Orbits, Spirals, and Trapped States: Dynamics of a Phoretic Janus Particle in a Radial Concentration Gradient.

A long-standing goal in colloidal active matter is to understand how gradients in fuel concentration influence the motion of phoretic Janus particles. Here, we present a theoretical description of the motion of a spherical phoretic Janus particle in the presence of a radial gradient of the chemical solute driving self-propulsion. Radial gradients are a geometry relevant to many scenarios in active matter systems and naturally arise due to the presence of a point source or sink of fuel. We derive an analytical solution for the Janus particle's velocity and quantify the influence of the radial concentration gradient on the particle's trajectory. Compared to a phoretic Janus particle in a linear gradient in fuel concentration, we uncover a much richer set of dynamic behaviors including circular orbits and trapped stationary states. We identify the ratio of the phoretic mobilities between the two domains of the Janus particle as a central quantity in tuning their dynamics. Our results provide a path for developing optimum protocols for tuning the dynamics of phoretic Janus particles and mixing fluid at the microscale. In addition, this work suggests a method for quantifying the surface properties of phoretic Janus particles, which have proven to be challenging to probe experimentally.

Controlled Surface Textures of Elastomeric Polyurethane Janus Particles: A Comprehensive Review.

Colloidal particle research has witnessed significant advancements in the past century, resulting in a plethora of studies, novel applications, and beneficial products. This review article presents a cost-effective and low-tech method for producing Janus elastomeric particles of varied geometries, including planar films, spherical particles, and cylindrical fibers, utilizing a single elastomeric material and easily accessible chemicals. Different surface textures are attained through strain application or solvent-induced swelling, featuring well-defined wavelengths ranging from sub-microns to millimeters and offering easy adjustability. Such versatility renders these particles potentially invaluable for medical applications, especially in bacterial adhesion studies. The coexistence of "young" regions (smooth, with a small surface area) and "old" regions (wrinkled, with a large surface area) within the same material opens up avenues for biomimetic materials endowed with additional functionalities; for example, a Janus micromanipulator where micro- or nano-sized objects are grasped and transported by an array of wrinkled particles, facilitating precise release at designated locations through wrinkle pattern adjustments. This article underscores the versatility and potential applications of Janus elastomeric particles while highlighting the intriguing prospects of biomimetic materials with controlled surface textures.

Biocompatible Janus microparticle synthesis in a microfluidic device.

Janus particles are popular in recent years due to their anisotropic physical and chemical properties. Even though there are several established synthesis methods for Janus particles, microfluidics-based methods are convenient and reliable due to low reagent consumption, monodispersity of the resultant particles and efficient control over reaction conditions. In this work a simple droplet-based microfluidic technique is utilized to synthesize magnetically anisotropic TiO2-Fe2O3 Janus microparticles. Two droplets containing reagents for Janus particle were merged by using an asymmetric device such that the resulting droplet contained the constituents within its two hemispheres distinct from each other. The synthesized Janus particles were observed under the optical microscope and the scanning electron microscope. Moreover, a detailed in vitro characterization of these particles was completed, and it was shown that these particles have a potential use for biomedical applications.

Characterizing self-assembled structures made with magnetic Janus nanoparticles.

Small-angle X-ray scattering has revealed how magnetic Janus particles pair up in solutions in small and large magnetic fields.

PAA-PU Janus Hydrogels Stabilized by Janus Particles and its Interfacial Performance During Hemostatic Processing.

Hydrogel is a very promising dressing for hemostasis and wound healing due to its good adhesion and long-term moist environment. However, secondary injury caused by tissue adhesion due to homogeneous hydrogel cannot be ignored. The obvious interface existing in Janus hydrogel will weaken its asymmetric function. Here, a hierarchical adhesive polyacrylic acid-polyurushiol water-oil Janus hydrogel (JPs@PAA-PU) without adhesive layer is fabricated by one-pot method in the stabilization of polystyrene@silica-siliver Janus particles (JPs). The morphological structure, mechanical properties, anisotropic chemical composition, and adhesion performance, in vivo, and in vitro hemostatic properties of Janus hydrogel are investigated. Result shows that the obtained Janus hydrogel possesses obvious compartmentalization in microstructure, functional groups, and chemical elements. Janus hydrogel is provided with asymmetric interfacial toughness with top 52.45 ± 2.29 Kpa and bottom 7.04 ± 0.88 Kpa on porcine liver. The adhesion properties of PAA side to tissue, red blood cells and platelets, promoting effect of PU side on coagulation cascade reaction and its physical battier endow Janus hydrogel with shorter hemostatic time and less blood loss than control group. It also exhibits excellent antibacterial effects against Escherichia coli and Staphylococcus aureus (>90%). Janus hydrogel possesses biosafety, providing safety guarantee for clinical applications in the future.

