Relation between oxidation kinetics and reactant transport in an aqueous foam.

HYPOTHESIS: Aqueous foams are expected to constitute exquisite particularly suitable reactive medium for the oxidation of metals, since the reactant H+ can be supplied through the continuous liquid phase, while the reactant O2 can be transported through the gas bubbles. EXPERIMENTS: To test this hypothesis, we investigated the oxidation of a metallic copper cylinder immersed in an aqueous foam. To study the relation between the transport of these reactants and the kinetics of the chemical reaction we use a forced drainage setup which enables us to control both the advection velocity of the H+ ions through the foam and the foam liquid fraction. FINDINGS: We find experimentally that the mass of dissolved copper presents a maximum with the drainage flow rate, and thus with the foam liquid fraction. Modeling analytically the transfer of H+ and O2 through the foams enables us to show that this non-monotonic behavior results from a competition between the advective flux of H+ ions and the unsteady diffusion of O2 through the thin liquid films which tends to be slower as the area of the thin liquid films decreases with the drainage flow rate and the liquid fraction. This study shows for the first time how to optimize the foam structure and drainage flow in reactive foams in which the reactants are present both in the liquid and gaseous phases.

Formation and stabilization of multiple w/o/w emulsions encapsulating catechin, by mechanical and microfluidic methods using a single pH-sensitive copolymer: Effect of copolymer/drug interaction.

Multiple w/o/w emulsions (MEs) are promising systems for protecting fragile hydrophilic drugs and controlling their release. We explore the capacity of a single pH-sensitive copolymer, PDMS60-b-PDMAEMA50, and salts, to form and stabilize MEs loaded with sucrose or catechin by a one-step mechanical process or a microfluidic method. ME cytotoxicity was evaluated in various conditions of pH. Using the mechanical process, the most stable emulsions were obtained with Miglyol®812 N and isopropyl myristate in a final pH range of 8-12 and [0.3 M-1 M] NaCl concentrations. Conversely, with the microfluidic method, isopropyl myristate at pH 3 without salt was more efficient. Catechin strongly affected the formation of droplets by the mechanical process but did not modify the conditions of stability of MEs obtained by the microfluidic method. The antioxidant power of catechin was preserved in the inner droplets, even in emulsions prepared by the mechanical method at pH 8. An incomplete release of sucrose and catechin from the emulsions was observed and attributed to the interaction of molecules with the copolymer through hydrogen bonding. This study highlights some of the barriers to break to formulate multiple emulsions stabilized by a PDMS-b-PDMAEMA copolymer or other polymers which can form hydrogen bonds interaction with encapsulated drugs.

Responsive Pickering Emulsions Stabilized by Frozen Complex Coacervate Core Micelles.

Frozen complex coacervate core micelles (C3Ms) were developed as a class of particle stabilizers for Pickering emulsions. The C3Ms are composed of a core of electrostatically interacting weak polyelectrolytes, poly(acrylic acid) (pAA) and poly(dimethylaminopropylacrylamide) (pDMAPAA), surrounded by a corona of water-soluble and surface active poly(N-isopropylacrylamide) (pNiPAM). Mixing parameters of the two polymer solutions, including pH, mixing method, charge ratio, and salinity of the medium, were carefully controlled, leading to monodisperse, colloidally stable C3Ms. A combination of dynamic light scattering and proton nuclear magnetic resonance experiments showed that the C3Ms gradually disassembled from a dynamically frozen core state in pure water into free polyelectrolyte chains above 0.8 M NaCl. Upon formulation of dodecane-in-water emulsions, the frozen C3Ms adsorb as particles at the droplet interfaces in striking contrast with most of the conventional micelles made of amphiphilic block copolymers which fall apart at the interface. Eventually, increasing the salt concentration of the system triggered disassembly of the C3Ms, which led to emulsion destabilization.

Growth Mechanism of Polymer Membranes Obtained by H-Bonding Across Immiscible Liquid Interfaces.

