Session E4: Polymer Physics Prize

Polymer Physics Prize: Designing "Materials that Compute": Exploiting the Properties of Self-oscillating Polymer Gels

Lightweight, deformable materials that can sense and respond to human touch and motion can be the basis of future wearable computers, where the material itself will be capable of performing computations. To facilitate the creation of "materials that compute", we draw from two emerging modalities for computation: chemical computing, which relies on reaction-diffusion mechanisms to perform operations, and oscillatory computing, which performs pattern recognition through synchronization of coupled oscillators. Chemical computing systems, however, suffer from the fact that the reacting species are coupled only locally; the coupling is limited by diffusion as the chemical waves propagate throughout the system. Additionally, oscillatory computing systems have not utilized a potentially wearable material. To address both these limitations, we develop the first model for coupling self-oscillating polymer gels to a piezoelectric (PZ) micro-electro-mechanical system (MEMS). The resulting transduction between chemo-mechanical and electrical energy creates signals that can be propagated quickly over long distances and thus, permits remote, non-diffusively coupled oscillators to communicate and synchronize. The oscillators can be organized into arbitrary topologies because the electrical connections lift the limitations of diffusive coupling. Using our model, we predict the synchronization behavior that can be used for computational tasks, ultimately enabling "materials that compute".   

Reaction-Diffusion Patterns in Structured Media

I will look at pattern formation in the Belousov-Zhabotinsky (BZ) oscillating chemical reaction in media that are structured at length scales ranging from ten nanometers to a few centimeters. A reverse microemulsion consisting of nanometer diameter droplets of water containing the reactants dispersed in oil allows the physical structure (size, spacing) of the droplets and their chemical composition to be controlled independently, enabling one to generate a remarkable variety of stationary and moving patterns, including Turing structures, ordinary and antispirals, packet waves and spatiotemporal chaos. One- and two-dimensional arrays of aqueous droplets in oil generated by microfluidic techniques have diameters of the order of 100 micrometers and produce a different array of patterns that can be precisely controlled with light. In particular, circular arrays of droplets provide a testing ground for some of Turing's ideas about morphogenesis. By attaching the BZ catalyst to a polymer that shrinks and swells in response to changes in the redox state of the catalyst, one can construct gel materials that transduce chemical changes to mechanical motion, a phenomenon modeled with considerable success by the Balazs group. If time permits, I will also discuss the BZ reaction in coupled macroscopic flow reactors that mimic small neural networks.   

Modeling Anisotropic Self-Assembly of Isotropic Objects: from Hairy Nanoparticles to Methylcellulose Fibrils

Spontaneous symmetry breaking and formation of anisotropic structures from apparently isotropic building blocks is an exciting and not fully understood topic. I will discuss two examples of such self-assembly. The first example is related to the assembly of ``hairy'' nanoparticles in homopolymer matrices$^{1}$. The particles can assemble into long strings (they can also form other morphologies, as well) even though the shape of each particle and the distribution of ligands on the particle surface is spherically symmetric. Using the approach developed by Thompson, Ginzburg, Matsen, and Balazs$^{2}$, we show that presence of other particles can re-distribute the ligands and effectively ``polarize'' the particle-particle interaction, giving rise to the formation of 1d particle strings$^{3}$. In the second example, we consider aqueous solutions of methylcellulose (MC) polymers. It has been shown recently$^{4}$ that at high temperature, the polymers form high-aspect ratio ``fibrils'' with diameter \textasciitilde 15 nm and length in the hundreds on nanometers. Using coarse-grained Molecular Dynamics (CG-MD), we propose that the ``fibrils'' are result of one-dimensional self-assembly of single molecule ``rings''. Each MC polymer chain is forced into a ring because of the balance between internal chain rigidity (favoring more expanded configuration) and unfavorable polymer-water interactions (favoring more collapsed conformation). We also develop a theory predicting rheology and phase behavior of aqueous MC, and validate it against experimental data$^{5}$. Both examples show that anisotropic self-assembly can show up in unexpected places, and various theoretical tools are needed to successfully model it. 1. P. Akcora et al., Nature Mater. 8, 354 (2009). 2. R. Thompson, V. Ginzburg, M. Matsen, and A. Balazs, Science 292, 2469 (2001). 3. V. Ginzburg, Macromolecules 46, 9898 (2013). 4. S. Arvidson et al., Macromolecules 46, 300 (2013). 5. V. Ginzburg, R. Sammler, W. Huang, and R. Larson, submitted for publication.   

Functional, Responsive Materials Assembled from Recombinant Oleosin.

Biological cells are surrounded by a plasma membrane made primarily of phospholipids that form a bilayer. This membrane is permselective and compartmentalizes the cell. A simple form of artificial cell is the vesicle, in which a phospholipid bilayer membrane surrounds an aqueous solution. However, there is no a priori reason why a membrane needs to be made of phospholipids. It could be made of any surfactant that forms a bilayer. We have assembled membranes and other structures from the recombinant plant protein oleosin. The ability to assemble from a recombinant protein means that every molecule is identical, we have complete control over the sequence, and hence can build in designer functionality with high fidelity, including adhesion and enzymatic activity. Such incorporation is trivial using the tools of molecular biology. We find that while many variants of oleosin make membranes, others make micelles and sheets. We show how the type of supramolecular structure can be altered by the conditions of solvent, such as ionic strength, and the architecture of the surfactant itself. We show that protease cleavable domains can be incorporated within oleosin, and be engineered to protect other functional domains such as adhesive motifs, to make responsive materials whose activity and shape depend on the action of proteases. We will also present the idea of making ``Franken''-oleosins, where large domains of native oleosin are replaced with domains from other functional proteins, to make hybrids conferred by the donor protein. Thus, we can view oleosin as a template upon which a vast array of designer functionalities can be imparted..   

\textbf{Moving HAIRS: Towards adaptive, homeostatic materials}

Dynamic structures that respond reversibly to changes in their environment are central to self-regulating thermal and lighting systems, targeted drug delivery, sensors, and self-propelled locomotion. Since an adaptive change requires energy input, an ideal strategy would be to design materials that harvest energy directly from the environment and use it to drive an appropriate response. This lecture will present the design of a novel class of reconfigurable materials that use surfaces bearing arrays of nanostructures put in motion by environment-responsive gels. Their unique hybrid architecture, and chemical and mechanical properties can be optimized to confer a wide range of adaptive behaviors. Using both experimental and modeling approaches, we are developing these hydrogel-actuated integrated responsive systems (HAIRS) as new materials with reversible optical and wetting properties, as a multifunctional platform for controlling cell differentiation and function, and as a first homeostatic system with autonomous self-regulation.