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.

Thermal Welding of Liquids.

Welding of thermoplastics is a common practice in many industrial sectors, but it has yet to be realized with fluids. Here, the thermal welding of liquids by using the assembly and jamming of nanoparticle surfactants (NPSs) at liquid-liquid interfaces is reported. By fine-tuning the dynamic interaction strength within NPSs, the interfacial activity of NPSs, as well as the binding energy of NPSs to the interface can be precisely controlled, leading to a dynamic exchange of NPSs, maximizing the reduction in the interfacial energy. With NPSs jammed at the interface, the structures of liquids can be manipulated to complex geometries by applying an external force and, due to the temperature responsiveness of NPSs, when bringing liquids into contact and heating the system, welding of liquids can be achieved. This work provides a straightforward strategy for the construction of modular all-liquid fluidics, opening up numerous opportunities in fields like biotechnology, healthcare, and materials science.

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.

Reconfigurable droplet networks.

Droplet networks stabilized by lipid interfacial bilayers or colloidal particles have been extensively investigated in recent years and are of great interest for compartmentalized reactions and biological functions. However, current design strategies are disadvantaged by complex preparations and limited droplet size. Here, by using the assembly and jamming of cucurbit[8]uril surfactants at the oil-water interface, we show a novel means of preparing droplet networks that are multi-responsive, reconfigurable, and internally connected over macroscopic distances. Openings between the droplets enable the exchange of matter, affording a platform for chemical reactions and material synthesis. Our work requires only a manual compression to construct complex patterns of droplet networks, underscoring the simplicity of this strategy and the range of potential applications.

Self-Assembly of Polyoxometalate-Based Nanoparticle Surfactants in Solutions.

Nanoparticle surfactants (NPSs) are an emergent class of amphiphiles attractive for their controllable assembly at the liquid-liquid interface. In this work, intriguing self-assembly behavior and stimuli-responsiveness of NPSs in homogeneous solutions are presented. With ß-cyclodextrin-grafted polyoxometalates (POMs) and ferrocene (or azobenzene)-terminated polystyrene in water/tetrahydrofuran, POM-based NPSs are formed via host-guest interactions and self-organize to vesicles driven by solvent-phobic effects. The tunable supramolecular interactions allow these assemblies to be responsive to redox or light stimulus, respectively, affording an on-demand assembly/disassembly capacity that shows promise in delivery and release applications.

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.

All-oil Constructs Stabilized by Cellulose Nanocrystal Surfactants.

Constructing all-oil systems with desired geometries and responsiveness would produce a new class of reconfigurable materials that can be used for applications that are not compatible with water or aqueous systems, a fascinating goal to achieve but severely limited by the lack of surfactants. Here, we demonstrate an efficient strategy to stabilize oil-oil interfaces by using the co-assembly between the cellulose nanocrystal and amine-functionalized polyhedral oligomeric silsesquioxane (POSS-NH2). Cellulose nanocrystal surfactants (CNCSs) form and assemble in situ at the interface, showing significantly enhanced binding energy and acid-dependent interfacial activity. When CNCSs jam at the interface, a robust assembly with exceptional mechanical properties can be achieved, allowing the 3D printing of all-oil devices on demand. Using CNCSs as emulsifiers, oil-in-oil high internal phase emulsions can be prepared by one-step homogenization and, when used as templates, porous materials that require water-sensitive monomers can be synthesized. These results open a new platform for stabilizing and structuring all-oil systems, providing numerous applications for microreactors, encapsulation, delivery, and tissue engineering scaffolds.

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.

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.

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.

Optimization method for ankle strength training during exercise / Método de otimização no treino de força do tornozelo durante o exercício / Método para optimizar el entrenamiento de la fuerza del tobillo durante el ejercicio

ABSTRACT Introduction Good ankle joint strength is a precondition for high-quality exercise and is an important factor in preventing joint injuries. Objective Explore the method of optimizing ankle strength training during exercise. Methods 40 volunteers were selected and randomly divided into an experimental group and a control group. The 20 athletes in the experimental group were trained three times a week for six weeks using a control variable method, while the control group performed only professional daily physical training. Pre-training and post-training methods were used to collect and investigate the data regarding the effect of strength training on the ankle joint and its impact on skill and strength tests submitted to the athletes. Results Ankle strength training can improve ankle muscle strength and athletes' ability to run and jump (P > 0.05). Conclusion Ankle joint strength training may improve athletes' baseline sporting ability, improve ankle joint muscle strength, reduce the likelihood of joint injuries, and contribute to improved outcomes of various abilities, meriting further study and replication. Level of evidence II; Therapeutic studies - investigation of treatment outcomes.