Urease-Powered Black TiO2 Micromotors for Photothermal Therapy of Bladder Cancer.

Urease-powered nano/micromotors can move at physiological urea concentrations, making them useful for biomedical applications, such as treating bladder cancer. However, their movement in biological environments is still challenging. Herein, Janus micromotors based on black TiO2 with urease asymmetric catalytic coating were designed to take benefit of the optical properties of black TiO2 under near-infrared light and the movement capability in simulated bladder environments (urea). The black TiO2 microspheres were half-coated with a thin layer of Au, and l-Cysteine was utilized to attach the urease enzyme to the Au surface using its thiol group. Biocatalytic hydrolysis of urea through urease at biologically relevant concentrations provided the driving force for micromotors. A variety of parameters, such as urea fuel concentration, viscosity, and ionic character of the environment, were used to investigate how micromotors moved in different concentrations of urea in water, PBS, NaCl, and urine. The results indicate that micromotors are propelled through ionic self-diffusiophoresis caused by urea enzymatic catalysis. Due to their low toxicity and in vitro anticancer effect, micromotors are effective agents for photothermal therapy, which can help kill bladder cancer cells. These promising results suggest that biocompatible micromotors hold great potential for improving cancer treatment and facilitating diagnosis.

Tadpole-Like Anisotropic Polymer/Lipid Janus Nanoparticles for Nose-to-Brain Drug Delivery: Importance of Geometry, Elasticity on Mucus-Penetration Ability.

Asymmetric geometry (aspect ratio >1), moderate stiffness (i.e., semielasticity), large surface area, and low mucoadhesion of nanoparticles are the main features to reach the brain by penetrating across the nasal mucosa. Herein, a new application has been presented for the use of multifunctional Janus nanoparticles (JNPs) with controllable geometry and size as a nose-to-brain (N2B) delivery system by changing proportions of Precirol ATO 5 and polycaprolactone compartments and other operating conditions. To bring to light the N2B application of JNPs, the results are presented in comparison with polymer and solid lipid nanoparticles, which are frequently used in the literature regarding their biopharmaceutical aspects: mucoadhesion and permeability through the nasal mucosa. The morphology and geometry of JPs were observed via cryogenic-temperature transmission electron microscopy images, and their particle sizes were verified by dynamic light scattering, atomic force microscopy, and scanning electron microscopy. Although all NPs showed penetration across the mucus barrier, the best increase in penetration was observed with asymmetric and semielastic JNPs, which have low interaction ability with the mucus layer. This study presents a new and promising field of application for a multifunctional system suitable for N2B delivery, potentially benefiting the treatment of brain tumors and other central nervous system diseases.

Self-Assembly Pathways of Triblock Janus Particles into 3D Open Lattices.

The self-assembly of triblock Janus particles is simulated from a fluid to 3D open lattices: pyrochlore, perovskite, and diamond. The coarse-grained model explicitly takes into account the chemical details of the Janus particles (attractive patches at the poles and repulsion around the equator) and it contains explicit solvent particles. Hydrodynamic interactions are accounted for by dissipative particle dynamics. The relative stability of the crystals depends on the patch width. Narrow, intermediate, and wide patches stabilize the pyrochlore-, the perovskite-, and the diamond-lattice, respectively. The nucleation of all three lattices follows a two-step mechanism: the particles first agglomerate into a compact and disordered liquid cluster, which does not crystallize until it has grown to a threshold size. Second, the particles reorient inside this cluster to form crystalline nuclei. The free-energy barriers for the nucleation of pyrochlore and perovskite are ≈10 kBT, which are close to the nucleation barriers of previously studied 2D kagome lattices. The barrier height for the nucleation of diamond, however, is much larger (>20 kBT), as the symmetry of the triblock Janus particles is not perfect for a diamond structure. The large barrier is associated with the reorientation of particles, i.e., the second step of the nucleation mechanism.

