A photochromic polymer exhibiting mechanochromic behavior is prepared by means of ring-opening polymerization (ROP) of ε-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%.

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.

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 polymer noncovalently 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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Increasing energy costs, the dependence on foreign oil supplies, and environmental concerns have emphasized the need to produce sustainable renewable fuels and chemicals. The strategy for producing next-generation biofuels must include efficient processes for biomass conversion to liquid fuels and the fuels must be compatible with current and future engines. Unfortunately, biofuel development generally takes place without any consideration of combustion characteristics, and combustion scientists typically measure biofuels properties without any feedback to the production design. We seek to optimize the fuel/engine system by bringing combustion performance, specifically for advanced next-generation engines, into the development of novel biosynthetic fuel pathways. Here we report an innovative coupling of combustion chemistry, from fundamentals to engine measurements, to the optimization of fuel production using metabolic engineering. We have established the necessary connections among the fundamental chemistry, engine science, and synthetic biology for fuel production, building a powerful framework for co-development of engines and biofuels. 4 ACKNOWLEDGMENTSThis work was funded under LDRD Project Number 151308, "Tailoring Next-Generation Biofuels and their Combustion in Next-Generation Engines."Prof. Fei Qi (University of Science and Technology of China) and Prof. Ravi X. Fernandes (RWTH Aachen University) are gratefully acknowledged for their collaborative experiments characterizing the pyrolysis and ignition chemistry of 2,4-dimethylpentan-3-one.