Nanoparticle Surfactants at Complex Emulsion Interfaces.

Using nanoparticle surfactants to stabilize the liquid-liquid interface has attracted significant attention for developing all-liquid constructs including emulsions and liquid devices. Here, an efficient strategy is demonstrated to stabilize complex emulsions that consist of multiphase droplets by using the co-assembly between the cellulose nanocrystal and amine-functionalized polystyrene. Cellulose nanocrystal surfactants (CNCSs) form and assembly in situ at the specified area of emulsion interface, showing a unique pH responsiveness due to their dynamic nature and allowing the reconfiguration of complex emulsion from encapsulated to Janus structures. Such complex emulsions can be further used as the templates to fabricate polymeric particles with hollow, semi-spherical, and spherical shapes on large scale. These findings establish a promising platform for designing intelligent soft matter that can be used in microreactors, sensors, and anisotropic materials.

Amphiphilic Polyphosphazene for Fluorocarbon Emulsion Stabilization.

High internal phase emulsions (HIPEs) have been of great interest for fabricating fluorinated porous polymers having controlled pore structures and excellent physicochemical properties. However, it remains a challenge to prepare stable fluorocarbon HIPEs, due to the lack of suitable surfactants. By randomly grating hydrophilic and fluorophilic side chains to polyphosphazene (PPZ), a comb-like amphiphilic PPZ surfactant with biodegradability is designed and synthesized for stabilizing water/fluorocarbon oil-based emulsions. The hydrophilic-lipophilic balance of PPZs can be controlled by tuning the grating ratio of the two side chains, leading to the preparation of stable water-in-oil HIPEs and oil-in-water emulsions, and the production of fluorinated porous polymers and particles by polymerizing the oil phase. These fluorinated porous polymers show excellent thermal stability and, due to the hydrophobicity and porous structure, applications in the field of oil/water separation can be achieved.

Interfacial Preparation of Polyoxometalate-Based Hybrid Supramolecular Polymers by Orthogonal Self-Assembly.

The construction of organic-inorganic hybrid supramolecular polymers using polyoxometalate (POM) as building block is expected to bring new opportunities to the functionalization of supramolecular polymers and the development of novel POM-based soft materials. Here, by using the orthogonal self-assembly based on host-guest interactions and metal-ligand interactions, we report the in situ construction of a novel POM-based hybrid supramolecular polymer (POM-SP) at the oil-water interface, while the redox and competitive responsiveness can be triggered independently. Moreover, the binding energy of POM-SP at the interface is sufficiently strong so that the assembly of POM-SP jams, allowing the stabilization of liquids in nonequilibrium shapes, offering the possibility of fabricating all-liquid constructs with reconfigurability.

Structured liquids stabilized by polyethyleneimine surfactants.

Using host-guest interactions between ß-cyclodextrin-modified branched polyethyleneimine and ferrocene-terminated poly-L-lactide, the formation, assembly and jamming of polyethyleneimine surfactants (PEISs) at the liquid-liquid interface is presented. With PEIS, reconfigurable liquids with electrochemical redox responsiveness can be constructed. In conjunction with microfluidic methods, continuous, selective diffusion and purification of ionic species can be achieved in all-liquid constructs.

pH- and Redox-Responsive Pickering Emulsions Based on Cellulose Nanocrystal Surfactants.

Nanoparticle surfactants (NPSs), formed by using dynamic interactions between nanoparticles and complementary ligands at the liquid-liquid interface, have emerged as "smart emulsifiers" with attributes of high emulsification efficiency, long-term stability, and on-demand emulsification/demulsification capabilities. However, only pH-responsiveness can be adopted for the assembly of reported NPSs formed by electrostatic interactions. Here, we propose an alternative design strategy, by taking advantage of the ferrocenium (Fc+ ) sulfate ion pair, to develop a new type of cellulose nanocrystal (CNC) surfactant. The Fc+ groups are sensitive to pH, redox reagents and voltage, imparting the CNC surfactants and derived Pickering emulsions with multi-stimuli-responsiveness, and showing promising applications in controllable delivery, release, and biphasic biocatalysis.

Stabilizing Liquids Using Interfacial Supramolecular Assemblies.

