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Natural and man-made robotic systems use the interfacial tension between two fluids to support dense objects on liquid surfaces. Here, we show that coacervate-encased droplets of an aqueous polymer solution can be hung from the surface of a less dense aqueous polymer solution using surface tension. The forces acting on and the shapes of the hanging droplets can be controlled. Sacs with homogeneous and heterogeneous surfaces are hung from the surface and, by capillary forces, form well-ordered arrays. Locomotion and rotation can be achieved by embedding magnetic microparticles within the assemblies. Direct contact of the droplet with air enables in situ manipulation and compartmentalized cascading chemical reactions with selective transport. Applications including functional microreactors, motors, and biomimetic robots are evident.
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Fine control over the mechanical properties of thin sheets underpins transcytosis, cell shape, and morphogenesis. Applying these principles to artificial, liquid-based systems has led to reconfigurable materials for soft robotics, actuation, and chemical synthesis. However, progress is limited by a lack of synthetic two-dimensional membranes that exhibit tunable mechanical properties over a comparable range to that seen in nature. Here, we show that the bending modulus, B, of thin assemblies of nanoparticle surfactants (NPSs) at the oil-water interface can be varied continuously from sub-kBT to 106kBT, by varying the ligands and particles that comprise the NPS. We find extensive departure from continuum behavior, including enormous mechanical anisotropy and a power law relation between B and the buckling spectrum width. Our findings provide a platform for shape-changing liquid devices and motivate new theories for the description of thin-film wrinkling.
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Nanopartículas , Tensoactivos , AnisotropíaRESUMEN
The effect of polymer surfactant structure and concentration on the self-assembly, mechanical properties, and solidification of nanoparticle surfactants (NPSs) at the oil-water interface was studied. The surface tension of the oil-water interface was found to depend strongly on the choice of the polymer surfactant used to assemble the NPSs, with polymer surfactants bearing multiple polar groups being the most effective at reducing interfacial tension and driving the NPS assembly. By contrast, only small variations in the shear modulus of the system were observed, suggesting that it is determined largely by particle density. In the presence of polymer surfactants bearing multiple functional groups, NPS assemblies on pendant drop surfaces were observed to spontaneously solidify above a critical polymer surfactant concentration. Interfacial solidification accelerated rapidly as polymer surfactant concentration was increased. On long timescales after solidification, pendant drop interfaces were observed to spontaneously wrinkle at sufficiently low surface tensions (approximately 5 mN m-1). Interfacial shear rheology of the NPS assemblies was elastic-dominated, with the shear modulus ranging from 0.1 to 1 N m-1, comparable to values obtained for nanoparticle monolayers elsewhere. Our work paves the way for the development of designer, multicomponent oil-water interfaces with well-defined mechanical, structural, and functional properties.
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Polyoxometalates (POMs) using {Mo72V30} as an example, dissolved in water, can interact with amine-terminated polydimethylsiloxane (PDMS-NH2) dissolved in toluene at the water/toluene interface to form POM-surfactants that significantly lower the interfacial tension and can be used to stabilize liquids via interfacial elasticity. The jamming of the POM-surfactants at the water/oil interface with consequent wrinkling occurs with a decrease in the interfacial area. The packing density of the POM-surfactants at the interface can be tuned by varying the strength of screening with the addition of cations with differing hydrated radii.
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Amine-functionalized polyhedral oligomeric silsesquioxane (POSS), the smallest, monodisperse cage-shaped silica cubic nanoparticle, is exceptionally interfacially active and can form assemblies that jam the toluene/water interface, locking in non-equilibrium shapes of one liquid phase in another. The packing density of the amine-functionalized POSS assembly at the water/toluene interface can be tuned by varying the concentration, the pH value, and the degree of POSS functionalization. Functionalized POSS gives a higher interface coverage, and hence a lower interfacial tension, than nanoparticle surfactants formed by interactions between functionalized nanoparticles and polymeric ligands. Hydrogen-bonded POSS surfactants are more stable at the interface, offering some unique advantages for generating Pickering emulsions over typical micron-sized colloidal particles and ligand-stabilized nanoparticle surfactants.