RESUMO Introdução A boa força articular do tornozelo é uma pré-condição para exercícios físicos de alta qualidade além de ser um fator importante na prevenção de lesões articulares. Objetivo Explorar o método de otimização do treino de força do tornozelo durante o exercício físico. Métodos 40 voluntários foram selecionados e aleatoriamente divididos em grupo experimental e grupo de controle. Os 20 atletas do grupo experimental foram treinados três vezes por semana durante 6 semanas usando um método de variáveis de controle enquanto o grupo controle efetuou apenas o treinamento físico diário profissional. Foram utilizados métodos pré-treino e pós-treino para coleta e investigação dos dados quanto ao efeito do treinamento de força sob a articulação do tornozelo e seu impacto em testes de habilidade e força submetidos aos atletas. Resultados O treinamento de força do tornozelo pode melhorar a força muscular do tornozelo e melhorar a capacidade dos atletas de correr e saltar (P > 0,05). Conclusão O treino de força articular do tornozelo pode melhorar a capacidade esportiva basal dos atletas, melhorar a força muscular da articulação do tornozelo, reduzir a probabilidade de lesões articulares e contribuir na melhoria dos resultados de várias habilidades, merecendo maiores estudos e replicação. Nível de evidência II; Estudos terapêuticos - investigação dos desfechos do tratamento.

RESUMEN Introducción Una buena resistencia de la articulación del tobillo es una condición previa para la realización de ejercicio físico de alta calidad y un factor importante en la prevención de lesiones articulares. Objetivo Explorar el método para optimizar el entrenamiento de la fuerza del tobillo durante el ejercicio. Métodos Se seleccionaron 40 voluntarios y se dividieron aleatoriamente en grupo experimental y grupo de control. Los 20 atletas del grupo experimental se entrenaron tres veces a la semana durante 6 semanas con un método variable de control, mientras que el grupo de control sólo realizó un entrenamiento físico profesional diario. Se utilizaron métodos de pre-entrenamiento y post-entrenamiento para recoger e investigar los datos relativos al efecto del entrenamiento de fuerza bajo la articulación del tobillo y su impacto en las pruebas de habilidad y fuerza a las que se sometieron los atletas. Resultados El entrenamiento de la fuerza del tobillo puede mejorar la fuerza muscular del tobillo y mejorar la capacidad de los atletas para correr y saltar (P > 0,05). Conclusión El entrenamiento de la fuerza de la articulación del tobillo puede mejorar la capacidad deportiva de base de los atletas, mejorar la fuerza muscular de la articulación del tobillo, reducir la probabilidad de lesiones articulares y contribuir a mejorar los resultados de varias habilidades, mereciendo más estudios y réplicas. Nivel de evidencia II; Estudios terapêuticos - investigación de los resultados del tratamiento.

Interfacial Assembly and Jamming of Soft Nanoparticle Surfactants into Colloidosomes and Structured Liquids.

Nanoparticle surfactant (NPS) offers a powerful strategy to generate all-liquid constructs that integrate the inherent properties of the NPs into 3D architectures. Here, using the co-assembly of fluorescent polymeric nanoparticles and amine-functionalized polyhedral oligomeric silsesquioxane, the assembly and jamming behavior of a new type of NPS at the oil-water interface is uncovered. Unlike "solid" inorganic nanoparticles, "soft" polymeric nanoparticles can reorganize when jammed, leading to a relaxation and deformation of the interfacial assemblies, for example, the 3D printed sugar-coated haw stick-like liquid tubules. With NPS serving as emulsifiers, stable Pickering emulsions are prepared that can be converted into robust colloidosomes with pH responsiveness, showing numerous potential applications for encapsulation and controlled release.

MXene-Based Porous Monoliths.

In the past decade, a thriving family of 2D nanomaterials, transition-metal carbides/nitrides (MXenes), have garnered tremendous interest due to its intriguing physical/chemical properties, structural features, and versatile functionality. Integrating these 2D nanosheets into 3D monoliths offers an exciting and powerful platform for translating their fundamental advantages into practical applications. Introducing internal pores, such as isotropic pores and aligned channels, within the monoliths can not only address the restacking of MXenes, but also afford a series of novel and, in some cases, unique structural merits to advance the utility of the MXene-based materials. Here, a brief overview of the development of MXene-based porous monoliths, in terms of the types of microstructures, is provided, focusing on the pore design and how the porous microstructure affects the application performance.

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.

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.

Layer-by-Layer Engineered All-Liquid Microfluidic Chips for Enzyme Immobilization.

Enzyme immobilization in the confines of microfluidic chips, that promote enzyme activity and stability, has become a powerful strategy to enhance biocatalysis and biomass conversion. Here, based on a newly developed all-liquid microfluidic chip, fabricated by the interfacial assembly of nanoparticle surfactants (NPSs) in a biphasic system, a layer-by-layer assembly strategy to generate polysaccharide multilayers on the surface of a microchannel, greatly enhancing the mechanical properties of the microchannel and offering a biocompatible microenvironment for enzyme immobilization, is presented. Using horseradish peroxidase and glucose oxidase as model enzymes, all-liquid microfluidic enzymatic and cascade reactors have been constructed and the crucial role of polysaccharide multilayers on enhancing the enzyme loading and catalytic efficiency is demonstrated.

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.

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.

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.