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.
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.
Many species rely on diverse selections of entirely organic photonic structures for the manipulation of light and the display of striking colours. Here we report the discovery of a mineralized hierarchical photonic architecture embedded within the translucent shell of the blue-rayed limpet Patella pellucida. The bright colour of the limpet’s stripes originates from light interference in a periodically layered zig-zag architecture of crystallographically co-oriented calcite lamellae. Beneath the photonic multilayer, a disordered array of light-absorbing particles provides contrast for the blue colour. This unique mineralized manifestation of a synergy of two distinct optical elements at specific locations within the continuum of the limpet’s translucent protective shell ensures the vivid shine of the blue stripes, which can be perceived under water from a wide range of viewing angles. The stripes’ reflection band coincides with the spectral range of minimal light absorption in sea water, raising intriguing questions regarding their functional significance.
Living organisms make extensive use of micro- and nanometre-sized pores as gatekeepers for controlling the movement of fluids, vapours and solids between complex environments. The ability of such pores to coordinate multiphase transport, in a highly selective and subtly triggered fashion and without clogging, has inspired interest in synthetic gated pores for applications ranging from fluid processing to 3D printing and lab-on-chip systems. But although specific gating and transport behaviours have been realized by precisely tailoring pore surface chemistries and pore geometries, a single system capable of controlling complex, selective multiphase transport has remained a distant prospect, and fouling is nearly inevitable. Here we introduce a gating mechanism that uses a capillary-stabilized liquid as a reversible, reconfigurable gate that fills and seals pores in the closed state, and creates a non-fouling, liquid-lined pore in the open state. Theoretical modelling and experiments demonstrate that for each transport substance, the gating threshold—the pressure needed to open the pores—can be rationally tuned over a wide pressure range. This enables us to realize in one system differential response profiles for a variety of liquids and gases, even letting liquids flow through the pore while preventing gas from escaping. These capabilities allow us to dynamically modulate gas–liquid sorting in a microfluidic flow and to separate a three-phase air–water–oil mixture, with the liquid lining ensuring sustained antifouling behaviour. Because the liquid gating strategy enables efficient long-term operation and can be applied to a variety of pore structures and membrane materials, and to micro- as well as macroscale fluid systems, we expect it to prove useful in a wide range of applications.
There is a dire need for infection prevention strategies that do not require the use of antibiotics, which exacerbate the rise of multi- and pan-drug resistant infectious organisms. An important target in this area is the bacterial attachment and subsequent biofilm formation on medical devices (e.g., catheters). Here we describe nonfouling, lubricant-infused slippery polymers as proof-of-concept medical materials that are based on oil-infused polydimethylsiloxane (iPDMS). Planar and tubular geometry silicone substrates can be infused with nontoxic silicone oil to create a stable, extremely slippery interface that exhibits exceptionally low bacterial adhesion and prevents biofilm formation. Analysis of a flow culture of Pseudomonas aeruginosa through untreated PDMS and iPDMS tubing shows at least an order of magnitude reduction of biofilm formation on iPDMS, and almost complete absence of biofilm on iPDMS after a gentle water rinse. The iPDMS materials can be applied as a coating on other polymers or prepared by simply immersing silicone tubing in silicone oil, and are compatible with traditional sterilization methods. As a demonstration, we show the preparation of silicone-coated polyurethane catheters and significant reduction of Escherichia coli and Staphylococcus epidermidis biofilm formation on the catheter surface. This work represents an important first step toward a simple and effective means of preventing bacterial adhesion on a wide range of materials used for medical devices.
Nature provides a multitude of examples of multifunctional structural materials in which trade-offs are imposed by conflicting functional requirements. One such example is the biomineralized armor of the chiton Acanthopleura granulata, which incorporates an integrated sensory system that includes hundreds of eyes with aragonite-based lenses. We use optical experiments to demonstrate that these microscopic lenses are able to form images. Light scattering by the polycrystalline lenses is minimized by the use of relatively large, crystallographically aligned grains. Multiscale mechanical testing reveals that as the size, complexity, and functionality of the integrated sensory elements increase, the local mechanical performance of the armor decreases. However, A. granulata has evolved several strategies to compensate for its mechanical vulnerabilities to form a multipurpose system with co-optimized optical and structural functions.
To adapt to a wide range of physically demanding environmental conditions, biological systems have evolved a diverse variety of robust skeletal architectures. One such example, Euplectella aspergillum, is a sediment-dwelling marine sponge that is anchored into the sea floor by a flexible holdfast apparatus consisting of thousands of anchor spicules (long, hair-like glassy fibers). Each spicule is covered with recurved barbs and has an internal architecture consisting of a solid core of silica surrounded by an assembly of coaxial silica cylinders, each of which is separated by a thin organic layer. The thickness of each silica cylinder progressively decreases from the spicule’s core to its periphery, which we hypothesize is an adaptation for redistributing internal stresses, thus increasing the overall strength of each spicule. To evaluate this hypothesis, we created a spicule structural mechanics model, in which we fixed the radii of the silica cylinders such that the force transmitted from the surface barbs to the remainder of the skeletal system was maximized. Compared with measurements of these parameters in the native sponge spicules, our modeling results correlate remarkably well, highlighting the beneficial nature of this elastically heterogeneous lamellar design strategy. The structural principles obtained from this study thus provide potential design insights for the fabrication of high-strength beams for load-bearing applications through the modification of their internal architecture, rather than their external geometry.
