Scalable Synthesis of Planar Macroscopic Lipid-Based Multi-Compartment Structures.

As life evolved, the path from simple single cell organisms to multicellular enabled increasingly complex functionalities. The spatial separation of reactions at the micron scale achieved by cellular structures allowed diverse and scalable implementation in biomolecular systems. Mimicking such spatially separated domains in a scalable approach could open a route to creating synthetic cell-like structured systems. Here, we report a facile and scalable method to create multicellular-like, multi-compartment (MC) structures. Aqueous droplet-based compartments ranging from 50 to 400 µm were stabilized and connected together by hydrophobic layers composed of phospholipids and an emulsifier. Planar centimeter-scale MC structures were formed by droplet deposition on a water interface. Further, the resulting macroscopic shapes were shown to be achieved by spatially controlled deposition. To demonstrate configurability and potential versatility, MC assemblies of both homogeneous and mixed compartment types were shown. Notably, magnetically heterogeneous systems were achieved by the inclusion of magnetic nanoparticles in defined sections. Such structures demonstrated actuated motion with structurally imparted directionality. These novel and functionalized structures exemplify a route toward future applications including compartmentally assembled "multicellular" molecular robots.

Surprising Lack of Influence on Water Droplet Motion by Hydrophilic Microdomains on Checkerboard-like Surfaces with Matched Contact Angle Hysteresis.

Chemically and spatially micropatterned surfaces have been successfully prepared for a number of diverse applications, including water/fog harvesting, screen printing, microfluidics, and cell/protein assays. While there have been quite some reports on micropatterned surfaces, less is known about the factors that influence dynamic surface wettability. To that end, smooth checkerboard-like micropatterned hydrophobic/(super)hydrophilic surfaces (2, 5, 10, 20 µm pattern sizes) with regions of matching/mismatching contact angle hysteresis (CAH) were prepared on the basis of a simple chemisorption/photopatterning of monolayers. The effects of regional wettability/CAH and pattern size on the overall dynamic wettability were then examined by measuring the dynamic contact angles (CAs) and substrate tilt angles (θT) of water. It was found that the dynamic wettability on samples with matching regional CAH remained unchanged, even when using hydrophilic regions or changing the pattern size. In contrast, surfaces containing mismatching CAH regions pinned water droplets, leading to overall dynamic wetting properties markedly dependent on pattern size. In addition, the experimental data did not match values predicted by the Cassie equation because dynamic wetting behavior is dominated not by interfacial area but by the interactions of the liquid and solid at the three-phase contact line.

Menthyl acetate powered self-propelled Janus sponge Marangoni motors with self-maintaining surface tension gradients and active mixing.

HYPOTHESIS: Small scale Marangoni motors, which self-generate motion by inducing surface tension gradients on water interfaces through release of surface-active "fuels", have recently been proposed as self-powered mixing devices for low volume fluids. Such devices however, often show self-limiting lifespans due to the rapid saturation of surface-active agents. A potential solution to this is the use volatile surface-active agents which do not persist in their environment. Here we investigate menthyl acetate (MA) as a safe, inexpensive and non-persistent fuel for Marangoni motors. EXPERIMENTS: MA was loaded asymmetrically into millimeter scale silicone sponges. Menthyl acetate reacts slowly with water to produce the volatile surface-active menthol, which induces surface tension gradients across the sponge to drive motion by the Marangoni effect. Videos were taken and trajectories determined by custom software. Mixing was assessed by the ability of Marangoni motors to homogenize milliliter scale aqueous solutions containing colloidal sediments. FINDINGS: Marangoni motors, loaded with asymmetric "Janus" distributions of menthyl acetate show velocities and rotational speeds up to 30 mm s-1 and 500 RPM respectively, with their functional lifetimes scaling linearly with fuel volume. We show these devices are capable of enhanced mixing of solutions at orders of magnitude greater rates than diffusion alone.

Symmetrical Catalytic Colloids Display Janus-Like Active Brownian Particle Motion.

