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.

C9ORF72-derived poly-GA DPRs undergo endocytic uptake in iAstrocytes and spread to motor neurons.

Dipeptide repeat (DPR) proteins are aggregation-prone polypeptides encoded by the pathogenic GGGGCC repeat expansion in the C9ORF72 gene, the most common genetic cause of amyotrophic lateral sclerosis and frontotemporal dementia. In this study, we focus on the role of poly-GA DPRs in disease spread. We demonstrate that recombinant poly-GA oligomers can directly convert into solid-like aggregates and form characteristic ß-sheet fibrils in vitro. To dissect the process of cell-to-cell DPR transmission, we closely follow the fate of poly-GA DPRs in either their oligomeric or fibrillized form after administration in the cell culture medium. We observe that poly-GA DPRs are taken up via dynamin-dependent and -independent endocytosis, eventually converging at the lysosomal compartment and leading to axonal swellings in neurons. We then use a co-culture system to demonstrate astrocyte-to-motor neuron DPR propagation, showing that astrocytes may internalise and release aberrant peptides in disease pathogenesis. Overall, our results shed light on the mechanisms of poly-GA cellular uptake and propagation, suggesting lysosomal impairment as a possible feature underlying the cellular pathogenicity of these DPR species.

3D inkjet printed self-propelled motors for micro-stirring.

HYPOTHESIS: Microscopic self-propelled motors (SPMs) are an area of active research, but very little investigation has been conducted on millimetre-scale or macroscopic SPMs and exploring their potential in biomedical research. In this study, we tested if 3D reactive inkjet (RIJ) printing could be used for precise fabrication of millimetre-scale self-propelled motors (SPMs) with well-defined shapes from regenerated silk fibroin (RSF) by converting water soluble RSF (silk I) to insoluble silk fibroin (silk II). Secondly, we compared the different propulsion behaviour of the SPMs to put forward the best geometry and propulsion mechanism for potential applications in enhancing the sensitivity of diffusion-rate limited biomedical assays by inducing fluid flow. EXPERIMENTS: SPMs with four different geometric shapes and propelled by two different mechanisms (catalysis and surface tension gradient) were fabricated by 3D RIJ printing and compared. For bubble propulsion, the structures were selectively doped in specific regions with the enzyme catalase in order to produce motion via bubble generation and detachment in hydrogen peroxide solutions. For surface tension propulsion, PEG400-doped structures were propelled through surface tension gradients caused by leaching of PEG400 surfactant in deionized water. FINDINGS: The results demonstrated the ability of 3D inkjet printing to fabricate SPMs with desired propulsion mechanism and fine-tune the propulsion by precisely fabricating the different geometric shapes. The resulting 3D structures were capable of generating motion without external actuation, thereby enabling applications in biomedicine such as micro-stirring small fluid volumes to enhance biological assay sensitivity. The surface tension gradient caused by the leaching of surfactant led to faster propulsion velocities with smooth deceleration, whereas, in comparison, catalysis-induced bubble propulsion tended to be jerky and uneven in deceleration, and therefore less suitable for aforementioned applications. Computational fluid dynamic simulations were used to compare the various experimental SPMs ability to enhance mixing when deployed within 96-well plate microwells, to reveal the effect of both SPM shape and motion character on performance, and show viability for small scale mixing applications.

Influence of Additives on the In Situ Crystallization Dynamics of Methyl Ammonium Lead Halide Perovskites.

Understanding the kinetics of the crystallization process for organometal halide perovskite formation is critical in determining the crystalline, nanoscale morphology and therefore the electronic properties of the films produced during thin film formation from solution. In this work, in situ grazing incidence small-angle X-ray scattering (GISAXS) and optical microscopy measurements are used to investigate the processes of nucleation and growth of pristine mixed halide perovskite (MAPbI3-x Cl x ) crystalline films deposited by bar coating at 60 °C, with and without additives in the solution. A small amount of 1,8-diiodooctane (DIO) and hydriodic acid (HI) added to MAPbI3-x Cl x is shown to increase the numbers of nucleation centers promoting heterogeneous nucleation and accelerate and modify the size of nuclei during nucleation and growth. A generalized formation mechanism is derived from the overlapping parameters obtained from real-time GISAXS and optical microscopy, which revealed that during nucleation, perovskite precursors cluster before becoming the nuclei that function as elemental units for subsequent formation of perovskite crystals. Additive-free MAPbI3-x Cl x follows reaction-controlled growth, in contrast with when DIO and HI are present, and it is highly possible that the growth then follows a hindered diffusion-controlled mechanism. These results provide important details of the crystallization mechanisms occurring and will help to develop greater control over perovskite films produced.

Experimental observation of flow fields around active Janus spheres.

