Janus Emulsions Research Articles

Optical Detection of Interleukin-6 Using Liquid Janus Emulsions Using Hyperthermophilic Affinity Proteins.

When equal volumes of two immiscible liquids are mixed (e.g., a hydrocarbon and a fluorocarbon), Janus droplets can form in an aqueous solution. In a gravity-aligned Janus droplet, the boundary between the two phases is flat and thus optically transparent when viewed from above. When tipped due to interactions with an analyte (i.e., agglutination), the resulting change in refraction and reflection yields an optical signal that can be detected and quantified. This study reports the detection and quantitation of interleukin-6 (IL-6) using emulsions functionalized at the hydrocarbon:aqueous interface with engineered proteins that bind IL-6 at high affinity and specificity. Hyperthermophilic affinity proteins (rcSso7d) are derived from thermophiles, giving them excellent thermal stability. Two rcSso7d affinity protein variants were synthesized with a noncanonical azide-functionalized amino acid to enable click chemistry to novel polymeric anchors embedded in the hydrocarbon phase. The two binding proteins recognize different epitopes, enabling the detection of both monomeric and dimeric IL-6 via agglutination. It is noteworthy that the rsSso7d protein variants, in addition to having superior thermal stability and facile recombinant synthesis in E. coli, show superior performance when compared to commercial antibodies for IL-6.

Ionic Polymerization-Based Synthesis of Bioinspired Adhesive Hydrogel Microparticles with Tunable Morphologies from Microfluidics.

Shape-anisotropic hydrogel microparticles have attracted considerable attention for drug-delivery applications. Particularly, nonspherical hydrogel microcarriers with enhanced adhesive and circulatory abilities have demonstrated value in gastrointestinal drug administration. Herein, inspired by the structures of natural suckers, we demonstrate an ionic polymerization-based production of calcium (Ca)-alginate microparticles with tunable shapes from Janus emulsion for the first time. Monodispersed Janus droplets composed of sodium alginate and nongelable segments were generated using a coflow droplet generator. The interfacial curvatures, sizes, and production frequencies of Janus droplets can be flexibly controlled by varying the flow conditions and surfactant concentrations in the multiphase system. Janus droplets were ionically solidified on a chip, and hydrogel beads of different shapes were obtained. The in vitro and in vivo adhesion abilities of the hydrogel beads to the mouse colon were investigated. The anisotropic beads showed prominent adhesive properties compared with the spherical particles owing to their sticky hydrogel components and unique shapes. Finally, a novel computational fluid dynamics and discrete element method (CFD-DEM) coupling simulation was used to evaluate particle migration and contact forces theoretically. This review presents a simple strategy to synthesize Ca-alginate particles with tunable structures that could be ideal materials for constructing gastrointestinal drug delivery systems.

Chiral Janus emulsions with gold nanocomposite for enantioselective catalysis

Chiral emulsions, with the chiral center of chiral-surfactant as the emulsifier, provide opportunities for selective catalysis and inorganic material synthesis. Janus emulsion draws researcher’s attention due to excellent multiple chambers, advanced structures and diverse interfaces. Chiral Janus emulsions are prepared with two immiscible oils of vegetable oil (VO)/dimethyl phthalate (DMP) and 2-(Perfluorooctyl)ethyl methacrylate (PFOEMA)/Ethoxylated trimethylolpropane triacrylate (ETPTA) as inner phases, by emulsified by chiral-surfactant [H-G-C16]FeCl4, in batch-scale by traditional vortex mixing. AuNPs as functional nanomaterials with peroxidase activity are then applied as active centers, adsorbing at the oil/water interface due to the electrostatic interactions between the positive charge of [H-G-C16]FeCl4 at Janus emulsion interfaces and the negative charge of AuNPs modified by SDS. Chiral Janus emulsion is endowed with catalytic activity and enantioselectivity. Catalytic results show two AuNPs@ Janus emulsions show better affinity to catalyze the oxidation of L-DOPA than D-DOPA. By investigating two AuNPs@ Janus emulsions with different inner phases, chiral Janus emulsion of AuNPs@ETPTA/PFOEMA/[H-G-C16]FeCl4(aq) has better catalytic activity and enantioselectivity than AuNPs@DMP/VO/[H-G-C16]FeCl4 (aq) because of the smaller droplets have larger interface areas could adsorb more [H-G-C16]FeCl4 molecules and AuNPs. The findings open an avenue in the production of chiral Janus emulsions with catalytic effect and enantioselectivity, which would push forward future applications in selective catalysis and inorganic material synthesis.

