Nonequilibrium sensing of volatile compounds using active and passive analyte delivery.

Although sensor technologies have allowed us to outperform the human senses of sight, hearing, and touch, the development of artificial noses is significantly behind their biological counterparts. This largely stems from the sophistication of natural olfaction, which relies on both fluid dynamics within the nasal anatomy and the response patterns of hundreds to thousands of unique molecular-scale receptors. We designed a sensing approach to identify volatiles inspired by the fluid dynamics of the nose, allowing us to extract information from a single sensor (here, the reflectance spectra from a mesoporous one-dimensional photonic crystal) rather than relying on a large sensor array. By accentuating differences in the nonequilibrium mass-transport dynamics of vapors and training a machine learning algorithm on the sensor output, we clearly identified polar and nonpolar volatile compounds, determined the mixing ratios of binary mixtures, and accurately predicted the boiling point, flash point, vapor pressure, and viscosity of a number of volatile liquids, including several that had not been used for training the model. We further implemented a bioinspired active sniffing approach, in which the analyte delivery was performed in well-controlled 'inhale-exhale' sequences, enabling an additional modality of differentiation and reducing the duration of data collection and analysis to seconds. Our results outline a strategy to build accurate and rapid artificial noses for volatile compounds that can provide useful information such as the composition and physical properties of chemicals, and can be applied in a variety of fields, including disease diagnosis, hazardous waste management, and healthy building monitoring.

Evaporation-Induced Self-Assembly of Metal Oxide Inverse Opals: From Synthesis to Applications.

ConspectusInverse opals (IOs) are highly interconnected three-dimensional macroporous structures with applications in a variety of disciplines from optics to catalysis. For instance, when the pore size is on the scale of the wavelength of visible light, IOs exhibit structural color due to diffraction and interference of light rather than due to absorption by pigments, making these structures valuable as nonfading paints and colorants. When IO pores are in an ordered arrangement, the IO is a 3D photonic crystal, a structure with a plethora of interesting optical properties that can be used in a multitude of applications, from sensors to lasers. IOs also have interesting fluidic properties that arise from the re-entrant geometry of the pores, making them excellent candidates for colorimetric sensors based on fluid surface tension. Metal oxide IOs, in particular, can also be photo- and thermally catalytically active due to the catalytic activity of the background matrix material or of functional nanoparticles embedded within the structure.Evaporation-induced self-assembly of sacrificial particles has been developed as a scalable method for forming IOs. The pore size and shape, surface chemistry, matrix material, and the macroscopic shape of the IO, as well as the inclusion of functional components, can be designed through the choice of deposition conditions such as temperature and humidity, types and concentrations of components in the self-assembly mixture, and the postassembly processing. These parameters allow researchers to tune the optical, mechanical, and thermal transport properties of IOs for optimum functionality.In this Account, we focus on experimental and theoretical studies to understand the self-assembly process and properties of metal oxide IOs without (bare) and with (hybrid) plasmonic or catalytic metal nanoparticles incorporated. Several synthetic approaches are first presented, together with a discussion of the various forces involved in the assembly process. The visualization of the deposition front with time-lapse microscopy is then discussed together with analytical theory and numerical simulations to determine the conditions needed for the deposition of a continuous IO film. Subsequently, we present high-resolution scanning electron microscopy (SEM) of assembled colloids over large areas, which provides a detailed view of the evolution of the assembly process, showing that the organization of the colloids is initially dictated by the meniscus of the evaporating suspension on the substrate, but that gradually all grains rotate to occupy the thermodynamically most favorable orientation. High-resolution 3D transmission electron microscopy (TEM) is then presented together with analysis of the wetting of the templating colloids by the matrix precursor to provide a detailed picture of the embedding of metallic nanoparticles at the pore-matrix interface. Finally, the resulting properties and applications in optics, wetting, and catalysis are discussed, concluding with an outlook on the future of self-assembled metal-oxide-based IOs.

Dilute Alloys Based on Au, Ag, or Cu for Efficient Catalysis: From Synthesis to Active Sites.

