Publications

Submitted
Davidson EC, Kotikian A, Li S, Aizenberg J, Lewis JA. 3D Printable and Reconfigurable Liquid Crystal Elastomers with Light-Induced Shape Memory via Dynamic Bond Exchange. Advanced Materials. Submitted.
Park D, Craig S, Bechthold M, Aizenberg J. Adaptive Building Envelope System with Integrated Thermal Insulation and Heat Recovery System. Building and Environment. Submitted.
2019
McCoy D, McCoy V, Mandsberg NK, Shneidman AV, Aizenberg J, Prum RO, Haig D. Structurally assisted super black in colorful peacock spiders. Proc. R. Soc. B [Internet]. 2019;286 (1902). Publisher's Version
2018
Howell C, Grinthal A, Sunny S, Aizenberg M, Aizenberg J. Designing Liquid-Infused Surfaces for Medical Applications: A Review. Advanced MaterialsAdvanced MaterialsAdv. Mater. [Internet]. 2018;30 (50) :1802724. Publisher's VersionAbstract
Abstract The development of new technologies is key to the continued improvement of medicine, relying on comprehensive materials design strategies that can integrate advanced therapeutic and diagnostic functions with a variety of surface properties such as selective adhesion, dynamic responsiveness, and optical/mechanical tunability. Liquid-infused surfaces have recently come to the forefront as a unique approach to surface coatings that can resist adhesion of a wide range of contaminants on medical devices. Furthermore, these surfaces are proving highly versatile in enabling the integration of established medical surface treatments alongside the antifouling capabilities, such as drug release or biomolecule organization. Here, the range of research being conducted on liquid-infused surfaces for medical applications is presented, from an understanding of the basics behind the interactions of physiological fluids, microbes, and mammalian cells with liquid layers to current applications of these materials in point-of-care diagnostics, medical tubing, instruments, implants, and tissue engineering. Throughout this exploration, the design parameters of liquid-infused surfaces and how they can be adapted and tuned to particular applications are discussed, while identifying how the range of controllable factors offered by liquid-infused surfaces can be used to enable completely new and dynamic approaches to materials and devices for human health.
Alvarenga J, Ainge Y, Williams C, Maltz A, Blough T, Khan M, Aizenberg J. Research Update: Liquid gated membrane filtration performance with inorganic particle suspensions. APL MaterialsAPL Materials [Internet]. 2018;6 (10) :100703. Publisher's Version
Yao Y, Waters JT, Shneidman AV, Cui J, Wang X, Mandsberg NK, Li S, Balazs AC, Aizenberg J. Multiresponsive polymeric microstructures with encoded predetermined and self-regulated deformability. Proceedings of the National Academy of Sciences [Internet]. 2018;115 (51) :12950. Publisher's VersionAbstract
The range of allowed deformation modes currently described for the actuation of microstructures is limited. In this work we introduce magnetic-field–guided encoding of highly controlled molecular anisotropy into 3D liquid-crystalline elastomer microstructures capable of displaying unique multiresponsive, shape-changing behaviors. The richness of the predetermined and self-regulated deformations and region-specific motions in these microstructural arrays gives rise to physicochemical insights, as well as potential applications in controlled adhesion, information encryption, soft robotics, and self-regulated light–material interactions.Dynamic functions of biological organisms often rely on arrays of actively deformable microstructures undergoing a nearly unlimited repertoire of predetermined and self-regulated reconfigurations and motions, most of which are difficult or not yet possible to achieve in synthetic systems. Here, we introduce stimuli-responsive microstructures based on liquid-crystalline elastomers (LCEs) that display a broad range of hierarchical, even mechanically unfavored deformation behaviors. By polymerizing molded prepolymer in patterned magnetic fields, we encode any desired uniform mesogen orientation into the resulting LCE microstructures, which is then read out upon heating above the nematic–isotropic transition temperature (TN–I) as a specific prescribed deformation, such as twisting, in- and out-of-plane tilting, stretching, or contraction. By further introducing light-responsive moieties, we demonstrate unique multifunctionality of the LCEs capable of three actuation modes: self-regulated bending toward the light source at T < TN–I, magnetic-field–encoded predetermined deformation at T > TN–I, and direction-dependent self-regulated motion toward the light at T > TN–I. We develop approaches to create patterned arrays of microstructures with encoded multiple area-specific deformation modes and show their functions in responsive release of cargo, image concealment, and light-controlled reflectivity. We foresee that this platform can be widely applied in switchable adhesion, information encryption, autonomous antennae, energy harvesting, soft robotics, and smart buildings.
Yao Y, Waters J, Shneidman AV, Cui J, Wang X, Mandsberg NK, Li S, Balazs AC, Aizenberg J. Multi-responsive polymeric microstructures with encoded pre-determined and self-regulated deformability. Proceedings of the National Academy of Sciences [Internet]. 2018;115 (51) :12950-12955. Publisher's Version
Timoshenko J, Wrasman C, Luneau M, Shirman T, Cargnello M, Bare S, Aizenberg J, Friend C, Frenkel A. Probing atomic distributions in mono- and bimetallic nanoparticles by supervised machine learning. Nano Letters. 2018. acs.nanolett.8b04461.pdf
Kreder MJ, Daniel D, Tetreault A, Cao Z, Lemaire B, Timonen JVI, Aizenberg J. Film Dynamics and Lubricant Depletion by Droplets Moving on Lubricated Surfaces. PHYSICAL REVIEW. 2018;8 (031053).Abstract

