In the past few years, spiropyran has emerged as the molecule-of-choice for the construction of novel dynamic materials. This unique molecular switch undergoes structural isomerisation in response to a variety of orthogonal stimuli, e.g. light, temperature, metal ions, redox potential, and mechanical stress. Incorporation of this switch onto macromolecular supports or inorganic scaffolds allows for the creation of robust dynamic materials. This review discusses the synthesis, switching conditions, and use of dynamic materials in which spiropyran has been attached to the surfaces of polymers, biomacromolecules, inorganic nanoparticles, as well as solid surfaces. The resulting materials show fascinating properties whereby the state of the switch intimately affects a multitude of useful properties of the support. The utility of the spiropyran switch will undoubtedly endow these materials with far-reaching applications in the near future.

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Spiropyran-based dynamic materials

Flexible and stretchable physical sensors capable of both energy harvesting and self-powered sensing are vital to the rapid advancements in wearable electronics Even so, there exist few studies that can integrate energy harvesting and self-powered sensing into a single electronic skin Here, a stretchable and washable skin-inspired triboelectric nanogenerator (SI-TENG) is developed for both biomechanical energy harvesting and versatile pressure sensing A planar and designable conductive yarn network constructed from a three-ply-twisted silver-coated nylon yarn is embedded into flexible elastomer, endowing the SI-TENG with desired stretchability, good sensitivity, high detection precision, fast responsivity, and excellent mechanical stability With a maximum average power density of 230 mW m-2 , the SI-TENG is able to light up 170 light-emitting diodes, charge various capacitors, and drive miniature electronic products As a self-powered multifunctional sensor, the SI-TENG is adopted to monitor human physiological signals, such as arterial pulse and voice vibrations Furthermore, an intelligent prosthetic hand, a self-powered pedometer/speedometer, a flexible digital keyboard, and a proof-of-concept pressure-sensor array with 8 × 8 sensing pixels are successively demonstrated to further confirm its versatile application prospects Based on these merits, the developed SI-TENG has promising applications in wearable powering technology, physiological monitoring, intelligent prostheses, and human-machine interfaces

A Stretchable Yarn Embedded Triboelectric Nanogenerator as Electronic Skin for Biomechanical Energy Harvesting and Multifunctional Pressure Sensing.

The detection of mechanical stress in polymeric materials through optical variations has attracted considerable interest over the past ten years. In this tutorial review, the current state of knowledge concerning the preparation of polymers with mechanochromic features is summarized. Two types of procedures are illustrated and thoroughly discussed along with their respective structure–property relationships: the first resides in the physical dispersion of the dye in the form of supramolecular aggregates in a preformed polymer matrix; the second involves the covalent insertion of chromophoric units into the macromolecule backbone or side chains. Herein we review the simplicity of the preparative routes available, and their influence over the properties of the resulting dye–polymer systems, by focussing on the most illustrative examples described in the literature. Special reference is made to stimuli-responsiveness as a mechanical means towards innovative smart and intelligent materials.

Dye-containing polymers: methods for preparation of mechanochromic materials

Recently developed triboelectric nanogenerators (TENGs) act as a promising power source for self-powered electronic devices. However, the majority of TENGs are fabricated using metallic electrodes and cannot achieve high stretchability and transparency, simultaneously. Here, slime-based ionic conductors are used as transparent current-collecting layers of TENG, thus significantly enhancing their energy generation, stretchability, transparency, and instilling self-healing characteristics. This is the first demonstration of using an ionic conductor as the current collector in a mechanical energy harvester. The resulting ionic-skin TENG (IS-TENG) has a transparency of 92% transmittance, and its energy-harvesting performance is 12 times higher than that of the silver-based electronic current collectors. In addition, they are capable of enduring a uniaxial strain up to 700%, giving the highest performance compared to all other transparent and stretchable mechanical-energy harvesters. Additionally, this is the first demonstration of an autonomously self-healing TENG that can recover its performance even after 300 times of complete bifurcation. The IS-TENG represents the first prototype of a highly deformable and transparent power source that is able to autonomously self-heal quickly and repeatedly at room temperature, and thus can be used as a power supply for digital watches, touch sensors, artificial intelligence, and biointegrated electronics.

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Highly Transparent, Stretchable, and Self-Healing Ionic-Skin Triboelectric Nanogenerators for Energy Harvesting and Touch Applications.

Covalent mechanochemistry within bulk polymers typically occurs with irreversible deformation of the parent material. Here we show that embedding mechanophores into an elastomeric poly(dimethylsiloxane) (PDMS) network allows for covalent bond activation under macroscopically reversible deformations. Using the colorimetric mechanophore spiropyran, we show that bond activation can be repeated over multiple cycles of tensile elongation with full shape recovery. Further, localized compression can be used to pattern strain-induced chemistry. The platform enables the reversibility of a secondary strain-induced color change to be characterized. We also observe mechanical acceleration of a flex-activated retro-Diels–Alder reaction, allowing a chemical signal to be released in response to a fully reversible deformation.