The development of new catalyst materials for energy-efficient chemical synthesis is critical as over 80% of industrial processes rely on catalysts, with many of the most energy-intensive processes specifically using heterogeneous catalysis. Catalytic performance is a complex interplay of phenomena involving temperature, pressure, gas composition, surface composition, and structure over multiple length and time scales. In response to this complexity, the integrated approach to heterogeneous dilute alloy catalysis reviewed here brings together materials synthesis, mechanistic surface chemistry, reaction kinetics, in situ and operando characterization, and theoretical calculations in a coordinated effort to develop design principles to predict and improve catalytic selectivity. Dilute alloy catalysts─in which isolated atoms or small ensembles of the minority metal on the host metal lead to enhanced reactivity while retaining selectivity─are particularly promising as selective catalysts. Several dilute alloy materials using Au, Ag, and Cu as the majority host element, including more recently introduced support-free nanoporous metals and oxide-supported nanoparticle "raspberry colloid templated (RCT)" materials, are reviewed for selective oxidation and hydrogenation reactions. Progress in understanding how such dilute alloy catalysts can be used to enhance selectivity of key synthetic reactions is reviewed, including quantitative scaling from model studies to catalytic conditions. The dynamic evolution of catalyst structure and composition studied in surface science and catalytic conditions and their relationship to catalytic function are also discussed, followed by advanced characterization and theoretical modeling that have been developed to determine the distribution of minority metal atoms at or near the surface. The integrated approach demonstrates the success of bridging the divide between fundamental knowledge and design of catalytic processes in complex catalytic systems, which can accelerate the development of new and efficient catalytic processes.

Highly Ordered Inverse Opal Structures Synthesized from Shape-Controlled Nanocrystal Building Blocks.

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.

Finite-difference Time-domain (FDTD) Optical Simulations: A Primer for the Life Sciences and Bio-Inspired Engineering.

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.

Enhanced condensation heat transfer using porous silica inverse opal coatings on copper tubes.

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.

Depletion of Lubricant from Nanostructured Oil-Infused Surfaces by Pendant Condensate Droplets.

Due to recent advances in nanofabrication, phase-change condensation heat transfer has seen a renaissance. Compared to conventional heat transfer surfaces, nanostructured surfaces impregnated with chemically matched lubrication films (hereinafter referred to as "nanostructured lubricated surfaces") have been demonstrated to improve vapor-side phase-change condensation heat transfer by facilitating droplet nucleation, growth, and departure. While the presence of nanoscale roughness improves performance longevity by stabilizing the lubrication film via capillary forces, such enhancement is short-lived due to the eventual loss of lubrication oil by the departing droplets. The objective of this study is to characterize oil depletion caused by pendant droplets during condensation. For our study, we nanostructured, chemically functionalized, and lubricated horizontal copper tubes that are widely used in shell-and-tube heat exchangers in power plants and process industries. Using high-speed fluorescence imaging and thermogravimetric analysis, we show that shedding droplets exert a shear force on the oil in the wetting ridge at the water-oil interface. The viscous shear draws the lubrication film from the nanostructured surface onto the upper portion of the droplet and forms a ring-like oil skirt. Through detailed theoretical analysis, we show that the thickness of this oil skirt scales with the classical Landau-Levich-Derjaguin (LLD) theory for dip-coating. Our results reveal that droplets falling from horizontal tubes break unequally and leave behind small satellite droplets that retain the bulk of the oil in the wetting ridge. This observation is in stark contrast with the earlier description of droplets shedding from tilted flat plates where the entire oil-filled wetting ridge is demonstrated to leave the surface upon droplet departure. By selecting lubrication oils of varying viscosity and spreading coefficient, we provide evidence that the contribution of the wrapping layer to the rate of oil depletion is insignificant. Furthermore, we show that due to the nanoscale features on the tubes, nearly half of the lubrication film remains on the surface after 10 h of continuous steam condensation at ambient pressure, 23 °C, and 60% relative humidity, a 2-3-fold improvement over previous results.The insights gained from this work will provide guidelines for the rational design of long-lasting nanostructured lubricated surfaces for phase-change condensation.