Lubricated surfaces have shown promise in numerous applications where impinging foreign droplets
must be removed easily; however, before they can be widely adopted, the problem of lubricant depletion,
which eventually leads to decreased performance, must be solved. Despite recent progress, a quantitative
mechanistic explanation for lubricant depletion is still lacking. Here, we first explain the shape of a droplet
on a lubricated surface by balancing the Laplace pressures across interfaces. We then show that the
lubricant film thicknesses beneath, behind, and wrapping around a moving droplet change dynamically

with the droplet’s speed—analogous to the classical Landau-Levich-Derjaguin problem. The intercon-
nected lubricant dynamics results in the growth of the wetting ridge around the droplet, which is the

dominant source of lubricant depletion. We then develop an analytic expression for the maximum amount
of lubricant that can be depleted by a single droplet. Counterintuitively, faster-moving droplets subjected to
higher driving forces deplete less lubricant than their slower-moving counterparts. The insights developed
in this work will inform future work and the design of longer-lasting lubricated surfaces.

physrevx.8.031053.pdf
Daniel D, Timonen JVI, Li R, Velling SJ, Kreder MJ, Tetreault A, Aizenberg J. Origins of liquid-repellency on structured, flat, and lubricated surfaces . Phys. Rev. Lett. 2018.Abstract
There are currently three main classes of liquid-repellent surfaces: micro-/nano-structured superhydrophobic surfaces, flat surfaces grafted with `liquid-like' polymer brushes, and lubricated surfaces. Despite recent progress, the mechanistic explanation for the differences in droplet behavior on such surfaces is still under debate. Here, we measured the dissipative force acting on a droplet moving on representatives of these surfaces at different velocities U = 0.01--1 mm/s using a cantilever force sensor with sub-μN accuracy, and correlated it to the contact line dynamics observed using optical interferometry at high spatial (micron) and temporal (lessthan 0.1s) resolutions. We find that the dissipative force---due to very different physical mechanisms at the contact line---is independent of velocity on superhydrophobic surfaces, but depends non-linearly on velocity for flat and lubricated surfaces. The techniques and insights presented here will inform future work on liquid-repellent surfaces and enable their rational design.
Hinz K, Alvarenga J, Kim P, Park D, Aizenberg J, Bechthold M. Pneumatically adaptive light modulation system (PALMS) for buildings. Materials & Design [Internet]. 2018;152 :156-167. Publisher's VersionAbstract

