Active self-assembly of colloidal machines with passive rotational parts via coordination of phoresis and osmosis.

The organization of microscopic objects into specific structures with movable parts is a prerequisite for building sophisticated micromachines with complex functions, as exemplified by their macroscopic counterparts. Here we report the self-assembly of active and passive colloids into micromachinery with passive rotational parts. Depending on the attachment of the active colloid to a substrate, which varies the degrees of free freedom of the assembly, colloidal machines with rich internal rotational dynamics are realized. Energetic analysis reveals that the energy efficiency increases with the degrees of freedom of the machine. The experimental results can be rationalized by the cooperation of phoretic interaction and osmotic flow encoded in the shape of the active colloid, which site-specifically binds and exerts a torque to passive colloids, supported by finite element calculations and mesoscale simulations. Our work offers a new design principle that utilizes nonequilibrium interfacial phenomena for spontaneous construction of multiple-component reconfigurable micromachinery.

Fabrication of three-lobed magnetic microrobots for cell transportation.

Mobile microrobots have the potential to transform medical treatments based on therapeutic delivery. Specifically, microrobots are promising candidates for cell transportation in cell-based therapies. Despite recent progress in cellular manipulation by microrobots, there is a significant need to design and fabricate microrobots to advance the field further. In this work, we present a facile approach to manufacturing three-lobed microrobots by a bench-top procedure. The microrobots are actuated by a harmless magnetic field which makes them biofriendly. Chemically, these microrobots are made of organosilica. The microrobots showed equally good control in both the open-loop and closed-loop settings. The three-lobed microrobots have two modes of motion during the open-loop control experiments. We employed these two modes for single-cell transportation. Our results show that the three-lobed microbots are very promising for cell transportation in a fluid.

Fabrication and open-loop control of three-lobed nonspherical Janus microrobots.

In this study, we propose a simple and efficient method to fabricate three-lobed nonspherical Janus microrobots. These microrobots can be actuated by a harmless magnetic field. Utilizing organosilica as the material of choice, we leverage its versatile silane chemistry to enable various surface modifications and functionalities. The fabricated microrobots demonstrate two distinct modes of motion, making them well-suited for cell transportation and drug delivery tasks. Their unique shape and motion characteristics allow for precise and targeted movement. Integrating these microrobots into therapeutic delivery platforms can revolutionize medical treatments, offering enhanced precision, efficiency, and versatility in delivering therapies to specific sites.

Multistimuli-responsive microrobots: A comprehensive review.

Untethered robots of the size of a few microns have attracted increasing attention for the potential to transform many aspects of manufacturing, medicine, health care, and bioengineering. Previously impenetrable environments have become available for high-resolution in situ and in vivo manipulations as the size of the untethered robots goes down to the microscale. Nevertheless, the independent navigation of several robots at the microscale is challenging as they cannot have onboard transducers, batteries, and control like other multi-agent systems, due to the size limitations. Therefore, various unconventional propulsion mechanisms have been explored to power motion at the nanoscale. Moreover, a variety of combinations of actuation methods has also been extensively studied to tackle different issues. In this survey, we present a thorough review of the recent developments of various dedicated ways to actuate and control multistimuli-enabled microrobots. We have also discussed existing challenges and evolving concepts associated with each technique.

Inorganic-Organic Hybrid Copolymeric Colloids as Multicolor Emission, Fuel-Free, UV- and Visible-Light-Actuated Micropumps.

Light-actuated micromachines are of enormous interest due to their ability to harvest light for triggering catalytic reactions to acquire free energy for mechanical work. This work presents an inorganic-organic hybrid copolymeric poly(cyclotriphosphazene-co-barbituric acid) colloid, which displays multiwavelength excited emission and catalytic activities, exploiting the unique structural, chemical, and optical features of inorganic heterocyclic ring hexachlorocyclotriphosphazene and organic co-monomer barbituric acid. Specifically, this work reveals particle-resolved unusual multicolor emission under excitation with the same or different wavelengths of light using fluorescence microscopy. The result is rationalized by density functional theory studies. In this work, the authors find that emission is coincident with fluorometric measurements, and the photocatalytic properties are anticipated from the overall band structure. This work also demonstrates the use of these colloids as micropumps, which can be remotely activated by UV, blue, and green lights under fuel-free conditions, and ascribe the behavior to ionic diffusiophoresis arising from light-triggered generation of H+ and other charged species. This work offers a new class of polymeric colloids with multiple-wavelength excited emission and catalytic activities, which is expected to open new opportunities in the design of fuel-free, photo-actuated micromachines and active systems.

