Monodisperse Plant Protein Nanoparticles Prepared by Cation-Exchange Resins for Stabilization of Pickering Emulsions.

Our understanding of the microstructure of many plant proteins is based on the ancient and conventional methods of alkali extraction and acid precipitation, which generate considerable amounts of NaCl causing salting-out effects and aggregation of their molecules. In this study, monodisperse rice protein (RP) nanoparticles were prepared using cation-exchange resins that release H+ and absorb Na+, thus avoiding the generation of NaCl during neutralization of the alkali extracts. The generated RP nanoparticles of small diameter (20 nm) and excellent uniformity (0.17 polydispersity) quickly diffuse to and stabilize the oil-water interface, producing oil-in-water Pickering emulsions. The emulsifying ability and emulsion stability afforded with these nanoparticles were 17 and 3.5 times higher than those of nanoparticles prepared by conventional alkali extraction and acid precipitation methods, respectively. Furthermore, increased RP nanoparticle concentration created more stable emulsions with smaller droplets and reduced flocculation index vital for practical applications. This study provides a convincing example of how to prepare monodisperse protein nanoparticles that adsorb at a fluid interface, which may find numerous applications in food and cosmetic formulations.

Smart Emulsions Stabilized by a Multi-headgroup Surfactant Tolerant to High Concentrations of Acids and Salts.

Retaining emulsions stable at high acidity and salinity is still a great challenge. Here, we report a novel multi-headgroup surfactant (C3 H7 -NH+ (C10 COOH)2 , di-UAPAc) which can be reversibly transformed among cationic, anionic and zwitterionic forms upon pH variation. Stable oil-in-dispersion (OID) emulsions in strong acidity (pH=2) can be co-stabilized by low concentrations of di-UAPAc and silica nanoparticles. High salinity at pH=2 improves the adsorption of di-UAPAc on silica particles through hydrogen bonding, resulting in the transformation of OID emulsions into Pickering emulsions. Moreover, emulsification/demulsification and interconversion between OID and Pickering emulsions together with control of the viscosity and droplet size can be triggered by pH. The present work provides a new protocol for designing surfactants for various applications in harsh aqueous media, such as strong acidity and high salinity, involved in oil recovery and sewerage treatments.

Universality of Scaling Laws Governing Contact and Spreading Time Spans of Bouncing Liquid Marbles and its Physical Origin.

The impact of liquid marbles coated with a diversity of hydrophobic powders with various solid substrates, including hydrophobic, hydrophilic, and superhydrophobic ones, was investigated. The contact time of the bouncing marbles was studied. Universal scaling behavior of the contact time tc as a function of the Weber number (We) was established; the scaling law tc = tc(We) was independent of the kind of powder and the type of solid substrate. The total contact time consists of spreading time and retraction time. It is weakly dependent on We and this is true for all kinds of studied powders and substrates. This observation hints to the surface tension/inertia spring model governing the impact. By contrast, the spreading time ts scales as [Formula: see text], n = 0.28 - 0.30 ± 0.002. We relate the origin of this scaling law to the viscous dissipation occurring within the spreading marbles. The retraction time tr grows weakly with the Weber number. The scaling law was changed at threshold values of We ≅ 15-20. It is reasonable to explain this change with the breaking of the Leidenfrost regime of spreading under high values of We.

Light-Driven Spatiotemporal Pickering Emulsion Droplet Manipulation Enabled by Plasmonic Hybrid Microgels.

The past decades have witnessed the development of various stimuli-responsive materials with tailored functionalities, enabling droplet manipulation through external force fields. Among different strategies, light exhibits excellent flexibility for contactless control of droplets, particularly in three-dimensional space. Here, we present a facile synthesis of plasmonic hybrid microgels based on the electrostatic heterocoagulation between cationic microgels and anionic Au nanoparticles. The hybrid microgels are effective stabilizers of oil-in-water Pickering emulsions. In addition, the laser irradiation on Au nanoparticles creats a "cascade effect" to thermally responsive microgels, which triggers a change in microgel wettability, resulting in microgel desorption and emulsion destabilization. More importantly, the localized heating generated by a focused laser induces the generation of a vapor bubble inside oil droplets, leading to the formation of a novel air-in-oil-in-water (A/O/W) emulsion. These A/O/W droplets are able to mimic natural microswimmers in an aqueous environment by tracking the motion of a laser spot, thus achieving on-demand droplet merging and chemical communication between isolated droplets. Such proposed systems are expected to extend the applications of microgel-stabilized Pickering emulsions for substance transport, programmed release and controlled catalytic reactions.

