experimental results are accounted for by a diffusion-advection model that is supplemented with a boundary condition at the hydrogel surface: we show that the latter can be determined from the equilibrium sorption isotherms of the polymer films. Altogether, this paper offers a predictive tool for the swelling kinetics of any hydrophilic hydrogel thin films.

International audience; The formation of interpolymer complexes (IPC) between poly(acrylic acid) (PM) and poly(acrylamide) (PAM), poly(N,N-dimethylacrylamide) (PDMA), and statistical copolymers of acrylamide (AM) and N,N-dimethylacrylamide (DMA) has been studied as a function of pH, salt concentration and temperature (0 -70 degrees C). The cloud points of dilute solutions were measured by turbidimetry and phase diagrams were determined as a function of temperature and pH in pure water and as a function of pH and salt concentration at room temperature. For each temperature and salt concentration a critical pH (pH(crit)) below which IPC are observed was defined. In the case of PAA/PAM, pH(crit) continuously decreased with increasing temperature, from pH 3.5 at 0 degrees C to pH 1.9 at 60 degrees C (UCST-type). In the case of PAA/PDMA, pH(crit), increased with temperature. The LCST-type behavior of the hydrogen-bonding complex formed between PM and PDMA was attributed to the dimethyl Substitution of amide groups that puts in hydrophobic interactions at high temperature. PAA and statistical copolymers P(AM-co-DMA) showed an intermediate behavior between PM/PAM and PAA/PDMA with a continuous shift from UCST-type to LCST-type with increasing amount of DMA. This behavior can be attributed to changes in configurational entropy due to the IPC formation and (for PDMA) to the release of water molecules initially confined in hydrophobic hydration cages around DMA units. While at low salt concentration, the stability of PM/PAM and PAA/PDMA complexes only slightly increases with the screening of ionized acrylic units, there is a sharp increase of pHcrit at high salt concentration in relation with the weakening of the solvent quality. In this regime, the complex formation of PAA/PDMA is greatly enhanced compared to PM/PAM due to the interference of hydrophobic interactions. (C) 2011 Elsevier Ltd. All rights reserved.

pH and thermoresponsive polymers have been prepared by copolymerizing N-isopropylacrylamide (NIPAM) with various amounts of ionizable comonomers, either acrylic acid (AA) or N-[3-(dimethylamino)propyl]methacrylamide (MADAP). In aqueous solution, the LCST-type phase transition of these copolymers studied by differential scanning calorimetry is strongly influenced by the comonomer ratio. Under un-ionized conditions, the phase transition temperature progressively increases with MADAP content at pH 12 while it remains unchanged or slightly decreases with AA at pH 3 due to the formation of hydrogen bonds between AA and NIPAM units. When the copolymer chains are progressively charged by tuning the pH, the phase transition of PNIPAM-AA and PNIPAM-MADAP is shifted at higher temperature and is no longer observable below 60 °C when the ionic content exceeds 10%. By comparison with these single systems, where the association properties can be finely adjusted by coupling hydrophobic attractions and electrostatic repu...

Many microfluidic applications require modified surface wettability of the microchannels. Patterning of wettability within enclosed microfluidic structures at high spatial resolution has been challenging in the past. In this paper, we report an improved method for altering the surface wettability in poly(dimethylsiloxane) (PDMS) microchannels by UV-induced graft polymerization of poly(acrylic acid). Our method presents significant improvements in terms of wettability contrast and spatial resolution of the patterned structures as compared to recent literature and is in particular applicable to complex microfluidic structures with a broad range of channel sizes and aspect ratios. A key part of our work is the clear description of the surface treatment process with the identification of key parameters, some of which have been overlooked, neglected, or misinterpreted in previous works. We have studied these key parameters in detail and provide recommended values for each parameter supported by experimental results. This detailed understanding of the treatment process and the effects of the critical parameters on it allowed us to significantly improve quality and reliability of the treatment process.

Scanning electrochemical microscopy (SECM) is employed to characterize the transport of redox-active probe ions through quenched polyelectrolyte brushes. The counterion exchange through polyelectrolyte brushes is also investigated by infrared spectroscopy in attenuated total reflection (FTIR-ATR), X-ray photolectron spectroscopy (XPS), and cyclic voltammetry (CV). The synthesis of poly(methacryloyloxy)ethyl trimethylammonium chloride (PMETAC) brushes is performed using surface-initiated atom transfer radical polymerization followed by in situ quaternization reaction. The chloride (Cl(-)) counterions of the positively charged polymer brush are exchanged by ferrocyanide (Fe(CN)(6)(4-)) and ferricyanide (Fe(CN)(6)(3-)) ions that are both detectable by spectroscopy and electrochemically active. A good agreement is found when comparing the results obtained by spectroscopic (FTIR-ATR and XPS) and electrochemical (SECM and CV) methods. The counterions exchange is completely reversible and reproducible. We show that (Fe(CN)(6)(4-)) and (Fe(CN)(6)(3-)) species form stable ion pairs with the quaternary ammonium groups of the polymer brush. The transport of iodide (I(-)) redox-active ions is also investigated. In all cases (ferrocyanide, ferricyanide, or iodide), we find that chloride counterions are partially replaced by electroactive ions. This partial exchange may be attributed to an osmotic effect, since the external salt concentration for the exchange is much lower than the counterion concentration inside the brush.

We study the pH-responsive behavior of random polyampholyte brushes synthesized by surface-initiated Atom Transfer Radical Polymerization. We define the “annealed” polyampholyte as the random copolymer that contains weak acid (methacrylic acid) and weak base (2-(dimethylamino)ethyl methacrylate) units. The “semi-annealed” polyampholyte is defined as the random copolymer that contains the methacrylic acid and a strong base unit (the quaternized amine). The structure of the polyampholyte brushes in aqueous solutions at different pH is determined using neutron reflectivity. The monomer density profile and therefore the brush thickness are obtained. Polymer brushes with various grafting densities are compared. We demonstrate that the structure of the polyampholyte brush depends strongly on the net charge of the chains. With an excess of charge, the brush is as stretched as a polyelectrolyte brush, and the swelling behavior is in good agreement with the scaling laws. At the isoelectric point corresponding to a...

Electrogeneration of reducers at a microelectrode allows us to locally debrominate a surface bound polymerization initiator. Once submitted to atom transfer radical polymerization, patterns of nanometer polymer structures are formed on the surfaces. The surface reduction rate, controlled by the microelectrode scan rate and the reducer strength, affects the dimensions of the patterns. The reducer strength allows to tune the surface density of the initiator layer and then the elongation of the polymer brushes grown in the locally etched regions.

