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.

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.

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.

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.

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.

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.

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.

Pickering Emulsions Stabilized by Polystyrene Particles Possessing Different Surface Groups.

Colloidal polystyrene (PS) latex particles in water can undergo interesting charge reversal in the presence of particular electrolytes. It is worth exploring the effect of charge reversal on the properties of Pickering emulsions they stabilize. Herein, emulsions stabilized by PS latex particles possessing different surface groups (sulfate, amidine, or carboxyl) were prepared in the presence of tetrapentylammonium bromide (TPeAB) or sodium thiocyanate (NaSCN) electrolytes. The effect of salt concentration on the charge of the particles and their colloid stability was measured. Emulsions were prepared from aqueous dispersions, and their type and stability were determined. The three-phase contact angle of particles at the planar oil-water interface was also measured using a gel trapping technique. It was found that the type of emulsion stabilized by latex particles is dominated by the hydrophobic PS portion on particle surfaces, although their surface charge is strongly affected by electrolyte addition. Preferred emulsions were always water-in-oil with dodecane, and charge reversal had little influence on the emulsion type and stability. However, transitional phase inversion of emulsions stabilized by carboxyl latex particles occurred on adding salt when the oil was a low-viscosity polydimethylsiloxane.

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.

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.

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.

Recyclable and re-usable smart surfactant for stabilization of various multi-responsive emulsions alone or with nanoparticles.

A novel multi-responsive surfactant (abbreviated as N+-8P8-N) was synthesized, in which one octyl trimethylamine group (quaternary ammonium) and one octyl dimethylamine group are connected to a benzene ring through ether bonds. This novel surfactant can stabilize conventional oil-in-water (O/W) emulsions alone, and O/W Pickering emulsions and novel oil-in-dispersion emulsions together with oppositely and similarly charged nanoparticles, respectively. In all cases rapid demulsification can be achieved through either pH or CO2/N2 triggers, by which the surfactant is reversibly converted between a normal cationic surfactant form (N+-8P8-N) and a strongly hydrophilic and surface-inactive bola form (N+-8P8-NH+). Notably, the bola form N+-8P8-NH+ dissolves in the aqueous phase alone or together with nanoparticles after demulsification without contamination of the oil phase, and the aqueous phase can be recycled many times triggered by pH or CO2/N2 in accordance with the principle of green chemistry. This newly designed re-usable smart surfactant is significant for the development of various temporarily stable emulsions, which are extensively applied in emulsion polymerization, new material synthesis, heterogeneous catalysis and oil transportation.

Aqueous and Oil Foams Stabilized by Surfactant Crystals: New Concepts and Perspectives.

Surfactant crystals can stabilize liquid foams. The crystals are adsorbed at bubble surfaces, slowing down coarsening and coalescence. Excess crystals in the liquid channels between bubbles arrest drainage, leading to ultrastable foams. The melting of crystals upon raising the temperature allows thermoresponsive foams to be designed. In the case of oil foams, the stabilization by crystals received substantial renewed interest in the last 5 years due to their potential applications, particularly in the food industry. For aqueous foams, several reports exist on foams stabilized by crystals. However, these two kinds of liquid foams possess similarities in terms of stabilization mechanisms and the design of surfactant crystal systems. This field will certainly grow in the coming years, and it will contribute to the engineering of new soft materials not only for food but also for cosmetics, pharmaceuticals, and biomedical applications.

Lipase-Immobilized Cellulosic Capsules with Water Absorbency for Enhanced Pickering Interfacial Biocatalysis.

Lipase-immobilized cellulosic capsules consisting of hydrophobic ethyl cellulose (EC) and hydrophilic carboxymethyl cellulose (CMC) were developed with a promising interfacial activity and water absorbency for the enhanced Pickering interfacial biocatalysis. Lipase was physically immobilized with water-absorbent materials (CMC) via hydrogen bonding and electrostatic interactions and acted as the interior catalytic core of the capsule. The interfacially active EC worked as the exterior shell, enabling capsules to stabilize the oil-in-water Pickering emulsion for the subsequent Pickering interfacial catalysis. The capsules with CMC created interior water-rich conditions to improve the conformational and enzymatic activity of the immobilized lipase. Compared with capsules without water-absorbent materials, the capsules with CMC enhanced the efficiency of the Pickering interfacial catalysis for the esterification of oleic acid and 1-octanol by 12%. Immobilized with a small amount of lipase (0.0625 g/g), the cellulosic capsules with water absorbency could convert 50.8% of the reactants after 10 h under room temperature, significantly higher than that by the same amount of free lipase in the biphasic system (15%) and a Pickering emulsion (24.1%) stabilized by empty capsules (without lipase). Moreover, the cellulosic capsules could be recycled by simple centrifugation while retaining their high relative catalytic activity for at least eight cycles, demonstrating their sustainable catalytic performance.

