Living cilia stir, sweep and steer via swirling strokes of complex bending and twisting, paired with distinct reverse arcs. Efforts to mimic such dynamics synthetically rely on multimaterial designs but face limits to programming arbitrary motions or diverse behaviours in one structure. Here we show how diverse, complex, non-reciprocal, stroke-like trajectories emerge in a single-material system through self-regulation. When a micropost composed of photoresponsive liquid crystal elastomer with mesogens aligned oblique to the structure axis is exposed to a static light source, dynamic dances evolve as light initiates a travelling order-to-disorder transition front, transiently turning the structure into a complex evolving bimorph that twists and bends via multilevel opto-chemo-mechanical feedback. As captured by our theoretical model, the travelling front continuously reorients the molecular, geometric and illumination axes relative to each other, yielding pathways composed from series of twisting, bending, photophobic and phototropic motions. Guided by the model, here we choreograph a wide range of trajectories by tailoring parameters, including illumination angle, light intensity, molecular anisotropy, microstructure geometry, temperature and irradiation intervals and duration. We further show how this opto-chemo-mechanical self-regulation serves as a foundation for creating self-organizing deformation patterns in closely spaced microstructure arrays via light-mediated interpost communication, as well as complex motions of jointed microstructures, with broad implications for autonomous multimodal actuators in areas such as soft robotics, biomedical devices and energy transduction materials, and for fundamental understanding of self-regulated systems.

 

Rational catalyst design is crucial toward achieving more energy-efficient and sustainable catalytic processes. Understanding and modeling catalytic reaction pathways and kinetics require atomic level knowledge of the active sites. These structures often change dynamically during reactions and are difficult to decipher. A prototypical example is the hydrogen-deuterium exchange reaction catalyzed by dilute Pd-in-Au alloy nanoparticles. From a combination of catalytic activity measurements, machine learning-enabled spectroscopic analysis, and first-principles based kinetic modeling, we demonstrate that the active species are surface Pd ensembles containing only a few (from 1 to 3) Pd atoms. These species simultaneously explain the observed X-ray spectra and equate the experimental and theoretical values of the apparent activation energy. Remarkably, we find that the catalytic activity can be tuned on demand by controlling the size of the Pd ensembles through catalyst pretreatment. Our data-driven multimodal approach enables decoding of reactive structures in complex and dynamic alloy catalysts.

We report how Raman difference imaging provides insight on cellular biochemistry in vivo as a function of sub-cellular dimensions and the cellular environment. We show that this approach offers a sensitive diagnostic to address blood biochemistry at the cellular level. We examine Raman microscopic images of the distribution of the different hemoglobins in both healthy (discocyte) and unhealthy (echinocyte) blood cells and interpret these images using pre-calculated, accurate pre-resonant Raman tensors for scattering intensities specific to hemoglobins. These tensors are developed from theoretical calculations of models of the oxy, deoxy and met forms of heme benchmarked against the experimental visible spectra of the corresponding hemoglobins. The calculations also enable assignments of the electronic transitions responsible for the colour of blood: these are mainly ligand to metal charge transfer transitions.

The crystallization of metastable liquid phase change materials releases stored energy as latent heat upon nucleation and may therefore provide a triggerable means of activating downstream processes that respond to changes in temperature. In this work, we describe a strategy for controlling the fast, exothermic crystallization of sodium acetate from a metastable aqueous solution into trihydrate crystals within a polyacrylamide hydrogel whose polymerization state has been patterned using photomasks. A comprehensive experimental study of crystal shapes, crystal growth front velocities and evolving thermal profiles showed that rapid growth of long needle-like crystals through unpolymerized solutions produced peak temperatures of up to 45˚C, while slower-crystallizing polymerized solutions produced polycrystalline composites and peaked at 30˚C due to lower rates of heat release relative to dissipation in these regions. This temperature difference in the propagating heat waves, which we describe using a proposed analytical model, enables the use of this strategy to selectively activate thermoresponsive processes in predefined areas.

