Rapid and reversible optical switching of cell membrane area by an amphiphilic azobenzene.

Cellular membrane area is a key parameter for any living cell that is tightly regulated to avoid membrane damage. Changes in area-to-volume ratio are known to be critical for cell shape, but are mostly investigated by changing the cell volume via osmotic shocks. In turn, many important questions relating to cellular shape, membrane tension homeostasis and local membrane area cannot be easily addressed because experimental tools for controlled modulation of cell membrane area are lacking. Here we show that photoswitching an amphiphilic azobenzene can trigger its intercalation into the plasma membrane of various mammalian cells ranging from erythrocytes to myoblasts and cancer cells. The photoisomerization leads to a rapid (250-500 ms) and highly reversible membrane area change (ca 2 % for erythrocytes) that triggers a dramatic shape modulation of living cells.

Wettability gradient-driven droplets with an applied external force.

On homogeneous substrates, droplets can slide due to external driving forces, such as gravity, whereas in the presence of wettability gradients, sliding occurs without external forces since this gradient gives rise to an internal driving force. Here, we study via molecular dynamics simulations the more complex behavior when droplets are driven under the combined influence of an external and internal driving force. For comparison, the limiting cases of a single driving force are studied as well. During a large part of the sliding process over the borderline of both substrates, separating both wettabilities, the velocity is nearly constant. When expressing it as the product of the effective mobility and the effective force, the effective mobility mainly depends on the mobility of the initial substrate, experienced by the receding contact line. This observation can be reconciled with the properties of the flow pattern, indicating that the desorption of particles at the receding contact line is the time-limiting step. The effective force is the sum of the external force and a renormalized internal force. This renormalization can be interpreted as stronger dissipation effects when driving occurs via wettability gradients.

Wetting dynamics under periodic switching on different scales: characterization and mechanisms.

The development of substrates with a switchable wettability is proceeding and the limit of switching frequencies and contact angle differences between substrate states has developed in the past years. In this paper we investigate the behavior of a droplet on a homogeneous substrate, which is switched between two wettabilities for a large range of switching frequencies. Here, we are particularly interested in the dependence of the wetting behavior on the switching frequency. We show that results obtained on the particle level via molecular dynamics simulations and on the continuum level via the thin-film model are consistent. Predictions of simple models as the molecular theory of wetting (MKT) and analytical calculations based on the MKT also show good agreement and offer deeper insights into the underlying mechanisms.

Dynamic Wetting of Photoresponsive Arylazopyrazole Monolayers is Controlled by the Molecular Kinetics of the Monolayer.

Smart surfaces that can change their wettability on demand are interesting for applications such as self-cleaning surfaces or lab-on-a-chip devices. We have synthesized arylazopyrazole (AAP) phosphonic acids as a new class of photoswitchable molecules for functionalization of aluminum oxide surfaces. AAP monolayers were deposited on α-Al2O3(0001) and showed reversible E/Z photoswitching that can trigger contact angle changes of up to ∼10°. We monitored these changes on the macroscopic level by recording the contact angle while the monolayer was switched in situ. On the molecular level, time-dependent vibrational sum-frequency generation (SFG) spectroscopy provided information on the kinetic changes within the AAP monolayer and the characteristic times for E/Z switching. In addition, vibrational SFG at different relative humidity indicates that the thermal stability of the Z configuration is largely influenced by the presence of water which can stabilize the Z state and hinder E → Z switching of the AAP monolayer when it is wetted with H2O. Having established the switching times on the molecular scale, we additionally measured the dynamic contact angle and show that the time scales of the substrate and droplet dynamics can be extracted individually. For that, we report on a relaxation model that is solved analytically and is verified via a comparison with simulations of a Lennard-Jones system and with experimental data. The slower E to Z switching in the presence of the droplet as compared to the vapor phase is rationalized in terms of specific interactions of water with the exposed AAP moieties.