This research introduces a novel approach to control light transmittance based on flexible polydimethylsiloxane (PDMS) films that have been plasma-treated such that micro-scale surface features have a visual effect as the film responds to applied strain. The effect is continuously tunable from optically clear (71.5% Transmittance over a 400–900 nm wavelength) to completely diffuse (18.1% T). Changes in the film's optical properties are triggered by bi-axial strains applied using a pneumatic system to form pressurized envelopes. This paper reports on a series of experimental studies and provides system integration research using prototypes, simulations and geometric models to correlate measured optical properties, strain, and global surface curvatures. In conclusion, a design is proposed to integrate PDMS light control within existing building envelopes.

Two alternatives are investigated and compared: System A uses positive pressure featuring an exterior grid to restrain and shape the inflated film during expansion; System B uses negative pressure where the films are shaped according to the geometry of an interstitial grid that serves as a spacer between two film surfaces. Both systems can provide effective control of opacity levels using pneumatic pressure and may be suitable for use with existing glazing systems or ethylene tetrafluoroethylene (ETFE) pneumatic envelopes.

pneumatically_adaptive_light_modulation_system_palms_for_buildings_materials_and_design_2018.pdf
Yao Y, Aizenberg J, Park K-C. Dropwise Condensation on Hydrophobic Bumps and Dimples. Appl. Phys. Lett. [Internet]. 2018;112 (15) :151605. Full TextAbstract
Surface topography plays an important role in promoting or suppressing localized condensation. In this work, we study the growth of water droplets on hydrophobic convex surface textures such as bumps and concave surface textures such as dimples with a millimeter scale radius of curvature. We analyze the spatio-temporal droplet size distribution under a supersaturation condition created by keeping the uniform surface temperature below the dew point and show its relationship with the sign and magnitude of the surface curvature. In particular, in contrast to the well-known capillary condensation effect, we report an unexpectedly less favorable condensation on smaller, millimeter-scale dimples where the capillary condensation effect is negligible. To explain these experimental results, we numerically calculated the diffusion flux of water vapor around the surface textures, showing that its magnitude is higher on bumps and lower on dimples compared to a flat surface. We envision that our understanding of millimetric surface topography can be applied to improve the energy efficiency of condensation in applications such as water harvesting, heating, ventilation, and air conditioning systems for buildings and transportation, heat exchangers, thermal desalination plants, and fuel processing systems.
Li L, Fijneman AJ, Kaandorp JA, Aizenberg J, Noorduin WL. Directed nucleation and growth by balancing local supersaturation and substrate/nucleus lattice mismatch. PNAS [Internet]. 2018;14 :3573-3580. Publisher's VersionAbstract
Controlling nucleation and growth is crucial in biological and artificial mineralization and self-assembly processes. The nucleation barrier is determined by the chemistry of the interfaces at which crystallization occurs and local supersaturation. Although chemically tailored substrates and lattice mismatches are routinely used to modify energy landscape at the substrate/nucleus interface and thereby steer heterogeneous nucleation, strategies to combine this with control over local supersaturations have remained virtually unexplored. Here we demonstrate simultaneous control over both parameters to direct the positioning and growth direction of mineralizing compounds on preselected polymorphic substrates. We exploit the polymorphic nature of calcium carbonate (CaCO3) to locally manipulate the carbonate concentration and lattice mismatch between the nucleus and substrate, such that barium carbonate (BaCO3) and strontium carbonate (SrCO3) nucleate only on specific CaCO3 polymorphs. Based on this approach we position different materials and shapes on predetermined CaCO3 polymorphs in sequential steps, and guide the growth direction using locally created supersaturations. These results shed light on nature’s remarkable mineralization capabilities and outline fabrication strategies for advanced materials, such as ceramics, photonic structures, and semiconductors.
Hou X, Li J, Tesler AB, Yao Y, Wang M, Min L, Sheng Z, Aizenberg J. Dynamic air/liquid pockets for guiding microscale flow. Nat. Commun. [Internet]. 2018;9 :733. Full TextAbstract

