Dynamic crosslinking of extremely stretchable hydrogels with rapid self-healing ability is described. Using this new strategy, the obtained hydrogels are able to elongate 100 times compared to their initial length and to completely self-heal within 30 s without external energy input.
We use computational modeling to design a device that can controllably trap and release particles in solution in response to variations in temperature. The system exploits the thermoresponsive properties of end-grafted fibers and the underlying gel substrate. The fibers mimic the temperature-dependent behavior of biological aptamers, which form a hairpin structure at low temperatures (T) and unfold at higher T, consequently losing their binding affinity. The gel substrate exhibits a lower critical solution temperature and thus, expands at low temperatures and contracts at higher T. By developing a new dissipative particle dynamics simulation, we examine the behavior of this hybrid system in a flowing fluid that contains buoyant nanoparticles. At low T, the expansion of the gel causes the hairpin-shaped fibers to extend into the path of the fluid-driven particle. Exhibiting a high binding affinity for these particles at low temperature, the fibers effectively trap and extract the particles from the surrounding solution. When the temperature is increased, the unfolding of the fiber and collapse of the supporting gel layer cause the particles to be released and transported away from the layer by the applied shear flow. Since the temperature-induced conformational changes of the fiber and polymer gel are reversible, the system can be used repeatedly to “catch and release” particles in solution. Our findings provide guidelines for creating fluidic devices that are effective at purifying contaminated solutions or trapping cells for biological assays.
Tissue engineering using whole, intact cell sheets has shown promise in many cell-based therapies. However, current systems for the growth and release of these sheets can be expensive to purchase or difficult to fabricate, hindering their widespread use. Here, we describe a new approach to cell sheet release surfaces based on silicone oil-infused polydimethylsiloxane. By coating the surfaces with a layer of fibronectin (FN), we were able to grow mesenchymal stem cells to densities comparable to those of tissue culture polystyrene controls (TCPS). Simple introduction of oil underneath an edge of the sheet caused it to separate from the substrate. Characterization of sheets post-transfer showed that they retain their FN layer and morphology, remain highly viable, and are able to grow and proliferate normally after transfer. We expect that this method of cell sheet growth and detachment may be useful for low-cost, flexible, and customizable production of cellular layers for tissue engineering.
Surface topography has been introduced as a new tool to coordinate cell selection, growth, morphology, and differentiation. The materials explored so far for making such structural surfaces are mostly rigid and impermeable. Hydrogel, on the other hand, was proved a better synthetic media for cell culture because of its biocompatibility, softness, and high permeability. Herein, we fabricated a poly(2-hydroxyethyl methacrylate) (pHEMA) hydrogel substrate with high-aspectratio surface microfeatures. Such structural surface could effectively guide the orientation and shape of human mesenchymal stem cells (HMSCs). Notably, on the flat hydrogel surface, cells rounded up, whereas on the microplate patterned hydrogel surface, cells elongated and aligned along the direction parallel to the plates. The microplates were 2 μm thick, 20 μm tall, and 10−50 μm wide. The interplate spacing was 5−15 μm, and the intercolumn spacing was 5 μm. The elongation of cell body was more pronounced on the patterns with narrower interplate spacing and wider plates. The cells behaved like soft solid. The competition between surface energy and elastic energy defined the shape of the cells on the structured surfaces. The soft permeable hydrogel scaffold with surface structures was also demonstrated as being viable for longterm cell culture, and could be used to generate interconnected tissues with finely tuned cell morphology and alignment across a few centimeter sizes.
