2013

Burgess IB, Nerger BA, Raymond KP, Goulet-Hanssens A, Singleton TA, Kinney MH, Shneidman AV, Koay N, Barrett CJ, Loncar M, et al. Wetting in Color: From photonic fingerprinting of liquids to optical control of liquid percolation. Proc. of SPIE. 2013;8632 :863201. Publisher's VersionAbstract

We provide an overview of our recent advances in the manipulation of wetting in inverse-opal photonic crystals. Exploiting photonic crystals with spatially patterned surface chemistry to confine the infiltration of fluids to liquidspecific spatial patterns, we developed a highly selective scheme for colorimetry, where organic liquids are distinguished based on wetting. The high selectivity of wetting, upon-which the sensitivity of the response relies, and the bright iridescent color, which disappears when the pores are filled with liquid, are both a result of the highly symmetric pore structure of our inverse-opal films. The application of horizontally or vertically orientated gradients in the surface chemistry allows a unique response to be tailored to specific liquids. While the generic nature of wetting makes our approach to colorimetry suitable for applications in liquid authentication or identification across a broad range of industries, it also ensures chemical non-specificity. However, we show that chemical specificity can be achieved combinatorially using an array of indicators that each exploits different chemical gradients to cover the same dynamic range of response. Finally, incorporating a photo-responsive polyelectrolyte surface layer into the pores, we are able to dynamically and continuously photo-tune the wetting response, even while the film is immersed in liquid. This in situ optical control of liquid percolation in our photonic-crystal films may also provide an error-free means to tailor indicator response, naturally compensating for batch-to-batch variability in the pore geometry.

Wong T-S, Sun T, Feng L, Aizenberg J. Interfacial materials with special wettability. MRS Bulletin. 2013;38 :366-371. Publisher's VersionAbstract

Various life forms in nature display a high level of adaptability to their environments through the use of sophisticated material interfaces. This is exemplifi ed by numerous biological systems, such as the self-cleaning of lotus leaves, the water-walking abilities of water striders and spiders, the ultra-slipperiness of pitcher plants, the directional liquid adhesion of butterfl y wings, and the water collection capabilities of beetles, spider webs, and cacti. The versatile interactions of these natural surfaces with fl uids, or special wettability, are enabled by their unique micro/nanoscale surface structures and intrinsic material properties. Many of these biological designs and principles have inspired new classes of functional interfacial materials, which have remarkable potential to solve some of the engineering challenges for industrial and biomedical applications. In this article, we provide a snapshot of the state of the art of biologically inspired materials with special wettability, and discuss some promising future directions for the field.