Microscale flows of fluids are mainly guided either by solid matrices or by liquid–liquid interfaces. However, the solid matrices are plagued with persistent fouling problems, while liquid–liquid interfaces are limited to low-pressure applications. Here we report a dynamic liquid/solid/gas material containing both air and liquid pockets, which are formed by partially infiltrating a porous matrix with a functional liquid. Using detailed theoretical and experimental data, we show that the distribution of the air- and liquid-filled pores is responsive to pressure and enables the formation and instantaneous recovery of stable liquid–liquid interfaces that sustain a wide range of pressures and prevent channel contamination. This adaptive design is demonstrated for polymeric materials and extended to metal-based systems that can achieve unmatched mechanical and thermal stability. Our platform with its unique adaptive pressure and antifouling capabilities may offer potential solutions to flow control in microfluidics, medical devices, microscale synthesis, and biological assays.

Phillips KR, Shirman T, Shirman E, Shneidman AV, Kay TM, Aizenberg J. Nanocrystalline Precursors for the Co-Assembly of Crack-Free Metal Oxide Inverse Opals. Adv. Mater. [Internet]. 2018;30 :1706329. Publisher's VersionAbstract

Inorganic microstructured materials are ubiquitous in nature. However, their formation in artificial self-assembly systems is challenging as it involves a complex interplay of competing forces during and after assembly. For example, colloidal assembly requires fine-tuning of factors such as the size and surface charge of the particles and electrolyte strength of the solvent to enable successful self-assembly and minimize crack formation. Co-assembly of templating colloidal particles together with a sol–gel matrix precursor material helps to release stresses that accumulate during drying and solidification, as previously shown for the formation of high-quality inverse opal (IO) films out of amorphous silica. Expanding this methodology to crystalline materials would result in microscale architectures with enhanced photonic, electronic, and catalytic properties. This work describes tailoring the crystallinity of metal oxide precursors that enable the formation of highly ordered, large-area (mm2) crack-free titania, zirconia, and alumina IO films. The same bioinspired approach can be applied to other crystalline materials as well as structures beyond IOs.

Wu F, Chen S, Chen B, Wang M, Min L, Alvarenga J, Ju J, Khademhosseini A, Yao Y, Zhang YS, et al. Bioinspired Universal Flexible Elastomer-Based Microchannels. Small [Internet]. 2018;14 :1702170. Publisher's VersionAbstract

Flexible and stretchable microscale fluidic devices have a broad range of potential applications, ranging from electronic wearable devices for convenient digital lifestyle to biomedical devices. However, simple ways to achieve stable flexible and stretchable fluidic microchannels with dynamic liquid transport have been challenging because every application for elastomeric microchannels is restricted by their complex fabrication process and limited material selection. Here, a universal strategy for building microfluidic devices that possess exceptionally stable and stretching properties is shown. The devices exhibit superior mechanical deformability, including high strain (967%) and recovery ability, where applications as both strain sensor and pressure-flow regulating device are demonstrated. Various microchannels are combined with organic, inorganic, and metallic materials as stable composite microfluidics. Furthermore, with surface chemical modification these stretchable microfluidic devices can also obtain antifouling property to suit for a broad range of industrial and biomedical applications.

Daniel D, Yao X, Aizenberg J. Stable Liquid Jets Bouncing off Soft Gels. Phys. Rev. Lett. [Internet]. 2018;120 (2) :028006. Publisher's VersionAbstract

A liquid jet can stably bounce off a sufficiently soft gel by following the contour of the dimple created upon impact. This new phenomenon is insensitive to the wetting properties of the gels and was observed for different liquids over a wide range of surface tensions, γ = 24 − 72 mN/m. In contrast, other jet rebound phenomena are typically sensitive to γ: only a high γ jet rebounds off a hard solid (e.g. superhydrophobic surface) and only a low γ jet bounces off a liquid bath. This is because an air layer must be stabilized between the two interfaces. For a soft gel, no air layer is necessary and the jet rebound remains stable even when there is direct liquid-gel contact.

