Publications

2014
Park D, Kim P, Alvarenga J, Jin K, Aizenberg J, Bechtold M. Dynamic daylight control system implementing thin cast arrays of polydimethylsiloxane-based millimeter-scale transparent louvers. Building and Environment [Internet]. 2014;82 :87-96. Publisher's VersionAbstract

The deep building layouts typical in the U.S. have led to a nearly complete reliance on artificial lighting in standard office buildings. The development of daylight control systems that maximize the penetration and optimize the distribution of natural daylight in buildings has the potential for saving a significant portion of the energy consumed by artificial lighting, but existing systems are either static, costly, or obstruct views towards the outside. We report the Dynamic Daylight Control System (DDCS) that in- tegrates a thin cast transparent polydimethylsiloxane (PDMS)-based deformable array of louvers and waveguides within a millimeter-scale fluidic channel system. This system can be dynamically tuned to the different climates and sun positions to control daylight quality and distribution in the interior space. The series of qualitative and quantitative tests confirmed that DDCS exceeds conventional double glazing system in terms of reducing glare near the window and distributing light to the rear of the space. The system can also be converted to a visually transparent or a translucent glazing by filling the channels with an appropriate fluid. DDCS can be integrated or retrofitted to conventional glazing systems and allow for diffusivity and transmittance control.

Mayzel B, Aizenberg J, Ilan M. The Elemental Composition of Demospongiae from the Red Sea, Gulf of Aqaba. PLoS ONE [Internet]. 2014;9 (4) :e95775. Full TextAbstract

Trace elements are vital for the growth and development of all organisms. Little is known about the elemental content and trace metal biology of Red Sea demosponges. This study establishes an initial database of sponge elemental content. It provides the necessary foundation for further research of the mechanisms used by sponges to regulate the uptake, accumulation, and storage of metals. The metal content of 16 common sponge species was determined using ICP measurements. A combination of statistical methods was used to determine the correlations between the metals and detect species with significantly high or low concentrations of these metals. Bioaccumulation factors were calculated to compare sponge metal content to local sediment. Theonella swinhoei contained an extremely high concentration of arsenic and barium, much higher (at least 200 times) than all other species and local sediment. Hyrtios erecta had significantly higher concentration of Al, Cr, Fe, Mn, Ti and V than all other species. This is due to sediment accumulation and inclusion in the skeleton fibers of this sponge species. Suberites clavatus was found to contain significantly higher concentration of Cd, Co, Ni and Zn than all other species and local sediment, indicating active accumulation of these metals. It also has the second highest Fe concentration, but without the comparably high concentrations of Al, Mn and Ti that are evident in H. erecta and in local sediment. These differences indicate active uptake and accumulation of Fe in S. clavatus, this was also noted in Niphates rowi. A significantly higher B concentration was found in Crella cyatophora compared to all other species. These results indicate specific roles of trace elements in certain sponge species that deserve further analysis. They also serve as a baseline to monitor the effects of anthropogenic disturbances on Eilat’s coral reefs.

Shillingford C, MacCallum N, Wong TS, Kim P, Aizenberg J. Fabrics coated with lubricated nanostructures display robust omniphobicity. Nanotechnology [Internet]. 2014;25 (1) :014019. Full TextAbstract

The development of a stain-resistant and pressure-stable textile is desirable for consumer and industrial applications alike, yet it remains a challenge that current technologies have been unable to fully address. Traditional superhydrophobic surfaces, inspired by the lotus plant, are characterized by two main components: hydrophobic chemical functionalization and surface roughness. While this approach produces water-resistant surfaces, these materials have critical weaknesses that hinder their practical utility, in particular as robust stain-free fabrics. For example, traditional superhydrophobic surfaces fail (i.e., become stained) when exposed to low-surface-tension liquids, under pressure when impacted by a high-velocity stream of water (e.g., rain), and when exposed to physical forces such as abrasion and twisting. We have recently introduced slippery lubricant-infused porous surfaces (SLIPS), a self-healing, pressure-tolerant and omniphobic surface, to address these issues. Herein we present the rational design and optimization of nanostructured lubricant-infused fabrics and demonstrate markedly improved performance over traditional superhydrophobic textile treatments: SLIPS-functionalized cotton and polyester fabrics exhibit decreased contact angle hysteresis and sliding angles, omni-repellent properties against various fluids including polar and nonpolar liquids, pressure tolerance and mechanical robustness, all of which are not readily achievable with the state-of-the-art superhydrophobic coatings.