We report the synthesis of random polyampholyte brushes containing 2-(dimethylamino)ethyl methacrylate (DMAEMA) and methacrylic acid (MAA). The preparation of polyampholyte brushes is performed by the “grafting from” strategy using surface-initiated atom transfer radical polymerization (ATRP). The first step consists in the formation of the self-assembled monolayer of the ATRP initiator. Secondly, the chains are grown from the surface by controlled/“living” radical polymerization. The random copolymer brushes and the corresponding homopolymers brushes containing 2-(dimethylamino)ethyl methacrylate and tert-butyl methacrylate (tBuMA) are prepared. The last step is the deprotection of the tBuMA form to the MAA segment by in situ hydrolysis reaction. The annealed DMAEMA group can also be converted to the quenched form by in situ quaternization reaction. This results in the formation of “annealed” and “semiannealed” polyampholyte brushes. The “annealed” polyampholyte corresponds to the random copolymer that contains only annealed units, weak acid and weak base. The “semiannealed” polyampholyte consists of the mixture of annealed (weak acid) and quenched (quaternized segment) units. Polyampholyte brushes with various grafting densities are synthesized and carefully characterized using surface techniques such as ellipsometry and FTIR-ATR. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 4305–4319, 2008

International audience; We report on the poroelastic indentation response of hydrogel thin films geometrically confined within contacts with rigid spherical probes of radii in the millimeter range. Poly(PEGMA) (poly(ethylene glycol)) methyl ether methacrylate), poly(DMA) (dimethylacrylamide) and poly(NIPAM) (N-isopropylacrylamide) gel films with thickness less than 15 µm were grafted onto glass substrates using a thiol-ene click chemistry route. Changes in the indentation depth under constant applied load were monitored over time as a function of the film thickness and the radius of curvature of the probe using an interferometric method. In addition, shear properties of the indented films were measured using a lateral contact method. In the case of poly(PEGMA) films, we show that poroelastic indentation behavior is adequately described within the framework of an approximate contact model derived within the limits of confined contact geometries. This model provides simple scaling laws for the characteristic poroelastic time and the equilibrium indentation depth. Conversely, deviations from this model are evidenced for poly(DMA) and poly(NIPAM) films. From lateral contact experiments, these deviations are found to result from strong changes in the shear properties as a result of glass transition (poly(DMA)) or phase separation (poly(NIPAM)) phenomena induced by the drainage of the confined films squeezed between the rigid substrates.

The interfacial thickness and mechanical strength of several model interfaces between immiscible polymer melts were investigated. The interfacial width at equilibrium was determined by neutron reflectivity, and the adhesion energy was determined with an asymmetric probe test method inspired of the tests used for soft adhesives. A very good correlation was found between the adhesion energy and the measured interfacial width in a qualitatively similar way as what was observed for interfaces between glassy polymers. For polymer pairs with χ values ranging from 0.002 to 0.05, the mechanical strength of the interface was controlled by the degree of interpenetration, or in other terms, by the interfacial free energy between the two polymers. For lower values of χ, the interfacial strength was comparable to the fracture strength of the weakest of the two bulk polymers, while for higher values of χ, the thermodynamic work of adhesion and the polymer surface mobility are probably controlling the interfacial strength.

We synthesize polybase brushes and investigate their swelling behavior. Poly(2-(dimethylamino)ethyl methacrylate)) (PDMAEMA) brushes are prepared by the "grafting from" method using surface-initiated Atom Transfer Radical Polymerization to obtain dense brushes with relatively monodisperse chains (PDI = 1.35). In situ quaternization reaction can be performed to obtain poly(2-(trimethylamino)ethyl methacrylate)) (PTMAEMA) brushes. We determine the swollen thickness of the brushes using ellipsometry and neutron reflectivity techniques. Brushes are submitted to different solvent conditions to be investigated as neutral brushes and weak and strong polyelectrolyte brushes. The swelling of the brushes is systematically compared to scaling models. It should be pointed out that the scaling analysis of different types of brushes (neutral polymer and weak and strong polyelectrolyte brushes) is performed with identical samples. The scaling behavior of the PDMAEMA brush in methanol and the PTMAEMA brush in water is in good agreement with the predicted scaling laws for a neutral polymer brush in a good solvent and a polyelectrolyte brush in the osmotic regime. The salt-induced contraction of the quaternized brush is observed for high salt concentration, in agreement with the predicted transition between the regimes of the osmotic brush and the salted brush. From the crossover concentration, we calculate the effective charge ratio of the brush following the Manning counterion condensation. We also use PDMAEMA brushes as pH-responsive polybase brushes. The swelling behavior of the polybase brush is intermediate with respect to the behavior of the neutral polymer brush in a good solvent and the behavior of the quenched polyelectrolyte brush, as expected. The effective charge ratio of the PDMAEMA brush is determined as a function of pH using the scaling law of the polyelectrolyte brush in the osmotic regime.

Temperature-responsive properties of surface-attached poly(N-isopropylacrylamide) (PNIPAM) network films with well-controlled chemistry are investigated. The synthesis consists of cross-linking and grafting preformed ene-reactive polymer chains through thiol--ene click chemistry. The formation of surface-attached and cross-linked polymer films has the advantage of being wellcontrolled without any caution of no-oxygen atmosphere or addition of initiators. PNIPAM hydrogel films with same cross-link density are synthesized on a wide range of thickness, from nanometers to micrometers. The swelling-collapse transition with temperature is studied by using ellipsometry, neutron reflectivity, and atomic force microscopy as complementary surface-probing techniques. Sharp and high amplitude temperature-induced phase transition is observed for all submicrometric PNIPAM hydrogel films. For temperature above LCST, surface-attached PNIPAM hydrogels collapse similarly but without complete expulsion of water. For temperature below LCST, the swelling of PNIPAM hydrogels depends on the film thickness. It is shown that the swelling is strongly affected by the surface attachment for ultrathin films below $\sim$150 nm. For thicker films above 150 nm (to micrometers), surface-attached polymer networks with the same cross-link density swell equally. The density profile of the hydrogel films in the direction normal to the substrate is confronted with in-plane topography of the free surface. It results that the free interface width is much larger than the roughness of the hydrogel film, suggesting pendant chains at the free surface., in Langmuir, American Chemical Society, 2015, LANGMUIR, 31 (42), pp.11516-11524

