Autonomous engulfment of active colloids by giant lipid vesicles.

Our ability to design artificial micro/nanomachines able to perform sophisticated tasks crucially depends on our understanding of their interaction with biosystems and their compatibility with the biological environment. Here, we design Janus colloids fuelled only by glucose and light, which can autonomously interact with cell-like compartments and trigger endocytosis. We evidence the crucial role played by the far-field hydrodynamic interaction arising from the puller/pusher swimming mode and adhesion. We show that a large contact time between the active particle and the lipid membrane is required to observe the engulfment of a particle inside a floppy giant lipid vesicle. Active Janus colloids showing relatively small velocities and a puller type swimming mode are able to target giant vesicles, deform their membranes and subsequently get stably engulfed. An instability arising from the unbound membrane segment is responsible for the transition between partial and complete stable engulfment. These experiments shed light on the physical criteria required for autonomous active particle engulfment in giant vesicles, which can serve as general principles in disciplines ranging from drug delivery and microbial infection to nanomedicine.

An Account on BiVO4 as Photocatalytic Active Matter.

Photocatalytic materials are gaining popularity and research investment for developing light-driven micromotors. While most of the early work used highly stable TiO2 as a material to construct micromotors, mostly in combination with noble metals, other semiconductors offer a wider range of properties, including independence from high-energy UV light. This review focuses on our work with BiVO4 which has shown promise due to its small band gap and resulting ability to absorb blue light. Additionally, this salt's well-defined crystal structures lead to exploitable charge separation on different crystal facets, providing sufficient asymmetry to cause active propulsion. These properties have given rise to fascinating physical and chemical behaviors that show how rich and variable active matter can become. Here, we present the synthesis of different BiVO4 microparticles and their material properties that make them excellent candidates as active micromotors. A critical factor in understanding inherently asymmetric micromotors is knowledge of their flow fields. However, due to their small size and the need to use even smaller tracer particles to avoid perturbing the flow field, measuring flow fields at the microscale is a difficult task. We also present these first results, which allow us to demonstrate the correlation between chemical reactivity and the flow generated, leading to active motion. Due to the nontoxic nature of BiVO4, these visible-light-responsive microswimmers have been used to study the first steps toward applications, even in sensitive areas such as food technology. Although these initial tests are far from being realized, we have to face the fact that a single microswimmer will not be able to perform macroscale tasks. Therefore, we present the reader with the first simple studies of collective motion, hoping for many new contributions to the field. The one-step synthesis of BiVO4 clearly paves the way for studies requiring large numbers of particles. We predict that the combination of promising applications for a nontoxic material which is readily synthesized in large quantities will contribute pivotally to advance the field of active matter beyond the proof-of-concept stage.

Active BiVO4 Swimmers Propelled by Depletion Gradients Caused by Photodeposition.

Artificial active matter often self-propels by creating gradients of one or more species or quantities. For chemical swimmers, most frequently either O2 or H+ that are created in certain catalytic reactions are causing the interfacial flows which drive the self-propulsion. While the palette of reactions is extending constantly, especially toward more bio-compatible fuels, the depletion of species is often overlooked. Here, the photodeposition of metal species on BiVO4 micro swimmers is considered. During the photodeposition reaction, metal ions are removed from the solution creating a depleted region around the particle. The ability of this depletion to drive active motion of artificial micro swimmers, as well as the influences of different metal ions and counter ions on the motion are investigated and cross compared.

Beyond Janus Geometry: Characterization of Flow Fields around Nonspherical Photocatalytic Microswimmers.

Catalytic microswimmers that move by a phoretic mechanism in response to a self-induced chemical gradient are often obtained by the design of spherical janus microparticles, which suffer from multi-step fabrication and low yields. Approaches that circumvent laborious multi-step fabrication include the exploitation of the possibility of nonuniform catalytic activity along the surface of irregular particle shapes, local excitation or intrinsic asymmetry. Unfortunately, the effects on the generation of motion remain poorly understood. In this work, single crystalline BiVO4 microswimmers are presented that rely on a strict inherent asymmetry of charge-carrier distribution under illumination. The origin of the asymmetrical flow pattern is elucidated because of the high spatial resolution of measured flow fields around pinned BiVO4 colloids. As a result the flow from oxidative to reductive particle sides is confirmed. Distribution of oxidation and reduction reactions suggests a dominant self-electrophoretic motion mechanism with a source quadrupole as the origin of the induced flows. It is shown that the symmetry of the flow fields is broken by self-shadowing of the particles and synthetic surface defects that impact the photocatalytic activity of the microswimmers. The results demonstrate the complexity of symmetry breaking in nonspherical microswimmers and emphasize the role of self-shadowing for photocatalytic microswimmers. The findings are leading the way toward understanding of propulsion mechanisms of phoretic colloids of various shapes.

Microswimming by oxidation of dibenzylamine.

Chemiophoretic nano- and micromotors require a constant flow of product molecules to maintain a gradient that enables their propulsion. Apart from a smaller number of redox reactions that have been used, catalytic reactions are the main source of energy with the obvious benefit of making on-board fuel storage obsolete. However, the decomposition of H2O2 seems to strongly dominate the literature and although motion in H2O through water splitting is becoming more popular, so far only a few different reactions have been used for propulsion of photocatalytic microswimmers. Here, we investigate the possibility of extending the range of possible fuelling reactions to organic reactions with high significance in organic synthesis - the oxidation of amines to imines. Herein, motion of the microswimmers is analysed at different amine concentrations and light intensities. The findings thereof are correlated with the reaction products identified and quantified by gas chromatography (GC).

Semiconductor-Based Microswimmers: Attention to Detail Matters.

Colloidal active matter is known for its sensitivity to external conditions; for example, the swimming speeds depend strongly on substrates, fuel concentration, and in the case of light-driven colloids, the illumination. While these points are regularly considered, the nanoscopic material properties of the motor bodies are often barely mentioned, but they are highly influential in the case of photocatalysts. In order to demonstrate the influence of subtle differences in chemical composition and interfacing between the different material compounds, we designed a system based on colloidal titania spheres asymmetrized by different nanoscale cobalt oxide species. We examine how the material properties and combinations lead to highly specific catalytic activity and cross-relate the subtle differences to the typical active behaviors of these complex materials.

Active spheres induce Marangoni flows that drive collective dynamics.

For monolayers of chemically active particles at a fluid interface, collective dynamics is predicted to arise owing to activity-induced Marangoni flow even if the particles are not self-propelled. Here, we test this prediction by employing a monolayer of spherically symmetric active [Formula: see text] particles located at an oil-water interface with or without addition of a nonionic surfactant. Due to the spherical symmetry, an individual particle does not self-propel. However, the gradients produced by the photochemical fuel degradation give rise to long-ranged Marangoni flows. For the case in which surfactant is added to the system, we indeed observe the emergence of collective motion, with dynamics dependent on the particle coverage of the monolayer. The experimental observations are discussed within the framework of a simple theoretical mean-field model.