Three-dimensional ordered porous materials known as inverse opal films (IOFs) were synthesized using nanocrystals with precisely defined morphologies. Comprehensive theoretical and experimental studies of the volume fraction ratio and electrostatic interactions between nanocrystals and polystyrene templating particles enabled the formation of highly ordered crack-free photonic structures. The synthetic strategy was first demonstrated using titanium dioxide (TiO2) nanocrystals of different shapes and then generalized to assemble nanocrystals of other functional materials, such as indium tin oxide and zinc-doped ferrite. Tunable photocatalytic activity of the TiO2 IOFs, modulated through the choice of the shape of TiO2 nanocrystals in conjunction with selecting desired macroscopic features of the IOF, was further explored. In particular, enhanced activity is observed for crack-free, highly ordered IOFs whose photonic properties can improve light absorption via the slow light effect. This study opens new opportunities in designing multi-length-scale porous nanoarchitectures having enhanced performance in a variety of applications.

Light-responsive, spiropyran-functionalized hydrogels have been used to create reversibly photoactuated structures for applications ranging from microfluidics to nonlinear optics. Tailoring a spiropyran-functionalized hydrogel system for a particular application requires an understanding of how co-monomer composition affects the switching dynamics of the spiropyran chromophore. Such gels are frequently designed to be responsive to different stimuli such as light, temperature, and pH. The coupling of these influences can significantly alter spiropyran behavior in ways not currently well understood. To better understand the influence of responsive co-monomers on the spiropyran isomerization dynamics, we use UV–vis spectroscopy and time-dependent fluorescence intensity measurements to study spiropyran-modified hydrogels polymerized from four common hydrogel precursors of different pH and temperature responsivity: acrylamide, acrylic acid, N-isopropylacrylamide, and 2-(dimethylamino)ethyl methacrylate. In acidic and neutral gels, we observe unusual nonmonotonic, triexponential fluorescence dynamics under 405 nm irradiation that cannot be explicated by either the established spiropyran–merocyanine interconversion model or hydrolysis. To explain these results, we introduce an analytical model of spiropyran interconversions that includes H-aggregated merocyanine and its light-triggered disaggregation under 405 nm irradiation. This model provides an excellent fit to the observed fluorescence dynamics and elucidates exactly how creating an acidic internal gel environment promotes the fast and complete conversion of the hydrophilic merocyanine speciesto the hydrophobic spiropyran form, which is desired in most light-sensitive hydrogel actuators. This can be achieved by incorporating acrylic acid monomers and by minimizing the aggregate concentration. Beyond spiropyran-functionalized gel actuators, these conclusions are particularly critical for nonlinear optical computing applications.

In this work, we report a paradigmatic shift in bioinspired microchannel heat exchanger design toward its integration into thin film wearable devices, thermally active surfaces in buildings, photovoltaic devices, and other thermoregulating devices whose typical cooling fluxes are below 1 kW m−2. The transparent thermoregulation device is fabricated by bonding a thin corrugated elastomeric film to the surface of a substrate to form a microchannel water-circuit with bioinspired unit cell geometry. Inspired by the dynamic scaling of flow systems in nature, we introduce empirically derived sizing rules and a novel numerical optimization method to maximize the thermoregulation performance of the microchannel network by enhancing the uniformity of flow distribution. The optimized network design results in a 25% to 37% increase in the heat flux compared to non-optimized designs. The study demonstrates the versatility of the presented design and architecture by fabricating and testing a scaled-up numerically optimized heat exchanger device for building-scale and wearable applications.