Stabilizing liquids based on supramolecular assembly (non-covalent intermolecular interactions) has attracted significant interest, due to the increasing demand for soft, liquid-based devices where the shape of the liquid is far from the equilibrium spherical shape. The components comprising these interfacial assemblies must have sufficient binding energies to the interface to prevent their ejection from the interface when the assemblies are compressed. Here, we highlight recent advances in structuring liquids based on non-covalent intermolecular interactions. We describe some of the progress made that reveals structure-property relationships. In addition to treating advances, we discuss some of the limitations and provide a perspective on future directions to inspire further studies on structured liquids based on supramolecular assembly.

Supramolecular Interfaces and Reconfigurable Liquids Derived from Cucurbit[7]uril Surfactants.

Nanoparticle surfactants (NPSs) offer a powerful means to stabilize the oil-water interface and construct all-liquid devices with advanced functions. However, as the nanoparticle size decreases to molecular-scale, the binding energy of the NPS to the interface reduces significantly, leading to a dynamic adsorption of NPS and "liquid-like" state of the interfacial assemblies. Here, by using the host-guest recognition between a water-soluble small molecule, cucurbit[7]uril (CB[7]) and an oil-soluble polymer ligand, methyl viologen-terminated polystyrene, a supramolecular NPS model, termed CB[7] surfactant, is described. CB[7] surfactants form and assemble rapidly at the oil-water interface, generating an elastic film with excellent mechanical properties. The binding energy of CB[7] surfactant to the interface is sufficiently high to hold it in a jammed state, transforming the interfacial assemblies from a "liquid-like" to "solid-like" state, enabling the structuring of liquids. With CB[7] surfactants as the emulsifier, O/W, W/O and O/W/O emulsions can be prepared in one step. Owing to the guest-competitive responsiveness of CB[7] surfactants, the assembly/disassembly and jamming/unjamming of CB[7] surfactants can be well controlled, leading to the reconfiguration of all-liquid constructs.

Reconfigurable Liquids Constructed by Pillar[6]arene-Based Nanoparticle Surfactants.

The interfacial jamming of nanoparticle surfactants offers the possibility of structuring liquids and fabricating all-liquid constructs with advanced functionality. However, less attention has been given to structured liquids with multiple responsiveness. Here, we show a novel, yet highly simplified nanoparticle surfactant model, pillar[6]arene (PA[6]) surfactant, by taking advantage of the host-guest interactions between a water-soluble PA[6] and an oil-soluble ligand, ferrocenium terminated polystyrene. PA[6] surfactants form rapidly at the oil-water interface, assemble into an elastic film with excellent mechanical strength, and when jammed, offer a "solid-like" assembly to lock-in highly nonequilibrium shapes of the liquids. The interfacial assembly/jamming and disassembly/unjamming of PA[6] surfactants can be controlled by chemical redox or competitive guest reagents, endowing the structured liquids with redox or guest-competitive responsiveness.

The Assembly and Jamming of Nanoparticle Surfactants at Liquid-Liquid Interfaces.

Using the interactions between nanoparticles (NPs) and polymeric ligands to generate nanoparticle surfactants (NPSs) at the liquid-liquid interface, the binding energy of the NP to the interface can be significantly increased, irreversibly binding the NPSs to the interface. By designing a simplified NPS model, where the NP size can be precisely controlled and the characteristic fluorescence of the NPs be used as a direct probe of their spatial distribution, we provide new insights into the attachment mechanism of NPSs at the liquid-liquid interface. We find that the binding energy of NPSs to the interface can be reduced by competitive ligands, resulting in the dissociation and disassembly of NPSs at the interface, and allowing the construction of responsive, reconfigurable all-liquid systems. Smaller NPSs that are loosely packed (unjammed) and irreversibly bound to the interface can be displaced by larger NPSs, giving rise to a size-dependent assembly of NPSs at the interface. However, when the smaller size NPSs are densely packed and jam at the interface, the size-dependent assembly of NPSs at the interface can be completely suppressed.

Polyoxometalate-Surfactant Assemblies: Responsiveness to Orthogonal Stimuli.