Controlling the microscopic wetting state of a liquid in contact with a structured surface is the basis for the design of liquid repellent as well as anti-fogging coatings by preventing or enabling a given liquid to infiltrate the surface structures. Similarly, a liquid can be confined to designated surface areas by locally controlling the wetting state, with applications ranging from liquid transport on a surface to creating tailored microenvironments for cell culture or chemical synthesis. The control of the wetting of a low-surfacetension liquid is substantially more difficult compared to water and requires surface structures with overhanging features, known as re-entrant geometries. Here, we use colloidal self-assembly and templating to create two-dimensional nanopore arrays with tailored re-entrant geometry. These pore arrays, termed inverse monolayers, are prepared by backfilling a sacrificial colloidal monolayer with a silica sol–gel precursor material. Varying the precursor concentration enables us to control the degree to which the colloids are embedded into the silica matrix. Upon calcination, nanopores with different opening angles result. The pore opening angle directly correlates with the re-entrant curvature of the surface nanostructures and can be used to control the macroscopic wetting behavior of a liquid sitting on the surface structures. We characterize the wetting of various liquids by static and dynamic contact angles and find correlation between the experimental results and theoretical predictions of the wetting state based on simple geometric considerations. We demonstrate the creation of omniphobic surface coatings that support Cassie–Baxter wetting states for liquids with low surface tensions, including octane (g ¼ 21.7 mN m1). We further use photolithography to spatially confine such low-surface-tension liquids to desired areas of the substrate with high accuracy.
Inspection devices are frequently occluded by highly contaminating fluids that disrupt the visual field and their effective operation. These issues are particularly striking in endoscopes, where the diagnosis and treatment of diseases are compromised by the obscuring of the operative field by body fluids. Here we demonstrate that the application of a liquid-infused surface coating strongly repels sticky biological secretions and enables an uninterrupted field of view. Extensive bronchoscopy procedures performed in vivo on a porcine model shows significantly reduced fouling, resulting in either unnecessary or ∼10–15 times shorter and less intensive lens clearing procedures compared with an untreated endoscope.
Camera-guided instruments, such as endoscopes, have become an essential component of contemporary medicine. The 15–20 million endoscopies performed every year in the United States alone demonstrate the tremendous impact of this technology. However, doctors heavily rely on the visual feedback provided by the endoscope camera, which is routinely compromised when body fluids and fogging occlude the lens, requiring lengthy cleaning procedures that include irrigation, tissue rubbing, suction, and even temporary removal of the endoscope for external cleaning. Bronchoscopies are especially affected because they are performed on delicate tissue, in high-humidity environments with exposure to extremely adhesive biological fluids such as mucus and blood. Here, we present a repellent, liquid-infused coating on an endoscope lens capable of preventing vision loss after repeated submersions in blood and mucus. The material properties of the coating, including conformability, mechanical adhesion, transparency, oil type, and biocompatibility, were optimized in comprehensive in vitro and ex vivo studies. Extensive bronchoscopy procedures performed in vivo on porcine lungs showed significantly reduced fouling, resulting in either unnecessary or ∼10–15 times shorter and less intensive lens clearing procedures compared with an untreated endoscope. We believe that the material developed in this study opens up opportunities in the design of next-generation endoscopes that will improve visual field, display unprecedented antibacterial and antifouling properties, reduce the duration of the procedure, and enable visualization of currently unreachable parts of the body, thus offering enormous potential for disease diagnosis and treatment.
Many industries require irreversibly responsive materials for use as sensors or detectors of environmental exposure. We describe the synthesis and fabrication of a nontoxic surface coating that reports oxygen exposure of the substrate material through irreversible formation of colored spots. The coating consists of a selectively permeable rubber film that contains the colorless organic precursors to darkly pigmented synthetic melanin. Melanin synthesis within the film is triggered by exposure to molecular oxygen. The selectively permeable rubber film regulates the rate of oxygen diffusion, enabling independent control of the sensitivity and response time of the artificial melanosome, while preventing leaching of melanin or its precursors.
Nature evolved a variety of hierarchical structures that produce sophisticated functions. Inspired by these natural materials, colloidal self-assembly provides a convenient way to produce structures from simple building blocks with a variety of complex functions beyond those found in nature. In particular, colloid-based porous materials (CBPM) can be made from a wide variety of materials. The internal structure of CBPM also has several key attributes, namely porosity on a sub-micrometer length scale, interconnectivity of these pores, and a controllable degree of order. The combination of structure and composition allow CBPM to attain properties important for modern applications such as photonic inks, colorimetric sensors, self-cleaning surfaces, water purification systems, or batteries. This review summarizes recent developments in the field of CBPM, including principles for their design, fabrication, and applications, with a particular focus on structural features and materials' properties that enable these applications. We begin with a short introduction to the wide variety of patterns that can be generated by colloidal self-assembly and templating processes. We then discuss different applications of such structures, focusing on optics, wetting, sensing, catalysis, and electrodes. Different fields of applications require different properties, yet the modularity of the assembly process of CBPM provides a high degree of tunability and tailorability in composition and structure. We examine the significance of properties such as structure, composition, and degree of order on the materials' functions and use, as well as trends in and future directions for the development of CBPM.