Mechanochemical Activation of Covalent Bonds in Polymers with Full and Repeatable Macroscopic Shape Recovery

A photochromic polymer exhibiting mechanochromic behavior is prepared by means of ring-opening polymerization (ROP) of epsilon-caprolactone by utilizing a difunctional indolinospiropyran as an initiator. The configuration of having the photochromic initiating species within the polymer backbone leads to a mechanochromic effect with deformation of polymer films leading to ring-opening of the spiro C-O bond to form the colored merocyanine. Active stress monitoring by dynamic mechanical analysis (DMA) in tension mode was used to probe the effects of UV irradiation on polymer films held under constant strain. Irradiation with UV light induces a negative change in the polymer stress of approximately 50 kPa. Finally, a model of the mechanochromic effect was performed using density functional theory (DFT) and time-dependent DFT (TDDFT) calculations. A sharp increase in the relative molecular energy and the absorption wavelength as well as a drastic decrease in the spiro-oxygen atom charge occurred at a molecular elongation of >39%.

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Stress Sensing in Polycaprolactone Films via an Embedded Photochromic Compound

This work describes a novel method of embedded damage detection within glass fiber–reinforced polymer composites. Damage detection is achieved by monitoring the spatially distributed electrical conductivity of a strain-sensitive multiwalled carbon nanotube thin film. First, thin films were spray-deposited directly upon glass fiber mats. Second, using electrical impedance tomography, the spatial conductivity distribution of the thin film was determined before and after damage-inducing events. The resolution of the sensor was determined by drilling progressively larger holes in the center of the composite specimens, and the corresponding electrical impedance tomography response was measured by recording the current–voltage data at the periphery of the monitored composite sample. In addition, the sensitivity to damage occurring at different locations in the composite was also investigated by comparing electrical impedance tomography spatial conductivity maps obtained for specimens with sets of holes drilled at different locations in the sensing area. Finally, the location and severity of damage from low-velocity impact events were detected using the electrical impedance tomography method. The work presented in this study indicates a paradigm shift in the available possibilities for structural health monitoring of fiber-reinforced polymer composites.

Detection of Spatially Distributed Damage in Fiber-Reinforced Polymer Composites.

The need for structural health monitoring has become critical due to aging infrastructures, legacy airplanes, and continuous development of new structural technologies. Based on an updated structural design, there is a need for new structural health monitoring paradigms that can sense the presence, location, and severity with a single measurement. This paper focuses on the first step of this paradigm, consisting of applying a sprayed conductive carbon nanotube-polymer film upon glass fiber-reinforced polymer composite substrates. Electrical impedance tomography is performed to measure changes in conductivity within the conductive films because of damage. Simulated damage is a method for validation of this approach. Finally, electrical impedance tomography measurements are taken while the conductive films are subjected to tensile and compressive strain states. This demonstrates the ability of electrical impedance tomography for not only damage detection, but active structural monitoring as well. This paper acts as a first step toward moving the structural health monitoring paradigm toward large-scale deployable spatial sensing.

Spatial Sensing Using Electrical Impedance Tomography.

This work describes a novel method of embedded damage detection within glass fiber–reinforced polymer composites. Damage detection is achieved by monitoring the spatially distributed electrical con...

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Detection of Spatially Distributed Damage in Fiber-Reinforced Polymer Composites

It has recently been shown that electronic transport in zigzag graphene nanoribbons becomes spin-polarized upon application of an electric field across the nanoribbon width. However, the electric fields required to experimentally induce this magnetic state are typically large and difficult to apply in practice. Here, using both first-principles density functional theory (DFT) and time-dependent DFT, we show that a new spiropyran-based, mechanochromic polymernoncovalently deposited on a nanoribbon can collectively function as a dual opto-mechanical switch for modulating its own spin-polarization. These calculations demonstrate that upon mechanical stress or photoabsorption, the spiropyran chromophore isomerizes from a closed-configuration ground-state to a zwitterionic excited-state, resulting in a large change in dipole moment that alters the electrostatic environment of the nanoribbon. We show that the electronic spin-distribution in the nanoribbon-spiropyran hybrid material can be reversibly modulated via noninvasive optical and mechanical stimuli without the need for large external electric fields. Our results suggest that the reversible spintronic properties inherent to the nanoribbon-spiropyran material allow the possibility of using this hybrid structure as a resettable, molecular-logic quantum sensor where opto-mechanical stimuli are used as inputs and the spin-polarized current induced in the nanoribbon substrate is the measured output.

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Greg O'Bryan

Papers

Stress Sensing in Polycaprolactone Films via an Embedded Photochromic Compound

Detection of Spatially Distributed Damage in Fiber-Reinforced Polymer Composites.

Spatial Sensing Using Electrical Impedance Tomography.

Detection of Spatially Distributed Damage in Fiber-Reinforced Polymer Composites

Reversible, opto-mechanically induced spin-switching in a nanoribbon-spiropyran hybrid material