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Soft machines will require soft materials that exhibit a rich diversity of functionality, including shape morphing and photoresponsivity. The combination of these functionalities enables useful behaviors in soft machines that can be further developed by synthesizing materials that exhibit localized responsivity. Localized responsivity of liquid crystal elastomers (LCEs), which are soft materials that exhibit shape morphing, can be enabled by formulating composite inks for direct ink writing (DIW). Gold nanorods (AuNRs) can be added to LCEs to enable photothermal shape change upon absorption of light through a localized surface plasmon resonance. We compared LCE formulations, focusing on their amenability for printing by DIW and the photoresponsivity of AuNRs. The local responsivity of different three-dimensional architectures enabled soft machines that could oscillate, crawl, roll, transport mass, and display other unique modes of actuation and motion in response to light, making these promising functional materials for advanced applications. 

Arrested soft materials such as gels and glasses exhibit a slow stress relaxation with a broad distribution of relaxation times in response to linear mechanical perturbations. Although this macroscopic stress relaxation is an essential feature in the application of arrested systems as structural materials, consumer products, foods, and biological materials, the microscopic origins of this relaxation remain poorly understood. Here, we elucidate the microscopic dynamics underlying the stress relaxation of such arrested soft materials under both quiescent and mechanically perturbed conditions through X-ray photon correlation spectroscopy. By studying the dynamics of a model associative gel system that undergoes dynamical arrest in the absence of aging effects, we show that the mean stress relaxation time measured from linear rheometry is directly correlated to the quiescent superdiffusive dynamics of the microscopic clusters, which are governed by a buildup of internal stresses during arrest. We also show that perturbing the system via small mechanical deformations can result in large intermittent fluctuations in the form of avalanches, which give rise to a broad non-Gaussian spectrum of relaxation modes at short times that is observed in stress relaxation measurements. These findings suggest that the linear viscoelastic stress relaxation in arrested soft materials may be governed by nonlinear phenomena involving an interplay of internal stress relaxations and perturbation-induced intermittent avalanches. 

The organization of plasmonic nanoparticles (NPs) determines the strength and polarization dependence of coupling of their surface plasmons. In this study, plasmon coupling of spherical Au NPs with an average diameter of 15 nm was investigated in shape-memory polymer films before and after mechanical stretching and then after thermally driving shape recovery. Clusters of Au NPs form when preparing the films that exhibit strong plasmon coupling. During stretching, a significant polarization-dependent response develops, where the optical extinction maximum corresponding to the surface plasmon resonance is redshifted by 19 nm and blueshifted by 7 nm for polarization parallel and perpendicular to the stretching direction, respectively. This result can be explained by non-uniform stretching on the nanoscale, where plasmon coupling increases parallel to the shear direction as Au NPs are pulled into each other during stretching. The polarization dependence vanishes after shape recovery, and structural characterization confirms the return of isotropy consistent with complete nanoscale recovery of the initial arrangement of Au NPs. Simulations of the polarized optical responses of Au NP dimers at different interparticle spacings establish a plasmon ruler for estimating the average interparticle spacings within the experimental samples. An investigation of the temperature-dependent recovery behavior demonstrates an application of these materials as optical thermal history sensors. 

Plasmonic nanoparticles that can be manipulated with magnetic fields are of interest for advanced optical applications, diagnostics, imaging, and therapy. Alignment of gold nanorods yields strong polarization‐dependent extinction, and use of magnetic fields is appealing because they act through space and can be quickly switched. In this work, cationic polyethyleneimine‐functionalized superparamagnetic Fe₃O₄nanoparticles (NPs) are deposited on the surface of anionic gold nanorods coated with bovine serum albumin. The magnetic gold nanorods (MagGNRs) obtained through mixing maintain the distinct optical properties of plasmonic gold nanorods that are minimally perturbed by the magnetic overcoating. Magnetic alignment of the MagGNRs arising from magnetic dipolar interactions on the anisotropic gold nanorod core is comprehensively characterized, including structural characterization and enhancement (suppression) of the longitudinal surface plasmon resonance and suppression (enhancement) of the transverse surface plasmon resonance for light polarized parallel (orthogonal) to the magnetic field. The MagGNRs can also be driven in rotating magnetic fields to rotate at frequencies of at least 17 Hz. For suitably large gold nanorods (148 nm long) and Fe₃O₄NPs (13.4 nm diameter), significant alignment is possible even in modest (<500 Oe) magnetic fields. An analytical model provides a unified understanding of the magnetic alignment of MagGNRs.

 

Cyclic‐poly(phthalaldehyde) (cPPHA) exhibits photo‐triggerable depolymerization on‐demand for applications like the photolithography of microfabricated electronics. However, cPPHA is inherently brittle and thermally sensitive; both of these properties limit its usefulness as an engineering plastic. Prior to this report, small molecule plasticizers are added to cPPHA‐based films to make the polymer more flexible. But plasticizers can eventually leach out of cPPHA, then leaving it increasingly more brittle throughout product lifetime. In this research, a new approach to fabricating flexible cPPHA blends for use as spun fibers is achieved through the incorporation of poly (ε‐caprolactone) (PCL) by a modified wet spinning method. Among blend compositions, the 50/50 cPPHA/PCL fiber shows fast transience (<50 s) in response to daylight while retaining the flexibility of PCL and mechanical properties of an elastomer (i.e., tensile strength of ≈8 MPa, Young's modulus of ≈118 MPa, and elongation at break of ≈190%). Embedding 2 wt% gold nanoparticles to cPPHA can further improve the transience rate of fibers comprising less than 50% cPPHA. These flexible, daylight‐triggerable cPPHA/PCL fibers can be applied to an extensive range of applications, such as wearable electronics, intelligent textiles, and zero waste packaging for which modest mechanical performance and fast transience are desired.

 

Transition metal chalcogenide nanoparticles (NPs) are of interest for energy applications, including batteries, supercapacitors, and electrocatalysis. Many methods have been established for synthesizing Ni NPs, and conversion chemistry to form Ni oxide and phosphides from template Ni NPs is well‐understood. Sulfidation and selenidation of Ni NPs have been much less explored, however. We report a method for the conversion of Ni template NPs into sulfide and selenide product NPs using elemental sulfur, 1‐hexadecanthiol, thiourea, trioctylphosphine sulfide, elemental selenium, and selenourea. While maintaining mole ratios of 2 mmol sulfur/selenium precursor: mmol Ni, products with phases of Ni₃S₂, Ni₉S₈, NiS, NiSO₄·6H₂O, Ni₃S₄, Ni₃Se₂, and NiSe have been obtained. The products have voids that form through the Kirkendall effect during interdiffusion. Trends relating the chemical properties of the precursors to the phases of the products have been identified. While some precursors contained phosphorus, there was no significant incorporation of phosphorus in any of the products. An increase of the NP size during sulfidation and selenidation is consistent with ripening. The application of Ni sulfide and selenide NPs as electrocatalysts for the hydrogen evolution reaction is also demonstrated.