Opto-chemo-mechanical transduction in photoresponsive gels elicits switchable self-trapped beams with remote interactions.

Next-generation photonics envisions circuitry-free, rapidly reconfigurable systems powered by solitonic beams of self-trapped light and their particlelike interactions. Progress, however, has been limited by the need for reversibly responsive materials that host such nonlinear optical waves. We find that repeatedly switchable self-trapped visible laser beams, which exhibit strong pairwise interactions, can be generated in a photoresponsive hydrogel. Through comprehensive experiments and simulations, we show that the unique nonlinear conditions arise when photoisomerization of spiropyran substituents in pH-responsive poly(acrylamide-co-acrylic acid) hydrogel transduces optical energy into mechanical deformation of the 3D cross-linked hydrogel matrix. A Gaussian beam self-traps when localized isomerization-induced contraction of the hydrogel and expulsion of water generates a transient waveguide, which entraps the optical field and suppresses divergence. The waveguide is erased and reformed within seconds when the optical field is sequentially removed and reintroduced, allowing the self-trapped beam to be rapidly and repeatedly switched on and off at remarkably low powers in the milliwatt regime. Furthermore, this opto-chemo-mechanical transduction of energy mediated by the 3D cross-linked hydrogel network facilitates pairwise interactions between self-trapped beams both in the short range where there is significant overlap of their optical fields, and even in the long range--over separation distances of up to 10 times the beam width--where such overlap is negligible.

Structurally assisted super black in colourful peacock spiders.

Male peacock spiders ( Maratus, Salticidae) compete to attract female mates using elaborate, sexually selected displays. They evolved both brilliant colour and velvety black. Here, we use scanning electron microscopy, hyperspectral imaging and finite-difference time-domain optical modelling to investigate the deep black surfaces of peacock spiders. We found that super black regions reflect less than 0.5% of light (for a 30° collection angle) in Maratus speciosus (0.44%) and Maratus karrie (0.35%) owing to microscale structures. Both species evolved unusually high, tightly packed cuticular bumps (microlens arrays), and M. karrie has an additional dense covering of black brush-like scales atop the cuticle. Our optical models show that the radius and height of spider microlenses achieve a balance between (i) decreased surface reflectance and (ii) enhanced melanin absorption (through multiple scattering, diffraction out of the acceptance cone of female eyes and increased path length of light through absorbing melanin pigments). The birds of paradise (Paradiseidae), ecological analogues of peacock spiders, also evolved super black near bright colour patches. Super black locally eliminates white specular highlights, reference points used to calibrate colour perception, making nearby colours appear brighter, even luminous, to vertebrates. We propose that this pre-existing, qualitative sensory experience-'sensory bias'-is also found in spiders, leading to the convergent evolution of super black for mating displays in jumping spiders.

Multiresponsive polymeric microstructures with encoded predetermined and self-regulated deformability.

Dynamic functions of biological organisms often rely on arrays of actively deformable microstructures undergoing a nearly unlimited repertoire of predetermined and self-regulated reconfigurations and motions, most of which are difficult or not yet possible to achieve in synthetic systems. Here, we introduce stimuli-responsive microstructures based on liquid-crystalline elastomers (LCEs) that display a broad range of hierarchical, even mechanically unfavored deformation behaviors. By polymerizing molded prepolymer in patterned magnetic fields, we encode any desired uniform mesogen orientation into the resulting LCE microstructures, which is then read out upon heating above the nematic-isotropic transition temperature (TN-I) as a specific prescribed deformation, such as twisting, in- and out-of-plane tilting, stretching, or contraction. By further introducing light-responsive moieties, we demonstrate unique multifunctionality of the LCEs capable of three actuation modes: self-regulated bending toward the light source at T < TN-I, magnetic-field-encoded predetermined deformation at T > TN-I, and direction-dependent self-regulated motion toward the light at T > TN-I We develop approaches to create patterned arrays of microstructures with encoded multiple area-specific deformation modes and show their functions in responsive release of cargo, image concealment, and light-controlled reflectivity. We foresee that this platform can be widely applied in switchable adhesion, information encryption, autonomous antennae, energy harvesting, soft robotics, and smart buildings.

