Photocharging of Carbon Nitride Thin Films for Controllable Manipulation of Droplet Force Gradient Sensors.

Intentional generation, amplification, and discharging of chemical gradients is central to many nano- and micromanipulative technologies. We describe a straightforward strategy to direct chemical gradients inside a solution via local photoelectric surface charging of organic semiconducting thin films. We observed that the irradiation of carbon nitride thin films with ultraviolet light generates local and sustained surface charges in illuminated regions, inducing chemical gradients in adjacent solutions via charge-selective immobilization of surfactants onto the substrate.

In situ Tracking of Exoenzyme Activity Using Droplet Luminescence Concentrators for Ratiometric Detection of Bacteria.

We demonstrate a novel, rapid, and cost-effective biosensing paradigm that is based on an in situ visualization of bacterial exoenzyme activity using biphasic Janus emulsion droplets. Sensitization of the droplets toward dominant extracellular enzymes of bacterial pathogens is realized via selective functionalization of one hemisphere of Janus droplets with enzyme-cleavable surfactants. Surfactant cleavage results in an interfacial tension increase at the respective droplet interface, which readily transduces into a microscopically detectable change of the internal droplet morphologies.

Multicompartment calcium alginate microreactors to reduce substrate inhibition in enzyme cascade reactions.

The formation of macromolecularly enriched condensates through associative or segregative liquid-liquid phase separation phenomena is known to play a central role in controlling various cellular functions in nature. The potential to spatially and temporally modulate multistep chemical reactions and pathways has inspired the use of phase-separated systems for the development of various synthetic colloidal micro- and nanoreactor systems. Here, we report a rational and synthetically minimal design strategy to emulate intended spatiotemporal functions in morphologically intricate and structurally defined calcium alginate hydrogel microreactors possessing multicompartmentalized internal architectures.

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.

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) can be evoked by titrating mono-, di-, and trivalent cationic counter-ions, which is coherent with the lyotropic (Hofmeister) series.

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.

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.

Actuation of Janus Emulsion Droplets via Optothermally Induced Marangoni Forces.

Microscale Janus emulsions represent a versatile material platform for dynamic refractive, reflective, and light-emitting optical components. Here, we present a mechanism for droplet actuation that exploits thermocapillarity. Using optically induced thermal gradients, an interfacial tension differential is generated across the surfactant-free internal capillary interface of Janus droplets.

Facile Monitoring of Water Hardness Levels Using Responsive Complex Emulsions.

The cationic content of water represents a major quality control parameter that needs to be followed by a rapid, on-site, and low-cost method. Herein, we report a novel method for a facile monitoring of the mineral content of drinking water by making use of responsive complex emulsions. The morphology of biphasic oil-in-water droplets solely depends on the balance of interfacial tensions, and we demonstrate that changes in the surfactant effectiveness, caused by variations in the mineral content inside the continuous phase, can be visualized by monitoring internal droplet shapes.

Synthesis of Polymer Janus Particles with Tunable Wettability Profiles as Potent Solid Surfactants to Promote Gas Delivery in Aqueous Reaction Media.

Janus particles exhibit a strong tendency to directionally assemble and segregate to interfaces and thus offer advantages as colloidal analogues of molecular surfactants to improve the stability of multiphasic mixtures. Investigation and application of the unique adsorption properties require synthetic procedures that enable careful design and reliable control over the particles' asymmetric chemistry and wettability profiles with high morphological uniformity across a sample. Herein, we report on a novel one-step synthetic approach for the generation of amphiphilic polymer Janus particles with highly uniform and tunable wettability contrasts, which is based on using reconfigurable bi-phasic Janus emulsions as versatile particle scaffolds.

Structurally Anisotropic Janus Particles with Tunable Amphiphilicity via Polymerization of Dynamic Complex Emulsions.

A facile one-step approach for the synthesis of physically and chemically anisotropic polymer particles with tunable size, shape, composition, wettability, and functionality is reported. Specifically, dynamically reconfigurable oil-in-water Janus emulsions containing photocurable hydrocarbon or fluorocarbon acrylate monomers as one of the droplet phases are used as structural templates to polymerize them into precision Janus particles with highly uniform anomalous morphologies including (hemi-) spheres, lenses, and bowls. During polymerization, each interface is exposed to a different chemical environment, yielding particles with an intrinsic Janus character that can be amplified via side-selective postfunctionalization.

Cascade communication in disordered networks of enzyme-loaded microdroplets.

A network of aqueous emulsion droplets that exhibits programmed and directional chemical inter-droplet communication is described. A non-reciprocal transfer of substrates between enzyme-containing aqueous emulsion droplets is realized by (biochemically) induced osmolarity gradients and concomitant concentration gradients are used to direct a multistep enzymatic cascade reaction across multiple droplets.

Responsive drop method: quantitative in situ determination of surfactant effectiveness using reconfigurable Janus emulsions.

