Mechanochemistry for Active Materials and Devices

The coupling of mechanical stress fields in polymers to covalent chemistry (polymer mechanochemistry) has provided access to previously unattainable chemical reactions and polymer transformations. In the bulk, mechanochemical activation has been used as the basis for new classes of stress-responsive polymers that demonstrate stress/strain sensing, shear-induced intermolecular reactivity for molecular level remodeling and self-strengthening, and the release of acids and other small molecules that are potentially capable of triggering further chemical response. The potential utility of polymer mechanochemistry in functional materials is limited, however, by the fact that to date, all reported covalent activation in the bulk occurs in concert with plastic yield and deformation, so that the structure of the activated object is vastly different from its nascent form. Mechanochemically activated materials have thus been limited to “single use” demonstrations, rather than as multi-functional materials for structural and/or device applications. Here, we report that filled polydimethylsiloxane (PDMS) elastomers provide a robust elastic substrate into which mechanophores can be embedded and activated under conditions from which the sample regains its original shape and properties. Fabrication is straightforward and easily accessible, providing access for the first time to objects and devices that either release or reversibly activate chemical functionality over hundreds of loading cycles.

While the mechanically accelerated ring-opening reaction of spiropyran to merocyanine and associated color change provides a useful method by which to image the molecular scale stress/strain distribution within a polymer, the magnitude of the forces necessary for activation had yet to be quantified. Here, we report single molecule force spectroscopy studies of two spiropyran isomers. Ring opening on the timescale of tens of milliseconds is found to require forces of ~240 pN, well below that of previously characterized covalent mechanophores. The lower threshold force is a combination of a low force-free activation energy and the fact that the change in rate with force (activation length) of each isomer is greater than that inferred in other systems. Importantly, quantifying the magnitude of forces required to activate individual spiropyran-based force-probes enables the probe behave as a “scout” of molecular forces in materials; the observed behavior of which can be extrapolated to predict the reactivity of potential mechanophores within a given material and deformation.

We subsequently translated the design platform to existing dynamic soft technologies to fabricate the first mechanochemically responsive devices; first, by remotely inducing dielectric patterning of an elastic substrate to produce assorted fluorescent patterns in concert with topological changes; and second, by adopting a soft robotic platform to produce a color change from the strains inherent to pneumatically actuated robotic motion. Shown herein, covalent polymer mechanochemistry provides a viable mechanism to convert the same mechanical potential energy used for actuation into value-added, constructive covalent chemical responses. The color change associated with actuation suggests opportunities for not only new color changing or camouflaging strategies, but also the possibility for simultaneous activation of latent chemistry (e.g., release of small molecules, change in mechanical properties, activation of catalysts, etc.) in soft robots. In addition, mechanochromic stress mapping in a functional actuating device might provide a useful design and optimization tool, revealing spatial and temporal force evolution within the actuator in a way that might also be coupled to feedback loops that allow autonomous, self-regulation of activity.

In the future, both the specific material and the general approach should be useful in enriching the responsive functionality of soft elastomeric materials and devices. We anticipate the development of new mechanophores that, like the materials, are reversibly and repeatedly activated, expanding the capabilities of soft, active devices and further permitting dynamic control over chemical reactivity that is otherwise inaccessible, each in response to a single remote signal.

Imaging through turbulence using compressive coherence sensing.

Previous studies have shown that the isoplanatic distortion due to turbulence and the image of a remote object may be jointly estimated from the 4D mutual intensity across an aperture. This Letter shows that decompressive inference on a 2D slice of the 4D mutual intensity, as measured by a rotational shear interferometer, is sufficient for estimation of sparse objects imaged through turbulence. The 2D slice is processed using an iterative algorithm that alternates between estimating the sparse objects and estimating the turbulence-induced phase screen. This approach may enable new systems that infer object properties through turbulence without exhaustive sampling of coherence functions.

Broadband electromagnetic cloaking with smart metamaterials.

The ability to render objects invisible with a cloak that fits all objects and sizes is a long-standing goal for optical devices. Invisibility devices demonstrated so far typically comprise a rigid structure wrapped around an object to which it is fitted. Here we demonstrate smart metamaterial cloaking, wherein the metamaterial device not only transforms electromagnetic fields to make an object invisible, but also acquires its properties automatically from its own elastic deformation. The demonstrated device is a ground-plane microwave cloak composed of an elastic metamaterial with a broad operational band (10-12 GHz) and nearly lossless electromagnetic properties. The metamaterial is uniform, or perfectly periodic, in its undeformed state and acquires the necessary gradient-index profile, mimicking a quasi-conformal transformation, naturally from a boundary load. This easy-to-fabricate hybrid elasto-electromagnetic metamaterial opens the door to implementations of a variety of transformation optics devices based on quasi-conformal maps.

Internal languages of retrieval: the bilingual encoding of memories for the personal past.

In contrast to most research on bilingual memory that focuses on how words in either lexicon are mapped onto memory for objects and concepts, we focus on memory for events in the personal past. Using a word-cue technique in sessions devoted exclusively to one language, we found that older Hispanic immigrants who had come to the United States as adults internally retrieved autobiographical memories in Spanish for events in the country of origin and in English for events in the U.S. These participants were consistently capable of discerning whether a memory had come to them "in words" or not, reflecting the distinction between purely imagistic or conceptual memories and specifically linguistic memories. Via examination of other phenomenological features of these memories (sense of re-living, sensory detail, emotionality, and rehearsal), we conclude that the linguistic/nonlinguistic distinction is fundamental and independent of these other characteristics. Bilinguals encode and retrieve certain autobiographical memories in one or the other language according to the context of encoding, and these linguistic characteristics are stable properties of those memories over time.