Salinity-Driven Interface Self-Assembly of a Biological Amphiphilic Emulsifier to Form Stable Janus Core-Shell Emulsion for Enhancing Agrichemical Delivery.

Agrichemical losses are a severe threat to the ecological environment. Additionally, some agrichemical compounds contain abundant salt, which increases the instability of formulations, leading to a lower agrichemical utilization and soil hardening. Fortunately, the biological amphiphilic emulsifier sodium deoxycholate alleviates these problems by forming stable Janus core-shell emulsions through salinity-driven interfacial self-assembly. According to the interfacial behavior, dilational rheology, and molecular dynamics simulations, Janus-emulsion molecules are more closely arranged than traditional-emulsion molecules and generate an oil-water interfacial film that transforms into a gel film. In addition, at the same spray volume, the deposition area of the Janus emulsion increased by 37.70% compared with that of the traditional emulsion. Owing to the topology effect and deformation, the Janus emulsion adheres to rice micropapillae, achieving better flush resistance. Meanwhile, based on response of the Janus emulsion to stimulation by carbon dioxide (CO2), the emulsion lost to the soil can form a rigid shell for inhibiting the release of pesticides and metal ions from harming the soil. The pyraclostrobin release rate decreased by 50.89% at 4 h after the Janus emulsion was exposed to CO2. The Chao1 index of the Janus emulsion was increased by 12.49% as compared to coconut oil delivery in soil microbial community. The Janus emulsion ingested by harmful organisms can be effectively absorbed in the intestine to achieve better control effects. This study provides a simple and effective strategy, which turns waste into treasure, by combining metal ions in agrichemicals with natural amphiphilic molecules to prepare stable emulsions for enhancing agrichemical rainfastness and weakening environmental risk.

Controllable enzymatic hydrolysis in reverse Janus emulsion microreactors

HypothesisThe key feature of living cells is multicompartmentalization for enzymatic reactions. Artificial cell-like multicompartments with micro domains are appealing to mimic the biological counterparts. In addition, establishing a sustainable, efficient, and controllable reaction system for enzymatic hydrolysis is imperative for the production of natural fatty acids from animal and plant-based fats. ExperimentsReverse Janus emulsion microreactors, i.e. (W1 + W2)/O, is constructed through directly using natural fats as continuous phase and aqueous two-phase solutions (ATPS) as inner phases. Enzyme is confined in the compartmented aqueous droplets dominated by the salt of Na2SO4 and polyethylene glycol (PEG). Enzyme catalyzed ester hydrolysis employed as a model reaction is performed under the conditions of agitation-free and mild temperature. Regulation of reaction kinetics is investigated by diverse droplet topology, composition of inner ATPS, and on-demand emulsification. FindingsExcellent enzymatic activity toward hydrolysis of plant and animal oils achieves 88.5 % conversion after 3 h. Compartmented micro domains contribute to condense and organize the enzymes spatially. Timely removal of the products away from reaction sites of oil/water interface “pushed” the reaction forward. Distribution and transfer of enzyme in two aqueous lobes provide extra freedom in the regulation of hydrolysis kinetics, with equilibrium conversion controlled freely from 14.5 % to 88.5 %. Reversible “open” and “shut” of hydrolysis is acheived by on-demand emulsification and spontaneous demulsification. This paper paves the way to advancing progress in compartmentalized emulsion as a sustainable and high-efficiency platform for biocatalytic applications.