Catalytic Janus colloids, with one hemi-sphere covered by a hydrogen peroxide reduction catalyst such as platinum, represent one of the most experimentally explored examples of self-motile active colloid systems. This paper comparatively investigates the motile behavior of symmetrical catalytic colloids produced by a solution-based metal salt reduction process. Despite the significant differences in the distribution of catalytic activity, this study finds that the motion produced by symmetrical colloids is equivalent to that previously reported for Janus colloids. It also shows that introducing a Janus structure to the symmetrical colloids via masking does not significantly modify their motion. These findings could indicate that very subtle variations in surface reactivity can be sufficient to produce Janus-like active Brownian particle-type motion, or that a symmetry-breaking phenomena is present. The study will consequently motivate fresh theoretical attention and also demonstrate a straightforward route to access large quantities of motile active colloids, which are expected to show subtly different phenomenology compared to those with Janus structures.

Perfluorinated compounds are not necessary: pegylated organosilanes can endow good water sliding/removal properties.

From a viewpoint of reducing the burden on both human health and the environment, alternative surface modification techniques for preparing highly water-repellent surfaces without the use of environmentally damaging perfluorocarbons are highly desirable. Among them, the development of hydrophilic surfaces showing superior water sliding/removal properties has been scarcely reported. In this study, we have successfully demonstrated the fabrication of smooth, transparent, and hydrophilic pegylated organosilanes (PEGn-Si, CH3O-(C2H4O)n-C3H6-Si(OCH3)3 where n = 3, 6-9, 9-12)-derived hybrid films showing excellent water sliding/removal properties using a simple sol-gel reaction of PEGn-Si and tetraethoxysilane (TEOS, Si(OC2H5)4). The final static/dynamic surface wetting properties of the samples were found to be significantly influenced by both the PEG chain length and their mixing ratios. The use of PEGn-Si with the longest PEG chain (n = 9-12) was found to be effective for improving water sliding/removal properties. Small volume water droplets (5 µL) on the PEG9-12-Si/TEOS hybrid film (static water contact angle (CA) of ∼40°) at a 90°-inclined surface could slide at an average speed of 3.4 mm/sec without pinning and tailing, which was about twice as fast as that on the PEG6-9-Si/TEOS hybrid film surface (1.5 mm/sec, static water CA of ∼40°), in spite of having similar static hydrophilic nature.

Light-driven locomotion of a centimeter-sized object at the air-water interface: effect of fluid resistance.

A centimeter-sized flat-headed push pin with photothermal properties can be moved on a water surface by a simple near-infrared laser. Using light as an external stimulus allows for the remote control of the timing, direction and velocity of its locomotion. It has been clarified that the vertical orientation of the pin at the air-water interface affects the friction of locomotion, and therefore velocity and acceleration. The pin placed on a water surface with a pin point upward (a point protruding into air phase) moved an average distance of 5.3 ± 2.9 cm following one pulse of laser irradiation, and that placed with a pin point downward (a point protruding into water phase) moved 2.0 ± 1.4 cm. The velocity and acceleration were larger when the pin was placed on the water surface with a pin pointing upward, compared to when placed with the pin pointing downward. Numerical analysis conducted for the locomotions of the pin concluded that the differences in traveling distance, velocity and acceleration were due to the difference in fluid resistance of the pin point in air and water phases during their locomotion. This demonstration of remote control of the motion of small objects by light can open up a wide range of future transport applications.

A Pickering Emulsion Route to Swimming Active Janus Colloids.

The field of active colloids is attracting significant interest to both enable applications and allow investigations of new collective colloidal phenomena. One convenient active colloidal system that has been much studied is spherical Janus particles, where a hemispherical coating of platinum decomposes hydrogen peroxide to produce rapid motion. However, at present producing these active colloids relies on a physical vapor deposition (PVD) process, which is difficult to scale and requires access to expensive equipment. In this work, it is demonstrated that Pickering emulsion masking combined with solution phase metallization can produce self-motile catalytic Janus particles. Comparison of the motion and catalytic activity with PVD colloids reveals a higher catalytic activity for a given thickness of platinum due to the particulate nature of the deposited coating. This Pickering emulsion based method will assist in producing active colloids for future applications and aid experimental research into a wide range of active colloid phenomena.