Jimmy Faivre

Wear Protection without Surface Modification Using a Synergistic Mixture of Molecular Brushes and Linear Polymers

We describe the design of lubricating and wear protecting fluids based on mixtures of bottle-brushes (BB) and linear polymer solutions. To illustrate this concept, we used hyaluronic acid (HA), a naturally occurring linear polyelectrolyte, and a water-soluble synthetic BB polymer. Individually, these two polymers exhibit poor wear protecting capabilities compared to that of saline solutions. Mixture of the two polymers in pure water or in saline allows the wear protection of surfaces over a wide range of shearing conditions to drastically increase. We demonstrate that this synergy between the BB and HA polymers emerges from a strong cohesion between the two components forming the boundary film due to entanglements between both polymers. We show that this concept can be applied to other types of linear polymers and surfaces and is independent of the chemical and mechanical properties of the surfaces.

Unraveling the Correlations between Conformation, Lubrication and Chemical Stability of Bottlebrush Polymers at Interfaces

In the present study, we monitored the conformation and chemical stability of a hydrophilic bottlebrush (BB) polymer in pure water and buffered saline solutions. We correlated these parameters to lubricating and wear protecting properties. Using the surface forces apparatus (SFA), we show that the BB polymer partially adsorbs on mica surfaces and extends half its contour length toward the aqueous media. This conformation gives rise to a strong repulsive interaction force when surfaces bearing BB polymer chains are pressed against each other. Analysis of these repulsive forces demonstrated that the adsorbed polymer chains could be described as end-attached elastic rods. After 2 months of aging at temperatures ranging from 4 to 37 °C, partial scission of the BB polymers lateral chains was observed by gel permeation chromatography with a half-life time of the polymer of at least two years. The thickness of the BB polymer layer assessed by SFA appeared to quickly decrease with aging time and temperature, which was mainly caused by the adsorption to the substrate of the released lateral chains. The gradual loss of the BB polymer lateral chains did not significantly impact the tribological properties of the BB polymer solution nor its wear protection capacity. The friction coefficient between mica surfaces immersed in the BB polymer solution was μ = 0.031 ± 0.002, was independent of the aging conditions, and remained constant up to an applied pressure P = 0.2 to 0.25 MPa. Altogether, this study demonstrates that, besides the gradual loss of lateral chains, the BB polymer is still able to perform adequately as a lubricant and wear protecting agent over a time period suitable for in vivo administration.

Effect of surface chemistry of polymeric nanoparticles on cutaneous penetration of cholecalciferol

&NA; We investigated the influence of nanoparticle (NP) surface composition on different aspects of skin delivery of a lipophilic drug: chemical stability, release and skin penetration. Cholecalciferol was chosen as a labile model drug. Poly(lactic acid) (PLA)‐based NPs without surface coating, with a non‐ionic poly(ethylene glycol) (PEG) coating, or with a zwitterionic poly(2‐methacryloyloxyethyl phosphorylcholine) (PMPC) coating were prepared using flash nanoprecipitation. Process was optimized to obtain similar hydrodynamic diameters. Polymeric NPs were compared to non‐polymeric cholecalciferol formulations. Cholecalciferol stability in aqueous medium was improved by polymeric encapsulation with a valuable effect of a hydrophilic coating. However, the in vitro release of the drug was found independent of the presence of any polymer, as for the drug penetration in an intact skin model. Such tendency was not observed in impaired skin since, when stratum corneum was removed, we found that a neutral hydrophilic coating around NPs reduced drug penetration compared to pure drug NPs and bare PLA NPs. The nature of the hydrophilic block (PEG or PMPC) had however no impact. We hypothesized that NPs surface influenced drug penetration in impaired skin due to different electrostatic interactions between NPs and charged skin components of viable skin layers.

Interaction Forces between Pegylated Star-Shaped Polymers at Mica Surfaces

We present a study focused on characterizing the interaction forces between mica surfaces across solutions containing star-shaped polymers with cationic ends. Using the surface forces apparatus, we show that the interaction forces in pure water between surfaces covered with the polymers can be adequately described by the dendronized brush model. In that framework, our experimental data suggest that the number of branches adsorbed at the surface decreases as the concentration of polymer in the adsorbing solution increases. The onset of interaction was also shown to increase with the concentration of polymer in solution up to distances much larger than the contour length of the polymer, suggesting that the nanostructure of the polymer film is significantly different from that of a monolayer. High compression of the polymer film adsorbed at low polymer concentration revealed the appearance of a highly structured hydration layer underneath the polymer layer. These results support that charged polymer chains do not necessarily come into close contact with the surface even if strong electrostatic interaction is present. Altogether, our results provide a comprehensive understanding of the interfacial behavior of star-shaped polymers and reveal the unexpected role of hydration water in the control of the polymer conformation.