Features of Anisotropic Drug Delivery Systems.

Natural materials are anisotropic. Delivery systems occurring in nature, such as viruses, blood cells, pollen, and many others, do have anisotropy, while delivery systems made artificially are mostly isotropic. There is apparent complexity in engineering anisotropic particles or capsules with micron and submicron sizes. Nevertheless, some promising examples of how to fabricate particles with anisotropic shapes or having anisotropic chemical and/or physical properties are developed. Anisotropy of particles, once they face biological systems, influences their behavior. Internalization by the cells, flow in the bloodstream, biodistribution over organs and tissues, directed release, and toxicity of particles regardless of the same chemistry are all reported to be factors of anisotropy of delivery systems. Here, the current methods are reviewed to introduce anisotropy to particles or capsules, including loading with various therapeutic cargo, variable physical properties primarily by anisotropic magnetic properties, controlling directional motion, and making Janus particles. The advantages of combining different anisotropy in one entity for delivery and common problems and limitations for fabrication are under discussion.

Orientational ordering and assembly of silica-nickel Janus particles in a magnetic field.

The orientation ordering and assembly behavior of silica-nickel Janus particles in a static external magnetic field were probed by ultra small-angle X-ray scattering (USAXS). Even in a weak applied field, the net magnetic moments of the individual particles aligned in the direction of the field, as indicated by the anisotropy in the recorded USAXS patterns. X-ray photon correlation spectroscopy (XPCS) measurements on these suspensions revealed that the corresponding particle dynamics are primarily Brownian diffusion [Zinn, Sharpnack & Narayanan (2023). Soft Matter, 19, 2311-2318]. At higher fields, the magnetic forces led to chain-like configurations of particles, as indicated by an additional feature in the USAXS pattern. A theoretical framework is provided for the quantitative interpretation of the observed anisotropic scattering diagrams and the corresponding degree of orientation. No anisotropy was detected when the magnetic field was applied along the beam direction, which is also replicated by the model. The method presented here could be useful for the interpretation of oriented scattering patterns from a wide variety of particulate systems. The combination of USAXS and XPCS is a powerful approach for investigating asymmetric colloidal particles in external fields.

Solidification-Controlled Compartmentalization of Bismuth-Tin Colloidal Particles.

Nucleation and growth are the main steps of microstructure formation. Nucleation occurs stochastically in a bulk material but can be controlled by introducing or removing catalytic sites, or creating local gradients. Such manipulations can already be implemented to bulk materials at a high level of sophistication but are still challenging on micrometer or smaller scales. Here, we explore the potential to transfer this vast knowledge in classical metallurgy to the fabrication of colloidal particles and report strategies to control phase distribution within a particle by adjusting its solidification conditions. Benefiting from the core-shell structure of liquid metals and the constrained volume of particles, we demonstrate that the same alloy particle can be transformed into a lamellar, composite, Janus, or striped particle by the felicitous choice of the phase separation process pathway. This methodology offers an unprecedented opportunity for the scalable production of compartmentalized particles in high yields that are currently limited to inherently unscalable methods.

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.

Preparation of Non-Spherical Janus Particles via an Orthogonal Dissolution Approach.

Post-synthesis modifications are valuable tools to alter functionalities and induce morphology changes in colloidal particles. Non-spherical polymer particles with Janus characteristics are prepared by combining seeded growth polymerization and selective dissolution. First, spherical polystyrene (PS) particles have been swollen with methyl methacrylate (MMA) with an activated swelling method. This is followed by polymerization that led to particles with two well-separated faces: one made of PS and the second of polymethyl methacrylate (PMMA). Subsequently, non-spherical particles are obtained by exposing the Janus colloids to various solvents. Using the two polymers' orthogonal solubility, solvents are identified to selectively dissolve only one face, leading to hemispherical PS or PMMA particles. It is further investigated how changing the composition of the PMMA face - by either co-polymerization with glycidyl methacrylate or by adding a cross-linker - affects the particles' morphology. The poly-methacrylate face can gain total or partial resistance towards the solvents, resulting in intriguing shapes, such as mushroom-like and Janus dimpled particles. The dissolution mechanisms are investigated via optical microscopy, where total or partial dissolutions can be directly observed. Lastly, prematurely quenching the dissolution of the particle's lobes with water can be used to control the Janus mushroom-like particle aspect ratio.