Fabrication of Hierarchical Macroporous ZIF-8 Monoliths Using High Internal Phase Pickering Emulsion Templates.

The shaping of metal-organic frameworks (MOFs), referring to the integration of small sub-millimeter MOF crystals into bulk samples of desired size and shape, is an important step in the practical use of this class of porous material in many applications. Herein, we demonstrate for the first time the fabrication of hierarchical 3D MOF monoliths in situ within an MOF particle-stabilized high internal phase emulsion (HIPE). In this approach, a subfamily MOF (ZIF-8) is selected as the sole Pickering emulsion stabilizer for an oil-in-water (O/W) HIPE. With 2-methylimidazole and zinc nitrate in the continuous phase, ZIF-8 is formed in the emulsion to "bond" the ZIF-8 particles fabricating a ZIF-8 monolith without the addition of a polymer or polymerization of monomers. Freeze-drying of the HIPE produces a 3D ZIF-8 monolith. The monolith is packed into a chromatography column to test its catalytic performance as a flow-through catalyst in the Knoevenagel reaction. The monolith catalyst exhibits very high catalytic efficiency. Almost all the reaction mixture transforms to product within 2 min. Besides, the 3D ZIF-8 monolith showed excellent performance as an oil absorbent in oil-water separation. It achieved an absorption equilibrium of oil in less than 5 s, much faster than traditional high oil absorption materials.

Correction: Spontaneous particle desorption and "Gorgon" drop formation from particle-armored oil drops upon cooling.

Correction for 'Spontaneous particle desorption and "Gorgon" drop formation from particle-armored oil drops upon cooling' by Diana Cholakova et al., Soft Matter, 2020, 16, 2480-2496, DOI: 10.1039/C9SM02354B.

Charge-Reversible Surfactant-Induced Transformation Between Oil-in-Dispersion Emulsions and Pickering Emulsions.

A novel charge-reversible surfactant, (CH3 )2 N-(CH2 )10 COONa, was designed and synthesized, which together with silica nanoparticles can stabilize a smart n-octane-in-water emulsion responsive to pH. At high pH (9.3) the surfactant is anionic carboxylate, which together with the negatively charged silica nanoparticles co-stabilize flowable oil-in-dispersion emulsions, whereas at low pH (4.1) it is turned to cationic form by forming amine salt which can hydrophobize in situ the negatively charged silica nanoparticles to stabilize viscous oil-in-water (O/W) Pickering emulsions. At neutral pH (7.5), however, this surfactant is converted to zwitterionic form, which only weakly hydrophobises the silica particles to stabilize O/W Pickering emulsions of large droplet size. Moreover, demulsification can be achieved rapidly triggered by pH. With this strategy particles can be controlled either dispersed in water or adsorbed at the oil-water interface endowing emulsions with the capacity for intelligent and precise control of stability as well as viscosity and droplet size.

Light-Responsive, Reversible Emulsification and Demulsification of Oil-in-Water Pickering Emulsions for Catalysis.

Pickering emulsions are an excellent platform for interfacial catalysis. However, developing simple and efficient strategies to achieve product separation and catalyst and emulsifier recovery is still a challenge. Herein, we report the reversible transition between emulsification and demulsification of a light-responsive Pickering emulsion, triggered by alternating between UV and visible light irradiation. The Pickering emulsion is fabricated from Pd-supported silica nanoparticles, azobenzene ionic liquid surfactant, n-octane, and water. This phase behavior is attributed to the adsorption of azobenzene ionic liquid surfactant on the surface of the nanoparticles and the light-responsive activity of ionic liquid surfactant. The Pickering emulsion can be used as a microreactor that enables catalytic reaction, product separation as well as emulsifier and catalyst recycling. Catalytic hydrogenation of unsaturated hydrocarbons at room temperature and atmospheric pressure has been performed in this system to demonstrate product separation and emulsifier and catalyst re-use.

Effect of Particle Wettability and Particle Concentration on the Enzymatic Dehydration of n-Octanaloxime in Pickering Emulsions.

Pickering emulsion systems have emerged as platforms for the synthesis of organic molecules in biphasic biocatalysis. Herein, the catalytic performance was evaluated for biotransformation using whole cells exemplified for the dehydration of n-octanaloxime to n-octanenitrile catalysed by an aldoxime dehydratase (OxdB) overexpressed in E. coli. This study was carried out in Pickering emulsions stabilised solely with silica particles of different hydrophobicity. We correlate, for the first time, the properties of the emulsions with the conversion of the reaction, thus gaining an insight into the impact of the particle wettability and particle concentration. When comparing two emulsions of different type with similar stability and droplet diameter, the oil-in-water (o/w) system displayed a higher conversion than the water-in-oil (w/o) system, despite the conversion in both cases being higher than that in a "classic" two-phase system. Furthermore, an increase in particle concentration prior to emulsification resulted in an increase of the interfacial area and hence a higher conversion.