The goal of this work is to make progress in the domain of near-wall velocimetry. The technique we use is based on the tracking of nanoparticles in an evanescent field, close to a wall, a technique called TIRF (Total Internal Reflection Fluorescence)-based velocimetry. At variance with the methods developed in the literature, we permanently keep track of the light emitted by each particle during the time the measurements of their positions ('altitudes') and speeds are performed. By performing the Langevin simulation, we quantified effect of biases such as Brownian motion, heterogeneities induced by the walls, statistical biases, photo bleaching, polydispersivity and limited depth of field. Using this method, we obtained slip length on hydrophilic surfaces of 1$ \pm $5 nm for sucrose solution, and 9$ \pm $10 nm for water; On hydrophobic surface, 32$ \pm $5 nm for sucrose solution, and 55$ \pm $9 nm for water. The errors (based on 95% confidence intervals) are significantly smaller than the state-of-the-art, but more importantly, the method demonstrates for the first time a capacity to measure slippage with a satisfactory accuracy, while providing a local information on the flow structure with a nanometric resolution. Our study confirms the discrepancy already pointed out in the literature between numerical and experimental slip length estimates. With the progress conveyed by the present work, TIRF based technique with continuous tracking can be considered as a quantitative method for investigating flow properties close to walls, providing both global and local information on the flow., 24 pages, 13 figures

We discuss the nematic order parameter and the polymer concentration profile for a solid surface carrying grafted chains. Different regimes are found, depending upon the polymer chain length and the grafting density. These ideas are compared with experimental results obtained with polystyrene in the presence of pentylcyanobiphenyl.

International audience; The goal of this paper is to review progress (mostly recent) made in micro and nanovelocimetry, focusing on two techniques: mu PIV (microparticle image velocimetry) and nanoPTV (nanoparticle tracking velocimetry). The paper focuses on the measurement of slippage (taken as a benchmark for these techniques), concentrating on work done in our group. We review the developments of mu PIV that led, in the last ten years, to the achievement of 100nm accuracy in the measurement of slip lengths. Later, this approach was complemented by nanoPTV, which recently obtained +/- 5nm precision. Here, we also mention recent application of these techniques toward better characterization of microgel and polymer flows. As a whole, the two techniques have conveyed valuable information on flow behavior within and close to the boundaries of microchannels, on the importance of wetting, and on the role of surface heterogeneities. mu PIV is commercially available but nanoPTV is not mature. Interesting instrumental developments are expected in the future for the latter technique.

International audience; We investigated the effect of specific interactions on the structure of interfaces between a brush and a hydrogel on the polymer chain length scale. We used a model system for which the interactions between the brush and the gel are switchable. We synthesized weak polyelectrolyte brushes of poly(acrylic acid) and hydrogels of polyacrylamide and poly(N,N-dimethylacrylamide) which interact solely when the poly(acrylic acid) is mainly in its acidic form. The monomer density profiles of the poly(acrylic acid) brush immersed in pure deuterium oxide (D2O) or in contact with a D2O-swollen gel were determined by neutron reflectivity. At pH 2 when the brush is in its neutral form, it interacts with the gel by hydrogen bonds while at pH 9 when the brush is a polyelectrolyte it is not interacting with the gel. Our results show that the presence of interactions with the gel at pH 2 increases the swelling ratio of the brush relative to that in pure D2O, meaning that the brushes exhibit conformations which are more extended from the surface than in the absence of interactions.

The complexation and the distribution of various cations, bound to a poly(styrene sulfonate) brush, have been investigated using infra-red spectroscopy and neutron reflectivity. Small counterions (like tetremethylammonium) are distributed throughout the brush in such a way that a local electroneutrality is ensured. They also exchange readily with other bulk small cations. On the other hand, model polycations are irreversibly trapped to the brush despite a relative small number of ionic bonds involved in the complexation. These complexed polycations are localized at the outer border of the brush, forming a macromolecular barrier. However, this spatial segregation does not allow the buildup of polyelectrolyte multilayers. Cationic surfactants are associated stoichiometrically with the brush sulfonates but unlike small counterions, this complexation is “irreversible” and induces a restructuring of the polymer interface.

We have prepared polyelectrolyte brushes on silicon blocks in two steps: first, we graft polystyrene (PS) chains terminated by a trichlorosilane group, and then, we convert the grafted PS to poly(s...

International audience; The swelling of poly(acrylic acid) brushes in aqueous solutions is studied by neutron reflectivity. The brushes are synthesized on silicon wafers using a grafting onto approach and their stretching is investigated at various pH, grafting densities, and chain lengths. Neutron reflectivity provides the average thickness and, more interestingly, the density profile of the brushes. The profiles obtained experimentally are in good agreement with theory. The swelling ratio of the poly(acrylic acid) brushes is compared with that of other polymer brushes formerly investigated using classic scaling laws. Owing to a new representation with the normalized thickness, it is demonstrated that there is a general behavior for all polymer brushes with a master curve for neutral polymer brushes and for polyelectrolyte brushes.

International audience; We investigated the surface structure of hydrogels of poly(N,N-dimethylacrylamide) (PDMA) hydrogels synthesized and cross-linked simultaneously by redox free radical polymerization. We demonstrate the existence of a less cross-linked layer at the surface of the gel at least at two different length scales characterized by shear rheology and by neutron reflectivity, suggesting the existence of a gradient in cross-linking. The composition of the layer is shown to depend on the degree of hydrophobicity of the mold surface and is weaker for more hydrophobic molds. While the macroscopic tests proved the existence of a relatively thick under-cross-linked layer, we also demonstrated by neutron reflectivity that the gel surface at the submicrometric scale (500 nm) was also affected by the surface treatment of the mold. These results should have important implications for the measurement of macroscopic surface properties of these hydrogels such as friction or adhesion.

International audience; We have developed a new experimental methodology to investigate the adhesive properties of hydrogels on solid surfaces under fully immersed conditions. The method, based on contact mechanics, provides time-resolved reproducible and quantitative data on the work of adhesion between a hydrogel at swelling equilibrium and a planar surface grafted with responsive brushes. We used poly(N,N-dimethylacrylamide) (PDMA) and polyacrylamide (PAM) as model gels and poly(acrylic acid) (PAA) as pH dependent polymer brush. The effect of pH, contact time and debonding velocity on adhesive interactions was specifically investigated. As expected from molecular interactions, we found that adhesion increased as the pH decreased and this was attributed to the formation of hydrogen bonds at the interface. Surprisingly, however, the buildup of adhesion increased slowly with the time of contact up to one hour and depended markedly on debonding velocity despite the very elastic nature of the hydrogels. Furthermore, the maximum pH where adhesion was observed was significantly higher for the couple PAM-PAA than for the couple PDMA-PAA, in contrast with the onset of molecular interactions in dilute solutions.