Spatial Precision Tailoring the Catalytic Activity of Graphene Monolayers for Designing Janus Swimmers.

Graphene monolayers have interesting applications in many fields due to their intrinsic physicochemical properties, especially when they can be postmodified with high precision. Herein, we describe the highly site-selective functionalization of freestanding graphene monolayers with platinum (Pt) clusters by bipolar electrochemistry. The deposition of such metal spots leads to catalytically active hybrid two-dimensional (2D) nanomaterials. Their catalytic functionality is illustrated by the spatially controlled decomposition of hydrogen peroxide, inducing motion at the water/air interface due to oxygen bubble evolution. A series of such 2D Janus structures with Pt deposition at predefined positions (corners and edges) is studied with respect to the generation of autonomous motion. The type and speed of motion can be fine-tuned by controlling the deposition time and location of the Pt clusters. These proof-of-principle experiments indicate that this type of hybrid 2D object opens up interesting perspectives in terms of applications, such as environmental detection or remediation.

Janus Composite Particles and Interfacial Catalysis Thereby.

Janus composite particles (JPs) with distinct compartmentalization of varied components thus performances and anisotropic shape display a variety of properties and have demonstrated great potentials in diversify practical applications. Especially, the catalytic JPs are advantageous for multi-phase catalysis with much easier separation of products and recycling the catalysts. In the first section of this review, typical methods to synthesize the JPs with varied morphologies are briefly surveyed in the category of polymeric, inorganic and polymer/inorganic composite. In the main section, recent progresses of the JPs in emulsion interfacial catalysis are summarized covering organic synthesis, hydrogenation, dye degradation, and environmental chemistry. The review will end by calling more efforts toward precision synthesis of catalytic JPs at large scale to meet the stringent requirements in practical applications such as catalytic diagnosis and therapy by the functional JPs.

Starch-based Janus particle: Fabrication, characterization and interfacial properties in stabilizing Pickering emulsion.

Janus particles (J-OSPs) based on the composite of chitosan nanoparticles (CSNPs) and octadecenyl succinic anhydride starch (OSPs) were tailor-made by Pickering emulsion method and electrostatic interaction. With different positions of OSPs embedded in the oil phase of Pickering emulsion template and the diversified shapes of starch particles, J-OSPs exhibited various asymmetric structures, which was verified by scanning electron microscope (SEM) and confocal laser microscope (CLSM). By characterizing the interfacial characteristics of J-OSPs, directional distribution of CSNPs was found to enhance the hydrophobicity of J-OSPs and changed its surface charges from positive to negative as pH increased. When J-OSPs were taken as stabilizers, the formed Pickering emulsion had the highest emulsion index and viscosity compared with OSPs and OSPs fully covered by CSNPs (F-OSPs), which was attributed to the self-assembly property of Janus particles that enabled them to form larger aggregates to hinder the collapse of droplets. This study provides a new idea for the construction of plant-derived Janus particles, and its superiority in stabilizing the Pickering emulsion will broaden the application of Janus particles in the field of storage and delivery of active substances.

Antibacterial activity of CuO-Ag Janus like nanoparticles against recombinant strain Escherichia coli.

The toxic action of CuO-Ag Janus particles and a bicomponent mixture of CuO and Ag particles have been studied against a recombinant strain Escherichia coli K12 TG1 with cloned luxCDABE genes of marine bacteria Photobacterium leiognathi 54D10. An original method was used for the preparation CuO-Ag Janus like  nanoparticles by simultaneous electrical explosion of twisted Cu and Ag wires in a mixture of argon and oxygen gases. The bioluminescence inhibition on recombinant strain E. coli shows that CuO-Ag Janus NPs were effective. The concentration by 50% (EC50) for CuO-Ag Janus NPs was 0.03 ± 0.001 mg/ml (p < 0.05). The bioactivity of the bicomponent mixture of CuO and Ag NPs (EC50) was 0.25 ± 0.002 mg/ml (p < 0.05). The effective concentration of CuO-Ag Janus NPs against E. coli was comparatively lower than those of bicomponent mixture CuO and Ag against which explains the higher activity of CuO-Ag Janus NPs. The toxicity values of CuO and Ag as monocomponent nanoparticles were 2-32 times lower compared with the bicomponent nanoparticles. A dose-dependent inhibition of bacterial luminescence developed over time was noted. The result of contact E. coli with CuO-Ag Janus particles was 100% suppression of bacterial luminescence from the first minutes of contact occured starting with a content of 2.0 mg/ml and within the next 180 min. The effect of bioactivity prolonged in the final concentration of nanopowder (EC100 = 0.0625 ± 0.002 mg/ml) (p < 0.05). CuO-Ag Janus particles exhibited more pronounced antibacterial activity compared to CuO, Ag nanoparticles and their mechanical mixture.