Highly efficient and recyclable monolithic bioreactor for interfacial enzyme catalysis.

HYPOTHESIS: Biocatalysts are key to the realization of all bioconversions in nature. However, the difficulty of combining the biocatalyst and other chemicals in one system limits their application in artificial reaction systems. Although some effort, such as Pickering interfacial catalysis and enzyme-immobilized microchannel reactors, have addressed this challenge an effective method to combine chemical substrates and biocatalysts in a highly efficient and re-usable monolith system is still to be developed. EXPERIMENTS: A repeated batch-type biphasic interfacial biocatalysis microreactor was developed using enzyme-loaded polymersomes in the void surface of porous monoliths. Polymersomes, loaded with Candida antarctica Lipase B (CALB), are fabricated by self-assembly of the copolymer PEO-b-P(St-co-TMI) and used to stabilize oil-in-water (o/w) Pickering emulsions as a template to prepare monoliths. By adding monomer and Tween 85 to the continuous phase, controllable open-cell monoliths are prepared to inlay CALB-loaded polymersomes in the pore walls. FINDINGS: The microreactor is proven to be highly effective and recyclable when a substrate flows through it, which offers superior benefits of absolute separation to a pure product and no enzyme loss. The relative enzyme activity is constantly maintained above 93% in 15 cycles. The enzyme is constantly present in the microenvironment of the PBS buffer ensuring its immunity to inactivation and facilitating its recycling.

Fabrication of Poly(ε-caprolactone)-embedded Lignin-Chitosan Nanocomposite Porous Scaffolds from Pickering Emulsions.

Poly(ε-caprolactone) (PCL)-incorporated lignin-chitosan biomass-based nanocomposite porous scaffolds have been effectively prepared by templating oil-in-water Pickering high internal phase emulsions (HIPEs). PCL is dissolved in oil and chitosan and lignin nanoparticles originate in water. The continuous phase of the emulsions is gelled by cross-linking of chitosan with genipin and then freeze-dried to obtain porous scaffolds. The resulting scaffolds display interconnected and tunable pore structures. An increase in PCL content increases the mechanical strength and greatly reduces the water absorption capacity of the scaffolds. Scaffolds loaded with the anti-bacterial drug enrofloxacin show a slow drug release profile, adjustable release rate, and favorable long-term anti-bacterial activity. Moreover, Pickering emulsion templates with suitable viscosity are used as 3D printing inks to construct porous scaffolds with personalized geometry. The results imply that the simplicity and versatility of the technique of combining freeze-drying with Pickering HIPE templates is a promising approach to fabricate hydrophobic biopolymer-incorporated biomass-based nanocomposite porous scaffolds for biomedical applications.

Biomolecular 1D Necklace-like Nanostructures Tailoring 2D Janus Interfaces for Controllable 3D Enteric Biomaterials.

Construction of well-ordered two-dimensional (2D) and three-dimensional (3D) assemblies using one-dimensional (1D) units is a hallmark of many biointerfaces such as skin. Mimicking the art of difunctional properties of biointerfaces, which skin exhibits as defense and shelter materials, has inspired the development of smart and responsive biomimetic interfaces. However, programming the long-range ordering of 1D base materials toward vigorous control over 2D and 3D hierarchical structures and material properties remains a daunting challenge. In this study, we put forward construction of 3D enteric biomaterials with a two-strata 2D Janus interface assembled from self-adaptation of 1D protein-polysaccharide nanostructures at an oil-water interface. The biomaterials feature a protein dermis accommodating oil droplets as a reservoir for bioactive compounds and a polysaccharide epidermis protecting them from gastric degradation. Furthermore, the epidermis can be fine-tuned with different thicknesses rendering enteric delivery of a bioactive cargo (coumarin-6) with controllable retention in the intestinal tract from 6 to 24 h. The results highlight a skin-inspired construction of enteric biomaterials by self-adaptation of 1D nanostructures at the oil-water interface toward 2D Janus biointerfaces and 3D microdevices, which can be tailored for intestinal treatments with intentional therapeutic efficacies.