Complexation of polymers at liquid interfaces is an emerging technique to produce all-liquid printable and self-healing devices and membranes. It is crucial to control the assembly process, but the mechanisms at play remain unclear. Using two different reflectometric methods, we investigate the spontaneous growth of H-bonded PPO-PMAA (polypropylene oxide-polymetacrylic acid) membranes at a flat liquid-liquid interface. We find that the membrane thickness h grows with time t as h ∼ t1/2, which is reminiscent of a diffusion-limited process. However, counterintuitively, we observe that this process is faster as the PPO molar mass increases. We are able to rationalize these results with a model which considers the diffusion of the PPO chains within the growing membrane. The architecture of the latter is described as a gel-like porous network, with a pore size much smaller than the radius of the diffusing PPO chains, thus inducing entropic barriers that hinder the diffusion process. From the comparison between the experimental data and the result of the model, we extract some key piece of information about the microscopic structure of the membrane. This study opens the route toward the rational design of self-assembled membranes and capsules with optimal properties.

Controlled Synthesis of Gold Nanoparticles in Copolymers Nanomolds by X-ray Radiolysis.

We show by X-ray and neutron small-angle scattering that gold nanoparticles with controlled sizes and morphologies can be obtained by the metallic reduction of AuCl4- ions trapped in 3D organic molds by X-ray radiolysis. The molds are spherical frozen micelles of polystyrene-b-poly(dimethylaminoethyl methacrylate) (PS-b-PDMAEMA) block copolymer in acidic aqueous solution with a PS spherical core surrounded by a corona of PDMAEMA chains in good solvent. The behavior of micelles is controlled by the [AuCl4-]/[DMAEMA] ratio RAuCl4-/DMAEMA. At low gold concentration, AuCl4- ions condense on the positively charged DMAEMA moieties without changing the behavior of the PDMAEMA chains. At intermediate gold concentration, the ions induce a progressive contraction of the corona's chains and dehydration of micelles. At large gold concentration, the corona becomes a fully dry phase loaded with gold ions, which induces micelle aggregation. Radiolysis of the solution by an intense X-ray beam produces different types of gold nanoparticles with respect to RAuCl4-/DMAEMA and irradiation time. At RAuCl4-/DMAEMA = 0.033, irradiation produces in the first step gold clusters in the micelle corona which in the second step merge to form nanoparticles of a similar size to that of the micelle. Conversely, at RAuCl4-/DMAEMA = 0.33, micelles do not operate as templates but only as nucleation zones and large nanoparticles grow outside the micelles.

Reversible Assembly of Microgels by Metallo-Supramolecular Chemistry.

The combination of supramolecular chemistry and soft colloids as microgels represents an ambitious way to develop multi-versatile colloidal assemblies. Hereafter, terpyridine-functionalized poly(N-isopropylacrylamide) (PNiPAM) microgel building blocks are shown to undergo an assemble-freeze-disassemble process. The microgel assemblies, which are controlled by monitoring the attractive and repulsive potentials between the soft colloidal particles, are then frozen by forming inter-particle metal-terpyridine bis-complexes upon addition of the metallic cation (such as FeII , CoII ). By oxidation of the metal-terpyridine bis-complex links, the aggregates open up, which is due to the complex dissociation releasing the connected particles in the form of single microgels. We extended our work to the development of 1D filaments and 2D membranes materials made of soft particles connected via supramolecular chemistry.

Oxidation-Responsive Emulsions Stabilized by Cleavable Metallo-Supramolecular Cross-Linked Microgels.

An original route to develop an advanced class of microgel emulsifiers containing stimulable metallo-supramolecular instead of frozen covalent cross-links is reported. The poly(N-isopropylmethacrylamide) (PNiPMAM) chains of the microgel are connected by iron(II)-bis(terpyridine) coordination supramolecular complexes that can be cleaved on demand, leading to unique properties both at interfaces and in volume. The microgel synthesis is not demanding, and the characterization of its supramolecular structure can be precisely achieved by standard methods. Singularly, interfaces of an oil-in-water emulsion stabilized by the supramolecular particles can be triggered at the molecular scale by oxidation of Fe(II) to Fe(III), leading to emulsion breaking. In bulk, we show that a microgel dispersion can indeed be transformed into a polymer solution upon oxidation. Our study paves the way to the discovery of unusual microgel properties as our proof-of-concept can be extended to different supramolecular chemistry and architecture.

