Jonathan R. Howse

Self-motile colloidal particles: from directed propulsion to random walk

The motion of an artificial microscale swimmer that uses a chemical reaction catalyzed on its own surface to achieve autonomous propulsion is fully characterized experimentally. It is shown that at short times it has a substantial component of directed motion, with a velocity that depends on the concentration of fuel molecules. At longer times, the motion reverts to a random walk with a substantially enhanced diffusion coefficient. Our results suggest strategies for designing artificial chemotactic systems.

In pursuit of propulsion at the nanoscale

This review describes recent developments in self-propelling nano- and micro-scale swimming devices. The ability of these devices to transport nano-scale components in a fluidic environment is demonstrated. Furthermore, the adaptations needed for these devices to meet biological transport challenges such as targeted drug delivery are highlighted. Particular emphasis is placed on describing autonomously powered devices driven by asymmetrical chemical reactions. Methods to control the speed and direction of such swimming devices using external fields are described, and contrasted to recent demonstrations of statistical autonomous migrations and organisations driven by chemical gradients, inter swimmer interactions and external photo-stimulus. Finally the challenges and advantages of converting other nature inspired swimming mechanisms into realistic artificial self-powered devices are considered.

Electrokinetic effects in catalytic platinum-insulator Janus swimmers

The effect of added salt on the propulsion of Janus platinum-polystyrene colloids in hydrogen peroxide solution is studied experimentally. It is found that micromolar quantities of potassium and silver nitrate salts reduce the swimming velocity by similar amounts, while leading to significantly different effects on the overall rate of catalytic breakdown of hydrogen peroxide. It is argued that the seemingly paradoxical experimental observations could be theoretically explained by using a generalised reaction scheme that involves charged intermediates and has the topology of two nested loops.

Direct Observation of the Direction of Motion for Spherical Catalytic Swimmers

Nonconductive Janus particle swimmers made by coating fluorescent polymer beads with hemispheres of platinum have been fully characterized using video microscopy to reveal that they undergo propulsion in hydrogen peroxide fuel away from the catalytic platinum patch. The platinum coating shadows the fluorescence signal from half of each swimmer to allow the orientation to be observed directly and correlated quantitatively with the resulting swimming direction. The observed swimmer direction is consistent with both the bubble release and diffusiophoretic propulsion mechanisms.

Boundaries can steer active Janus spheres

The advent of autonomous self-propulsion has instigated research towards making colloidal machines that can deliver mechanical work in the form of transport, and other functions such as sensing and cleaning. While much progress has been made in the last 10 years on various mechanisms to generate self-propulsion, the ability to steer self-propelled colloidal devices has so far been much more limited. A critical barrier in increasing the impact of such motors is in directing their motion against the Brownian rotation, which randomizes particle orientations. In this context, here we report directed motion of a specific class of catalytic motors when moving in close proximity to solid surfaces. This is achieved through active quenching of their Brownian rotation by constraining it in a rotational well, caused not by equilibrium, but by hydrodynamic effects. We demonstrate how combining these geometric constraints can be utilized to steer these active colloids along arbitrary trajectories.

Importance of particle tracking and calculating the mean-squared displacement in distinguishing nanopropulsion from other processes.

In this paper we show that processes such as Brownian motion, convection, sedimentation, and bacterial contamination can cause small particles to move through liquids in a fashion which may be mistaken as nanopropulsion. It is shown that particle tracking and subsequent statistical analysis is essential to ascertain if small particles actually propel themselves, or if they are propelled by another process. Specifically we find that it is necessary to calculate the mean-squared displacement of particles at both short and long time intervals, to show that the direction of propulsion changes coincident with rotation of the particle by Brownian motion, as this allows nanopropulsion to be differentiated from Brownian motion, convection and sedimentation. We also find that bacteria can attach themselves to particles and cause them to be propelled. This leads to motion which appears very similar to nanopropulsion and cannot be differentiated using particle tracking and therefore find that carefully designed control experiments must be performed. Finally, we suggest an experimental protocol which can be used to investigate the motion of small objects and prove if they move due to nanopropulsion.

