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.

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.

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.

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.

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.

Janus particles: A review of their applications in food and medicine.

In contrast to conventional particles that have isotropic surfaces, Janus ("two-faced") particles have anisotropic surfaces, which leads to novel physicochemical properties and functional attributes. Janus particles with differing compositions, structures, and functional attributes have been prepared using a variety of fabrication methods. Depending on their composition, Janus particles have been classified as inorganic, polymeric, or polymeric/inorganic types. Recently, there has been growing interest in preparing Janus particles from biological macromolecules to meet the demand for a more sustainable and environmentally friendly food and pharmaceutical supply. At interfaces, Janus particles exhibit the characteristics of both surfactants and Pickering stabilizers, and so their behavior can be described using adsorption theories developed to describe these surface-active substances. Research has highlighted several potential applications of Janus particles in food and medicine, including emulsion formation and stabilization, toxin detection, antimicrobial activity, drug delivery, and medical imaging. Nevertheless, further research is needed to design and fabricate Janus particles that are suitable as functional ingredients in the food and biomedicine industries.

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.

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.

Lipid Phase Separation in Vesicles Enhances TRAIL-Mediated Cytotoxicity.

Ligand spatial presentation and density play important roles in signaling pathways mediated by cell receptors and are critical parameters when designing protein-conjugated therapeutic nanoparticles. Here, we harness lipid phase separation to spatially control the protein presentation on lipid vesicles. We use this system to improve the cytotoxicity of TNF-related apoptosis inducing ligand (TRAIL), a therapeutic anticancer protein. Vesicles with phase-separated TRAIL presentation induce more cell death in Jurkat cancer cells than vesicles with uniformly presented TRAIL, and cytotoxicity is dependent on TRAIL density. We assess this relationship in other cancer cell lines and demonstrate that phase-separated vesicles with TRAIL only enhance cytotoxicity through one TRAIL receptor, DR5, while another TRAIL receptor, DR4, is less sensitive to TRAIL density. This work demonstrates a rapid and accessible method to control protein conjugation and density on vesicles that can be adopted to other nanoparticle systems to improve receptor signaling by nanoparticles.

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.

Electrical Propulsion and Cargo Transport of Microbowl Shaped Janus Particles.

Herein the effective electrical propulsion, cargo trapping, and transport capabilities of microbowl-shaped Janus particles (JPs) are demonstrated and evaluated. These active JPs are made by deposition of Au and Ti layers onto sacrificial spherical polystyrene particles, followed by oxidation of the Ti to TiO2 . In contrast to the commonly studied spherical JP, the dual broken symmetry of both geometrical and electrical properties of the microbowl renders a strong dependence of its mobility and cargo loading on the order of the layering of Au and TiO2 . Specifically, an opposite direction of motion is obtained for interchanged layers of Au and TiO2 , using only electrical propulsion as the sole mechanism of motion. The concave side of the microbowl exhibits a negative dielectrophoretic trap of large size wherein trapped cargo is protected from hydrodynamic shearing, leading to an enhanced cargo loading capacity compared to that obtained using common spherical JP. Such enhanced cargo capability of the microbowl along with the ease of engineering it by interchanging the order of the layers are very attractive for future in vitro biological and biomedical applications.

Powering bioanalytical applications in biomedicine with light-responsive Janus micro-/nanomotors.

Possessing both unique asymmetric structures and remote-controlled active movement, light-responsive Janus micro-/nanomotors offer the possibility of breaking through the limitations of traditional biomedicine, and have fascinated and inspired researchers. Despite many obstacles toward the clinical application, impressive progress of light-responsive Janus micro-/nanomotors for bioanalytical applications has been made over the past decades. In this review, we first briefly introduced several main light-driven Janus micro-/nanomotors, then focused on their typical bioanalytical applications such as biosensing, bioimaging, and theranostic. In the end, we summarized the remaining challenges of light-responsive Janus micro-/nanomotors in the practical application and also proposed potential solutions in the future.