Integrating different types of supramolecular interactions opens the possibility to generate nanoparticle surfactants (NPSs) at the liquid-liquid interface that are responsive to multiple stimuli. Here we develop a covalently modified polyoxometalate/ß-cyclodextrin (POM/ß-CD) organic-inorganic hybrid, consisting of a negatively charged POM cluster with ß-CD host groups. The POM/ß-CD hybrid can be dispersed in water and interacts at a water/oil interface with ligands dissolved in an oil phase through electrostatic or host-guest interactions, thereby generating POM-surfactants (POMSs) having pH, redox, and guest-competitive responsiveness, respectively. By taking advantage of the jamming of POMSs at the interface, a reconfigurable all-liquid system could be produced that is responsive to orthogonal changes in the external environment.

Redox-Responsive, Reconfigurable All-Liquid Constructs.

Using host-guest chemistries in a biphasic system, a novel supramolecular nanoparticle surfactant (s-NPS) with redox-responsiveness is presented to structure liquids. The in situ assembly/jamming and disassembly/unjamming of s-NPSs at the oil-water interface are reversibly controlled by a switchable redox process, imparting a nanoscale redox-responsiveness, affecting the assemblies on all length scales. "Smart" all-liquid constructs including structured emulsions and programmable liquid devices are easily prepared, showing promising applications in responsive delivery, release, and reaction systems.

Molecular Brush Surfactants: Versatile Emulsifiers for Stabilizing and Structuring Liquids.

Using amphiphilic molecular brushes to stabilize emulsions usually requires the synthesis of specific side chains, which can be a time-consuming and difficult challenge to meet. By taking advantage of the electrostatic interactions between water-soluble molecular brushes and oil-soluble oligomeric ligands, the in situ formation, assembly and jamming of molecular brush surfactants (MBSs) at the oil-water interface is described. With MBSs, stable emulsions including o/w, w/o and o/w/o can be easily prepared by varying the molar ratios of the molecular brushes to the ligands. Moreover, when jammed, the binding energy of MBSs at the interface is sufficiently strong to allow the stabilization of liquids in nonequilibrium shapes, i.e., structuring liquids, producing an elastic film at the interface with exceptional mechanical properties. These structured liquids have numerous potential applications, including chemical biphasic reactions, liquid electronics, and all-liquid biomimetic system.

Gated Molecular Diffusion at Liquid-Liquid Interfaces.

The jamming of nanoparticle surfactants (NPSs) at liquid-liquid interface imparts attractive properties to the interfacial assemblies and enables the structuring of liquids. Herein, we report photoresponsive supramolecular microcapsules with jammed NPS assemblies at the oil-water interface, taking advantage of host-guest molecular recognition. The permeability of the colloidal membrane can be effectively manipulated by switching the NPSs from a jammed state to an unjammed state with a photo trigger, leading to a controlled molecular diffusion and release, affording a versatile platform for the construction of next generation smart microcapsule systems.

Responsive Interfacial Assemblies Based on Charge-Transfer Interactions.

Charge transfer (CT) interactions have been widely used to construct supramolecular systems, such as functional nanostructures and gels. However, to date, there is no report on the generation of CT complexes at the liquid-liquid interface. Here, by using an electron-deficient acceptor dissolved in water and an electron-rich donor dissolved in oil, we present the in situ formation and assembly of CT complex surfactants (CTCSs) at the oil-water interface. With time, CTCSs can assemble into higher-order nanofilms with exceptional mechanical properties, allowing the stabilization of liquids and offering the possibility to structure liquids into nonequilibrium shapes. Moreover, due to the redox-responsiveness of the electron-deficient acceptor, the association and dissociation of CTCSs can be reversibly manipulated in a redox process, leading to the switchable assembly and disassembly of the resultant constructs.

Visualizing Interfacial Jamming Using an Aggregation-Induced-Emission Molecular Reporter.

With the interfacial jamming of nanoparticles (NPs), a load-bearing network of NPs forms as the areal density of NPs increases, converting the assembly from a liquid-like into a solid-like assembly. Unlike vitrification, the lineal packing of the NPs in the network is denser, while the remaining NPs can remain in a liquid-like state. It is a challenge to determine the point at which the assemblies jam, since both jamming and vitrification lead to a solid-like behavior of the assemblies. Herein, we show a real-time fluorescence imaging method to probe the evolution of the interfacial dynamics of NP surfactants at the water/oil interface using aggregation-induced emission (AIE) as a reporter for the transition of the assemblies into the jammed state. The AIEgens show typical fluorescence behavior at densities at which they can move and rotate. However, when aggregation of these fluorophores occurs, the smaller intermolecular separation distance arrests rotation, and a significant enhancement in the fluorescence intensity occurs.