Following the great success of traditional microfluidic devices across many disciplines, a new class of microfluidic systems emerged in recent years, which features finely tuned, localized surface modifications within the microstructures in order to keep up with the demand for devices of ever increasing complexity (lab on chip, assay on chip, etc.). Graft photopolymerization has become a powerful tool for such localized surface modifications particularly in combination with poly(dimethylsiloxane) (PDMS) devices, as it is compatible with many functional monomers and allows for high spatial resolution. However, application within enclosed PDMS microstructures and in particular well-controlled surface-directed polymerization remains challenging. Detailed understanding of the interaction between photoinitiator, benzophenone (BP), and polymer matrix is needed. We have developed a visualization technique, which allows for observation of reacted BP in situ within the PDMS matrix. We present a detailed study on solvent-driven BP diffusion providing results essential to successful surface treatment. We also identified and investigated photoinitiator inhibition by oxygen and provide appropriate mitigation strategies.

Responsive polymers were prepared by copolymerizing a small amount of ionizable monomers, acrylic acid or N,N-dimethylaminopropylmethacrylamide, with N-isopropylacrylamide (NIPA) and the solubility in aqueous solution of these PNIPA derivatives were quantitatively studied. From differential scanning calorimetry experiments, it was shown that the pH strongly influences the phase separation of these copolymers (temperature and enthalpy), which totally disappears when ionizable groups are fully charged. At pH 7, all PNIPA copolymers remain soluble in water at all temperatures but their mixtures show a phase separation above a critical temperature due to the formation of a reversible inter-polyelectrolyte complex. When the responsive stickers are grafted on a poly(acrylamide) backbone, pH and temperature are still able to drive the association process at a local scale, giving rise to a sol/gel transition of semi-dilute solutions. The structure and the viscoelastic properties of these macromolecular assemblies are investigated by small angle neutron scattering and rheology and their responsivity is discussed as a function of pH and temperature.

We synthesize and investigate the swelling behavior of polyelectrolyte and polyampholyte grafted layers on planar substrates. The polymer brushes are prepared using the "grafting from" method with surface-initiated atom transfer radical polymerization (ATRP), which allows a good control of the chain length and a weak polydispersity of chains. Ellipsometry and neutron reflectivity are used to determine the swollen thickness and the monomer volume fraction profile. The scaling behavior of the neutral polymer brush and the strong polyelectrolyte brush is in good agreement with scaling laws predicted by mean-field theories. The swelling behavior of the pH-responsive polybase brush is between the situation of the neutral polymer brush in good solvent and the quenched polyelectrolyte. Polyampholyte brushes are contracted in the pH range of zero net charge. A barrier zone likely due to the attraction between positively and negatively charged monomer units is observed in the density profile. This barrier could prevent from a collective ionization of the chains and reduce the expected collapse of the brush.

Dense poly(styrene sulfonate sodium salt) brushes were prepared on silicone wafers using a two-step procedure: polystyrene (PS) chains, terminated by a reactive trichlorosilane group, were first covalently grafted, and then the PS brush was converted to a poly(styrene sulfonate) brush by a soft sulfonation reaction. Ellipsometry and infrared spectroscopy in ATR were used to characterize the samples and to optimize the procedure: in particular, the sulfonation was shown to be homogeneous along the chain backbone and the neutralization complete. In some cases, the polymer layer revealed to be quite fragile: the chains were pulled out of the brush. A consolidation treatment which consisted in grafting oligomers inbetween the long PS chains significantly increased the robustness of the layer. This might be relevant for industrial applications.

We investigate the macroscopic adhesion energy (Wa) in pure water between a positively charged hydrogel of varying cross-link densities made from (methacryloyloxyethyl)trimethylammonium chloride an...

We report on the frictional behaviour of thin poly(dimethylacrylamide) (PDMA) hydrogels films grafted on glass substrates in sliding contact with a glass spherical probe. Friction experiments are carried out at various velocities and applied normal loads with the contact fully immersed in water. In addition to friction force measurements, a novel optical set-up is designed to image the shape of the contact under steady-state sliding. The velocity-dependence of both friction force $F_t$ and contact shape is found to be controlled by a P��clet number Pe defined as the ratio of the time $��$ needed to drain the water out of the contact region to a contact time $a/v$, where $v$ is the sliding velocity and $a$ is the contact radius. When Pe1, a decrease in the contact area is observed together with the development of a contact asymmetry when the sliding velocity is increased. A maximum in $F_t$ is also observed at Pe~$\approx$~1. These experimental observations are discussed in the light of a poroelastic contact model based on a thin film approximation. This model indicates that the observed changes in contact geometry are due to the development of a pore pressure imbalance when Pe>1. An order of magnitude estimate of the friction force and its dependence on normal load and velocity is also provided under the assumption that most of the frictional energy is dissipated by poroelastic flow at the leading and trailing edges of the sliding contact.

The structure of dense grafted polyelectrolyte layers has been studied with a combination of neutron reflectivity and infrared spectroscopy techniques. The polyelectrolyte brushes were made of poly(styrene sulfonate) neutralized by different counterions. Small counterions are distributed throughout the brush in order to ensure a highly local electroneutrality. In addition, they can be readily exchanged with other small ions. On the other hand, macromolecular counterions (as well as some proteins) are irreversibly trapped by the brush, but are located outside the grafted layer and cannot reach the surface.