PEGylated NiPAM microgels: synthesis, characterization and colloidal stability.

The objective of this work is to synthesize highly stable thermoresponsive microgels that could be used in diverse applications. To achieve this, N-isopropylacrylamide (NiPAM) based microgels were first synthesized by surfactant-free precipitation polymerization of NiPAM in the presence of poly(ethylene glycol)methacrylate (PEG) as a macro-comonomer and methylenebisacrylamide (MBA) as a chemical crosslinker. By combining a complete set of techniques such as dynamic light scattering (DLS), scanning electron microscopy (SEM), zetametry, 1H NMR and micro-differential scanning calorimetry (µDSC), we clearly demonstrate that (i) the incorporation of the PEG chains controls the size and the polydispersity of the NiPAM-based microgels, whereas the thermal behavior in solution (enthalpy, volume phase transition temperature (VPTT)) remains almost the same as for pure NiPAM microgels; (ii) the PEG chains are mainly located on the microgel periphery; and (iii) the presence of the PEG chains strongly increases the colloidal stability of microgels in electrolyte solutions at high temperatures.

Coupled Effects of Spreading Solvent Molecules and Electrostatic Repulsions on the Behavior of PS-b-PAA Monolayers at the Air-Water Interface.

We describe the surface behavior of PS-b-PAA monolayers at the air/water interface using N,N-dimethyformamide (DMF) as spreading solvent. At low pH, when the PAA blocks are neutral, the surface pressure versus molecular area isotherm shows a pseudoplateau associated with the presence of remaining spreading solvent molecules in the monolayer, as we described in a former study (Guennouni et al., Langmuir, 2016). We show here that the width of the plateau decreases when increasing pH up to its complete disappearance at high pH, when PAA blocks are fully charged, although two regimes of compressibilities on the isotherm still exist. A refined structural study at pH 9 combining specular neutron reflectivity (SNR), grazing-incidence small-angle X-ray scattering (GISAXS), and atomic force microscopy (AFM) in liquid measurements shows that (i) PAA blocks are stretched in solution, as expected from polyelectrolyte brushes in the osmotic regime; (ii) the system undergoes a spinodal decomposition during deposit at the air/water interface in the presence of DMF. Upon compression, the Qxy* position of the peak associated with the spinodal structure remains almost constant but its intensity evolves strongly and passes through a maximum at intermediate pressures. This reveals two operating processes in the system: strong electrostatic repulsions between chains that prevent in-plane reorganizations and force such reorganizations to occur from the surface to the volume and progressive expulsion of the DMF molecules from the monolayer. These processes have antagonist effects on the intensity of the peak: the increase of the repulsions makes it more pronounced, whereas the expulsion of solvent makes it vanish due to the loss of contrast.

One-Step Fabrication of pH-Responsive Membranes and Microcapsules through Interfacial H-Bond Polymer Complexation.

Biocompatible microencapsulation is of widespread interest for the targeted delivery of active species in fields such as pharmaceuticals, cosmetics and agro-chemistry. Capsules obtained by the self-assembly of polymers at interfaces enable the combination of responsiveness to stimuli, biocompatibility and scaled up production. Here, we present a one-step method to produce in situ membranes at oil-water interfaces, based on the hydrogen bond complexation of polymers between H-bond acceptor and donor in the oil and aqueous phases, respectively. This robust process is realized through different methods, to obtain capsules of various sizes, from the micrometer scale using microfluidics or rotor-stator emulsification up to the centimeter scale using drop dripping. The polymer layer exhibits unique self-healing and pH-responsive properties. The membrane is viscoelastic at pH = 3, softens as pH is progressively raised, and eventually dissolves above pH = 6 to release the oil phase. This one-step method of preparation paves the way to the production of large quantities of functional capsules.

Biocompatible Stimuli-Responsive W/O/W Multiple Emulsions Prepared by One-Step Mixing with a Single Diblock Copolymer Emulsifier.