Light influences most ecosystems on earth, from sun-dappled forests to bioluminescent creatures in the ocean deep. Biologists have long studied nano- and micro-scale organismal adaptations to manipulate light using ever-more sophisticated microscopy, spectroscopy, and other analytical equipment. In combination with experimental tools, simulations of light interacting with objects can help researchers determine the impact of observed structures and explore how variations affect optical function. In particular, the finite-difference time-domain (FDTD) method is widely used throughout the nanophotonics community to efficiently simulate light interacting with a variety of materials and optical devices. More recently, FDTD has been used to characterize optical adaptations in nature, such as camouflage in fish and other organisms, colors in sexually-selected birds and spiders, and photosynthetic efficiency in plants. FDTD is also common in bioengineering, as the design of biologically-inspired engineered structures can be guided and optimized through FDTD simulations. Parameter sweeps are a particularly useful application of FDTD, which allows researchers to explore a range of variables and modifications in natural and synthetic systems (e.g., to investigate the optical effects of changing the sizes, shape, or refractive indices of a structure). Here, we review the use of FDTD simulations in biology and present a brief methods primer tailored for life scientists, with a focus on the commercially available software Lumerical FDTD. We give special attention to whether FDTD is the right tool to use, how experimental techniques are used to acquire and import the structures of interest, and how their optical properties such as refractive index and absorption are obtained. This primer is intended to help researchers understand FDTD, implement the method to model optical effects, and learn about the benefits and limitations of this tool. Altogether, FDTD is well-suited to (i) characterize optical adaptations and (ii) provide mechanistic explanations; by doing so, it helps (iii) make conclusions about evolutionary theory and (iv) inspire new technologies based on natural structures.

Nanoparticle (NP) sintering is a major cause of the deactivation of supported catalysts. Raspberry-Colloid-Templated (RCT) catalysts are an emerging class of materials that show an unprecedented level of sinter-resistance and exhibit high catalytic activity. Here a comprehensive study of the origin of NP stability and accessibility in RCT catalysts using theoretical modeling, 3D electron microscopy, and epitaxial overgrowth is reported. The approach is showcased for silica-based RCT catalysts containing dilute Pd-in-Au NPs previously used in hydrogenation and oxidation catalysis. Modeling of the contact line of the silica precursor infiltrating into the assembled raspberry colloids suggests that a large part of the particles must be embedded into silica, which is confirmed by quantitative visualization of >200 individual NPs by dual-axis electron tomography. The RCT catalysts have a unique structure in which all NPs reside at the pore wall but have >50% of their surface embedded in the matrix, giving rise to the strongly enhanced thermal and mechanical stability. Importantly, epitaxial overgrowth of Ag on the supported NPs reveals that not only the NP surface exposed to the pore but the embedded interface as well remained chemically accessible. This mechanistic understanding provides valuable guidance in the design of stable catalytic materials.

Geometric reconfigurations in cellular structures have recently been exploited to realize adaptive materials with applications in mechanics, optics, and electronics. However, the achievable symmetry breakings and corresponding types of deformation and related functionalities have remained rather limited, mostly due to the fact that the macroscopic geometry of the structures is generally co-aligned with the molecular anisotropy of the constituent material. To address this limitation, cellular microstructures are fabricated out of liquid crystalline elastomers (LCEs) with an arbitrary, user-defined liquid crystal (LC) mesogen orientation encrypted by a weak magnetic field. This platform enables anisotropy to be programmed independently at the molecular and structural levels and the realization of unprecedented director-determined symmetry breakings in cellular materials, which are demonstrated by both finite element analyses and experiments. It is illustrated that the resulting mechanical reconfigurations can be harnessed to program microcellular materials with switchable and direction-dependent frictional properties and further exploit ”area-specific” deformation patterns to locally modulate transmitted light and precisely guide object movement. As such, the work provides a clear route to decouple anisotropy at the materials level from the directionality of the macroscopic cellular structure, which may lead to a new generation of smart and adaptive materials and devices.

Self-assembly is one of the central themes in biologically controlled synthesis, and it also plays a pivotal role in fabricating a variety of advanced engineering materials. In particular, evaporation-induced self-assembly of colloidal particles enables versatile fabrication of highly ordered two- or three-dimensional nanostructures for optical, sensing, catalytic, and other applications. While it is well known that this process results in the formation of the face-centered cubic (fcc) lattice with the close-packed {111} plane parallel to the substrate, the crystallographic texture development of colloidal crystals is less understood. In this study, we show that the preferred <110> growth in the fcc colloidal crystals synthesized through evaporation-induced assembly is achieved through a gradual crystallographic rotation facilitated by mechanical stress-induced geometrically necessary dislocations.