Quantitative evaluation of evaporation rate during spin-coating of polymer blend films: Control of film structure through defined-atmosphere solvent-casting

Abstract.Thin films of polymer mixtures made by spin-coating can phase separate in two ways: by forming lateral domains, or by separating into distinct layers. The latter situation (self-stratification or vertical phase separation) could be advantageous in a number of practical applications, such as polymer optoelectronics. We demonstrate that, by controlling the evaporation rate during the spin-coating process, we can obtain either self-stratification or lateral phase separation in the same system, and we relate this to a previously hypothesised mechanism for phase separation during spin-coating in thin films, according to which a transient wetting layer breaks up due to a Marangoni-type instability driven by a concentration gradient of solvent within the drying film. Our results show that rapid evaporation leads to a laterally phase-separated structure, while reducing the evaporation rate suppresses the interfacial instability and leads to a self-stratified final film.

In situ imaging and height reconstruction of phase separation processes in polymer blends during spin coating

Spin coating polymer blend thin films provides a method to produce multiphase functional layers of high uniformity covering large surface areas. Applications for such layers include photovoltaics and light-emitting diodes where performance relies upon the nanoscale phase separation morphology of the spun film. Furthermore, at micrometer scales, phase separation provides a route to produce self-organized structures for templating applications. Understanding the factors that determine the final phase-separated morphology in these systems is consequently an important goal. However, it has to date proved problematic to fully test theoretical models for phase separation during spin coating, due to the high spin speeds, which has limited the spatial resolution of experimental data obtained during the coating process. Without this fundamental understanding, production of optimized micro- and nanoscale structures is hampered. Here, we have employed synchronized stroboscopic illumination together with the high light gathering sensitivity of an electron-multiplying charge-coupled device camera to optically observe structure evolution in such blends during spin coating. Furthermore the use of monochromatic illumination has allowed interference reconstruction of three-dimensional topographies of the spin-coated film as it dries and phase separates with nanometer precision. We have used this new method to directly observe the phase separation process during spinning for a polymer blend (PS-PI) for the first time, providing new insights into the spin-coating process and opening up a route to understand and control phase separation structures.

Effect of the Hofmeister Anions upon the Swelling of a Self-Assembled pH-Responsive Hydrogel

We report the effect of a range of monovalent sodium salts on the molecular equilibrium swelling of a simple synthetic microphase separated poly(methyl methacrylate)-block-poly(2-(diethylamino)ethyl methacrylate)-block-poly(methyl methacrylate) (PMMA(88)-b-PDEA(223)-b-PMMA(88)) pH-responsive hydrogel. Sodium acetate, sodium chloride, sodium bromide, sodium iodide, sodium nitrate and sodium thiocyanate were selected for study at controlled ionic strength and pH; all salts are taken from the Hofmeister series (HS). The influence of the anions on the expansion of the hydrogel was found to follow the reverse order of the classical HS. The expansion ratio of the gel measured in solutions containing the simple sodium halide salts (NaCl, NaBr, and NaI) was found to be strongly related to parameters which describe the interaction of the ion with water; surface charge density, viscosity coefficient, and entropy of hydration. A global study which also included nonspherical ions (NaAce, NaNO(3) and NaSCN) showed the strongest correlation with the viscosity coefficient. Our results are interpreted in terms of the Collins model, where larger ions have more mobile water in the first hydration cage immediately surrounding the gel, therefore making them more adhesive to the surface of the stationary phase of the gel and ultimately reducing the level of expansion.

Floating lipid bilayers deposited on chemically grafted phosphatidylcholine surfaces

Floating supported bilayers (FSBs) are new systems which have emerged over the past few years to produce supported membrane mimics, where the bilayers remain associated with the substrate, but are cushioned from the substrates constraining influence by a large hydration layer. In this paper we describe a new approach to fabricating FSBs using a chemically grafted phospholipid layer as the support for the floating membrane. The grafted lipid layer was produced using a Langmuir-Schaeffer transfer of acryloyl-functionalized lipid onto a pre-prepared substrate, with AIBN-induced cross-polymerization to permanently bind the lipids in place. A bilayer of DSPC was then deposited onto this grafted monolayer using a combination of Langmuir-Blodgett and Langmuir-Schaeffer transfer. The resulting system was characterized by neutron reflection under two water contrasts, and we show that the new system shows a hydrating layer of approximately 17.5 A in the gel phase, which is comparable to previously described FSB systems. We provide evidence that the grafted substrate is reusable after cleaning and suggest that this greatly simplifies the fabrication and characterization of FSBs compared to previous methods.