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.

Redox-Triggered Control of Cell Adhesion and Deadhesion on Poly(lysine)-g-poly(ethylene oxide) Adlayers.

Spontaneous adsorption of poly(lysine)-g-poly(ethylene glycol) comb-like copolymers (PLL-g-PEG) is a versatile mean to coat substrates with polymer layers that resist cell adhesion. We prepared redox cleavable PLL-g-PEG to switch adhesion on demand. Redox sensitivity was obtained by introducing disulfide linkers between the PLL backbone and PEG strands. This modification was done alone or in combination with an azide end on the PEG strands that enabled in situ conjugations of adhesion peptides or fluorescent labels (by a simple application of commercially available molecules for copper-free click chemistry compatible with cell survival). To balance the functional (adhesion-promoting) vs cell-repellent copolymers, mixed layers of adjusted compositions were obtained by coadsorption from mixed solutions of the cleavable copolymer with noncleavable and repellant PLL-g-PEG. The deposition of copolymers and quantitative cleavage as triggered by reductive conditions (application of solutions of tris(carboxyethyl)phosphine, dithiothreitol, or glutathione) were characterized by QCM-D, XPS, and fluorescence microscopy. In cell culture conditions, redox-triggered cleavage was obtained by a nontoxic application of TCEP for a few minutes, enabling either to release cell attachment points (i.e., cleavage of RGD-presenting areas) or to "open" nonspecific adherent areas (i.e., transition from PEG-presenting areas to adherent PLL-like coatings).

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.

Shape and Effective Spring Constant of Liquid Interfaces Probed at the Nanometer Scale: Finite Size Effects.

We investigate the shape and mechanical properties of liquid interfaces down to nanometer scale by atomic force microscopy (AFM) and scanning electron microscopy (SEM) combined with in situ micromanipulation techniques. In both cases, the interface is probed with a cylindrical nanofiber with radius R of the order of 25-100 nm. The effective spring constant of the nanomeniscus oscillated around its equilibrium position is determined by static and frequency-modulation (FM) AFM modes. In the case of an unbounded meniscus, we find that the effective spring constant k is proportional to the surface tension γ of the liquid through k = (0.51 ± 0.06)γ, regardless of the excitation frequency from quasi-static up to 450 kHz. A model based on the equilibrium shape of the meniscus reproduces well the experimental data. Electron microscopy allowed to visualize the meniscus profile around the fiber with a lateral resolution of the order of 10 nm and confirmed its catenary shape. The influence of a lateral confinement of the interface is also investigated. We showed that the lateral extension L of the meniscus influences the effective spring constant following a logarithmic evolution k ∼ 2πγ/ln(L/R) deduced from the model. This comprehensive study of liquid interface properties over more than 4 orders of magnitude in meniscus size shows that advanced FM-AFM and SEM techniques are promising tools for the investigation of mechanical properties of liquids down to nanometer scale.