Yao X, Dunn S, Kim P, Duffy M, Alvarenga J, Aizenberg J. Fluorogel Elastomers with Tunable Transparency, Elasticity, Shape- Memory, and Antifouling Properties. Angew. Chem. Int. Ed [Internet]. 2014;53 (17) :4418-4422. Full TextAbstract

Omniphobic fluorogel elastomers were prepared by photocuring perfluorinated acrylates and a perfluoropolyether crosslinker. By tuning either the chemical composition or the temperature that control the crystallinity of the resulting polymer chains, a broad range of optical and mechanical properties of the fluorogel can be achieved. After infusing with fluorinated lubricants, the fluorogels showed excellent resist- ance to wetting by various liquids and anti-biofouling behavior, while maintaining cytocompatiblity.

Koay N, Burgess I, Kay T, Nerger B, Miles-Rossouw M, Shirman T, Vu T, England G, Phillips K, Utech S, et al. Hierarchical structural control of visual properties in self-assembled photonic-plasmonic pigments. Opt. Express [Internet]. 2014;22 (23) :27750-27768. Publisher's VersionAbstract

We present a simple one-pot co-assembly method for the synthesis of hierarchically structured pigment particles consisting of silica inverse-opal bricks that are doped with plasmonic absorbers. We study the interplay between the plasmonic and photonic resonances and their effect on the visual appearance of macroscopic collections of photonic bricks that are distributed in randomized orientations. Manipulating the pore geometry tunes the wavelength- and angle-dependence of the scattering profile, which can be engineered to produce angle-dependent Bragg resonances that can either enhance or contrast with the color produced by the plasmonic absorber. By controlling the overall dimensions of the photonic bricks and their aspect ratios, their preferential alignment can either be encouraged or suppressed. This causes the Bragg resonance to appear either as uniform color travel in the former case or as sparse iridescent sparkle in the latter case. By manipulating the surface chemistry of these photonic bricks, which introduces a fourth length-scale (molecular) of independent tuning into our design, we can further engineer interactions between liquids and the pores. This allows the structural color to be maintained in oil-based formulations, and enables the creation of dynamic liquid-responsive images from the pigment.

Sunny S, Vogel N, Howell C, Vu TL, Aizenberg J. Lubricant-infused Nanoparticulate Coatings Assembled by Layer-by-layer Deposition. Adv. Funct. Mater. 2014;24 (42) :6658-6667.Abstract

Omniphobic coatings are designed to repel a wide range of liquids without leaving stains on the surface. A practical coating should exhibit stable repel- lency, show no interference with color or transparency of the underlying substrate and, ideally, be deposited in a simple process on arbitrarily shaped surfaces. We use layer-by-layer (LbL) deposition of negatively charged silica nanoparticles and positively charged polyelectrolytes to create nanoscale sur- face structures that are further surface-functionalized with fluorinated silanes and infiltrated with fluorinated oil, forming a smooth, highly repellent coating on surfaces of different materials and shapes. We show that four or more
LbL cycles introduce sufficient surface roughness to effectively immobilize the lubricant into the nanoporous coating and provide a stable liquid inter- face that repels water, low-surface-tension liquids and complex fluids. The absence of hierarchical structures and the small size of the silica nanoparti- cles enables complete transparency of the coating, with light transmittance exceeding that of normal glass. The coating is mechanically robust, maintains its repellency after exposure to continuous flow for several days and prevents adsorption of streptavidin as a model protein. The LbL process is conceptu- ally simple, of low cost, environmentally benign, scalable, automatable and therefore may present an efficient synthetic route to non-fouling materials.