From co-delivery to synergistic anti-inflammatory effect: Studies on chitosan-stabilized Janus emulsions having chloroquine phosphate and flavopiridol in Complete Freund's Adjuvant induced arthritis rat model

For the first time, the co-delivery of chloroquine phosphate and flavopiridol by intra-articular route was achieved to provide local joint targeting in Complete Freund's Adjuvant-induced arthritis rat model. The presence of paired-bean structure onto the dispersed oil droplets of o/w nanosized emulsions allows efficient entrapment of two drugs (85.86–96.22 %). The dual drug-loaded emulsions displayed a differential in vitro drug release behavior, near normal cell viability in MTT assay, better cell uptake (internalization) and better reducing effect of mean immunofluorescence intensity of inflammatory proteins such as NF-κB and iNOS at in vitro RAW264.7 macrophage cell line. The radiographical study, ELISA test, RT-PCR study and H & E staining also indicated a reduction in joint tissue swelling, IL-6 and TNF-α levels diminution, fold change diminution in the mRNA expressions for NF-κB, IL-1β, IL-6 and PGE2 and maintenance of near normal histology at bone cartilage interface respectively. The results of metabolomic pathway analysis performed by LC-MS/MS method using the rat blood (plasma) collected from disease control and dual drug-loaded emulsions treatment groups revealed a new follow-up study to understand not only the disease progression but also the formulation therapeutic efficacy assessment.

Morphology‐Directed Light Emission from Fluorescent Janus Colloids for Programmable Chemical‐To‐Optical Signal Transduction

AbstractMaterials capable of dynamically and reversibly altering their emission are relevant for numerous optical applications. Here, the anisotropic morphology‐directed light emission from fluorescent Janus emulsion droplets, an intrinsically chemo‐responsive material platform, is investigated. Informed by experimental observations of morphology‐dependent optical confinement of internally emitted light within the higher refractive index phases, ray‐tracing is used to predict and fine‐tune the droplets’ optical properties and their ability to concentrate light. Theoretical prediction and closely matching experimental results show that the collection of incident light and the confinement of emitted light in the internal droplet phase due to total internal reflection both contribute to the droplets’ anisotropic light emission profile. A novel ratiometric dual‐angle fluorescence detection approach that exploits the gravitational alignment of the droplets is implemented to quantify the morphology‐dependent large‐scale chemically‐induced modulation of the anisotropic emission of droplet layers. Relevant emulsion design parameters are systematically examined to enhance the signal‐to‐noise ratio, and a second emitter is co‐compartmentalized inside the droplets to amplify the anisotropic light confinement via an absorption–emission cascade. Preferential excitation of dyes in proximity to the internal droplet interface enhances the collected light intensity, demonstrating that dye‐loaded Janus emulsion droplets function as stimuli‐responsive, tunable, fluorescent optical elements.

Responsive Janus droplets as modular sensory layers for the optical detection of bacteria

The field of biosensor development is fueled by innovations in new functional transduction materials and technologies. Material innovations promise to extend current sensor hardware limitations, reduce analysis costs, and ensure broad application of sensor methods. Optical sensors are particularly attractive because they enable sensitive and noninvasive analyte detection in near real-time. Optical transducers convert physical, chemical, or biological events into detectable changes in fluorescence, refractive index, or spectroscopic shifts. Thus, in addition to sophisticated biochemical selector designs, smart transducers can improve signal transmission and amplification, thereby greatly facilitating the practical applicability of biosensors, which, to date, is often hampered by complications such as difficult replication of reproducible selector-analyte interactions within a uniform and consistent sensing area. In this context, stimuli-responsive and optically active Janus emulsions, which are dispersions of kinetically stabilized biphasic fluid droplets, have emerged as a novel triggerable material platform that provides as a versatile and cost-effective alternative for the generation of reproducible, highly sensitive, and modular optical sensing layers. The intrinsic and unprecedented chemical-morphological-optical coupling inside Janus droplets has facilitated optical signal transduction and amplification in various chemo- and biosensor paradigms, which include examples for the rapid and cost-effective detection of major foodborne pathogens. These initial demonstrations resulted in detection limits that rival the capabilities of current commercial platforms. This trend article aims to present a conceptual summary of these initial efforts and to provide a concise and comprehensive overview of the pivotal kinetic and thermodynamic principles that govern the ability of Janus droplets to sensitively and selectively respond to and interact with bacteria.Graphical abstract

Enhanced catalytic degradation performance of azo dyes based on Janus emulsification