Ionic Effects in Ionic Diffusiophoresis in Chemically Driven Active Colloids.

We study experimentally the effect of added salt in the phoretic motion of chemically driven colloidal particles. We show that the response of passive colloids to a fixed active colloid, be it attractive or repulsive, depends on the ionic strength, the ζ potential, and the size of the passive colloids. We further report that the direction of self-propulsion of Janus colloids can be reversed by decreasing their ζ potential below a critical value. By constructing an effective model that treats the colloid and ions as a whole subjected to the concentration field of generated ions and takes into account the joint effect of both generated and background ions in determining the Debye length, we demonstrate that the response of the passive colloids and the velocity of the Janus colloids can be quantitatively captured by this model under the ionic diffusiophoresis theory beyond the infinitely-thin-double-layer limit.

Magnetic Manipulation and Assembly of Nonmagnetic Colloidal Rods in a Ferrofluid.

We investigated experimentally and theoretically the interactions and assembly of rodlike colloids in a ferrofluid confined at solid/liquid interface by the gravity under external magnetic fields. We first derived analytical expressions for the interaction energy of a single rod with the external magnetic field and the interaction between two rods using classical electromagnetism. The theory well captured the experimentally observed alignment of a single rod along the field direction under an in-plane field and switching between the horizontal and the vertical configurations in an out-of-plane field due to the competition between the magnetic energy and the gravitational energy. The theory can also predict the symmetric position fluctuations of a free rod on a fixed one at 90° and the gradual bias toward the end of the fixed rod as the angle was reduced to 0°, favoring the tip-toe arrangement. Finally, we showed that this anisotropic interaction led to the formation of chain-like structures, whose growth kinetics followed a simple scaling behavior with time. This work provides a theoretical framework for understanding the behaviors of rodlike colloids in ferrofluids and highlights the importance of shape anisotropy in manipulating colloids and their self-assembly.

Highly efficient chemically-driven micromotors with controlled snowman-like morphology.

We report the synthesis of silver-based Janus micromotors that self-propel at 3.5 µm s-1 and speed up to 45 µm s-1 in 0.044 and 1.5 mM of H2O2, respectively, via ionic diffusiophoresis. Morphology optimization further accelerates the speed to 90 µm s-1, which leads to a force of 1 pN and a power of 0.1 fW, similar to biomolecular motors. Their efficiency reaches 10-5, at least two orders of magnitude higher than other chemically-driven micromotors. These micromotors hold great promises in various applications.

Design and One-Pot Synthesis of Capsid-like Gold Colloids with Tunable Surface Roughness and Their Enhanced Sensing and Catalytic Performances.

Viral capsid-like particles tiled with mosaic patches have attracted great attention as they imitate nature's design to achieve advanced material properties and functions. Here, we develop a facile one-pot soft-template method to synthesize biomimetic gold capsid-like colloids with tunable particle size and surface roughness. Uniform submicron-to-micron-sized hollow gold colloidal particles are successfully achieved by using tannic acids as soft templates and reducing agents, which first self-assemble into spherical complex templates before the reduction of Au3+ ions via their surface hydroxyl groups. The surface roughness, the size, and the total number of the patches of the prepared gold particles are further tuned, utilizing a mechanism that offers morphology control by varying the number of surface hydroxyl groups participating in the reduction reactions. Among different capsid-like gold colloids, those possessing a rough surface display superior catalytic properties and show promising results as surface-enhanced Raman spectroscopy (SERS) solid substrates for detecting small organic molecules and biomimetic enzymes in a liquid phase for sensing biomolecules in real samples. These capsid-like gold colloids are also expected to find practical applications in delivery systems, electronics, and optics. We believe that our strategy of imitating nature's design of capsid-like structures should also be used in the design and fabrication of other functional colloidal particles.

PtNi/NiO Clusters Coated by Hollow Sillica: Novel Design for Highly Efficient Hydrogen Production from Ammonia-Borane.

