Andrew I. Campbell

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.

Gravitaxis in Spherical Janus Swimming Devices

In this work, we show that the asymmetrical distribution of mass at the surface of catalytic Janus swimmers results in the devices preferentially propelling themselves upward in a gravitational field. We demonstrate the existence of this gravitaxis phenomenon by observing the trajectories of fueled Janus swimmers, which generate thrust along a vector pointing away from their metallically coated half. We report that as the size of the spherical swimmer increases, the propulsive trajectories are no longer isotropic with respect to gravity, and they start to show a pronounced tendency to move in an upward direction. We suggest that this effect is due to the platinum caps asymmetric mass exerting an increasing influence on the azimuthal angle of the Janus sphere with size, biasing its orientation toward a configuration where the heavier propulsion generating surface faces down. This argument is supported by the good agreement we find between the experimentally observed azimuthal angle distribution for the Janus swimmers and predictions made by simple Boltzmann statistics. This gravitaxis phenomenon provides a mechanism to autonomously control and direct the motion of catalytic swimming devices and so enable a route to make autonomous transport devices and develop new separation, sensing, and controlled release applications.

Kinetics of Electroless Deposition: The Copper-Dimethylamine Borane System

A kinetic study of the electroless deposition of copper on gold, using dimethylamine borane (DMAB) as a reducing agent, has been carried out. The copper deposition rate in the electroless bath was determined to be 50 nm min(-1), through electrochemical stripping of the copper deposits as well as from direct measurements of the film thickness using atomic force microscopy (AFM). Comparison with a galvanic cell setup, where the two half-reactions were physically separated, yielded a lower deposition rate of 30 nm min(-1). An important kinetic effect of the surface on the oxidation of the reducing agent, and thus on the overall process, was therefore revealed. The efficiency of the process was measured over time, revealing the contribution of side reactions in the cathodic half-cell, particularly during the initial stages of the electroless process.

Can the semiempirical PM3 scheme describe iron‐containing bioinorganic molecules?

A set of iron parameters for use in the semiempirical PM3 method have been developed to allow the structure and redox properties of the active sites of iron‐containing proteins to be accurately modeled, focussing on iron–sulfur, iron–heme, and iron‐only hydrogenases. Data computed at the B3LYP/6‐31G* level for a training set of 60 representative complexes have been employed. A gradient‐based optimization algorithm has been used, and important modifications of the core repulsion function have been highlighted. The derived parameters lead in general to good predictions of the structure and energetics of molecules both within and outside the training set, and overcome the extensive deficiencies of a B3LYP/STO‐3G model. Particularly encouraging is the success of the parameters in describing [4Fe‐4S] cubanes. The derived parameter set provides a starting point should greater accuracy for a more restricted range of compounds be required.

Helical paths, gravitaxis, and separation phenomena for mass-anisotropic self-propelling colloids : Experiment versus theory

The self-propulsion mechanism of active colloidal particles often generates not only translational but also rotational motion. For particles with an anisotropic mass density under gravity, the motion is usually influenced by a downwards oriented force and an aligning torque. Here we study the trajectories of self-propelled bottom-heavy Janus particles in three spatial dimensions both in experiments and by theory. For a sufficiently large mass anisotropy, the particles typically move along helical trajectories whose axis is oriented either parallel or antiparallel to the direction of gravity (i.e., they show gravitaxis). In contrast, if the mass anisotropy is small and rotational diffusion is dominant, gravitational alignment of the trajectories is not possible. Furthermore, the trajectories depend on the angular self-propulsion velocity of the particles. If this component of the active motion is strong and rotates the direction of translational self-propulsion of the particles, their trajectories have many loops, whereas elongated swimming paths occur if the angular self-propulsion is weak. We show that the observed gravitational alignment mechanism and the dependence of the trajectory shape on the angular self-propulsion can be used to separate active colloidal particles with respect to their mass anisotropy and angular self-propulsion, respectively.

A Pickering Emulsion Route to Swimming Active Janus Colloids

Abstract 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.