Amphiphilic Janus nanosheets with an asymmetric structure of non-polar phenyl side and polar ionic liquid side (1-Butyl-3-methylimidazolium chloride, [BMIM]Cl), denoted as Janus-[BMIM]Cl, were prepared and used as a carrier to achieve the integration of catalyst and emulsifier. Catalytic heteropolyanions (e.g., [PW12O40]3-, [PMo12O40]3- or [SiW12O40]4-) were selectively decorated on the polar side induced by anion-exchange of [BMIM]Cl moieties, Janus catalysts (Janus-[BMIM][heteropolyanions]) were assembled and utilized as an open degradation platform for azo dyes such as methyl orange (MO). Morphology, structure, and properties were characterized by SEM, FT-IR, XPS, UV–Vis, Zeta potential, etc. The inbuilt amphipathy of Janus nanosheets endowed the decolorization process of dyes to perform in the emulsified system. The extremely increased interface coupled with the effective dispersion of catalysts at the interface synergistically improved the catalytic degradation performance. Compared with the decolorization catalyzed in a conventional immiscible system, the removal efficiency of MO achieved in the Janus emulsion greatly improved from 78.6 to 98.2% within 3 h. Besides, the Janus emulsion could be demulsified easily by centrifugation, and the degradation efficiency was still maintained at 93.7% after five cycles. These results provide valuable information for exploring and enriching the applications of Janus functional materials.

Cover Feature: Morphology‐Dependent Aggregation‐Induced Emission of Janus Emulsion Surfactants (Chem. Eur. J. 18/2023)

Stimuli-triggered alterations in biphasic Janus emulsion droplet morphologies enable controllable modulation of the area of surfactant-functionalized liquid–liquid interfaces. This effect can be used to induce aggregation-induced emission from tetraphenylethylene-functionalized surfactants, yielding a novel stimuli-responsive fluorescent material platform. Here, TPE aggregation and emission on an interface are shown in front of a fluorescence micrograph of the actual system. More information can be found in the Research Article by L. Zeininger and co-workers (DOI: 10.1002/chem.202203790).

Morphology-Dependent Aggregation-Induced Emission of Janus Emulsion Surfactants.

We report a novel stimuli-responsive fluorescent material platform that relies on an evocation of aggregation-induced emission (AIE) from tetraphenylethylene (TPE)-based surfactants localized at one hemisphere of biphasic micro-scale Janus emulsion droplets. Dynamic alterations in the available interfacial area were evoked through surfactant-induced dynamic changes of the internal droplet morphology that can be modulated as a function of the balance of interfacial tensions of the droplet constituent phases. Thus, by analogy with a Langmuir-Blodgett trough that enables selective concentration of surfactants at a liquid-gas interface, we demonstrate here a method for controllable modulation of the available interfacial area of surfactant-functionalized liquid-liquid interfaces. We show that a morphology-dependent alteration of the interfacial area can be used to evoke an optical signal, by selectively assembling synthesized TPE-based surfactants on the respective droplet interfaces. A trigger-induced increase in the concentration of TPE-based surfactants at the liquid-liquid interfaces results in an evocation of aggregation-induced emission (AIE), inducing an up to 3.9-fold increase in the measured emission intensity of the droplets.

Dynamic In Situ Monitoring of the Salt Counter-ion Effect on Surfactant Effectiveness Using Reconfigurable Janus Emulsions

A straightforward method for visualization and quantification of surfactant effectiveness within different electrolyte environments based on using reconfigurable Janus emulsions as novel optical probes is reported. More specifically, we investigated the effect of different types and concentrations of salt counter-ions on the surfactant surface excess of commercial ionic and non-ionic surfactants, namely sodium dodecyl sulfate (SDS) and Tween 80 via in situ monitoring the morphological reconfigurations of biphasic Janus emulsions comprising hydrocarbon and fluorocarbon oils. We find that significant variations in interfacial tensions of SDS-stabilized interfaces (up to 15 mN·m-1) can be evoked by titrating mono-, di-, and trivalent cationic counter-ions, which is coherent with the lyotropic (Hofmeister) series. In contrast, the salt counter-ion effect on the surfactant effectiveness was less pronounced for the non-ionic surfactant Tween 80 (∼3 mN·m-1). Our results reveal a facile in situ method for monitoring the central role of electrolyte type and concentration on surfactant effectiveness and, more broadly, illustrate that Janus emulsions serve as powerful optical probes to dynamically study the properties of surfactants at liquid interfaces. We demonstrate the utility of our findings for an electro-induced morphological reconfiguration of Janus droplet morphologies by dynamically tuning Cu2+ concentration in solution using an electrode setup. The latter provides a unique platform for liquid-phase, real-time, and continuous tuning of Janus droplet morphologies, e.g., for their application in sensing and dynamic optical device platforms.