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Structured liquids, generated by the interfacial formation, assembly, and jamming of nanoparticle (NP)-surfactants at liquid/liquid interfaces, maintain all the desirable characteristics of each liquid, while providing a spatially structured framework. Herein, we show that rod-like cellulose nanocrystal (CNC)-based NP-surfactants, termed CNC-surfactants, are formed rapidly at the liquid/liquid interface, assemble into a monolayer, and, when jammed, offer a robust assembly with exceptional mechanical properties. Plateau-Rayleigh (PR) instabilities of a free-falling jet of an aqueous medium containing the CNCs into a toluene solution of amine end-functionalized polystyrene are completely suppressed, allowing the jetting of aqueous tubules that are stabilized when the CNC-surfactants are jammed at the interface. These results open a new platform for the additive manufacturing techniques, for example, three-dimensional (3D) printing, of all-liquid constructs.
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Colloidal PMMA particles and an interfacially assembled, pH-switchable lipid film (tetradecylammonium hydrogen phosphate, TAHP) were combined to form emulsion droplets with composite interfaces. Two time scales govern the interfacial structure and droplet size of the system: the rate of particle adsorption and the rate of film assembly. We tune these two time scales by varying the particle size (in the case of the particles) and aqueous pH (in the case of the lipid film). Three rates of film assembly are studied: rapid (pH 5), slow (pH 7), and inactive (pH 9). At pH 5, small droplets coated with a mixed interfacial structure are formed, and increasing particle volume fraction does not change the droplet size. At pH 7, the slowed kinetics of TAHP film assembly results in the particle size having a systematic effect upon droplet size: the smaller the particles, the smaller the droplets. At pH 9, TAHP plays no role in the system, and more familiar Pickering emulsions are observed. Finally, we show that at pH 5 both the interfacial particle density and droplet size can be readily tuned in our system. This suggests potential applications in the rational design of capsules and emulsion droplets with tunable interfacial structure.
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We study the films formed by tetradecylamine (TDA) at the water-dodecane interface in the presence of hydrogen phosphate ions. Using Fourier transform infrared spectroscopy (FTIR), interfacial shear rheology, confocal fluorescence microscopy, cryo-scanning electron microscopy (cryo-SEM), and small-angle neutron scattering (SANS), we find that between pH 5 and 8 tetradecylammonium cations bind to hydrogen phosphate anions to form needle-shaped crystallites of tetradecylammonium hydrogen phosphate (TAHP). These crystallites self-assemble into films with a range of morphologies; below pH 7, they form brittle, continuous sheets, and at pH 8, they form lace-like networks that deform plastically under shear. They are also temperature-responsive: when the system is heated, the film thins and its rheological moduli drop. We find that the temperature response is caused by dissolution of the film in to the bulk fluid phases. Finally, we show that these films can be used to stabilize temperature-responsive water-in-oil emulsions with potential applications in controlled release of active molecules.
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Alcanos/química , Grasas/química , Aceites/química , Fosfatos/química , Temperatura , Agua/química , Concentración de Iones de Hidrógeno , SolubilidadRESUMEN
Millimeter-scale tubes are observed to sprout from water droplets injected into a bath of toluene containing ethanol and silica colloids. This phenomenon requires that first a membrane is formed by the colloids which self-assemble at the droplet interface, and second, that the ethanol preferentially partitions into the aqueous phase leading to an internal over-pressure. Tube growth, eruption, and shuffling droplets are subsequently observed, depending on the concentration of ethanol and colloids selected. This work opens many possibilities in the field of biomimetic droplets for fundamental studies of artificial growth at the microscale and for emulsion-related applications.
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Agua/química , Coloides/química , Etanol/química , Reología , Dióxido de Silicio/química , Propiedades de Superficie , Tolueno/químicaRESUMEN
[This corrects the article DOI: 10.1021/acscentsci.2c00146.].
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A bottom-up approach to fabricating monodisperse, two-component polymersomes that possess phase-separated ("patchy") chemical topology is presented. This approach is compared with already-existing top-down preparation methods for patchy polymer vesicles, such as film rehydration. These findings demonstrate a bottom-up, solvent-switch self-assembly approach that produces a high yield of nanoparticles of the target size, morphology, and surface topology for drug delivery applications, in this case patchy polymersomes of a diameter of ≈50 nm. In addition, an image processing algorithm to automatically calculate polymersome size distributions from transmission electron microscope images based on a series of pre-processing steps, image segmentation, and round object identification is presented.