One-Step Fabrication of Coconut-Like Capsules via Competitive Reactions at an All-Aqueous Interface for Enzyme Immobilization.

A concept of interfacial competitive reaction between biomineralization and alginate gelation at an all-aqueous single-emulsion droplet interface to prepare robust coconut-like capsules (inner hard wall and outer soft wall) is developed. The concept is further applied for enzyme immobilization with high encapsulation efficiency, enzyme loading, mass transfer coefficient, and recyclability. The thickness and swelling properties of the shell are simply tunable by a competitive reaction. Our platform may open a green, facile, and efficient way to prepare organic-inorganic hybrid sustainable materials with tailored compositions and structures.

Phase Inversion of Pickering Emulsions Induced by Interfacial Electrostatic Attraction.

Phase inversion of Pickering emulsions from water-in-oil (W/O) to oil-in-water (O/W) is achieved by the formation of an interfacial particle bilayer using negatively charged and positively charged particles dispersed in water and oil, respectively, before emulsification. A mechanism based on electrostatic attraction across the toluene-water interface is proposed and verified by systematic investigation of the parameters that affect the surface charge of negatively charged particles such as pH and salt concentration. Cationic silica-FITC particles (600 nm) can be dispersed in toluene and stabilize W/O emulsions alone; phase inversion of this emulsion can be induced by the addition of anionic silica-RB particles in the aqueous phase at a concentration of 1.0 wt % or above. It is revealed that silica-RB particles of a smaller size (100 nm) can induce emulsion phase inversion at a much lower concentration (0.4 wt %) and an interfacial particle bilayer is clearly revealed by CLSM and SEM images. By tuning the surface charge density of silica-RB particles, the electrostatic attraction mechanism leading to the formation of the interfacial particle bilayer is confirmed and emulsion stability can be tuned as demonstrated by osmotic pressure enhancement results obtained from centrifugation.

Recyclable Nonionic-Anionic Bola Surfactant as a Stabilizer of Size-Controllable and pH-Responsive Pickering Emulsions.

A novel nonionic-anionic Bola surfactant (abbreviated as CH3O(EO)7-R11-COOH) was designed and synthesized by condensation of methyl polyoxyethylene (7) ether with 12-bromododecanoic acid. In neutral aqueous solution, the surfactant behaves as a nonionic one and can stabilize oil-in-water (O/W) conventional emulsions alone and costabilize O/W Pickering emulsions with positively charged alumina nanoparticles with n-decane as the oil. In alkaline solution, the carboxylic acid group is deprotonated, becoming anionic and the surfactant is converted to Bola form, which is an inferior emulsifier and does not adsorb on particle surfaces, resulting in demulsification of both kinds of emulsions. With strong hydrophilicity, both the Bola surfactant and the bare particles return to the aqueous phase after demulsification, which is therefore recyclable and reusable in accordance with sustainable chemistry and engineering. In acidic media between pH 3 and 6, the ethyleneoxy groups tend to desorb from particle surfaces, slightly reducing the hydrophobicity of the particles. However, Pickering emulsions are still stable but their droplet size increases on lowering the pH. The Pickering emulsions are therefore pH-responsive and size-controllable. This newly designed Bola surfactant is effective in preparing smart emulsions, which are extensively applied in heterogeneous catalysis, oil product transportation, emulsion polymerization, and new material preparation.

Charge Density Overcomes Steric Hindrance of Ferrocene Surfactant in Switchable Oil-in-Dispersion Emulsions.