Multicompartment colloid systems with lipid and polymer membranes for biomedical applications.

Multicompartment structures have the potential for biomedical applications because they can act as multifunctional systems and provide simultaneous delivery of drugs and diagnostics agents of different types. Moreover, some of them mimic biological cells to some extent with organelles as separate sub-compartments. This article analyses multicompartment colloidal structures with smaller sub-units covered with lipid or polymer membranes that provide additional protection for the encapsulated substances. Vesosomes with small vesicles encapsulated in the inner pools of larger liposomes are the most studied systems to date. Dendrimer molecules are enclosed by a lipid bilayer shell in dendrosomes. Capsosomes, polymersomes-in-polymer capsules, and cubosomes-in-polymer capsules are composed of sub-compartments encapsulated within closed multilayer polymer membranes. Janus or Cerberus emulsions contain droplets composed of two or three phases: immiscible oils in O/W emulsions and aqueous polymer or salt solutions that are separated into two or three phases and form connected droplets in W/O emulsions. In more cases, the external surface of engulfed droplets in Janus or Cerberus emulsions is covered with a lipid or polymer monolayer. eLiposomes with emulsion droplets encapsulated into a bilayer shell have been given little attention so far, but they have very great prospects. In addition to nanoemulsion droplets, solid lipid nanoparticles, nanostructured lipid carriers and inorganic nanoparticles can be loaded into eLiposomes. Molecular engineering of the external membrane allows the creation of ligand-targeted and stimuli-responsive multifunctional systems. As a result, the efficacy of drug delivery can be significantly enhanced.

Polyethyleneimine functionalized crescent-shaped microgel templated by Janus emulsion for rapid eliminating lead from water

Microgels is recognized as one of the most important functional sorbents for heavy metal removal from contaminated water. However, their simple synthesis and group-specific modifications are still challenging. Herein, polyethyleneimine (PEI) functionalized crescent-shaped microgel sorbent (CPNIPAM-AGE-PEI) was prepared for rapid eliminating Lead ions (Pb(II)) from water. CPNIPAM-AGE-PEI (diameter about 10 µm) exhibited well-defined crescent morphology with preferred orientation of cavity from DEX phase. The adsorption kinetics and isotherm data of Pb(II) on CPNIPAM-AGE-PEI demonstrate that the unique crescent-shaped structure enhanced the kinetic performance, achieving 89.52 % of the saturation adsorption capacity in the first 30 min. A favorable and monolayer adsorption capacity at 298.15 K was 52.27 mg g−1, and chemisorption based on N atoms of functionalized PEI chains may be the main adsorption mechanism. In the case of competition with other ions, CPNIPAM-AGE-PEI has excellent selective adsorption capacity for Pb(II), and the adsorption capacity remained above 87 % after five adsorption/desorption cycles.

Construction and regulation of aqueous-based Cerberus droplets by vortex mixing

Hypothesis: The emerging aqueous-based Cerberus emulsion droplets with multi-domains behave as an excellent platform to design cyto-mimetic compartmentalization for fabrication of anisotropic biomimetic materials and microreactors. However, the ultralow water/water interfacial tension impedes fabrication of aqueous Cerberus droplets in batch-scale and precisely topology regulation especially under lack of deep understanding of w/w interface properties.Experiments: Aqueous-based ternary phase diagram composed by salt, hydrophilic polymer and fluorocarbon compound is determined. Different emulsions employing the multiple aqueous solutions as internal phase and vegetable oil as continuous phase, are prepared by traditional vortex mixing based on the diagram. The construction mechanism of (W1 + W2 + W3)/O Cerberus droplets and relationship between droplet topology and the diagram are investigated.Findings: Diverse categories of aqueous-based emulsions from single emulsions, Janus emulsions, to Cerberus emulsions are delicately controlled in the same system based on the diagram. Various morphologies of Cerberus droplets such as linear and fan-like configurations are obtained, although spreading coefficient based on interfacial tension indicates preference of onion-like configuration. The viscosity plays an unexpected role in the construction of Cerberus droplets due to highly sensitive water/water interfaces within the droplets. Moreover, an empirical equation is perfectly applied, which endows quantitative prediction and control of lobe volume ratio within Cerberus droplets.