The stability and longevity of surface-stabilized lubricant layers is a critical question in their application as low- and nonfouling slippery surface treatments in both industry and medicine. Here, we investigate lubricant loss from surfaces under flow in water using both quantitative analysis and visualization, testing the effects of underlying surface type (nanostructured versus flat), as well as flow rate in the physiologically relevant range, lubricant type, and time. We find lubricant losses on the order of only ng/cm2 in a closed system, indicating that these interfaces are relatively stable under the flow conditions tested. No notable differences emerged between surface type, flow rate, lubricant type, or time. However, exposure of the lubricant layers to an air/water interface did significantly increase the amount of lubricant removed from the surface, leading to disruption of the layer. These results may help in the development and design of materials using surface-immobilized lubricant interfaces for repellency under flow conditions.
Formation of unwanted deposits on steels during their interaction with liquids is an inherent problem that often leads to corrosion, biofouling and results in reduction in durability and function. Here we report a new route to form anti-fouling steel surfaces by electrodeposition of nanoporous tungsten oxide (TO) films. TO-modified steels are as mechanically durable as bare steel and highly tolerant to compressive and tensile stresses due to chemical bonding to the substrate and island-like morphology. When inherently superhydrophilic TO coatings are converted to superhydrophobic, they remain non-wetting even after impingement with yttria-stabilized-zirconia particles, or exposure to ultraviolet light and extreme temperatures. Upon lubrication, these surfaces display omniphobicity against highly contaminating media retaining hitherto unseen mechanical durability. To illustrate the applicability of such a durable coating in biofouling conditions, we modified naval construction steels and surgical instruments and demonstrated significantly reduced marine algal film adhesion, Escherichia coli attachment and blood staining.
Marine biofouling, the process of accumulation of microorganisms, plants, algae and animals on submerged surfaces, is an age-old problem associated with any maritime activity affecting commercial and recreational shipping activities, naval operations, aquaculture facilities and marine renewable energy structures alike. The adverse effects of marine biofouling include the increase of drag on ship hulls, damage to ships and maritime equipment such as corrosion, the spread of diseases in aquaculture and the distribution of invasive species causing extensive damage to coastal ecosystems and the benefits derived from them. An estimated global annual total of $60 billion in fuel cost alone can be saved by the application of marine antifouling coatings, making the treatment of marine biofouling a necessity not an option.
Recently, diffraction elements that reverse the color sequence normally observed in planar diffraction gratings have been found in the wing scales of the butterfly Pierella luna. Here, we describe the creation of an artificial photonic material mimicking this re- verse color-order diffraction effect. The bioinspired system con- sists of ordered arrays of vertically oriented microdiffraction gratings. We present a detailed analysis and modeling of the cou- pling of diffraction resulting from individual structural compo- nents and demonstrate its strong dependence on the orientation of the individual miniature gratings. This photonic material could provide a basis for novel developments in biosensing, anticoun- terfeiting, and efficient light management in photovoltaic systems and light-emitting diodes.
Thrombosis and biofouling of extracorporeal circuits and indwelling medical devices cause significant morbidity and mortality worldwide. We apply a bioinspired, omniphobic coating to tubing and catheters and show that it completely repels blood and suppresses biofilm formation. The coating is a covalently tethered, flexible molecular layer of perfluorocarbon, which holds a thin liquid film of medical-grade perfluorocarbon on the surface. This coating prevents fibrin attachment, reduces platelet adhesion and activation, suppresses biofilm formation and is stable under blood flow in vitro. Surface-coated medical-grade tubing and catheters, assembled into arteriovenous shunts and implanted in pigs, remain patent for at least 8 h without anticoagulation. This surface-coating technology could reduce the use of anticoagulants in patients and help to prevent thrombotic occlusion and biofouling of medical devices.
A biologically inspired thermoresponsive polymer has been developed that mechanically induces tooth differentiation in vitro and in vivo by promoting mesenchymal cell compaction as seen in each pore of the scaffold. This normally occurs during the physiological mesenchymal condensation response that triggers tooth formation in the embryo.
Porous materials display interesting transport phenomena due to restricted motion of fluids within the nano- to microscale voids. Here, we investigate how liquid wetting in highly ordered inverse opals is affected by anisotropy in pore geometry. We compare samples with different degrees of pore asphericity and find different wetting patterns depending on the pore shape. Highly anisotropic structures are infiltrated more easily than their isotropic counterparts. Further, the wetting of anisotropic inverse opals is directional, with liquids filling from the side more easily. This effect is supported by percolation simulations as well as direct observations of wetting using time-resolved optical microscopy.