In the design of multifunctional materials, harnessing structural and compositional synergies while avoiding unnecessary trade-offs is critical in achieving high performance of all required functions. Biological material systems like the cuticles of many arthropods often fulfill multifunctionality through the intricate design of material structures, simultaneously achieving mechanical, optical, sensory, and other vital functionalities. A better understanding of the structural basis for multifunctionality and the functional synergies and trade-offs in biological materials could thus provide important insights for the design of bioinspired multifunctional materials. In this study, we demonstrate a concerted experimental, theoretical, and computational approach that uncovers the structure–mechanics–optics relationship of the beetle’s cuticle, opening avenues to investigate biological materials and design photonic materials with robust mechanical performance.

Dilute alloy catalysts have the potential to enhance selectivity and activity for large-scale reactions. Highly dilute Pd-in-Au nanoparticle alloys partially embedded in porous silica (“raspberry colloid templated” (RCT)-SiO2) prove to be robust and selective catalysts for oxidative coupling of methanol. Palladium concentrations in the bimetallic nanoparticles as low as ~3.4 at.% catalyze the production of methyl formate with a selectivity of ~95% at conversions of ~55%, whereas conversions are low (<10%) for ~1.7 at.% Pd-in-Au nanoparticle and pure Au nanoparticle catalysts. Fractional reaction orders for both CH3OH and O2measured for ~3.4 at.% Pd-in-Au nanoparticles supported on RCT-SiO2 indicated a complex mechanism in which the sites for O2 dissociation are not saturated. Optimal methyl formate production was found for an equimolar mixture. There is no conversion of methanol in the absence of O2 between 360 and 450 K. All observations are consistent with a mechanism derived from model studies, requiring that clusters of Pd be available on the catalyst for O2 dissociation.

Dilute Pd-in-Au alloy catalysts are promising materials for selective hydrogenation catalysis. Extensive surface science studies have contributed mechanistic insight on the energetic aspect of hydrogen dissociation, migration, and recombination on dilute alloy systems. Yet, translating these fundamental concepts to the kinetics and free energy of hydrogen dissociation on nanoparticle catalysts operating at ambient pressures and temperatures remains challenging. Here, the effect of the Pd concentration and Pd ensemble size on the catalytic activity, apparent activation energy, and rate-limiting process is addressed by combining experiment and theory. Experiments in a flow reactor show that a compositional change from 4 to 8 atm% Pd of the Pd-in-Au alloy catalyst leads to a strong increase in activity, even exceeding the activity per Pd atom of monometallic Pd under the same conditions, albeit with an increase in apparent activation energy. First-principles calculations show that the rate and apparent activation enthalpy for HD exchange increase when increasing the Pd ensemble size from single Pd atoms to Pd trimers in a Au surface, suggesting that the ensemble size distribution shifts from mainly single Pd atoms on the 4 atm% Pd alloy to larger Pd ensembles of at least three atoms for the 8 atm% Pd/Au catalyst. The DFT studies also indicated that the rate-controlling process is different: H2 (D2) dissociation determines the rate for single atoms, whereas recombination of adsorbed H and D determines the rate on Pd trimers, similar to bulk Pd. Both experiment and theory suggest that the increased reaction rate with increasing Pd content and ensemble size stems from an entropic driving force. Finally, our results support hydrogen migration between Pd sites via Au and indicate that the dilute alloy design prevents the formation of subsurface hydrogen, which is crucial in achieving high selectivity in hydrogenation catalysis.

Phase-change condensation is commonplace in nature and industry. Since the 1930s, it is well understood that vapor condenses in filmwise mode on clean metallic surfaces whereas it condenses by forming discrete droplets on surfaces coated with a promoter material. In both filmwise and dropwise modes, the condensate is removed when gravity overcomes pinning forces. In this work, we show rapid condensate transport through cracks that formed due to material shrinkage when a copper tube is coated with silica inverse opal structures. Importantly, the high hydraulic conductivity of the cracks promote axial condensate transport that is beneficial for condensation heat transfer. In our experiments, the cracks improved the heat transfer coefficient from ≈ 12 kW/m2 K for laminar filmwise condensation on smooth clean copper tubes to ≈ 80 kW/m2 K for inverse opal coated copper tubes; nearly a sevenfold increase from filmwise condensation and identical enhancement with state-of-the-art dropwise condensation. Furthermore, our results show that impregnating the porous structure with oil further improves the heat transfer coefficient by an additional 30% to ≈ 103 kW/m2 K. Importantly, compared to the fast-degrading dropwise condensation, the inverse opal coated copper tubes maintained high heat transfer rates when the experiments were repeated > 20 times; each experiment lasting 3–4 h. In addition to the new coating approach, the insights gained from this work present a strategy to minimize oil depletion during condensation from lubricated surfaces.