Photoresponsive Structured Liquids Enabled by Molecular Recognition at Liquid-Liquid Interfaces.

Using host-guest molecular recognition at the oil-water interface, a new type of photoresponsive nanoparticle surfactant (NPS) was designed and prepared to structure liquids. With the help of a polymeric surfactant, the interfacial host-guest interactions can be significantly enhanced, leading to the rapid formation and assembly of a NP monolayer and offering sufficient binding energy to hold the NPs in a jammed state. The assembly of the NPSs can be reversibly manipulated via a photoswitchable jamming-to-unjamming transition, endowing the interface as well as the macroscopic assemblies with responsiveness to the external trigger (photons). This study for the first time opens a pathway for the construction of multiresponsive, structured all-liquid systems by introducing host-guest chemistry, showing promising potential applications in encapsulation, delivery systems, and unique microfluidic devices.

Poly(oxime-ester) Vitrimers with Catalyst-Free Bond Exchange.

Vitrimers are network polymers that undergo associative bond exchange reactions in the condensed phase above a threshold temperature, dictated by the exchangeable bonds comprising the vitrimer. For vitrimers, chemistries reliant on poorly nucleophilic bond exchange partners (e.g., hydroxy-functionalized alkanes) or poorly electrophilic exchangeable bonds, catalysts are required to lower the threshold temperature, which is undesirable in that catalyst leaching or deactivation diminishes its influence over time and may compromise reuse. Here we show how to access catalyst-free bond exchange reactions in catalyst-dependent polyester vitrimers by obviating conventional ester bonds in favor of oxime-esters. Poly(oxime-ester) (POE) vitrimers are synthesized using thiol-ene click chemistry, affording high stretchability and malleability. POE vitrimers are readily recycled with little degradation of their initial mechanical properties, suggesting exciting opportunities for sustainable plastics.

Vapor-induced motion of two pure liquid droplets.

The movement of evaporating liquid droplets on a surface can be triggered by the Marangoni effect arising from heterogeneities in the surface tension or a gradient in the surface energy of the substrate. Here, we show that, on a high energy surface that remains uniform, the motion of two pure liquid droplets can be induced by a gradient in the liquid vapor resulting from evaporation. The droplets always attract each other, moving from the high evaporation side to the low evaporation side, to reduce energy dissipation. By varying the volume of the droplets or the distance between droplets, the motion of the droplets can be effectively controlled.

Self-Assembly of MXene-Surfactants at Liquid-Liquid Interfaces: From Structured Liquids to 3D Aerogels.

2D transition metal carbides and nitrides (MXenes), a class of emerging nanomaterials with intriguing properties, have attracted significant attention in recent years. However, owing to the highly hydrophilic nature of MXene nanosheets, assembly strategies of MXene at liquid-liquid interfaces have been very limited and challenging. Herein, through the cooperative assembly of MXene and amine-functionalized polyhedral oligomeric silsesquioxane at the oil-water interface, we report the formation, assembly, and jamming of a new type MXene-based Janus-like nanoparticle surfactants, termed MXene-surfactants (MXSs), which can significantly enhance the interfacial activity of MXene nanosheets. More importantly, this simple assembly strategy opens a new platform for the fabrication of functional MXene assemblies from mesoscale (e.g., structured liquids) to macroscale (e.g., aerogels), that can be used for a range of applications, including nanocomposites, electronic devices, and all-liquid microfluidic devices.

Atomic Force Microscopy Nanomechanical Mapping Visualizes Interfacial Broadening between Networks Due to Chemical Exchange Reactions.

The interfacial broadening between two different epoxy networks having different moduli was nanomechanically mapped. The interfacial broadening of the two networks produced an interfacial zone having a gradient in the concentration and, hence, properties of the original two networks. This interfacial broadening of the networks leads to the generation of a new network with a segmental composition corresponding to a mixture of the original two network segments. The intermixing of the two, by nature of the exchange reactions, was on the segmental level. By mapping the time dependence of the variation in the modulus at different temperatures, the kinetics of the exchange reaction was measured and, by varying the temperature, the activation energy of the exchange reaction was determined.