England GT, Aizenberg J. Emerging Optical Properties from the Combination of Simple Optical Effects. Rep. Prog. Phys. [Internet]. 2018;81 (1) :016402. Publisher's VersionAbstract

Structural color arises from the patterning of geometric features or refractive indices of the constituent materials on the length-scale of visible light. Many different organisms have developed structurally colored materials as a means of creating multifunctional structures or displaying colors for which pigments are unavailable. By studying such organisms, scientists have developed artificial structurally colored materials that take advantage of the hierarchical geometries, frequently employed for structural coloration in nature. These geometries can be combined with absorbers—a strategy also found in many natural organisms—to reduce the effects of fabrication imperfections. Furthermore, artificial structures can incorporate materials that are not available to nature—in the form of plasmonic nanoparticles or metal layers—leading to a host of novel color effects. Here, we explore recent research involving the combination of different geometries and materials to enhance the structural color effect or to create entirely new effects, which cannot be observed otherwise.

Shirman T, Lattimer J, Luneau M, Shirman E, Reece C, Aizenberg M, Madix RJ, Aizenberg J, Friend CM. New Architectures for Designed Catalysts: Selective Oxidation using AgAu Nanoparticles on Colloid-Templated Silica. Chem. Eur. J. [Internet]. 2018;24 :1833 –1837 . Publisher's VersionAbstract

A highly modular synthesis of designed catalysts with controlled bimetallic nanoparticle size and composition and a well-defined structural hierarchy is demonstrated. Exemplary catalysts—bimetallic dilute Ag-in-Au nanoparticles partially embedded in a porous SiO2 matrix (SiO2–AgxAuy)— were synthesized by the decoration of polymeric colloids with the bimetallic nanoparticles followed by assembly into a colloidal crystal backfilled with the matrix precursor and subsequent removal of the polymeric template. This work reports that these new catalyst architectures are significantly better than nanoporous dilute AgAu alloy catalysts (nanoporous Ag3Au97) while retaining a clear predictive relationship between their surface reactivity with that of single-crystal Au surfaces. This paves the way for broadening the range of new catalyst architectures required for translating the designed principles developed under controlled conditions to designed catalysts under operating conditions for highly selective coupling of alcohols to form esters. Excellent catalytic performance of the porous SiO2–AgxAuy structure for selective oxidation of both methanol and ethanol to produce esters with high conversion efficiency, selectivity, and stability was demonstrated, illustrating the ability to translate design principles developed for support-free materials to the colloid-templated structures. The synthetic methodology reported is customizable for the design of a wide range of robust catalytic systems inspired by design principles derived from model studies. Fine control over the composition, morphology, size, distribution, and availability of the supported nanoparticles was demonstrated.

2017
Shirman E, Shirman T, Shneidman AV, Grinthal A, Phillips KR, Whelan H, Bulger E, Abramovitch M, Patil J, Nevarez R, et al. Modular Design of Advanced Catalytic Materials Using Hybrid Organic–Inorganic Raspberry Particles. Adv. Func. Mater. [Internet]. 2017 :1704559. Publisher's VersionAbstract

Catalysis is one of the most sophisticated areas of materials research that encompasses a diverse set of materials and phenomena occurring on multiple length and time scales. Designing catalysts that can be broadly applied toward global energy and environmental challenges requires the development of universal frameworks for complex catalytic systems through rational and independent (or quasi-independent) optimization of multiple structural and compositional features. Toward addressing this goal, a modular platform is presented in which sacrificial organic colloids bearing catalytic nanoparticles on their surfaces self-assemble with matrix precursors, simultaneously structuring the resulting porous networks and fine-tuning the locations of catalyst particles. This strategy allows combinatorial variations of the material building blocks and their organization, in turn providing numerous degrees of freedom for optimizing the material’s functional properties, from the nanoscale to the macroscale. The platform enables systematic studies and rational design of efficient and robust systems for a wide range of catalytic and photocatalytic reactions, as well as their integration into industrial and other real-life environments.

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