The phoretic mechanisms at stake in the propulsion of asymmetric colloids have been the subject of debates during the past years. In particular, the importance of electrokinetic effects on the motility of Pt-PS Janus sphere was recently discussed. Here, we probe the hydrodynamic flow field around a catalytically active colloid using particle tracking velocimetry both in the freely swimming state and when kept stationary with an external force. Our measurements provide information about the fluid velocity in the vicinity of the surface of the colloid, and confirm a mechanism for propulsion that was proposed recently. In addition to offering a unified understanding of the nonequilibrium interfacial transport processes at stake, our results open the way to a thorough description of the hydrodynamic interactions between such active particles and understanding their collective dynamics.

Reactive Inkjet Printing and Propulsion Analysis of Silk-based Self-propelled Micro-stirrers.

In this study, a protocol for using reactive inkjet printing to fabricate enzymatically propelled silk swimmers with well-defined shapes is reported. The resulting devices are an example of self-propelled objects capable of generating motion without external actuation and have potential applications in medicine and environmental sciences for a variety of purposes ranging from micro-stirring, targeted therapeutic delivery, to water remediation (e.g., cleaning oil spills). This method employs reactive inkjet printing to generate well-defined small-scale solid silk structures by converting water soluble regenerated silk fibroin (silk I) to insoluble silk fibroin (silk II). These structures are also selectively doped in specific regions with the enzyme catalase in order to produce motion via bubble generation and detachment. The number of layers printed determines the three-dimensional (3D) structure of the device, and so here the effect of this parameter on the propulsive trajectories is reported. The results demonstrate the ability to tune the motion by varying the dimensions of the printed structures.

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.

Reactive Inkjet Printing of Functional Silk Stirrers for Enhanced Mixing and Sensing.

Stirring small volumes of solution can reduce immunoassay readout time, homogenize cell cultures, and increase enzyme reactivity in bioreactors. However, at present many small scale stirring methods require external actuation, which can be cumbersome. To address this, here, reactive inkjet printing is shown to be able to produce autonomously rotating biocompatible silk-based microstirrers that can enhance fluid mixing. Rotary motion is generated either by release of a surface active agent (small molecular polyethylene glycol) resulting in Marangoni effect, or by catalytically powered bubble propulsion. The Marangoni driven devices do not require any chemicals to be added to the fluid as the "fuel," while the catalytically powered devices are powered by decomposing substrate molecules in solution. A comparison of Marangoni effect and enzyme powered stirrers is made. Marangoni effect driven stirrers rotate up to 600 rpm, 75-100-fold faster than enzyme driven microstirrers, however enzyme powered stirrers show increased longevity. Further to stirring applications, the sensitivity of the motion generation mechanisms to fluid properties allows the rotating devices to also be exploited for sensing applications, for example, acting as motion sensors for water pollution.

Catalytic Janus Colloids: Controlling Trajectories of Chemical Microswimmers.

Catalytic Janus colloids produce rapid motion in fluids by decomposing dissolved fuel. There is great potential to exploit these "autonomous chemical swimmers" in applications currently performed by diffusion limited passive colloids. Key application areas for colloids include transporting active ingredients for drug delivery, gathering analytes for medical diagnostics, and self-assembling into regular structures used for photonic materials and lithographic templating. For drug delivery and medical diagnostics, controlling colloidal motion is key in order to target therapies, and transport analytes through lab-on-a-chip devices. Here, the autonomous motion of catalytic Janus colloids can remove the current requirements to induce and control colloid motion using external fields, thereby reducing the technological complexity required for medical therapies and diagnostics. For materials applications exploiting colloidal self-assembly, the additional interactions introduced by catalytic activity and rapid motion are predicted to allow access to new reconfigurable and responsive structures. In order to realize these goals, it is vital to develop methods to control both individual colloidal paths and collective behavior in motile catalytic colloidal systems. However, catalytic Janus colloids' trajectories are randomized by Brownian effects, and so require new strategies in order to be harnessed for transport. This is achievable using a variety of different approaches. For example, self-assembly and control of catalyst geometry can introduce controlled amounts of rotary motion, or "spin" into chemical swimmer trajectories. Furthermore, rotary motion combined with gravity, produces well-defined orientated helical trajectories. In addition, when catalytic colloids interact with topographical features, such as edges and trenches, they are steered. This gives rise to a new approach for autonomous colloidal microfluidic transport that could be deployed in future lab-on-a-chip devices. Chemical gradients can also influence the motion of catalytic Janus colloids, for example, to cause collective accumulations at specific locations. However, at present, the predicted theoretical degree of control over this phenomenon has not been fully verified in experimental systems. Collective behavior control for chemical swimmers is also possible by exploiting the potential for the complex interactions in these systems to allow access to self-assembled, dynamic and reconfigurable ordered structures. Again, current experiments have not yet accessed the breadth of possible behavior. Consequently, continued efforts are required to understand and control these interaction mechanisms in real world systems. Ultimately, this will help realize the use of catalytic Janus colloids for tasks that require well-controlled motion and structural organization, enabling functions such as analyte capture and concentration, or targeted drug delivery.