Multiple water-in-oil-in-water (W/O/W) emulsions are promising materials in designing carriers of hydrophilic molecules or drug delivery systems, provided stability issues are solved and biocompatible chemicals can be used. In this work, we designed a biocompatible amphiphilic copolymer, poly(dimethylsiloxane)-b-poly(2-(dimethylamino)ethyl methacrylate) (PDMS-b-PDMAEMA), that can stabilize emulsions made with various biocompatible oils. The hydrophilic/hydrophobic properties of the copolymer can be adjusted using both pH and ionic strength stimuli. Consequently, the making of O/W (oil in water), W/O (water in oil), and W/O/W emulsions can be achieved by sweeping the pH and ionic strength. Of importance, W/O/W emulsions are formulated over a large pH and ionic strength domain in a one-step emulsification process via transitional phase inversion and are stable for several months. Cryo-TEM and interfacial tension studies show that the formation of these W/O/W emulsions is likely to be correlated to the interfacial film curvature and microemulsion morphology.

Interfacial Rheology of Hydrogen-Bonded Polymer Multilayers Assembled at Liquid Interfaces: Influence of Anchoring Energy and Hydrophobic Interactions.

We study the 2D rheological properties of hydrogen-bonded polymer multilayers assembled directly at dodecane-water and air-water interfaces using pendant drop/bubble dilation and the double-wall ring method for interfacial shear. We use poly(vinylpyrrolidone) (PVP) as a proton acceptor and a series of polyacrylic acids as proton donors. The PAA series of chains with varying hydrophobicity was fashioned from poly(acrylic acid), (PAA), polymethacrylic acid (PMAA), and a homemade hydrophobically modified polymer. The latter consisted of a PAA backbone covalently grafted with C12 moieties at 1% mol (referred to as PAA-1C12). Replacing PAA with the more hydrophobic PMAA provides a route for combining hydrogen bonding and hydrophobic interactions to increase the strength and/or the number of links connecting the polyacid chains to PVP. This systematic replacement allows for control of the ability of the monomer units inside the absorbed polymer layer to reorganize as the interface is sheared or compressed. Consequently, the interplay of hydrogen bonding and hydrophobic interactions leads to control of the resistance of the polymer multilayers to both shear and dilation. Using PAA-1C12 as the first layer improves the anchoring energy of a few monomers of the chain without changing the strength of the monomer-monomer contact in the complex layer. In this way, the layer does not resist shear but resists compression. This strategy provides the means for using hydrophobicity to control the interfacial dynamics of the complexes adsorbed at the interface of the bubbles and droplets that either elongate or buckle upon compression. Moreover, we demonstrate the pH responsiveness of these interfacial multilayers by adding aliquots of NaOH to the acidic water subphase surrounding the bubbles and droplets. Subsequent pH changes can eventually break the polymer complex, providing opportunities for encapsulation/release applications.

Self-Organization of Polystyrene-b-polyacrylic Acid (PS-b-PAA) Monolayer at the Air/Water Interface: A Process Driven by the Release of the Solvent Spreading.

We present an in situ structural study of the surface behavior of PS-b-PAA monolayers at the air/water interface at pH 2, for which the PAA blocks are neutral and using N,N-dimethyformamide (DMF) as spreading solvent. The surface pressure versus molecular area isotherm shows a perfectly reversible pseudoplateau over several cycles of compression/decompression. The width of such plateau enlarges when increasing temperature, conversely to what is classically observed in the case of an in-plane first order transition. We combined specular neutron reflectivity (SNR) experiments with contrast variation to solve the profile of each block perpendicular to the surface with grazing-incidence small-angle scattering (GISAXS) measurements to determine the in-plane structure of the layer. SNR experiments showed that both PS and PAA blocks remain adsorbed on the surface for all surface pressure probed. A correlation peak at Q(xy)* = 0.021 Å(-1) is evidenced by GISAXS at very low surface pressure which intensity first increases on the plateau. When compressing further, its intensity decays while Q(xy)* is shifted toward low Q(xy). The peak fully disappears at the end of the plateau. These results are interpreted by the formation of surface aggregates induced by DMF molecules at the surface. These DMF molecules remain adsorbed within the PS core of the aggregates. Upon compression, they are progressively expelled from the monolayer, which gives rise to the pseudoplateau on the isotherm. The intensity of the GISAXS correlation peak is set by the amount of DMF within the monolayer as it vanishes when all DMF molecules are expelled. This result emphizes the role of the solvent in Langmuir monolayer formed by amphiphilic copolymers which hydrophobic and hydrophilic parts are composed by long polymer chains.

