Grinthal, Alison

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.

Grinthal A, Noorduin WL, Aizenberg J. A Constructive Chemical Conversation. American Scientist [Internet]. 2016;104 (4) :228-235. Publisher's VersionAbstract

Using simple ingredients and processing, the authors discuss how they create vastly complex three-dimensional structures that assemble themselves.

Park K-C, Kim P, Grinthal A, He N, Fox D, Weaver JC, Aizenberg J. Condensation on slippery asymmetric bumps. Nature. 2016;531 (7592) :78-82.Abstract
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.
Cui J, Daniel D, Grinthal A, Lin K, Aizenberg J. Dynamic polymer systems with self-regulated secretion for the control of surface properties and material healing. Nat. Mater. [Internet]. 2015;14 (8) :790-795. Publisher's VersionAbstract
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.
Hou X, Hu Y, Grinthal A, Khan M, Aizenberg J. Liquid-based gating mechanism with tunable multiphase selectivity and antifouling behaviour. Nature [Internet]. 2015;519 (7541) :70-73. Full TextAbstract
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.
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.

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.
Grinthal A, Aizenberg J. Hydrogel-Actuated Integrated Responsive Systems (HAIRS): Creating Cilia-like "Hairy" Surfaces. In: den Toonder J, Onck P Cambridge, U.K. RSC ; 2013. pp. 162-185.
Noorduin W, Grinthal A, Mahadevan L, Aizenberg J. Rationally Designed Complex Hierarchical Microarchitectures. Science [Internet]. 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.
Grinthal A, Kang SH, Epstein AK, Aizenberg M, Khan M, Aizenberg J. Steering nanofibers: An integrative approach to bio-inspired fiber fabrication and assembly. Nano Today. 2012;7 (1) :35-52. 2012_NanoToday_review.pdf
Wong T-S, Kang SH, Tang SKY, Smythe EJ, Hatton BD, Grinthal A, and Aizenberg J. Bioinspired self-repairing slippery surfaces with pressure-stable omniphobicity. Nature. 2011;477 :443-447. SLIPS%20paper.pdf
Kim P, Zarzar LD, He X, Grinthal A, Aizenberg J. Hydrogel-Actuated Integrated Responsive Systems (HAIRS): Moving towards Adaptive Materials. Current Opinion in Solid State & Materials Science. 2011;15 :236-245. COSSMS2011.HAIRS.authorcopy.pdf
Kang SH, Wu N, Grinthal A, and Aizenberg J. Meniscus Lithography: Evaporation-Induced Self-Organization of Pillar Arrays into Moire Patterns. Phys. Rev. Lett. 2011;107 (17) :177802. PRL_2011.pdf