A ferrocene surfactant can be switched between single and double head form (FcN+ C12 /Fc+ N+ C12 ) triggered by redox reaction. FcN+ C12 can neither stabilize an O/W emulsion alone nor an oil-in-dispersion emulsion in combination with alumina nanoparticles due to the steric hindrance of the ferrocene group. However, such steric hindrance can be overcome by increasing the charge density in Fc+ N+ C12 , so that oil-in-dispersion emulsions can be co-stabilized by Fc+ N+ C12 and alumina nanoparticles at very low concentrations (1×10-7  M (≈50 ppb) and 0.001 wt %, respectively). Not only can reversible formation/destabilization of oil-in-dispersion emulsions be achieved by redox reaction, but also reversible transformation between oil-in-dispersion emulsions and Pickering emulsions can be obtained through reversing the charge of alumina particles by adjusting the pH. The results provide a new protocol for the design of surfactants for stabilization of smart oil-in-dispersion emulsions.

Fabrication of Stable Oleofoams with Sorbitan Ester Surfactants.

Sorbitan esters have been extensively used as surfactants to stabilize emulsions in many fields. However, the preparation of an oleofoam with sorbitan ester alone has not been reported. Here, we apply a novel protocol to fabricate stable oleofoams of high air volume fraction from mixtures of vegetable oil and sorbitan ester. To incorporate more air bubbles into the oil matrix, aeration is first carried out in the one-phase region at high temperatures, during which the highest over-run can reach 280%. Due to foam instability at high temperatures, the foam is then submitted to rapid cooling, followed by storage at low temperatures. For high-melting sorbitan monostearate, the resulting foams containing many crystal-encased air bubbles are ultrastable to drainage, coarsening, and coalescence for several months. On the contrary, the cooled foams with low-melting sorbitan monooleate go through a gradual decay lasting for more than 1 month. We highlight the importance of hydrogen bond formation between surfactant and oil in enhancing foam stability. The generic nature of the above findings is demonstrated by preparing oil foams with various vegetable oils and sorbitan monooleate.

Influence of particle wettability on foam formation in honey.

The rising level of obesity is often attributed to high sugar and/or fat consumption. Therefore, the food industry is constantly searching for ways to reduce or eliminate sugar or fat in food products. Therefore, honey foam, which contains little sugar and no fat, can be used as cake, cracker or bread spread instead of butter or margarine which contains a substantial amount of fat or jam that contains a substantial amount of sugar. Small solid particles (nanometers to micrometers) of suitable wettability are now considered outstanding foam-stabilizing agents. However, while the degree of particle wettability necessary to obtain very stable aqueous and nonaqueous foams is well-known, that needed to obtain very stable honey foam is unknown. In this study, the influence of the degree of wettability of fumed silica particles, indicated by their % SiOH (14-100), was investigated in honey in relation to foam formation and foam stability. The honephilic particles (61%-100% SiOH) formed particle dispersion in honey, while foams were obtained with the honephobic particles (14%-50% SiOH). The thread-off between particle dispersion and foam formation occurs at 50% SiOH, meaning foam formation in honey is possible when the particles are at least 50% honephobic. At relatively low particle concentration <1 wt.%, foam volume decreases with increasing honephobicity, but increases with honephobicity at relatively high concentration >1 wt.%. Also, as particle concentration increases, the shape of the air bubbles in the foam changes from spherical to non-spherical. After a little drainage, the foams remain stable to drainage and did not coalesce substantially for more than six months. These findings will guide the formulation of edible Pickering honey foams.

Liquid Marbles under Electric Fields: New Capabilities for Non-wetting Droplet Manipulation and Beyond.