Grinthal A, Aizenberg J. Mobile Interfaces: Liquids as a Perfect Structural Material for Multifunctional, Antifouling Surfaces. Chem. Mater. [Internet]. 2014;26 (1) :698-708. Full TextAbstract

Life creates some of its most robust, extreme surface materials not from solids but from liquids: a purely liquid interface, stabilized by underlying nanotexture, makes carnivorous plant leaves ultraslippery, the eye optically perfect and dirt-resistant, our knees lubricated and pressure-tolerant, and insect feet reversibly adhesive and shape-adaptive. Novel liquid surfaces based on this idea have recently been shown to display unprecedented omniphobic, self-healing, anti-ice, antifouling, optical, and adaptive properties. In this Perspective, we present a framework and a path forward for developing and designing such liquid surfaces into sophisticated, versatile multifunctional materials. Drawing on concepts from solid materials design and fluid dynamics, we outline how the continuous dynamics, responsiveness, and multiscale patternability of a liquid surface layer can be harnessed to create a wide range of unique, active interfacial functions -able to operate in harsh, changing environments- not achievable with static solids. We discuss how, in partnership with the underlying substrate, the liquid surface can be programmed to adaptively and reversibly reconfigure from a defect-free, molecularly smooth, transparent interface through a range of finely tuned liquid topographies in response to environmental stimuli. With nearly unlimited design possibilities and unmatched interfacial properties, liquid materials -as long-term stable interfaces yet in their fully liquid state- may potentially transform surface design everywhere from medicine to architecture to energy infrastructure.

Singleton TA, Burgess IB, Nerger BA, Goulet-Hanssens A, Koay N, Barrett CJ, Aizenberg J. Photo-tuning of Highly Selective Wetting in Inverse Opals. Soft Matter [Internet]. 2014;10 (9) :1325-1328. Publisher's VersionAbstract

Crack-free inverse opals exhibit a sharply defined threshold wettability for infiltration that has enabled their use as colourimetric indicators for liquid identification. Here we demonstrate direct and continuous photo-tuning of this wetting threshold in inverse opals whose surfaces are function- alized with a polymer doped with azobenzene chromophores.

Balazs AC, Aizenberg J. Reconfigurable soft matter. Soft Matter [Internet]. 2014;10 (9) :1244-1245. Publisher's Version
Howell C, Vu TL, Lin JJ, Kolle S, Juthani N, Watson E, Weaver JC, Alvarenga J, Aizenberg J. Self-Replenishing Vascularized Fouling-Release Surfaces. ACS Appl. Mater. Interfaces [Internet]. 2014;6 (15) :13299-13307. Full TextAbstract

Inspired by the long-term effectiveness of living
antifouling materials, we have developed a method for the self-
replenishment of synthetic biofouling-release surfaces. These
surfaces are created by either molding or directly embedding
3D vascular systems into polydimethylsiloxane (PDMS) and
filling them with a silicone oil to generate a nontoxic oil-
infused material. When replenished with silicone oil from an
outside source, these materials are capable of self-lubrication
and continuous renewal of the interfacial fouling-release layer.
Under accelerated lubricant loss conditions, fully infused vascularized samples retained significantly more lubricant than equivalent nonvascularized controls. Tests of lubricant-infused PDMS in static cultures of the infectious bacteria Staphylococcus aureus and Escherichia coli as well as the green microalgae Botryococcus braunii, Chlamydomonas reinhardtii, Dunaliella salina, and Nannochloropsis oculata showed a significant reduction in biofilm adhesion compared to PDMS and glass controls containing no lubricant. Further experiments on vascularized versus nonvascularized samples that had been subjected to accelerated lubricant evaporation conditions for up to 48 h showed significantly less biofilm adherence on the vascularized surfaces. These results demonstrate the ability of an embedded lubricant-filled vascular network to improve the longevity of fouling-release surfaces.