Characterization of surfactant effectiveness and thus an evaluation of their performance in a wide range of emulsion technologies requires a precise determination of key parameters including their critical micelle concentrations as well as their ability to lower the surface tension at interfaces. In this study, we describe a new approach to quantify marginal variations in interfacial tension of surfactant stabilized fluid interfaces. The method is based on a unique chemical-morphological coupling inside bi-phasic oil-in-water Janus emulsions that undergo dynamic morphological transitions in response to changes in the surfactant type, concentration, ratio, and configuration.

Temperature sensitive water-in-water emulsions.

A novel approach for a temperature-sensitive stabilization of water-in-water (W/W) emulsions is described. Specifically, we leveraged the thermal induced conformation change of tailored thermoresponsive block copolymers to reversibly stabilize and destabilize water-water interfaces. In addition, we investigated our approach to reversibly tune the reaction kinetics of enzymes compartmentalized within aqueous two-phase systems.

Responsive Janus and Cerberus emulsions via temperature-induced phase separation in aqueous polymer mixtures.

Complex aqueous emulsions represent a promising material platform for the encapsulation of cells, pharmaceuticals, or nutrients, for the fabrication of structured particles, as well as for mimicking the barrier-free compartmentalization of biomolecules found in living cells. Herein, we report a novel, simple, and scalable method of creating multicomponent aqueous droplets with highly uniform internal droplet morphologies that can be controllably altered after emulsification by making use of a thermal phase separation approach. Specifically, temperature-induced phase separation inside as-formed emulsion droplets comprising aqueous mixtures of two or more hydrophilic polymers allows for the generation of Janus and Cerberus emulsion droplets with adjustable internal morphologies that are solely controlled by a balance of interfacial tensions.

Cascade Kinetics in an Enzyme-Loaded Aqueous Two-Phase System.

Macromolecular crowding plays a critical role in the kinetics of enzymatic reactions. Dynamic compartmentalization of biological components in living cells due to liquid-liquid phase separation represents an important cell regulatory mechanism that can increase enzyme concentration locally and influence the diffusion of substrates. In the present study, we probed partitioning of two enzymes (horseradish-peroxidase and urate-oxidase) in a poly(ethylene glycol)-dextran aqueous two-phase system (ATPS) as a function of salt concentration and ion position in the Hofmeister series.

Rapid Detection of via Directional Emission from Carbohydrate-Functionalized Dynamic Double Emulsions.

Reliable early-stage detection of foodborne pathogens is a global public health challenge that requires new and improved sensing strategies. Here, we demonstrate that dynamically reconfigurable fluorescent double emulsions can function as highly responsive optical sensors for the rapid detection of carbohydrates fructose, glucose, mannose, and mannan, which are involved in many biological and pathogenic phenomena. The proposed detection strategy relies on reversible reactions between boronic acid surfactants and carbohydrates at the hydrocarbon/water interface leading to a dynamic reconfiguration of the droplet morphology, which alters the angular distribution of the droplet's fluorescent light emission.

Janus Graphene: Scalable Self-Assembly and Solution-Phase Orthogonal Functionalization.

Orthogonal functionalization of 2D materials by selective assembly at interfaces provides opportunities to create new materials with transformative properties. Challenges remain in realizing controllable, scalable surface-selective, and orthogonal functionalization. Herein, dynamic covalent assembly is reported that directs the functionalization of graphene surfaces at liquid-liquid interfaces.

Morphology-Dependent Luminescence in Complex Liquid Colloids.

Complex liquid colloids hold great promise as transducers in sensing applications as a result of their tunable morphology and intrinsic optical properties. Herein, we introduce meta-amino substituted green fluorescence protein chromophore (GFPc) surfactants that localize at the organic-water interface of complex multiphase liquid colloids. The meta-amino GFPc exhibits hydrogen-bonding (HB) mediated fluorescence quenching, and are nearly nonemissive in the presence of protic solvents.

Emulsion Agglutination Assay for the Detection of Protein-Protein Interactions: An Optical Sensor for Zika Virus.

A new class of Janus emulsion agglutination assay is reported for the detection of interfacial protein-protein interactions. Janus emulsion droplets are functionalized with a thermally stable, antigen binding protein rcSso7d variant (rcSso7d-ZNS1) for the detection of Zika NS1 protein. The emulsion droplets containing fluorescent dyes in their hydrocarbon and fluorocarbon phases intensify the intrinsic optical signal with the emission intensity ratio, which can be detected by a simple optical fiber.

Resistive and Capacitive γ-Ray Dosimeters Based On Triggered Depolymerization in Carbon Nanotube Composites.

We report γ-ray dosimeters using carbon nanotubes wrapped with metastable poly(olefin sulfone)s (POSs) that readily depolymerize when exposed to ionizing radiation. New POSs, designed for wrapping single-walled carbon nanotubes (SWCNTs), are synthesized and characterized. The resulting POS-SWCNT composites serve as the active transducer in a novel class of γ-ray dosimeters.