The study of liquid marbles (LMs) composed of stabilizing liquid droplets with solid particles in a gaseous environment has matured into an established area in surface and colloid science. The minimized "solid-liquid-air" triphase interface enables LMs to drastically reduce adhesion to a solid substrate, making them unique non-wetting droplets transportable with limited energy. The small volume, enclosed environment, and simple preparation render them suitable microreactors in industrial applications and processes such as cell culture, material synthesis, and blood coagulation. Extensive application contexts request precise and highly efficient manipulations of these non-wetting droplets. Many external fields, including magnetic, acoustic, photothermal, and pH, have emerged to prepare, deform, actuate, coalesce, mix, and disrupt these non-wetting droplets. Electric fields are rising among these external stimuli as an efficient source for manipulating the LMs with high controllability and a significant ability to contribute further to proposed applications. This Feature Article attempts to outline the recent developments related to LMs with the aid of electric fields. The effects of electric fields on the preparation and manipulation of LMs with intricate interfacial processes are discussed in detail. We highlight a wealth of novel electric field-involved LM-based applications and beyond while also envisaging the challenges, opportunities, and new directions for future development in this emerging research area.

Hierarchical liquid marbles formed using floating hydrophobic powder and levitating water droplets.

HYPOTHESIS: Liquid marbles i.e. droplets coated by hydrophobic particles may be formed not only on the solid substrates but also on the floating layers of hydrophobic powders such as fluorinated fumed silica or polytetrafluoroethylene. EXPERIMENTS: Formation and growth of liquid marbles on fluorinated fumed silica or polytetrafluoroethylene powder floating on a heated water-vapor interface is reported. Marbles emerge from condensation of water droplets levitating above the powder layer. FINDINGS: The kinetics of the growth of droplets is reported. Growth of droplets results from three main mechanisms: water condensation, absorption of small droplets and merging of droplets with neighboring ones. Growing droplets are coated with the hydrophobic powder, eventually giving rise to the formation of stable liquid marbles. Formation of hierarchical liquid marbles is reported. Growth of liquid marbles emerging from water condensation follows the linear temporal dependence. A phenomenological model of the liquid marble growth is suggested.

Oil-in-Water emulsions stabilized by alumina nanoparticles with organic electrolytes: Fate of particles.

HYPOTHESIS: Oil-in-dispersion emulsions can be stabilized by like charged particles and surfactant. Surfactant adsorbs at the oil-water interface to reduce the interfacial tension and endow the interface with charge, while particles remain dispersed in the aqueous phase to provide electrostatic repulsion between droplets and particles. Can weakly surface-active organic electrolytes adsorb at the oil-water interface and behave like surfactants in stabilizing oil-in-dispersion emulsions with like charged particles? EXPERIMENTS: Symmetrical organic electrolytes, tetraalkylammonium bromides (R4NBr), with either no or very low interfacial activity endowing oil droplets with charge were combined with alumina nanoparticles to stabilize emulsions. The effect of R chain length (varying from methyl to butyl) on the type and stability of emulsions was investigated. FINDINGS: Mixtures of high concentrations of short chain R4NBr salts (R = methyl or ethyl) and alumina particles stabilise oil-in-water Pickering emulsions, whereas longer chain (R = propyl or butyl) analogues stabilize oil-in-dispersion emulsions assisted by alumina particles. Tetrapropylammonium and tetrabutylammonium cations adsorb at the oil-water interface reducing the interfacial tension and endowing the interface with charge. The stability of the oil-in-dispersion emulsions is dominated by the electrostatic repulsion between the droplets and between droplets and particles in the continuous aqueous phase.

Stabilisation of oleofoams by lauric acid and its glycerol esters.

Four types of pure lipid, namely lauric acid (LA), glycerol monolaurate (MAG), diglycerol laurate (DAG) and triglyceride laurate (TAG) were used to prepare oleofoams. The relationship between crystal profiles and their performance in oleofoams was established. DAG formed small needle-like crystals while MAG formed large flake-like crystals in oleogels, and crystal shells around air bubbles were observed in LA-, MAG- and DAG-based oleofoams. LA and DAG displayed higher over-run whereas DAG-stabilised foam possessed smaller bubbles and higher physical stability due to the presence of small ß and ß' crystals. Upon heating, DAG and TAG-based foams showed varying extents of oil drainage indicating the crystals were distributed in a different manner. Therefore, DAG was shown to be an excellent gelator in the fabrication of ultra-stable oleofoams. This work extends the lipid varieties with nutritional features and allows a better understanding on the stabilization mechanisms of lauric acid lipids in oleofoams.