Controlling dropwise condensation is fundamental to water-harvesting systems, desalination, thermal power generation, air conditioning, distillation towers, and numerous other applications. For any of these, it is essential to design surfaces that enable droplets to grow rapidly and to be shed as quickly as possible. However, approaches based on microscale, nanoscale or molecular-scale textures suffer from intrinsic trade-offs that make it difficult to optimize both growth and transport at once. Here we present a conceptually different design approach—based on principles derived from Namib desert beetles, cacti, and pitcher plants—that synergistically combines these aspects of condensation and substantially outperforms other synthetic surfaces. Inspired by an unconventional interpretation of the role of the beetle’s bumpy surface geometry in promoting condensation, and using theoretical modelling, we show how to maximize vapour diffusion flux at the apex of convex millimetric bumps by optimizing the radius of curvature and cross-sectional shape. Integrating this apex geometry with a widening slope, analogous to cactus spines, directly couples facilitated droplet growth with fast directional transport, by creating a free-energy profile that drives the droplet down the slope before its growth rate can decrease. This coupling is further enhanced by a slippery, pitcher-plant-inspired nanocoating that facilitates feedback between coalescence-driven growth and capillary-driven motion on the way down. Bumps that are rationally designed to integrate these mechanisms are able to grow and transport large droplets even against gravity and overcome the effect of an unfavourable temperature gradient. We further observe an unprecedented sixfold-higher exponent of growth rate, faster onset, higher steady-state turnover rate, and a greater volume of water collected compared to other surfaces. We envision that this fundamental understanding and rational design strategy can be applied to a wide range of water-harvesting and phase-change heat-transfer applications.
Passive anti-icing surfaces, or icephobic surfaces, are an area of great interest because of their significant economic, energy and safety implications in the prevention and easy removal of ice in many facets of society. The complex nature of icephobicity, which requires performance in a broad range of icing scenarios, creates many challenges when designing ice-repellent surfaces. Although superhydrophobic surfaces incorporating micro- or nanoscale roughness have been shown to prevent ice accumulation under certain conditions, the same roughness can be detrimental in other environments. Surfaces that present a smooth liquid interface can eliminate some of the drawbacks of textured superhydrophobic surfaces, but additional study is needed to fully realize their potential. As attention begins to shift towards alternative anti-icing strategies, it is important to consider and to understand the nature of ice repellency in all environments to identify the limitations of current solutions and to design new materials with robust icephobicity.
Although common in biological systems, synthetic self-assembly routes to complex 3D photonic structures with tailored degrees of disorder remain elusive. Here we show how liquids can be used to finely control disorder in porous 3D photonic crystals, leading to complex and hierarchical geometries. In these optofluidic crystals, dynamically tunable disorder is superimposed onto the periodic optical structure through partial wetting or evaporation. In both cases, macroscopic symmetry breaking is driven by subtle sub-wavelength variations in the pore geometry. These variations direct site-selective infiltration of liquids through capillary interactions. Incorporating cross-linkable resins into our liquids, we developed methods to freeze in place the filling patterns at arbitrary degrees of partial wetting and intermediate stages of drying. These percolation lithography techniques produced permanent photonic structures with adjustable disorder. By coupling strong changes in optical properties to subtle differences in fluid behavior, optofluidic crystals may also prove useful in rapid analysis of liquids.