Zarzar LD, Aizenberg J. Stimuli-Responsive Chemomechanical Actuation: A Hybrid Materials Approach. Acc. Chem. Res. [Internet]. 2014;47 (2) :530-539. Full TextAbstract

Dynamic materials that can sense changes in their surroundings and functionally respond by altering many of their physical characteristics are primed to be integral components of future “smart” technologies. A fundamental reason for the adaptability of biological organisms is their innate ability to convert environmental or chemical cues into mechanical motion and reconfiguration on both the molecular and macroscale. However, design and engineering of robust chemomechanical behavior in artificial materials has proven a challenge. Such systems can be quite complex and often require intricate coordination between both chemical and mechanical inputs and outputs, as well as the combination of multiple materials working cooperatively to achieve the proper functionality. It is critical to not only understand the fundamental behaviors of existing dynamic chemo- mechanical systems but also apply that knowledge and explore new avenues for design of novel materials platforms that could provide a basis for future adaptive technologies.
In this Account, we explore the chemomechanical behavior, properties, and applications of hybrid-material surfaces consisting of environmentally sensitive hydrogels integrated within arrays of high-aspect-ratio nano- or microstructures. This bio-inspired approach, in which the volume-changing hydrogel acts as the “muscle” that reversibly actuates the microstructured “bones”, is highly tunable and customizable. Although straightforward in concept, the combination of just these two materials (structures and hydrogel) has given rise to a far more complex set of actuation mechanisms and behaviors. Variations in how the hydrogel is physically integrated within the structure array provide the basis for three fundamental mechanisms of actuation, each with its own set of responsive properties and chemomechanical behavior. Further control over how the chemical stimulus is applied to the surface, such as with microfluidics, allows for generation of more precise and varied patterns of actuation. We also discuss the possible applications of these hybrid surfaces for chemomechanical manipulation of reactions, including the generation of chemomechanical feedback loops. Comparing and contrasting these many approaches and techniques, we aim to put into perspective their highly tunable and diverse capabilities but also their future challenges and impacts.

Vasquez Y, Kolle M, Mishchenko L, Hatton BD, Aizenberg J. Three-Phase Co-Assembly: In-situ Incorporation of Nanoparticles into Tunable, Highly-Ordered, Porous Silica FIlms. ACS Photonics [Internet]. 2014;1 (1) :53-60. Full TextAbstract

We present a reproducible, one-pot colloidal co-assembly approach that results in large-scale, highly ordered porous silica films with embedded, uniformly distributed, accessible gold nanoparticles. The unique coloration of these inverse opal films combines iridescence with plasmonic effects. The coupled optical properties are easily tunable either by changing the concentration of added nanoparticles to the solution before assembly or by localized growth of the embedded Au nanoparticles upon exposure to tetrachloroauric acid solution, after colloidal template removal. The presence of the selectively absorbing particles furthermore enhances the hue and saturation of the inverse opals’ color by suppressing incoherent diffuse scattering. The composition and optical properties of these films are demonstrated to be locally tunable using selective functionalization of the doped opals.

Phillips KR, Vogel N, Hu Y, Kolle M, Perry CC, Aizenberg J. Tunable Anisotropy in Inverse Opals and Emerging Optical Properties. Chem. Mater. [Internet]. 2014;26 (4) :1622-1628. Publisher's VersionAbstract

Using self-assembly, nanoscale materials can be fabricated from the bottom up. Opals and inverse opals are examples of self-assembled nanomaterials made from crystallizing colloidal particles. As self-assembly requires a high level of control, it is challenging to use building blocks with anisotropic geometry to form complex opals, which limits the possible structures. Typically, spherical colloids are employed as building blocks, leading to symmetric, isotropic superstructures. However, a significantly richer palette of directionally dependent properties are expected if less symmetric, anisotropic structures can be created, especially originating from the assembly of regular, spherical particles. Here we show a simple method for introducing anisotropy into inverse opals by subjecting them to a post-assembly thermal treatment that results in directional shrinkage of the silica matrix caused by condensation of partially hydrated sol−gel silica structures. In this way, we can tailor the shape of the pores, and the anisotropy of the final inverse opal preserves the order and uniformity of the self-assembled structure. Further, we prevent the need to synthesize complex oval-shaped particles and crystallize them into such target geometries. Detailed X-ray photoelectron spectroscopy and infrared spectroscopy studies clearly identify increasing degrees of sol−gel condensation in confinement as a mechanism for the structure change. A computer simulation of structure changes resulting from the condensation-induced shrinkage further confirmed this mechanism. As an example of property changes induced by the introduction of anisotropy, we characterized the optical spectra of the anisotropic inverse opals and found that the optical properties can be controlled in a precise way using calcination temperature.

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 [Internet]. 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 [Internet]. 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.