Wilson PW, Lu W, Xu H, Kim P, Kreder MJ, Alvarenga J, Aizenberg J. Inhibition of Ice Nucleation by Slippery Liquid-Infused Porous Surfaces (SLIPS). Physical Chemistry Chemical Physics. 2013;15 :581-585. Full TextAbstract
Ice repellent coatings have been studied and keenly sought after for many years, where any advances in the durability of such coatings will result in huge energy savings across many fields. Progress in creating anti-ice and anti-frost surfaces has been particularly rapid since the discovery and development of slippery, liquid infused porous surfaces (SLIPS). Here we use SLIPS-coated differential scanning calorimeter (DSC) pans to investigate the effects of the surface modification on the nucleation of supercooled water. This investigation is inherently different from previous studies which looked at the adhesion of ice to SLIPS surfaces, or the formation of ice under high humidity conditions. Given the stochastic nature of nucleation of ice from supercooled water, multiple runs on the same sample are needed to determine if a given surface coating has a real and statistically significant effect on the nucleation temperature. We have cycled supercooling to freezing and then thawing of deionized water in hydrophilic (untreated aluminum), hydrophobic, superhydrophobic, and SLIPS-treated DSC pans multiple times to determine the effects of surface treatment on the nucleation and subsequent growth of ice. We find that SLIPS coatings lower the nucleation temperature of supercooled water in contact with statistical significance and show no deterioration or change in the coating performance even after 150 freeze–thaw cycles.
Kats MA, Byrnes SJ, Blanchard R, Kolle M, Genevet P, Aizenberg J, Capasso F. Enhancement of absorption and color contrast in ultra-thin highly absorbing optical coatings. Appl. Phys. Lett. 2013;103 :101104. Publisher's VersionAbstract
Recently a new class of optical interference coatings was introduced which comprises ultra-thin, highly absorbing dielectric layers on metal substrates. We show that these lossy coatings can be augmented by an additional transparent subwavelength layer. We fabricated a sample comprising a gold substrate, an ultra-thin film of germanium with a thickness gradient, and several alumina films. The experimental reflectivity spectra showed that the additional alumina layer increases the color range that can be obtained, in agreement with calculations. More generally, this transparent layer can be used to enhance optical absorption, protect against erosion, or as a transparent electrode for optoelectronic devices.
Noorduin W, Grinthal A, Mahadevan L, Aizenberg J. Rationally Designed Complex Hierarchical Microarchitectures. Science. 2013;340 :832-837. Publisher's VersionAbstract
The emergence of complex nano- and microstructures is of fundamental interest, and the ability to program their form has practical ramifications in fields such as optics, catalysis, and electronics. We developed carbonate-silica microstructures in a dynamic reaction-diffusion system that allow us to rationally devise schemes for precisely sculpting a great variety of elementary shapes by diffusion of carbon dioxide (CO2) in a solution of barium chloride and sodium metasilicate. We identify two distinct growth modes and show how continuous and discrete modulations in CO2 concentration, pH, and temperature can be used to deterministically switch between different regimes and create a bouquet of hierarchically assembled multiscale microstructures with unprecedented levels of complexity and precision. These results outline a nanotechnology strategy for "collaborating" with self-assembly processes in real time to build arbitrary tectonic architectures.
Burgess IB, Aizenberg J, Loncar M. Creating bio-inspired hierarchical 3D–2D photonic stacks via planar lithography on self-assembled inverse opals. Bioinspiration & Biomimetics. 2013;8 :045004. Publisher's VersionAbstract
Structural hierarchy and complex 3D architecture are characteristics of biological photonic designs that are challenging to reproduce in synthetic materials. Top–down lithography allows for designer patterning of arbitrary shapes, but is largely restricted to planar 2D structures. Self-assembly techniques facilitate easy fabrication of 3D photonic crystals, but controllable defect-integration is difficult. In this paper we combine the advantages of top–down and bottom–up fabrication, developing two techniques to deposit 2D-lithographically-patterned planar layers on top of or in between inverse-opal 3D photonic crystals and creating hierarchical structures that resemble the architecture of the bright green wing scales of the butterfly, Parides sesostris. These fabrication procedures, combining advantages of both top–down and bottom–up fabrication, may prove useful in the development of omnidirectional coloration elements and 3D–2D photonic crystal devices.
Friedlander RS, Vlamakis H, Kim P, Khan M, Kolter R, Aizenberg J. Bacterial flagella explore microscale hummocks and hollows to increase adhesion. Proc. Nat. Acad. Sci. 2013;110 (14) :5624-5629. Publisher's VersionAbstract