Ammonia-borane (NH3·BH3; AB) has been considered as an excellent chemical material for hydrogen storage. However, developing highly efficient catalysts for continuous hydrogen generation from AB is still a challenge for future fuel cell applications. The combination of Pt with Ni is an effective strategy to achieve active bimetallic nanocatalyst, and the particle size has proved to play a crucial role in determining its final activity. However, the synthesis of PtNi bimetallic catalyst in the size of highly dispersed clusters has always been a challenge. In this report, PtNi/NiO clusters coated by small-sized hollow silica (R-PtNi/NiO@SiO2) were designed for efficient hydrogen generation from the hydrolysis of ammonia-borane. The newly designed catalysis system showed extremely high activity with the initial turnover frequency value reaching 1240.3 mol of H2·mol-1 of Pt·min-1, which makes it one the most active Pt-based catalysts for this reaction. Detailed characterization by means of scanning transmission electron microscopy, X-ray photoelectron spectroscopy, energy-dispersive X-ray spectroscopy element mapping, etc. revealed that the excellent performance of R-PtNi/NiO@SiO2 is derived from the highly dispersed PtNi/NiO clusters and the reduction of extra Pt4+ on the surface of PtNi/NiO clusters to Pt0 at relatively low temperature.

Highly efficient silica coated CuNi bimetallic nanocatalyst from reverse microemulsion.

Silica protected CuNi bimetallic nanoparticles (CuNi@SiO2) were successfully prepared by a modified co-reduction method. Typically, ammoniacal Cu(II) and Ni(II) were firstly dispersed and encapsulated inside silica by the method of reverse microemulsion. Then, ultra small CuO and NiO particles were in-situ formed during calcination under air. CuNi bimetallic nanoparticles were obtained by the co-reduction of CuO and NiO under H2 at high temperature. The composition and size of CuNi bimetallic nanoparticles was tuned simply by varying the concentration of precursor solutions. The samples were characterized by FT-IR, TEM, XPS, XRD and ICP-OES. The reduction of p-nitrophenol by NaBH4 was chosen as model reaction to evaluate the catalytic activity. The results indicate that CuNi bimetallic nanoparticles prepared by our method show size and composition dependent catalytic activity. The activation energy of Cu54Ni46@SiO2 for the same reaction was calculated as to be 16.6kJ/mol which was much lower than that of Cu@SiO2 (29.0kJ/mol) and Ni@SiO2 (39.5kJ/mol).

Chloride capping of CdTiO3 for higher crystallinity and enhanced photocatalytic activity.

The crystallinity of cadmium titanate (CdTiO3) was greatly improved when synthesized under mild reaction conditions, in the presence of chloride. The highly crystalline CdTiO3 showed much enhanced photodegradation of methyl orange (MO) under simulated sunlight. CdTiO3 was characterized using X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), N2 adsorption/desorption, photoluminescence (PL), and UV/vis spectrometry. The enhanced photodegradation was attributed to the better charge separation owing to its higher crystallinity.

In Situ Encapsulation of Ultrasmall CuO Quantum Dots with Controlled Band-Gap and Reversible Thermochromism.

Silica encapsulated ultrasmall CuO quantum dots (QDs; CuO@SiO2) were synthesized by reverse microemulsion. The CuO QDs with sizes ranging from 2.0 to 1.0 nm with corresponding band gaps of 1.4 to 2.6 eV were prepared simply by varying the concentration of the Cu(2+) precursor. The samples were characterized by Fourier transform infrared spectroscopy (FT-IR), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), and UV-vis spectroscopy. The CuO@SiO2 composite displayed reversible thermochromism which resulted from the strong electron-phonon coupling of ultrasmall CuO in the confined space of SiO2 and the enhanced band-gap shift in the visible light region depending on temperature. Besides, the as synthesized CuO@SiO2 was found to be highly stable for reversible thermochromism due to the micropore structure of silica matrix and local confinement of the QDs.

Silica-based nanocomposites via reverse microemulsions: classifications, preparations, and applications.

Silica-based nanocomposites with amorphous silica as the matrix or carrier along with a functional component have been extensively investigated. These nanocomposites combine the advantages of both silica and the functional components, demonstrating great potential for various applications. To synthesize such composites, one of the most frequently used methods is reverse microemulsion due to its convenient control over the size, shape, and structures. The structures of the composites have a decisive significance for their properties and applications. In this review, we tried to categorize the silica-based nanocomposites via reverse microemulsions based on their structures, discussed the syntheses individually for each structure, summarized their applications, and made some perspectives based on the current progress of this field.