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Nanopartículas , Polímeros , Sistemas de Liberación de Medicamentos , Microscopía , SolventesRESUMEN
Phenotypic targeting requires the ability of the drug delivery system to discriminate over cell populations expressing a particular receptor combination. Such selectivity control can be achieved using multiplexed-multivalent carriers often decorated with multiple ligands. Here, we demonstrate that the promiscuity of a single ligand can be leveraged to create multiplexed-multivalent carriers achieving phenotypic targeting. We show how the cellular uptake of poly(2-(methacryloyloxy)ethyl phosphorylcholine)-poly(2-(diisopropylamino)ethyl methacry-late) (PMPC-PDPA) polymersomes varies depending on the receptor expression among different cells. We investigate the PMPC-PDPA polymersome insertion at the single chain/receptor level using all-atom molecular modeling. We propose a theoretical statistical mechanics-based model for polymersome-cell association that explicitly considers the interaction of the polymersome with the cell glycocalyx shedding light on its effect on the polymersome binding. We validate our model experimentally and show that the binding energy is a nonlinear function, allowing us to tune the interaction by varying the radius and degree of polymerization. Finally, we show that PMPC-PDPA polymersomes can be used to target monocytes in vivo due to their promiscuous interaction with SRB1, CD36, and CD81.
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Soft robots, made from elastomers, easily bend and flex, but deformability constraints severely limit navigation through and within narrow, confined spaces. Using aqueous two-phase systems we print water-in-water constructs that, by aqueous phase-separation-induced self-assembly, produce ultrasoft liquid robots, termed aquabots, comprised of hierarchical structures that span in length scale from the nanoscopic to microsciopic, that are beyond the resolution limits of printing and overcome the deformability barrier. The exterior of the compartmentalized membranes is easily functionalized, for example, by binding enzymes, catalytic nanoparticles, and magnetic nanoparticles that impart sensitive magnetic responsiveness. These ultrasoft aquabots can adapt their shape for gripping and transporting objects and can be used for targeted photocatalysis, delivery, and release in confined and tortuous spaces. These biocompatible, multicompartmental, and multifunctional aquabots can be readily applied to medical micromanipulation, targeted cargo delivery, tissue engineering, and biomimetics.
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Biomimética , Robótica , Elastómeros/química , AguaRESUMEN
We report the design, simulation, synthesis, and reversible self-assembly of nanofibrils using polyhistidine-based oligopeptides. The inclusion of aromatic amino acids in the histidine block produces distinct antiparallel ß-strands that lead to the formation of amyloid-like fibrils. The structures undergo self-assembly in response to a change in pH. This creates the potential to produce well-defined fibrils for biotechnological and biomedical applications that are pH-responsive in a physiologically relevant range.
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The targeted delivery of therapeutic compounds to the brain is arguably the most significant open problem in drug delivery today. Nanoparticles (NPs) based on peptides and designed using the emerging principles of molecular engineering show enormous promise in overcoming many of the barriers to brain delivery faced by NPs made of more traditional materials. However, shortcomings in our understanding of peptide self-assembly and blood-brain barrier (BBB) transport mechanisms pose significant obstacles to progress in this area. In this review, we discuss recent work in engineering peptide nanocarriers for the delivery of therapeutic compounds to the brain: from synthesis, to self-assembly, to in vivo studies, as well as discussing in detail the biological hurdles that a nanoparticle must overcome to reach the brain.