Water-in-oil high internal phase Pickering emulsions formed by spontaneous interfacial hydrolysis of monomer oil.

HYPOTHESIS: Alcohols can strongly reduce the interfacial tension between immiscible liquids, thus facilitating the formation of emulsions. By combining non-surface-active hydrophobic particles with medium-chain alcohols, stable water-in-oil (w/o) high internal phase Pickering emulsions (HIPPEs) can be easily prepared without high-energy emulsification methods. EXPERIMENTS: The emulsions containing acrylate monomer as the oil phase were prepared at different pH values in the presence of hydrophobic silica particles. Further, by replacing monomer oil with organic solvents (e.g., toluene) and a certain concentration of alcohol, the promoted particle adsorption at the oil-water interface has been systematically investigated. The morphology and interfacial structure of HIPPEs were visualized by confocal laser scanning microscopy (CLSM). FINDING: At high pH, stable water-in-acrylate monomer HIPPEs can be formed using commercial fumed silica nanoparticles alone with simple stirring or vortexing. The hydrolysis of the acrylate group at high pH can generate alcohols in situ which adsorb at the oil-water interface to reduce the interfacial tension and promote particle adsorption to hinder droplet coalescence. The novel strategy for forming stable and processable HIPPEs can be universally applied to different hydrophobic silica particles with the help of various alcohols as the co-stabilizer, which provides a flexible approach for the fabrication of lightweight, closed-cell solid foams for a range of applications.

Buckling versus Crystal Expulsion Controlled by Deformation Rate of Particle-Coated Air Bubbles in Oil.

Oil foams stabilized by crystallizing agents exhibit outstanding stability and show promise for applications in consumer products. The stability and mechanics imparted by the interfacial layer of crystals underpin product shelf life, as well as optimal processing conditions and performance in applications. Shelf life is affected by the stability against bubble dissolution over a long time scale, which leads to slow compression of the interfacial layer. In processing flow conditions, the imposed deformation is characterized by much shorter time scales. In practical situations, the crystal layer is therefore subjected to deformation on extremely different time scales. Despite its importance, our understanding of the behavior of such interfacial layers at different time scales remains limited. To address this gap, here we investigate the dynamics of single, crystal-coated bubbles isolated from an oleofoam, at two extreme time scales: the diffusion-limited time scale characteristic of bubble dissolution, ∼104 s, and a fast time scale characteristic of processing flow conditions, ∼10-3 s. In our experiments, slow deformation is obtained by bubble dissolution, and fast deformation in controlled conditions with real-time imaging is obtained using ultrasound-induced bubble oscillations. The experiments reveal that the fate of the interfacial layer is dramatically affected by the dynamics of deformation: after complete bubble dissolution, a continuous solid layer remains; after fast, oscillatory deformation of the layer, small crystals are expelled from the layer. This observation shows promise toward developing stimuli-responsive systems, with sensitivity to deformation rate, in addition to the already known thermoresponsiveness and photoresponsiveness of oleofoams.

Pickering emulsion droplet-based biomimetic microreactors for continuous flow cascade reactions.

A continuous flow cascade of multi-step catalytic reactions is a cutting-edge concept to revolutionize stepwise catalytic synthesis yet is still challenging in practical applications. Herein, a method for practical one-pot cascade catalysis is developed by combining Pickering emulsions with continuous flow. Our method involves co-localization of different catalytically active sub-compartments within droplets of a Pickering emulsion yielding cell-like microreactors, which can be packed in a column reactor for continuous flow cascade catalysis. As exemplified by two chemo-enzymatic cascade reactions for the synthesis of chiral cyanohydrins and chiral ester, 5 - 420 fold enhancement in the catalysis efficiency and as high as 99% enantioselectivity were obtained even over a period of 80 - 240 h. The compartmentalization effect and enriching-reactant properties arising from the biomimetic microreactor are theoretically and experimentally identified as the key factors for boosting the catalysis efficiency and for regulating the kinetics of cascade catalysis.