Research in the field of synthetic photonic crystals has been advancing at high speed. In thedevelopment of this field, additional performances in terms of modularity and switchabilityusing soft matter and polymers provide unprecedented enhanced devices. In this thesis, wedeveloped a platform of stimuli-responsive nano- and microstructured polymer hydrogelsthat are surface-grafted to ensure chemical stability regardless of environmental change.This strategy is based on CLAG chemistry which consists in simultaneous Cross-Linking AndGrafting of polymer chains on the substrate. This platform is exploited to fabricate stimulableBragg mirrors with large amplitude of spectral shift. We also developed a strategy allowingus to design two-dimensional photonic cristals by using photolithographic masks. Finally, wedemonstrated that the hydrogel platform allows the coupling of temperature with otherstimuli: chemical, mechanical, light and electromagnetic field for plasmonic and magnetichyperthermia.; La recherche dans le domaine des cristaux photoniques synthétiques progresse à grande vitesse. En parallèle, les progrès réalisés dans le domaine de la matière molle et des polymères permettent également des avancées considérables pour des dispositifs stimulables. Dans ces travaux de thèse, nous avons développé une plateforme permettant désynthétiser des nano- et microstructures d'hydrogel stimulables stables et à grandes amplitudes de déformation. Pour ce faire, nous avons utilisé la méthode CLAG (Cross-LinkingAnd Grafting) qui consiste en la réticulation et le greffage simultanés de chaînes de polymère sur le substrat. Nous avons exploité cette plateforme pour mettre au point des miroirs de Bragg stimulables à grande amplitude de décalage spectral, avec des multicouches alternéesd’hydrogels et des couches d’or ou d’oxyde de titane Nous avons également développé des cristaux photoniques bidimensionnels en utilisant des masques photolithographiques. De plus, l’hyperthermie plasmonique ou magnétique est envisagée pour induire la transition des films d’hydrogel. Enfin, nous avons montré que la plateforme d’hydrogels permet également de coupler la température avec d’autres stimuli: chimiques, mécaniques.

Research in the field of synthetic photonic crystals has been advancing at high speed. In thedevelopment of this field, additional performances in terms of modularity and switchabilityusing soft matter and polymers provide unprecedented enhanced devices. In this thesis, wedeveloped a platform of stimuli-responsive nano- and microstructured polymer hydrogelsthat are surface-grafted to ensure chemical stability regardless of environmental change.This strategy is based on CLAG chemistry which consists in simultaneous Cross-Linking AndGrafting of polymer chains on the substrate. This platform is exploited to fabricate stimulableBragg mirrors with large amplitude of spectral shift. We also developed a strategy allowingus to design two-dimensional photonic cristals by using photolithographic masks. Finally, wedemonstrated that the hydrogel platform allows the coupling of temperature with otherstimuli: chemical, mechanical, light and electromagnetic field for plasmonic and magnetichyperthermia., La recherche dans le domaine des cristaux photoniques synthétiques progresse à grande vitesse. En parallèle, les progrès réalisés dans le domaine de la matière molle et des polymères permettent également des avancées considérables pour des dispositifs stimulables. Dans ces travaux de thèse, nous avons développé une plateforme permettant désynthétiser des nano- et microstructures d'hydrogel stimulables stables et à grandes amplitudes de déformation. Pour ce faire, nous avons utilisé la méthode CLAG (Cross-LinkingAnd Grafting) qui consiste en la réticulation et le greffage simultanés de chaînes de polymère sur le substrat. Nous avons exploité cette plateforme pour mettre au point des miroirs de Bragg stimulables à grande amplitude de décalage spectral, avec des multicouches alternéesd’hydrogels et des couches d’or ou d’oxyde de titane Nous avons également développé des cristaux photoniques bidimensionnels en utilisant des masques photolithographiques. De plus, l’hyperthermie plasmonique ou magnétique est envisagée pour induire la transition des films d’hydrogel. Enfin, nous avons montré que la plateforme d’hydrogels permet également de coupler la température avec d’autres stimuli: chimiques, mécaniques.

This work attempts to unravel some of the intricacies of the aqueous adhesion of elastic or viscoelastic highly swollen charged polymers. In Part I the first model synthetic system permitted us to successfully link the molecular architecture of the elastic hydrogels, their interfacial charge density and the ionic strength of the medium with the underwater adhesion properties at a macroscopic level using probe-tack experiments and a microscopic level using atomic force microscopy. In Part II we successfully expanded the synthetic elastic system to measure macroscopic adhesion between oppositely charged gelatin-based hydrogels. Finally, in Part III we developed a synthetic and bio-inspired adhesive based on complex coacervation. This novel adhesive system combines the contribution of electrostatic interactions and thermoresponsive domains resulting in a material with promising properties as an injectable viscoelastic adhesive for medical applications., Ce travail essaie de décortiquer les multiples paramètres régissant l’adhésion en phase aqueuse de polymères chargés. Nous cherchons d’abord à établir un lien entre les interactions électrostatiques moléculaires et les différentes architectures moléculaires de matériaux gonflés élastiques (Parties I et II) ou viscoélastiques (Partie III), avant de nous intéresser à l’adhésion en milieu immergé. (Partie I) Le premier système modèle de matériaux synthétiques nous a permis de corréler l’architecture moléculaire des hydrogels élastiques, la densité de charge interfaciale, et la force ionique du milieu avec les propriétés adhésives en phase aqueuse, à un niveau macroscopique en utilisant la technique du Probe-tack, et également à un niveau microscopique avec la microscopie à force atomique. (Partie II) Par ailleurs, étant inspirés par les systèmes adhésifs naturels, nous avons cherché à étendre ce système modèle à la mesure d’adhésion macroscopique entre hydrogels de gélatine de charges opposées. Nous montrons que le système modèle permettant de contrôler et de prédire l’adhésion en milieu aqueux en modifiant la densité de charge interfaciale et les propriétés mécaniques du matériau est transposable aux systèmes à base de gélatine. (Partie III) Enfin, nous avons développé un adhésif bio-inspiré entièrement synthétique à base de coacervation complexe. Ce nouveau système d’adhésif associe les interactions électrostatiques avec des domaines thermo-sensibles, donnant ainsi naissance à un matériau prometteur pour l’adhésion en milieu immergé.