Biofilms, surface-bound communities of microbes, are economically and medically important due to their pathogenic and obstructive properties. Among the numerous strategies to prevent bacterial adhesion and subsequent biofilm formation, surface topography was recently proposed as a highly nonspecific method that does not rely on small-molecule antibacterial compounds, which promote resistance. Here, we provide a detailed investigation of how the introduction of submicrometer crevices to a surface affects attachment of Escherichia coli. These crevices reduce substrate surface area available to the cell body but increase overall surface area. We have found that, during the first 2 h, adhesion to topographic surfaces is significantly reduced compared with flat controls, but this behavior abruptly reverses to significantly increased adhesion at longer exposures. We show that this reversal coincides with bacterially induced wetting transitions and that flagellar filaments aid in adhesion to these wetted topographic surfaces. We demonstrate that flagella are able to reach into crevices, access additional surface area, and produce a dense, fibrous network. Mutants lacking flagella show comparatively reduced adhesion. By varying substrate crevice sizes, we determine the conditions under which having flagella is most advantageous for adhesion. These findings strongly indicate that, in addition to their role in swimming motility, flagella are involved in attachment and can furthermore act as structural elements, enabling bacteria to overcome unfavorable surface topographies. This work contributes insights for the future design of antifouling surfaces and for improved understanding of bacterial behavior in native, structured environments.
Burgess IB, Loncar M, and Aizenberg J. Structural Colour in Colourimetric Sensors and Indicators. J. Mater. Chem. C. 2013;1 (38) :6075-6086. Publisher's VersionAbstract
Colourimetric sensors and indicators are widely used because of their low cost and simplicity. A significant challenge associated with the design of this type of device is that the sensing mechanism must be simultaneously optimised for the sensitivity of the response and a visually perceptible colour change. Structural colour, derived from coherent scattering rather than molecular absorption, is a promising route to colourimetric sensor design because colour shifts are tied to changes in one of many physical properties of a material, rather than a specific chemical process. This Feature Article presents an overview of the development of low-cost sensors and indicators that exploit structural colour. Building upon recent advances in structurally adaptive materials design, structural colour sensors have been developed for a wide variety of previously inaccessible physical (e.g. temperature, strain, electric fields) and chemical stimuli (e.g. small organic molecules, charged species, biomacromolecules and metabolites). These devices, often exceeding the state of the art in performance, simplicity or both, have bright prospects for market impact in areas such as environmental monitoring, workplace hazard identification, threat detection, and point-of-care diagnostics. Finding the ideal balance between performance (e.g. sensitivity, specificity, reproducibility, etc.) and simplicity (e.g. colourimetric vs. spectroscopic readout) will be one of the most critical elements in the further development of structural colour sensors. This balance should be driven largely by the market demands and competing technologies.
Kim P, Hu Y, Alvarenga J, Kolle M, Suo Z, Aizenberg J. Rational Design of Mechano-Responsive Optical Materials by Fine Tuning the Evolution of Strain-Dependent Wrinkling Patterns. Adv. Optical Mater. 2013;1 (5) :381-388. Publisher's VersionAbstract
Rational design strategies for mechano‐responsive optical material systems are created by introducing a simple experimental system that can continuously vary the state of bi‐axial stress to induce various wrinkling patterns, including stripes, labyrinths, herringbones, and rarely observed checkerboards, that can dynamically tune the optical properties. In particular, a switching of two orthogonally oriented stripe wrinkle patterns from oxidized polydimethylsiloxane around the critical strain value is reported, as well as the coexistence of these wrinkles forming elusive checkerboard patterns, which are predicted only in previous simulations. These strain‐induced wrinkle patterns give rise to dynamic changes in optical transmittance and diffraction patterns. A theoretical description of the observed pattern formation is presented which accounts for the residual stress in the membrane and allows for the fine‐tuning of the window of switching of the orthogonal wrinkles. Applications of wrinkle‐induced changes in optical properties are demonstrated, including a mechanically responsive instantaneous privacy screen and a transparent sheet that reversibly reveals a message or graphic and dynamically switches the transmittance when stretched and released.
Vogel N, Belisle RA, Hatton B, Wong TS, Aizenberg J. Transparency and damage tolerance of patternable omniphobic lubricated surfaces based on inverse colloidal monolayers. Nature Communications. 2013;4. Publisher's VersionAbstract
A transparent coating that repels a wide variety of liquids, prevents staining, is capable of self-repair and is robust towards mechanical damage can have a broad technological impact, from solar cell coatings to self-cleaning optical devices. Here we employ colloidal templating to design transparent, nanoporous surface structures. A lubricant can be firmly locked into the structures and, owing to its fluidic nature, forms a defect-free, self-healing interface that eliminates the pinning of a second liquid applied to its surface, leading to efficient liquid repellency, prevention of adsorption of liquid-borne contaminants, and reduction of ice adhesion strength. We further show how this method can be applied to locally pattern the repellent character of the substrate, thus opening opportunities to spatially confine any simple or complex fluids. The coating is highly defect-tolerant due to its interconnected, honeycomb wall structure, and repellency prevails after the application of strong shear forces and mechanical damage. The regularity of the coating allows us to understand and predict the stability or failure of repellency as a function of lubricant layer thickness and defect distribution based on a simple geometric model.

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