The extraction of nanoscopic particulates from flowing fluids is a vital step in filtration processes, as well as the fabrication of nanocomposites. Inspired by the ability of carnivorous plants to use hair-like filaments to entrap species, we use computational modeling to design a multi-component system that integrates compliant fibers and thermo-responsive gels to extract particles from the surrounding solution. In particular, hydrophobic fibers are embedded in a gel that exhibits a lower critical solution temperature (LCST). With an increase in temperature, the gel collapses to expose fibers that self assemble into bundles, which act as nanoscale ‘‘grippers’’ that bind the particles and draw them into the underlying gel. By varying the relative stiffness of the fibers, the fiber–particle interaction strength and the shear rate in the solution, we identify optimal parameters where the particles are effectively drawn from the solution and remain firmly bound within the gel layer. Hence, the system can be harnessed in purifying fluids and creating novel hybrid materials that integrate nanoparticles with polymer gels.
When a fluid-immersed array of supported plates or pillars is dried, evaporation leads to the formation of menisci on the tips of the plates or pillars that bring them together to form complex patterns. Building on prior experimental observations, we use a combination of theory and computation to understand the nature of this instability and its evolution in both the two- and three-dimensional setting of the problem. For the case of plates, we explicitly derive the interaction torques based on the relevant physical parameters associated with pillar deformation, contact-line pinning/depinning and fluid volume changes. A Bloch-wave analysis for our periodic mechanical system captures the window of volumes where the two-plate eigenvalue characterizes the onset of the coalescence instability. We then study the evolution of these binary clusters and their eventual elastic arrest using numerical simulations that account for evaporative dynamics coupled to capillary coalescence. This explains both the formation of hierarchical clusters and the sensitive dependence of the final structures on initial perturbations, as seen in our experiments. We then generalize our analysis to treat the problem of pillar collapse in three dimensions, where the fluid domain is completely connected and the interface is a minimal surface with the uniform mean curvature. Our theory and simulations capture the salient features of experimental observations in a range of different situations and may thus be useful in controlling the ensuing patterns.
Understanding the interfacial activity of bacteria is of critical importance due to the huge economic and public health implications associated with surface fouling and biofilm formation. The complexity of the process and difficulties of predicting microbial adhesion to novel materials demand study of the properties of specific bacterial surface features and their potential contribution to surface attachment. Here, we examine flagella, cell appendages primarily studied for their cell motility function, to elucidate their potential role in the surface adhesion of Escherichia coli - a model organism and potential pathogen. We use self-assembled monolayers (SAMs) of thiol-bearing molecules on gold films to generate surfaces of varying hydrophobicity, and measure adhesion of purified flagella using quartz crystal microbalance. We show that flagella adhere more extensively and bind more tightly to hydrophobic SAMs than to hydrophilic ones, and we propose a two-step vs a single-step adhesion mechanism that accounts for the observed dissipation and frequency changes for the two types of surfaces, respectively. Subsequently, study of the adhesion of wild-type and flagella knockout cells confirms that flagella improve adhesion to hydrophobic substrates, whereas cells lacking flagella do not show preferred affinity to hydrophobic substrates. Together, these properties bring about an interesting ability of cells with flagella to stabilize emulsions of aqueous culture and dodecane, not observed for cells lacking flagella. This work contributes to our overall understanding of nonspecific bacterial adhesion and confirms that flagella, beyond motility, may play an important role in surface adhesion.
The efficient extraction of (bio)molecules from fluid mixtures is vital for applications ranging from target characterization in (bio)chemistry to environmental analysis and biomedical diagnostics. Inspired by biological processes that seamlessly synchronize the capture, transport and release of biomolecules, we designed a robust chemomechanical sorting system capable of the concerted catch and release of target biomolecules from a solution mixture. The hybrid system is composed of target-specific, reversible binding sites attached to microscopic fins embedded in a responsive hydrogel that moves the cargo between two chemically distinct environments. To demonstrate the utility of the system, we focus on the effective separation of thrombin by synchronizing the pH-dependent binding strength of a thrombin-specific aptamer with volume changes of the pH-responsive hydrogel in a biphasic microfluidic regime, and show a non-destructive separation that has a quantitative sorting efficiency, as well as the system's stability and amenability to multiple solution recycling.