Reversible morphology-resolved chemotactic actuation and motion of Janus emulsion droplets

We report, for the first time, a chemotactic motion of emulsion droplets that can be controllably and reversibly altered. Our approach is based on using biphasic Janus emulsion droplets, where each phase responds differently to chemically induced interfacial tension gradients. By permanently breaking the symmetry of the droplets’ geometry and composition, externally evoked gradients in surfactant concentration or effectiveness induce anisotropic Marangoni-type fluid flows adjacent to each of the two different exposed interfaces. Regulation of the competitive fluid convections then enables a controllable alteration of the speed and the direction of the droplets’ chemotactic motion. Our findings provide insight into how compositional anisotropy can affect the chemotactic behavior of purely liquid-based microswimmers. This has implications for the design of smart and adaptive soft microrobots that can autonomously regulate their response to changes in their chemical environment by chemotactically moving towards or away from a certain target, such as a bacterium.

Responsive emulsions with Janus topology constructed by magneto-surfactants and remote control of emulsion stability

The fluids with well-defined inner structure and intrinsic responsibility are demanding to the maintenance and regulation of normal functions in living systems. Inspired by this, responsive Janus droplets are constructed by small molecules of magneto-surfactants, and the traditional vortex mixing is applied to guarantee large-scale fabrication. Silicone oil (SO) and Vegetable oil (VO) as two immiscible oils are introduced as inner phases of the Janus emulsions. The topology and subsequently the magnetic responsive performance of Janus emulsion is controlled by adjusting the oil composition with various viscosity, the surfactant concentration and the mass ratio of two oils. Moreover, the remote control of the emulsion stability is realized by the external magnetic field, of which the demulsification mechanism is investigated. The anisotropic and responsive droplets with advantages of deformability, encapsulation capability, and biocompatibility would expand the application of emulsions in targeted therapy, drug delivery and magnetic materials science.

Chemical design of self-propelled Janus droplets

Chemical design of self-propelled Janus droplets

Single and double toroid formation during oil droplet impact on an air–water interface at low Reynolds number

The impact of an oil droplet on an air–water interface is explored for low to moderate impact velocities. A computational fluid dynamic framework has been employed with appropriate boundary conditions to uncover the finer features of post-impact dynamics of such ternary systems. Simulations reveal that the impacting oil droplet opens up a “crater” on the water surface, which initially expands and then collapses during the evolution. Simultaneously, the oil droplet flattens, spreads, stretches, immerses, or dewets on the crater surface to manifest interesting metastable or unstable flow morphologies. At lower impact velocities, we observe the formation of oil droplets or air bubbles entrapped in water, oil lens, oil toroids, and compound droplets to name a few. The interfacial tension, density and viscosity contrasts across the interface play key roles in the formation of such flow morphologies. Energy analysis of the droplet impact reveals that a part of the kinetic energy of the droplet gets converted into surface energy, which, in turn, facilitates the interfacial deformation, formation of new interfaces, and metastable flow morphologies, such as single or twin toroids. All the different flow morphologies are categorized into eight fundamental regimes, which are mapped with the variation of Reynolds number and capillary number. The results provide insight into the complex physics associated with ternary phase drop impacts, and the different flow morphologies shown in the present study can be of significance in the production of double or Janus emulsions, as well as the development of next-generation microfluidic devices for bio-analysis, drug delivery, and multiphase reactions.

Polyethyleneimine Functionalized Crescent-Shaped Microgel Templated by Janus Emulsion for Rapid Eliminating Lead from Water

Polyethyleneimine Functionalized Crescent-Shaped Microgel Templated by Janus Emulsion for Rapid Eliminating Lead from Water