Soft actuators have the potential of revolutionizing the field of robotics. However, it has been a long-standing challenge to achieve simultaneously: i) miniaturization of soft actuators, ii) high contrast between materials properties at their “on” and “off” states, iii) significant actuation for high-payload mechanical work, and iv) ability to perform diverse shape transformations. This challenge is addressed by synergistically utilizing structural concepts found in the dermis of sea cucumbers and the tendrils of climbing plants, together with microfluidic fabrication to create diatomite-laden hygroscopically responsive fibers with a discontinuous ribbon of stiff, asymmetrically shaped, and hygroscopically inactive microparticles embedded inside. The microactuators can undergo various deformations and have very high property contrast ratios (20–850 for various mechanical characteristics of interest) between hydrated and dehydrated states. The resulting energy density, actuation strain, and actuation stress are shown to exceed those of natural muscle by ≈4, >2, and >30 times, respectively, and their weight-lifting ratio is 2–3 orders of magnitude higher than the value of recent hygroscopic actuators. This work offers a new and general way to design and fabricate next-generation soft microactuators, and thus advances the field of soft robotics by tailoring the structure and properties of deformable elements to suit a desired application.

The fundamental topology of cellular structures—the location, number and connectivity of nodes and compartments—can profoundly affect their acoustic, electrical, chemical, mechanical, and optical properties, as well as heat, fluid and particle transport. Approaches that harness swelling, electromagnetic actuation and mechanical instabilities in cellular materials have enabled a variety of interesting wall deformations and compartment shape alterations, but the resulting structures generally preserve the defining connectivity features of the initial topology. Achieving topological transformation presents a distinct challenge for existing strategies: it requires complex reorganization, repacking, and coordinated bending, stretching and folding, particularly around each node, where elastic resistance is highest owing to connectivity. Here we introduce a two-tiered dynamic strategy that achieves systematic reversible transformations of the fundamental topology of cellular microstructures, which can be applied to a wide range of materials and geometries. Our approach requires only exposing the structure to a selected liquid that is able to first infiltrate and plasticize the material at the molecular scale, and then, upon evaporation, form a network of localized capillary forces at the architectural scale that ‘zip’ the edges of the softened lattice into a new topological structure, which subsequently restiffens and remains kinetically trapped. Reversibility is induced by applying a mixture of liquids that act separately at the molecular and architectural scales (thus offering modular temporal control over the softening–evaporation–stiffening sequence) to restore the original topology or provide access to intermediate modes. Guided by a generalized theoretical model that connects cellular geometries, material stiffness and capillary forces, we demonstrate programmed reversible topological transformations of various lattice geometries and responsive materials that undergo fast global or localized deformations. We then harness dynamic topologies to develop active surfaces with information encryption, selective particle trapping and bubble release, as well as tunable mechanical, chemical and acoustic properties.

Porous lubricated surfaces (aka slippery liquid-infused porous surfaces, SLIPS) have been demonstrated to repel various liquids. The origin of this repellency, however, is not fully understood. By using surface-sensitive sum frequency generation vibrational spectroscopy, we characterized the water/oil interface of a water droplet residing on (a) an oil-impregnated nanostructured surface (SLIPS) and (b) the same oil layer without the underlying nanostructures. Different from water molecules in contact with bulk oil without nanostructures, droplets on SLIPS adopt a molecular orientation that is predominantly parallel to the water/oil interface, leading to weaker hydrogen bonding interactions between water droplets and the lubrication film, giving SLIPS their water repellency. Our results demonstrate that the molecular interactions between two contacting liquids can be manipulated by the implementation of nanostructured substrates. The results also offer the molecular principles for controlling nanostructure to reduce oil depletion—one of the limitations and major concerns of SLIPS.