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Barrera Hematoencefálica/metabolismo , Encéfalo/efectos de los fármacos , Sistemas de Liberación de Medicamentos/métodos , Nanopartículas/química , Péptidos/química , Administración Intranasal , Animales , Transporte Biológico/fisiología , Implantes de Medicamentos , Humanos , Proteínas Recombinantes/administración & dosificación , Proteínas Recombinantes/químicaRESUMEN
Producing artificial multicellular structures to process multistep cascade reactions and mimic the fundamental aspects of living systems is an outstanding challenge. Highly biocompatible, artificial systems consisting of all-aqueous, compartmentalized multicellular systems have yet to be realized. Here, a rapid multilevel compartmentalization of an all-aqueous system where a 3D sheet of subcolloidosomes encloses a mother colloidosome by interfacial phase separation is demonstrated. These spatially organized multicellular structures are termed "blastosomes" since they are similar to blastula in appearance. The barrier to nanoparticle assembly at the water-water interface is overcome using oppositely charged polyelectrolytes that form a coacervate-nanoparticle-composite network. The conditions required to trigger interfacial phase separation and form blastosomes are quantified in a mapped state diagram. We show a versatile model for constructing artificial multicellular spheroids in all-aqueous systems. The rapid interfacial assembly of charged particles and polyelectrolytes can lock in nonequilibrium shapes of water, which also enables top-down technologies, such as 3D printing and microfluidics, to program flexible compartmentalized structures.
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Nanopartículas , Agua , Microfluídica , Polielectrolitos , Esferoides CelularesRESUMEN
The blood-brain barrier is made of polarized brain endothelial cells (BECs) phenotypically conditioned by the central nervous system (CNS). Although transport across BECs is of paramount importance for nutrient uptake as well as ridding the brain of waste products, the intracellular sorting mechanisms that regulate successful receptor-mediated transcytosis in BECs remain to be elucidated. Here, we used a synthetic multivalent system with tunable avidity to the low-density lipoprotein receptor-related protein 1 (LRP1) to investigate the mechanisms of transport across BECs. We used a combination of conventional and super-resolution microscopy, both in vivo and in vitro, accompanied with biophysical modeling of transport kinetics and membrane-bound interactions to elucidate the role of membrane-sculpting protein syndapin-2 on fast transport via tubule formation. We show that high-avidity cargo biases the LRP1 toward internalization associated with fast degradation, while mid-avidity augments the formation of syndapin-2 tubular carriers promoting a fast shuttling across.
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Systems comprised of immiscible liquids held in non-equilibrium shapes by the interfacial assembly and jamming of nanoparticle-polymer surfactants have significant potential to advance catalysis, chemical separations, energy storage and conversion. Spatially directing functionality within them and coupling processes in both phases remains a challenge. Here, we exploit nanoclay-polymer surfactant assemblies at an oil-water interface to produce a semi-permeable membrane between the liquids, and from them all-liquid fluidic devices with bespoke properties. Flow channels are fabricated using micropatterned 2D substrates and liquid-in-liquid 3D printing. The anionic walls of the device can be functionalized with cationic small molecules, enzymes, and colloidal nanocrystal catalysts. Multi-step chemical transformations can be conducted within the channels under flow, as can selective mass transport across the liquid-liquid interface for in-line separations. These all-liquid systems become automated using pumps, detectors, and control systems, revealing a latent ability for chemical logic and learning.
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Liquid-fluid interfaces provide a platform both for structuring liquids into complex shapes and assembling dimensionally confined, functional nanomaterials. Historically, attention in this area has focused on simple emulsions and foams, in which surface-active materials such as surfactants or colloids stabilize structures against coalescence and alter the mechanical properties of the interface. In recent decades, however, a growing body of work has begun to demonstrate the full potential of the assembly of nanomaterials at liquid-fluid interfaces to generate functionally advanced, biomimetic systems. Here, a broad overview is given, from fundamentals to applications, of the use of liquid-fluid interfaces to generate complex, all-liquid devices with a myriad of potential applications.
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Solid ferromagnetic materials are rigid in shape and cannot be reconfigured. Ferrofluids, although reconfigurable, are paramagnetic at room temperature and lose their magnetization when the applied magnetic field is removed. Here, we show a reversible paramagnetic-to-ferromagnetic transformation of ferrofluid droplets by the jamming of a monolayer of magnetic nanoparticles assembled at the water-oil interface. These ferromagnetic liquid droplets exhibit a finite coercivity and remanent magnetization. They can be easily reconfigured into different shapes while preserving the magnetic properties of solid ferromagnets with classic north-south dipole interactions. Their translational and rotational motions can be actuated remotely and precisely by an external magnetic field, inspiring studies on active matter, energy-dissipative assemblies, and programmable liquid constructs.