Hybrid Nanoparticles at Fluid-Fluid Interfaces: Insight from Theory and Simulation.

Hybrid nanoparticles that combine special properties of their different parts have numerous applications in electronics, optics, catalysis, medicine, and many others. Of the currently produced particles, Janus particles and ligand-tethered (hairy) particles are of particular interest both from a practical and purely cognitive point of view. Understanding their behavior at fluid interfaces is important to many fields because particle-laden interfaces are ubiquitous in nature and industry. We provide a review of the literature, focusing on theoretical studies of hybrid particles at fluid-fluid interfaces. Our goal is to give a link between simple phenomenological models and advanced molecular simulations. We analyze the adsorption of individual Janus particles and hairy particles at the interfaces. Then, their interfacial assembly is also discussed. The simple equations for the attachment energy of various Janus particles are presented. We discuss how such parameters as the particle size, the particle shape, the relative sizes of different patches, and the amphiphilicity affect particle adsorption. This is essential for taking advantage of the particle capacity to stabilize interfaces. Representative examples of molecular simulations were presented. We show that the simple models surprisingly well reproduce experimental and simulation data. In the case of hairy particles, we concentrate on the effects of reconfiguration of the polymer brushes at the interface. This review is expected to provide a general perspective on the subject and may be helpful to many researchers and technologists working with particle-laden layers.

Microdynamics of active particles in defect-rich colloidal crystals.

HYPOTHESIS: Because they are self-propulsive, active colloidal particles can interact with their environment in ways that differ from passive, Brownian particles. Here, we explore how interactions in different microstructural regions may contribute to colloidal crystal annealing. EXPERIMENTS: We investigate active particles propagating in a quasi-2D colloidal crystal monolayer produced by alternating current electric fields (active-to-passive particle ratio âˆ¼ 1:720). The active particle is a platinum Janus sphere propelled by asymmetric decomposition of hydrogen peroxide. Crystals are characterized for changes in void properties. The mean-squared-displacement of Janus particles are measured to determine how active microdynamics depend on the local microstructure, which is comprised of void regions, void-adjacent regions (defined as within three particle diameters of a void), and interstitial regions. FINDINGS: At active particle energy EA = 2.55 kBT, the average void size increases as much as three times and the average void anisotropy increases about 40% relative to the passive case. The average microdynamical enhancement, <δ(t)>, of Janus particles in the crystal relative to an equivalent passive Janus particle is reduced compared to that of a free, active particle (<δ(t) > is 1.88 ± 0.04 and 2.66 ± 0.08, respectively). The concentration of active particles is enriched in void and void-adjacent regions. Active particles exhibit the greatest change in dynamics relative to the passive control in void-adjacent regions (<δ(t)> = 2.58 ± 0.06). The results support the conjecture that active particle microdynamical enhancement in crystal lattices is affected by local defect structure.

Amphiphilic Bowl-Shaped Janus Particles Prepared via Thiol-Ene Click Reaction for Effective Oil-Water Separation.

Janus particles for oil-water separation have attracted widespread attention in recent years. Herein, we prepared a bowl-shaped Janus particle that could rapidly separate oil and water through a thiol-ene click reaction and selective etching. Firstly, snowman-like composite microspheres based on silica and mercaptopropyl polysilsesquioxane (SiO2@MPSQ) were prepared by a hydrolytic condensation reaction and phase separation, and the effects of the rotational speed and molar ratios on their microscopic morphologies were investigated. Subsequently, bowl-shaped Janus particles with convex hydrophilic and concave oleophilic surfaces were prepared via a thiol-ene click reaction followed by HF etching. Our amphiphilic bowl-shaped Janus particles could remarkably separate micro-sized oil droplets from an n-heptane-water emulsion with a separation efficiency of >98% within 300 s. Based on the experimental and theoretical results, we proposed the underlying mechanism for the coalescence of oil droplets upon the addition of the amphiphilic bowl-shaped Janus particles.