Aizenberg J, Fratzl P. New Materials through Bioinspiration and Nanoscience. Adv. Funct. Mater. [Internet]. 2013;23 :4398-4399. Publisher's Version
Grinthal A, Aizenberg J. Adaptive all the way down: Building responsive materials from hierarchies of chemomechanical feedback. Chem. Soc. Rev. [Internet]. 2013;42 (17) :7072-7085. Publisher's VersionAbstract
A living organism is a bundle of dynamic, integrated adaptive processes: not only does it continuously respond to constant changes in temperature, sunlight, nutrients, and other features of its environment, but it does so by coordinating hierarchies of feedback among cells, tissues, organs, and networks all continuously adapting to each other. At the root of it all is one of the most fundamental adaptive processes: the constant tug of war between chemistry and mechanics that interweaves chemical signals with endless reconfigurations of macromolecules, fibers, meshworks, and membranes. In this tutorial we explore how such chemomechanical feedback – as an inherently dynamic, iterative process connecting size and time scales – can and has been similarly evoked in synthetic materials to produce a fascinating diversity of complex multiscale responsive behaviors. We discuss how chemical kinetics and architecture can be designed to generate stimulus-induced 3D spatiotemporal waves and topographic patterns within a single bulk material, and how feedback between interior dynamics and surface-wide instabilities can further generate higher order buckling and wrinkling patterns. Building on these phenomena, we show how yet higher levels of feedback and spatiotemporal complexity can be programmed into hybrid materials, and how these mechanisms allow hybrid materials to be further integrated into multicompartmental systems capable of hierarchical chemo-mechano-chemical feedback responses. These responses no doubt represent only a small sample of the chemomechanical feedback behaviors waiting to be discovered in synthetic materials, and enable us to envision nearly limitless possibilities for designing multiresponsive, multifunctional, self-adapting materials and systems.
Yao X, Hu Y, Grinthal A, Wong T-S, Mahadevan L, Aizenberg J. Adaptive fluid-infused porous films with tunable transparency and wettability. Nature Materials [Internet]. 2013;12 :529-534. Full TextAbstract
Materials that adapt dynamically to environmental changes are currently limited to two-state switching of single properties, and only a small number of strategies that may lead to materials with continuously adjustable characteristics have been reported1-3. Here we introduce adaptive surfaces made of a liquid film supported by a nanoporous elastic substrate. As the substrate deforms, the liquid flows within the pores causing the smooth and defect-free surface to roughen through a continuous range of topographies. We show that a graded mechanical stimulus can be directly translated into finely tuned, dynamic adjustments of optical transparency and wettability. In particular, we demonstrate simultaneous control of the film's transparency and its ability to continuously manipulate various low-surface-tension droplets from free-sliding to pinned. This strategy should make possible the rational design of tunable, multifunctional adaptive materials for a broad range of applications.
Hatton BD, Wheeldon I, Hancock MJ, Kolle M, Aizenberg J, Ingber DE. An artificial vasculature for adaptive thermal control of windows. Solar Energy Materials and Solar Cells [Internet]. 2013;117 :429-436. Publisher's VersionAbstract
Windows are a major source of energy inefficiency in buildings. In addition, heating by thermal radiation reduces the efficiency of photovoltaic panels. To help reduce heating by solar absorption in both of these cases, we developed a thin, transparent, bio-inspired, convective cooling layer for building windows and solar panels that contains microvasculature with millimeter-scale, fluid-filled channels. The thin cooling layer is composed of optically clear silicone rubber with microchannels fabricated using microfluidic engineering principles. Infrared imaging was used to measure cooling rates as a function of flow rate and water temperature. In these experiments, flowing room temperature water at 2 mL/min reduced the average temperature of a model 10×10 cm2 window by approximately 7–9 °C. An analytic steady-state heat transfer model was developed to augment the experiments and make more general estimates as functions of window size, channel geometry, flow rate, and water temperature. Thin cooling layers may be added to one or more panes in multi-pane windows or as thin film non-structural central layers. Lastly, the color, optical transparency and aesthetics of the windows could be modulated by flowing different fluids that differ in their scattering or absorption properties.
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. [Internet]. 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.

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