Janus Vitrification of Droplet via Cold Leidenfrost Phenomenon.

Janus particles with asymmetric crystals show great importance in optoelectronics and photocatalysis, but their synthesis usually requires complicated procedures. Here, an unexpected Janus vitrification phenomenon is observed in a droplet caused by the Leidenfrost effect at a cryogenic temperature, which is commonly regarded as symmetric. The Leidenfrost phenomenon levitates the droplet when it comes in contact with liquid nitrogen causing different cooling conditions on the droplet's top and bottom surfaces. It induces asymmetric crystallization in the droplet, forming a Janus vitrified particle with an asymmetric crystallization borderline after cooling, as further evidenced by cryotransmission electron microscopy (cryo-TEM) experiments. Theoretical analysis and experimental study indicate that the position of the asymmetric crystallization borderline is determined by the droplet radius and density, and the observation window of asymmetric crystallization borderline is determined by the chemical concentration. The finding reveals the asymmetric crystallization phenomenon in droplet vitrification for the first time, and provides a new insight for creating Janus particles through the Leidenfrost phenomenon.

Phase Transitions in Two-Dimensional Systems of Janus-like Particles on a Triangular Lattice.

We studied the phase behavior of two-dimensional systems of Janus-like particles on a triangular lattice using Monte Carlo methods. The model assumes that each particle can take on one of the six orientations with respect to the lattice, and the interactions between neighboring particles were weighted depending on the degree to which their A and B halves overlap. In this work, we assumed that the AA interaction was fixed and attractive, while the AB and BB interactions varied. We demonstrated that the phase behavior of the systems considered strongly depended on the magnitude of the interaction energies between the AB and BB halves. Here, we considered systems with non-repulsive interactions only and determined phase diagrams for several systems. We demonstrated that the phase diagram topology depends on the temperature at which the close-packed systems undergo the orientational order-disorder transition.

Photoinduced Self-Assembly of Carbon Nitride Quantum Dots.

The study of nanocrystal self-assembly into superlattices or superstructures is of great significance in nanoscience. Carbon nitride quantum dots (CNQDs), being a promising new group of nanomaterials, however, have hardly been explored in their self-organizing behavior. Here we report of a unique irradiation-triggered self-assembly and recrystallization phenomenon of crystalline CNQDs (c-CNQDs) terminated by abundant oxygen-containing groups. Unlike the conventional self-assembly of nanocrystals into ordered superstructures, the photoinduced self-assembly of c-CNQDs resembles a "click reaction" process of macromolecules, in which the activated -OH and -NH2 functional groups along the perimeters initiate cross-linking of adjacent QDs through a photocatalytic effect. Our findings unveil fundamental physiochemical features of CNQDs and open up new possibilities of manipulating carbon nitride nanomaterials via controlled assembly. Prospects for potential applications are discussed as well.

Real-Time Simultaneous Imaging of Acidification and Proteolysis in Single Phagosomes Using Bifunctional Janus-Particle Probes.

The digestion of pathogens inside phagosomes by immune cells occurs through a sequence of reactions including acidification and proteolysis, but how the reactions are orchestrated in the right order is unclear due to a lack of methods to simultaneously measure more than one reaction in phagosomes. Here we report a bifunctional Janus-particle probe to simultaneously monitor acidification and proteolysis in single phagosomes in live cells. Each probe consists of a pH reporter and a proteolysis reporter that are spatially separated but function concurrently. Using the Janus probes, we found the acidic pH needed to initiate and maintain proteolysis, revealing the mechanism for the sequential occurrence of both reactions during pathogen digestion. We showed how bacterium-derived lipopolysaccharides alter the acidification and proteolysis in phagosomes. This study showcases Janus-particle probes as a generally applicable tool for monitoring multiple reactions in intracellular vesicles.

Temperature-Responsive Janus Particles as Microsurfactants for On-Demand Coalescence of Emulsions.