This work attempts to unravel some of the intricacies of the aqueous adhesion of elastic or viscoelastic highly swollen charged polymers. In Part I the first model synthetic system permitted us to successfully link the molecular architecture of the elastic hydrogels, their interfacial charge density and the ionic strength of the medium with the underwater adhesion properties at a macroscopic level using probe-tack experiments and a microscopic level using atomic force microscopy. In Part II we successfully expanded the synthetic elastic system to measure macroscopic adhesion between oppositely charged gelatin-based hydrogels. Finally, in Part III we developed a synthetic and bio-inspired adhesive based on complex coacervation. This novel adhesive system combines the contribution of electrostatic interactions and thermoresponsive domains resulting in a material with promising properties as an injectable viscoelastic adhesive for medical applications.; Ce travail essaie de décortiquer les multiples paramètres régissant l’adhésion en phase aqueuse de polymères chargés. Nous cherchons d’abord à établir un lien entre les interactions électrostatiques moléculaires et les différentes architectures moléculaires de matériaux gonflés élastiques (Parties I et II) ou viscoélastiques (Partie III), avant de nous intéresser à l’adhésion en milieu immergé. (Partie I) Le premier système modèle de matériaux synthétiques nous a permis de corréler l’architecture moléculaire des hydrogels élastiques, la densité de charge interfaciale, et la force ionique du milieu avec les propriétés adhésives en phase aqueuse, à un niveau macroscopique en utilisant la technique du Probe-tack, et également à un niveau microscopique avec la microscopie à force atomique. (Partie II) Par ailleurs, étant inspirés par les systèmes adhésifs naturels, nous avons cherché à étendre ce système modèle à la mesure d’adhésion macroscopique entre hydrogels de gélatine de charges opposées. Nous montrons que le système modèle permettant de contrôler et de prédire l’adhésion en milieu aqueux en modifiant la densité de charge interfaciale et les propriétés mécaniques du matériau est transposable aux systèmes à base de gélatine. (Partie III) Enfin, nous avons développé un adhésif bio-inspiré entièrement synthétique à base de coacervation complexe. Ce nouveau système d’adhésif associe les interactions électrostatiques avec des domaines thermo-sensibles, donnant ainsi naissance à un matériau prometteur pour l’adhésion en milieu immergé.

Hydrogel films are proposed as anti-fog coatings on glazings. Indeed, they may delay mist formation by absorbing water up to several times their volume. However, their mechanical resistance in the swollen state remains an issue. In this work, we investigate water transport towards and within non-equilibrium hydrogel films in two situations. First, we have studied the swelling kinetics of the cooled films when submitted to a humid air flow. Second, we have characterized their indentation and frictional response in relation to the drainage of the poroelastic network which results from contact stresses. For this purpose, model micrometric hydrogel films, with a varied and controlled physical-chemistry, are prepared. Experimental set-ups have been developed and the results are modelled in relation with the architecture of hydrogels and their physical-chemistry. We show how the hygroscopy of the polymer, the architecture and the thickness of the films control their swelling kinetics in a vapor flux. We also demonstrate that the friction force on hydrogel films mostly originates in the flow of water forced within the permeable polymer network in the sliding contact. Finally, at large indentation depths where the water content becomes low enough, we highlight the role of the transitions (glass transition or LCST-type) of the polymer on the mechanical response of the films.; Les films d’hydrogel sont envisagés comme revêtements anti-buée sur les vitrages. En effet, ils peuvent retarder l’apparition de la buée en absorbant plusieurs fois leur volume en eau. Cependant, une fois gonflés, la question de leur résistance mécanique se pose. Nous nous intéressons ici aux transferts d’eau vers et au sein de films d’hydrogel hors équilibre dans deux situations. D’abord, lorsqu’ils sont secs puis soumis à un flux d’air humide sur un substrat refroidi, nous avons étudié leur cinétique de gonflement. Ensuite, nous avons caractérisé leur réponse mécanique en indentation et en frottement lorsque l’eau retenue par l’hydrogel draine au sein du contact. Dans ce but, des films micrométriques d’hydrogel modèles, de physico-chimie variée et contrôlée, sont réalisés. Des dispositifs expérimentaux ont été développés, dont les résultats sont modélisés en lien avec l’architecture des hydrogels et leur physico-chimie. Nous montrons comment l’hygroscopie du polymère, l’architecture et l’épaisseur des films contrôlent leur cinétique de gonflement dans un flux de vapeur. Nous établissons aussi que le frottement de films d’hydrogel a pour origine l’écoulement forcé de l’eau au sein du réseau perméable de polymère. Enfin, à forte indentation où la teneur en eau devient faible, nous mettons en évidence le rôle des transitions (vitreuse ou de type LCST) du polymère sur la réponse mécanique des films.

Temperature-responsive surface-attached hydrogel thin films with various LCST/UCST (Lower/Upper Critical Solution Temperature) were designed for specific applications. The chemical polymer networks covalently attached on plane solid substrates were synthesized by a versatile and straightforward approach using thiol-ene click chemistry. It consists in coating ene-reactive polymers and dithiol crosslinkers on thiol-modified substrates, the thiol-ene click reaction allowing simultaneous cross-linking between chains and grafting on the surface. The CLAG (Cross-Linking And Grafting) strategy provides chemically stable and reproducible hydrogel films with a wide range of thickness and with the desired temperature-responsive properties. Ene-functionalized hydrophilic polymers can be synthesized using free radical copolymerization of the desired monomer with allyl methacrylate in organic solvent or co-solvent with water. Another way is the synthesis in water in two steps: the desired monomer is copolymerized with acrylic acid and then the copolymer is post-modified by amidification. Three polymer families were investigated: poly(PEGMA), poly(acrylamide) derivatives and poly(zwitterions). The transition temperature of the hydrogel films is determined by measuring the thickness in aqueous solutions at different temperatures with ellipsometry. Poly(PEGMA) hydrogel films show LCST properties with the transition temperature increasing with the number of PEG units. The LCST ranges from 15 °C to 60 °C with two to five PEG units in the pendant chains. The LCST can also be adjusted using mixed copolymers hydrogel. Poly(acrylamide) derivatives hydrogel films have both LCST and UCST properties. Poly(sulfobetaine) hydrogel films show very interesting UCST behavior in addition to be anti-fouling, which is very promising for biology applications., Les films minces d'hydrogels thermosensibles à propriétés LCST/UCST (Lower/Upper Critical Solution Temperature) avec des températures de transition variables ont été mis au point pour des applications spécifiques. Les réseaux chimiques de polymères fixés de manière covalente sur des substrats solides plans ont été synthétisés par une approche polyvalente et facile à mettre en œuvre en utilisant la chimie click thiol-ène. Elle consiste à déposer des polymères préformés et réactifs en présence des réticulants dithiol sur des substrats modifiés thiol, la réaction de thiol-ène permettant la réticulation simultanée entre chaînes et le greffage en surface. La stratégie CLAG (Cross-Linking And Grafting) donne des films d'hydrogel chimiquement stables et reproductibles avec une large gamme d'épaisseur et avec les propriétés thermostimulables désirées. Les polymères hydrophiles fonctionnalisés par des groupes fonctionnels alcène peuvent être synthétisés en utilisant une copolymérisation radicalaire du monomère souhaité avec du méthacrylate d'allyle dans un solvant organique ou un co-solvant avec de l'eau. Une autre voie est la synthèse dans l'eau en deux étapes: le monomère désiré est copolymérisé avec l'acide acrylique puis le copolymère est modifié par l’allylamine. Trois familles de polymères ont été étudiées: poly(PEGMA), poly(acrylamide) et poly(zwitterion). La température de transition des films d'hydrogel est déterminée en mesurant l'épaisseur dans des solutions aqueuses par ellipsométrie. Les films d'hydrogel de poly(PEGMA) montrent des propriétés de LCST avec la température de transition augmentant avec le nombre d'unités de PEG. La LCST varie de 15°C à 60°C avec deux à cinq unités de PEG dans les chaînes pendantes. La LCST peut également être ajustée en utilisant des copolymères avec différents ratios. Les films d'hydrogel acrylamide ont à la fois des propriétés LCST et UCST. Les films d'hydrogel de poly(sulfobetaïne) montrent un comportement UCST très intéressant en plus d’être « anti-fouling », ce qui est très prometteur pour les applications en biologie.