Interplay of Hydrogen Bonding and Hydrophobic Interactions to Control the Mechanical Properties of Polymer Multilayers at the Oil-Water Interface.

We probe the mechanical shear and compression properties of hydrogen-bonded polymer multilayers directly assembled at the oil-water interface using interfacial rheology techniques. We show that the polymer multilayers behave mechanically like a transient network, with elastic moduli that can be varied over 2 orders of magnitude by controlling the type and strength of physical interactions involved in the multilayers, which are controlled by the pH and the hydrophobicity of the polymer. Indeed, the interplay of hydrogen and hydrophobic interactions enables one to obtain a tighter and stronger network at the interface. Moreover, we show how a simple LBL process applied directly on emulsion droplets leads to encapsulation of a model oil, dodecane, as well as perfume molecules.

Multiple emulsions controlled by stimuli-responsive polymers.

The phase inversion of water-toluene emulsions stabilized with a single thermo- and pH-sensitive copolymer occurs through the formation of multiple emulsions. At low pH and ambient temperature, oil in water emulsions are formed which transform into highly stable multiple emulsions at pHs immediately lower than the inversion border. At higher pHs, the emulsion turns into a water in oil one.

Poly(N-isopropylacrylamide) microgels at the oil-water interface: interfacial properties as a function of temperature.

Highly monodisperse poly(N-isopropylacrylamide), PNiPAM, microgels were prepared by the conventional radical polymerization of NiPAM in the presence of dimethylamino ethyl methacrylate (DMAEMA) monomers at various concentrations. The effect of DMAEMA on the polymerization of PNiPAM microgels was examined at constant initiator (V50) and cross-linker (MBA) concentrations. The presence of DMAEMA in the synthesis batch allows for the preparation of PNiPAM microgels with controlled size and a narrow size distribution. The oil(dodecane)/water interfacial properties of the model PNiPAM microgels were then investigated. The pendant drop technique was used to measure the interfacial tensions as a function of temperature. Over the whole range of temperature (20-45 degrees C), the interfacial tension remains low (on the order of 17 mN/m) and goes through a minimum (12 mN/m) at a temperature of about 34 degrees C, which well matches the volume phase transition temperature (VPTT) of PNiPAM microgels. Below the VPTT, the decrease in the interfacial tension with temperature is likely to be due to the adsorption of dense layers because of the decrease of the excluded volume interactions. Above the VPTT, we suggest that the increase in the interfacial tension with temperature comes from the adsorption of loosely packed PNiPAM microgels. We also studied the effect of temperature on the stability of emulsions. Dodecane in water emulsions, which form at ambient temperature, are destabilized as the temperature exceeds the VPTT. In light of the interfacial tension results, we suggest that emulsion destabilization arises from the adsorption of aggregates above the VPTT and not from an important desorption of microgels. Aggregate adsorption would bring a sufficiently high number of dodecane molecules into contact with water to induce coalescence without changing the interfacial tension very much.

Emulsion stabilization and inversion using a pH- and temperature-sensitive amphiphilic copolymer.

We describe how a versatile amphiphilic diblock copolymer can form oil-in-water (o/w) or water-in-oil (w/o) emulsions depending on pH and temperature. At high pH and temperature, this copolymer is mostly hydrophobic and forms w/o emulsions. Its spontaneous curvature is greatly increased upon pH and/or temperature lowering (due to protonation and/or hydration, respectively), which allows the formation of o/w emulsions. Conductivity measurements and confocal fluorescence micrographs evidence the two kinds of structures obtained over a wide range of pH and temperature. We also show how the emulsion type can be reversibly switched along a temperature scan under stirring. The lower stability of the w/o emulsions as compared to the o/w ones is attributed to a lack of electrostatic repulsion. The importance of the copolymer architecture and conformation with regards to droplet stability is discussed.