Materials in nature are characterized by structural order over multiple length scales have evolved for maximum performance and multifunctionality, and are often produced by self-assembly processes. A striking example of this design principle is structural coloration, where interference, diffraction, and absorption effects result in vivid colors. Mimicking this emergence of complex effects from simple building blocks is a key challenge for man-made materials. Here, we show that a simple confined self-assembly process leads to a complex hierarchical geometry that displays a variety of optical effects. Colloidal crystallization in an emulsion droplet creates micron-sized superstructures, termed photonic balls. The curvature imposed by the emulsion droplet leads to frustrated crystallization. We observe spherical colloidal crystals with ordered, crystalline layers and a disordered core. This geometry produces multiple optical effects. The ordered layers give rise to structural color from Bragg diffraction with limited angular dependence and unusual transmission due to the curved nature of the individual crystals. The disordered core contributes nonresonant scattering that induces a macroscopically whitish appearance, which we mitigate by incorporating absorbing gold nanoparticles that suppress scattering and macroscopically purify the color. With increasing size of the constituent colloidal particles, grating diffraction effects dominate, which result from order along the crystal’s curved surface and induce a vivid polychromatic appearance. The control of multiple optical effects induced by the hierarchical morphology in photonic balls paves the way to use them as building blocks for complex optical assemblies—potentially as more efficient mimics of structural color as it occurs in nature.
Colloidal particles can assemble into ordered crystals, creating periodically structured materials at the nanoscale without relying on expensive equipment. The combination of small size and high order leads to strong interaction with visible light, which induces macroscopic, iridescent structural coloration. To increase the complexity and functionality, it is important to control the organization of such materials in hierarchical structures with high degrees of order spanning multiple length scales. Here, a bottom-up assembly of polystyrene particles in the presence of a silica sol–gel precursor material (tetraethylorthosilicate, TEOS), which creates crack-free inverse opal films with high positional order and uniform crystal alignment along the (110) crystal plane, is combined with top-down microfabrication techniques. Micrometer scale hierarchical superstructures having a highly regular internal nanostructure with precisely controlled crystal orientation and wall profiles are produced. The ability to combine structural order at the nano- and microscale enables the fabrication of materials with complex optical properties resulting from light–matter interactions at different length scales. As an example, a hierarchical diffraction grating, which combines Bragg reflection arising from the nanoscale periodicity of the inverse opal crystal with grating diffraction resulting from a micrometer scale periodicity, is demonstrated.
Approaches for regulated fluid secretion, which typically rely on fluid encapsulation and release from a shelled compartment, do not usually allow a fine continuous modulation of secretion, and can be difficult to adapt for monitoring or function-integration purposes. Here, we report self-regulated, self-reporting secretion systems consisting of liquid-storage compartments in a supramolecular polymer-gel matrix with a thin liquid layer on top, and demonstrate that dynamic liquid exchange between the compartments, matrix and surface layer allows repeated, responsive self-lubrication of the surface and cooperative healing of the matrix. Depletion of the surface liquid or local material damage induces secretion of the stored liquid via a dynamic feedback between polymer crosslinking, droplet shrinkage and liquid transport that can be read out through changes in the system’s optical transparency. We foresee diverse applications in fluid delivery, wetting and adhesion control, and material self-repair.
Drying suspensions often leave behind complex patterns of particulates, as might be seen in the coffee stains on a table. Here, we consider the dynamics of periodic band or uniform solid film formation on a vertical plate suspended partially in a drying colloidal solution. Direct observations allow us to visualize the dynamics of band and film deposition, where both are made of multiple layers of close packed particles. We further see that there is a transition between banding and filming when the colloidal concentration is varied. A minimal theory of the liquid meniscus motion along the plate reveals the dynamics of the banding and its transition to the filming as a function of the ratio of deposition and evaporation rates. We also provide a complementary multiphase model of colloids dissolved in the liquid, which couples the inhomogeneous evaporation at the evolving meniscus to the fluid and particulate flows and the transition from a dilute suspension to a porous plug. This allows us to determine the concentration dependence of the bandwidth and the deposition rate. Together, our findings allow for the control of drying-induced patterning as a function of the colloidal concentration and evaporationrate.