Temperature-responsive surface-attached hydrogel thin films with various LCST/UCST (Lower/Upper Critical Solution Temperature) were designed for specific applications. The chemical polymer networks covalently attached on plane solid substrates were synthesized by a versatile and straightforward approach using thiol-ene click chemistry. It consists in coating ene-reactive polymers and dithiol crosslinkers on thiol-modified substrates, the thiol-ene click reaction allowing simultaneous cross-linking between chains and grafting on the surface. The CLAG (Cross-Linking And Grafting) strategy provides chemically stable and reproducible hydrogel films with a wide range of thickness and with the desired temperature-responsive properties. Ene-functionalized hydrophilic polymers can be synthesized using free radical copolymerization of the desired monomer with allyl methacrylate in organic solvent or co-solvent with water. Another way is the synthesis in water in two steps: the desired monomer is copolymerized with acrylic acid and then the copolymer is post-modified by amidification. Three polymer families were investigated: poly(PEGMA), poly(acrylamide) derivatives and poly(zwitterions). The transition temperature of the hydrogel films is determined by measuring the thickness in aqueous solutions at different temperatures with ellipsometry. Poly(PEGMA) hydrogel films show LCST properties with the transition temperature increasing with the number of PEG units. The LCST ranges from 15 °C to 60 °C with two to five PEG units in the pendant chains. The LCST can also be adjusted using mixed copolymers hydrogel. Poly(acrylamide) derivatives hydrogel films have both LCST and UCST properties. Poly(sulfobetaine) hydrogel films show very interesting UCST behavior in addition to be anti-fouling, which is very promising for biology applications.; Les films minces d'hydrogels thermosensibles à propriétés LCST/UCST (Lower/Upper Critical Solution Temperature) avec des températures de transition variables ont été mis au point pour des applications spécifiques. Les réseaux chimiques de polymères fixés de manière covalente sur des substrats solides plans ont été synthétisés par une approche polyvalente et facile à mettre en œuvre en utilisant la chimie click thiol-ène. Elle consiste à déposer des polymères préformés et réactifs en présence des réticulants dithiol sur des substrats modifiés thiol, la réaction de thiol-ène permettant la réticulation simultanée entre chaînes et le greffage en surface. La stratégie CLAG (Cross-Linking And Grafting) donne des films d'hydrogel chimiquement stables et reproductibles avec une large gamme d'épaisseur et avec les propriétés thermostimulables désirées. Les polymères hydrophiles fonctionnalisés par des groupes fonctionnels alcène peuvent être synthétisés en utilisant une copolymérisation radicalaire du monomère souhaité avec du méthacrylate d'allyle dans un solvant organique ou un co-solvant avec de l'eau. Une autre voie est la synthèse dans l'eau en deux étapes: le monomère désiré est copolymérisé avec l'acide acrylique puis le copolymère est modifié par l’allylamine. Trois familles de polymères ont été étudiées: poly(PEGMA), poly(acrylamide) et poly(zwitterion). La température de transition des films d'hydrogel est déterminée en mesurant l'épaisseur dans des solutions aqueuses par ellipsométrie. Les films d'hydrogel de poly(PEGMA) montrent des propriétés de LCST avec la température de transition augmentant avec le nombre d'unités de PEG. La LCST varie de 15°C à 60°C avec deux à cinq unités de PEG dans les chaînes pendantes. La LCST peut également être ajustée en utilisant des copolymères avec différents ratios. Les films d'hydrogel acrylamide ont à la fois des propriétés LCST et UCST. Les films d'hydrogel de poly(sulfobetaïne) montrent un comportement UCST très intéressant en plus d’être « anti-fouling », ce qui est très prometteur pour les applications en biologie.

Hydrogel films are proposed as anti-fog coatings on glazings. Indeed, they may delay mist formation by absorbing water up to several times their volume. However, their mechanical resistance in the swollen state remains an issue. In this work, we investigate water transport towards and within non-equilibrium hydrogel films in two situations. First, we have studied the swelling kinetics of the cooled films when submitted to a humid air flow. Second, we have characterized their indentation and frictional response in relation to the drainage of the poroelastic network which results from contact stresses. For this purpose, model micrometric hydrogel films, with a varied and controlled physical-chemistry, are prepared. Experimental set-ups have been developed and the results are modelled in relation with the architecture of hydrogels and their physical-chemistry. We show how the hygroscopy of the polymer, the architecture and the thickness of the films control their swelling kinetics in a vapor flux. We also demonstrate that the friction force on hydrogel films mostly originates in the flow of water forced within the permeable polymer network in the sliding contact. Finally, at large indentation depths where the water content becomes low enough, we highlight the role of the transitions (glass transition or LCST-type) of the polymer on the mechanical response of the films., Les films d’hydrogel sont envisagés comme revêtements anti-buée sur les vitrages. En effet, ils peuvent retarder l’apparition de la buée en absorbant plusieurs fois leur volume en eau. Cependant, une fois gonflés, la question de leur résistance mécanique se pose. Nous nous intéressons ici aux transferts d’eau vers et au sein de films d’hydrogel hors équilibre dans deux situations. D’abord, lorsqu’ils sont secs puis soumis à un flux d’air humide sur un substrat refroidi, nous avons étudié leur cinétique de gonflement. Ensuite, nous avons caractérisé leur réponse mécanique en indentation et en frottement lorsque l’eau retenue par l’hydrogel draine au sein du contact. Dans ce but, des films micrométriques d’hydrogel modèles, de physico-chimie variée et contrôlée, sont réalisés. Des dispositifs expérimentaux ont été développés, dont les résultats sont modélisés en lien avec l’architecture des hydrogels et leur physico-chimie. Nous montrons comment l’hygroscopie du polymère, l’architecture et l’épaisseur des films contrôlent leur cinétique de gonflement dans un flux de vapeur. Nous établissons aussi que le frottement de films d’hydrogel a pour origine l’écoulement forcé de l’eau au sein du réseau perméable de polymère. Enfin, à forte indentation où la teneur en eau devient faible, nous mettons en évidence le rôle des transitions (vitreuse ou de type LCST) du polymère sur la réponse mécanique des films.