A new strategy that utilizes temperature-responsive wax-based Janus particles as microsurfactants to simultaneously achieve enhanced emulsion stability, as well as, on-demand coalescence of emulsion droplets is presented. The dumbbell structure with different surface wetting properties on each side of the Janus particle enables the particles to strongly adsorb at the liquid-liquid interface, leading to excellent stability against coalescence for both water-in-oil (W/O) and oil-in-water (O/W) emulsions. Moreover, these Janus microparticles are composed of a hydrophilic acrylate resin and a hydrophobic wax compartment which transitions from a frozen to an oil-soluble molten state above the melting point. This allows the particle-adsorbed droplets to coalesce above a designated temperature, depending on the type of wax material used. It is envisioned that the excellent emulsion stability and the tunable and rapid response to local temperature enabled by the wax-based Janus particle offers new and exciting opportunities in the advancing technologies including micro-reactors and drug delivery systems to name a few.

Janus dendrimersomes coassembled from fluorinated, hydrogenated, and hybrid Janus dendrimers as models for cell fusion and fission.

A three-component system of Janus dendrimers (JDs) including hydrogenated, fluorinated, and hybrid hydrogenated-fluorinated JDs are reported to coassemble by film hydration at specific ratios into an unprecedented class of supramolecular Janus particles (JPs) denoted Janus dendrimersomes (JDSs). They consist of a dumbbell-shaped structure composed of an onion-like hydrogenated vesicle and an onion-like fluorinated vesicle tethered together. The synthesis of dye-tagged analogs of each JD component enabled characterization of JDS architectures with confocal fluorescence microscopy. Additionally, a simple injection method was used to prepare submicron JDSs, which were imaged with cryogenic transmission electron microscopy (cryo-TEM). As reported previously, different ratios of the same three-component system yielded a variety of structures including homogenous onion-like vesicles, core-shell structures, and completely self-sorted hydrogenated and fluorinated vesicles. Taken together with the JDSs reported herein, a self-sorting pathway is revealed as a function of the relative concentration of the hybrid JD, which may serve to stabilize the interface between hydrogenated and fluorinated bilayers. The fission-like pathway suggests the possibility of fusion and fission processes in biological systems that do not require the assistance of proteins but instead may result from alterations in the ratios of membrane composition.

Optimal run-and-tumble-based transportation of a Janus particle with active steering.

Although making artificial micrometric swimmers has been made possible by using various propulsion mechanisms, guiding their motion in the presence of thermal fluctuations still remains a great challenge. Such a task is essential in biological systems, which present a number of intriguing solutions that are robust against noisy environmental conditions as well as variability in individual genetic makeup. Using synthetic Janus particles driven by an electric field, we present a feedback-based particle-guiding method quite analogous to the "run-and-tumbling" behavior of Escherichia coli but with a deterministic steering in the tumbling phase: the particle is set to the run state when its orientation vector aligns with the target, whereas the transition to the "steering" state is triggered when it exceeds a tolerance angle [Formula: see text] The active and deterministic reorientation of the particle is achieved by a characteristic rotational motion that can be switched on and off by modulating the ac frequency of the electric field, which is reported in this work. Relying on numerical simulations and analytical results, we show that this feedback algorithm can be optimized by tuning the tolerance angle [Formula: see text] The optimal resetting angle depends on signal to noise ratio in the steering state, and it is shown in the experiment. The proposed method is simple and robust for targeting, despite variability in self-propelling speeds and angular velocities of individual particles.

Light-driven nanomotors and micromotors: envisioning new analytical possibilities for bio-sensing.

The aim of this conceptual review is to cover recent developments of light-propelled micromotors for analytical (bio)-sensing. Challenges of self-propelled light-driven micromotors in complex (biological) media and potential solutions from material aspects and propulsion mechanism to achieve final analytical detection for in vivo and in vitro applications will be comprehensively covered. Graphical abstract.