Critical analysis of adhesion work measurements from AFM-based techniques for soft contact.

HYPOTHESIS: The work of adhesion is a thermodynamic quantity that is frequently measured by atomic force microscopy (AFM). Determination of the work of adhesion requires quasi-equilibrium measurements, where we address the question of to what extent atomic force microscopy qualifies for quasi-equilibrium measurements. EXPERIMENT: To measure the work of adhesion, we combined soft colloidal probe AFM (SCP AFM) with reflection interference contrast microscopy (RICM). This allowed us to extract the work of adhesion either from the pull-off force or from the contact radius. With these methods, we investigated the adhesion behavior of poly(N-isopropylacrylamide) (PNIPAM) polymer brushes in the swollen and solvent-induced collapsed state by systematically analyzing contact radii and adhesive forces. FINDINGS: In the swollen state, the adhesion to the PNIPAM brush was fivefold larger and exhibited significant time dependencies when measured with SCP AFM. A strong rate dependence of the pull-off force method was indicative of a non-equilibrium process. In order to reliably determine the equilibrium work of adhesion, the contact radius method was found to be the better because it is not rate dependent. Our work highlights the important benefits of using optical measurements to determine the contact radius when deriving the works of adhesion between colloidal probes and polymer brush surfaces.

Influence of the Atmosphere on the Wettability of Polymer Brushes.

Polymer brushes, i.e., end-tethered polymer chains on substrates, are sensitive to adaptation, e.g., swelling, adsorption, and reorientation of the surface molecules. This adaptation can originate from a contacting liquid or atmosphere for partially wetted substrates. The macroscopic contact angle of the aqueous drop can depend on both adaptation mechanisms. We analyze how the atmosphere around an aqueous droplet determines the resulting contact angle of the wetting droplet on polymer brush surfaces. Poly(N-isopropylacrylamide) (PNiPAAm)-based brushes are used due to their exceptional sensitivity to solvation and liquid mixture composition. We develop a method that reliably measures wetting properties when the drop and the surrounding atmosphere are not in equilibrium, e.g., when evaporation and condensation tend to contaminate the liquid of the drop and the atmosphere. For this purpose, we use a coaxial needle in the droplet, which continuously exchanges the wetting liquid, and in addition, we constantly exchange the almost saturated atmosphere. Depending on the wetting history, PNiPAAm can be prepared in two states, state A with a large water contact angle (∼65°) and state B with a small water contact angle (∼25°). With the coaxial needle, we can demonstrate that the water contact angle of a sample in state B significantly increases by ∼30° when a water-free atmosphere is almost saturated with ethanol, compared to an ethanol-free atmosphere at 50% relative humidity. For a sample in state A, the relative humidity has little influence on the water contact angle.

Molecular Transport within Polymer Brushes: A FRET View at Aqueous Interfaces.

Molecular permeability through polymer brush chains is implicated in surface lubrication, wettability, and solute capture and release. Probing molecular transport through polymer brushes can reveal information on the polymer nanostructure, with a permeability that is dependent on chain conformation and grafting density. Herein, we introduce a brush system to study the molecular transport of fluorophores from an aqueous droplet into the external "dry" polymer brush with the vapour phase above. The brushes consist of a random copolymer of N-isopropylacrylamide and a Förster resonance energy transfer (FRET) donor-labelled monomer, forming ultrathin brush architectures of about 35 nm in solvated height. Aqueous droplets containing a separate FRET acceptor are placed onto the surfaces, with FRET monitored spatially around the 3-phase contact line. FRET is used to monitor the transport from the droplet to the outside brush, and the changing internal distributions with time as the droplets prepare to recede. This reveals information on the dynamics and distances involved in the molecular transport of the FRET acceptor towards and away from the droplet contact line, which are strongly dependent on the relative humidity of the system. We anticipate our system to be extremely useful for studying lubrication dynamics and surface droplet wettability processes.

Mechanofluorescent Polymer Brush Surfaces that Spatially Resolve Surface Solvation.

Polymer brushes, consisting of densely end-tethered polymers to a surface, can exhibit rapid and sharp conformational transitions due to specific stimuli, which offer intriguing possibilities for surface-based sensing of the stimuli. The key toward unlocking these possibilities is the development of methods to readily transduce signals from polymer conformational changes. Herein, we report on single-fluorophore integrated ultrathin (<40 nm) polymer brush surfaces that exhibit changing fluorescence properties based on polymer conformation. The basis of our methods is the change in occupied volume as the polymer brush undergoes a collapse transition, which enhances the effective concentration and aggregation of the integrated fluorophores, leading to a self-quenching of the fluorophores' fluorescence and thereby reduced fluorescence lifetimes. By using fluorescence lifetime imaging microscopy, we reveal spatial details on polymer brush conformational transitions across complex interfaces, including at the air-water-solid interface and at the interface of immiscible liquids that solvate the surface. Furthermore, our method identifies the swelling of polymer brushes from outside of a direct droplet (i.e., the polymer phase with vapor above), which is controlled by humidity. These solvation-sensitive surfaces offer a strong potential for surface-based sensing of stimuli-induced phase transitions of polymer brushes with spatially resolved output in high resolution.

Memory effects in polymer brushes showing co-nonsolvency effects.

Densely packed polymer chains grafted to a substrate, especially polymer brushes, have been studied intensively. Of special interest are systems that react to changes in external conditions or"remember" previous conditions. With this focus, we explore the properties of PNiPAAm brushes and relate published work to own results. The co-nonsolvency effect leads to a collapse of a PNiPAAm brush for a certain mixing ratio of ethanol in water. This also influences the wetting behavior of PNiPAAm brushes. We show that through prewetting of a brush with different liquids (water and ethanol), the contact angle of subsequent water drops changes significantly. To explain this change, the swelling of the brush was investigated with spectroscopic ellipsometry and the orientation of the molecules at the surface with sum-frequency generation (SFG). Only little change in swelling was found. The SFG measurements reveal in the ethanol prewetted case a well ordered hydrophobic methyl layer at the interface, which is consistent with the contact angle measurement.