We develop a new method to build microactuators using stimuli-responsive hydrogels. The hydrogel is synthesized with covalent attachment to the microchannel bottom walls prior to closing the microsystem, contrarily to previous approaches. We use a new stimuli-responsive hydrogel films synthesis pathway. This synthesis is based on thiol-ene click chemistry. The formation of films is achieved by adding bifunctional thiol molecules as cross-linkers to ene-functionalized preformed polymers on thiol-modified surfaces. The cross-linking and grafting are simultaneously performed either by thermal activation or UV-irradiation. Hydrogel films and micro-patterns are easily obtained in a wide range of thickness from hundred nanometers to several microns. We show that these responsive hydrogels patterns can be integrated into microfluidics channels to build microactuators. We focus on thermo-sensitive actuators made from poly(N-isopropylacrylamide). Under temperature, hydrogel patterns reversibly swell and collapse by absorbing/expulsing water. The phase transition is rapid (lower than 1 second), abrupt (a few degrees around the LCST at 32°C) and the deformation amplitude is high (400% swelling). Microvalves obtained by this approach exhibit high performances and durability. Moreover, we develop new reconfigurable actuators functioning as microfluidic traps. These new-concept microfluidic actuators offer wide possibilities because of their ease of fabrication, their performances and their ability to be integrated into high density.; Nous développons une nouvelle approche des actuateurs microfluidiques à base d’hydrogels stimulables. Contrairement aux approches précédentes, les hydrogels sont synthétisés et greffés à la paroi inférieure du microcanal avant la fermeture du système. Nous utilisons une nouvelle stratégie de synthèse pour les films d’hydrogels stimulables par chimie click thiol-ène. Les films sont obtenus par dépôt, sur des surfaces fonctionnalisées avec des thiols, d’un mélange de chaînes polymères préformées et d’un réticulant dithiol. Le greffage et la réticulation s’obtiennent simultanément par une activation thermique ou par irradiation UV. Des films et des micro-motifs sont obtenus sur une large gamme d’épaisseur allant de la centaine de nanomètres à plusieurs microns. Nous intégrons les motifs d’hydrogels stimulables dans les microcanaux pour réaliser des actionneurs. Nous étudions des actionneurs thermosensibles réalisés avec des hydrogels de poly(N-isopropylacrylamide). Avec la température, les motifs d’hydrogels gonflent ou dégonflent en absorbant/expulsant l’eau de manière réversible. L’effet est rapide (inférieur à la seconde), la transition abrupte (quelques degrés autour de la LCST à 32°C) et l’amplitude de déformation est importante (gonflement de 400%). Les micro-vannes réalisées avec cette nouvelle approche présentent de très bonnes performances et une grande durabilité. Nous avons aussi réalisé de nouveaux actionneurs reconfigurables fonctionnant comme des pièges microfluidiques. Ces actionneurs microfluidiques innovants offrent de nombreuses perspectives de par la facilité de leur mise en œuvre, leurs performances et l’intégration sur des micro-puces à haute densité.

Thin films of hydrogels we study are chemical polymer networks covalently grafted on solid substrates. These versatile coatings allow the control of various interfacial properties such as responsive properties, wetting or mechanical properties. Here, thin films of stimuli-responsive hydrogels (with temperature, light or electric field) are the point of interest. The surface-attached gel films are synthesized by following a straightforward strategy based on thiol-ene click chemistry. The formation of the films is achieved by adding bifunctional thiol molecules as cross-linkers to the ene-reactive polymers on thiol-modified surfaces. This strategy allows us to obtain hydrogel films with a wide range of thickness and with the desired properties. We study the structure of surface-attached poly(N-isopropylacrylamide) gel films which show thermo-responsive properties. We determine the effect of confinement and constraints due to the surface-attachment on the swelling/collapse phase transition of hydrogels with two approaches: the one-dimension swelling normal to the surface using ellipsometry and neutron reflectivity and the in-plane observation of the free surface of the gel using AFM. New and complex hydrogel films are also developed by targeting the architecture of the polymer networks. Inspired from macroscopic hydrogels architecture, we design various architectures: multilayer gel films, interpenetrating networks (IPN) gel films and hybrid gel films.; Les films minces d'hydrogels que nous étudions sont des réseaux chimiques de polymères greffés par liaison covalente sur des substrats solides. Ces revêtements versatiles permettent le contrôle des propriétés interfaciales tel que les propriétés stimulables, le mouillage ou les propriétés mécaniques. Ici, nous nous intéressons aux films minces d'hydrogels stimulables (par la température, la lumière ou le champ électrique).La synthèse des films de gels greffés suit une stratégie simple basée sur la chimie click thiol-ène. Les films sont fabriqués en déposant les polymères stimulables fonctionnalisés par des groupes diène en présence de réticulants dithiols sur des surfaces modifiées thiol. Cette stratégie permet d'obtenir des films d'hydrogels sur une large gamme d'épaisseur avec les propriétés stimulables visées. Nous nous intéressons à la structure des films d'hydrogels greffés de poly(N-isopropylacrylamide) aux propriétés thermo-stimulables. Nous étudions l'effet du confinement et des contraintes dues au greffage sur la surface sur la transition de phase gonflement/dégonflement des gels avec deux approches : le gonflement unilatéral (perpendiculaire à la surface) par ellipsométrie et réflectivité de neutrons, et la topographie (dans le plan) de la surface libre du gel par AFM. Nous développons également de nouveaux films d'hydrogels avec des réseaux d'architectures ciblées. En s'inspirant de l'architecture des gels macroscopiques, nous élaborons diverses architectures : films de gels multicouches, films de réseaux interpénétrés et films de gels hybrides.