Nanocrystalline Precursors for the Co-Assembly of Crack-Free Metal Oxide Inverse Opals.

Inorganic microstructured materials are ubiquitous in nature. However, their formation in artificial self-assembly systems is challenging as it involves a complex interplay of competing forces during and after assembly. For example, colloidal assembly requires fine-tuning of factors such as the size and surface charge of the particles and electrolyte strength of the solvent to enable successful self-assembly and minimize crack formation. Co-assembly of templating colloidal particles together with a sol-gel matrix precursor material helps to release stresses that accumulate during drying and solidification, as previously shown for the formation of high-quality inverse opal (IO) films out of amorphous silica. Expanding this methodology to crystalline materials would result in microscale architectures with enhanced photonic, electronic, and catalytic properties. This work describes tailoring the crystallinity of metal oxide precursors that enable the formation of highly ordered, large-area (mm2 ) crack-free titania, zirconia, and alumina IO films. The same bioinspired approach can be applied to other crystalline materials as well as structures beyond IOs.

Tuning and Freezing Disorder in Photonic Crystals using Percolation Lithography.

Although common in biological systems, synthetic self-assembly routes to complex 3D photonic structures with tailored degrees of disorder remain elusive. Here we show how liquids can be used to finely control disorder in porous 3D photonic crystals, leading to complex and hierarchical geometries. In these optofluidic crystals, dynamically tunable disorder is superimposed onto the periodic optical structure through partial wetting or evaporation. In both cases, macroscopic symmetry breaking is driven by subtle sub-wavelength variations in the pore geometry. These variations direct site-selective infiltration of liquids through capillary interactions. Incorporating cross-linkable resins into our liquids, we developed methods to freeze in place the filling patterns at arbitrary degrees of partial wetting and intermediate stages of drying. These percolation lithography techniques produced permanent photonic structures with adjustable disorder. By coupling strong changes in optical properties to subtle differences in fluid behavior, optofluidic crystals may also prove useful in rapid analysis of liquids.

Quantification of cell edge velocities and traction forces reveals distinct motility modules during cell spreading.

Actin-based cell motility and force generation are central to immune response, tissue development, and cancer metastasis, and understanding actin cytoskeleton regulation is a major goal of cell biologists. Cell spreading is a commonly used model system for motility experiments -- spreading fibroblasts exhibit stereotypic, spatially-isotropic edge dynamics during a reproducible sequence of functional phases: 1) During early spreading, cells form initial contacts with the surface. 2) The middle spreading phase exhibits rapidly increasing attachment area. 3) Late spreading is characterized by periodic contractions and stable adhesions formation. While differences in cytoskeletal regulation between phases are known, a global analysis of the spatial and temporal coordination of motility and force generation is missing. Implementing improved algorithms for analyzing edge dynamics over the entire cell periphery, we observed that a single domain of homogeneous cytoskeletal dynamics dominated each of the three phases of spreading. These domains exhibited a unique combination of biophysical and biochemical parameters -- a motility module. Biophysical characterization of the motility modules revealed that the early phase was dominated by periodic, rapid membrane blebbing; the middle phase exhibited continuous protrusion with very low traction force generation; and the late phase was characterized by global periodic contractions and high force generation. Biochemically, each motility module exhibited a different distribution of the actin-related protein VASP, while inhibition of actin polymerization revealed different dependencies on barbed-end polymerization. In addition, our whole-cell analysis revealed that many cells exhibited heterogeneous combinations of motility modules in neighboring regions of the cell edge. Together, these observations support a model of motility in which regions of the cell edge exhibit one of a limited number of motility modules that, together, determine the overall motility function. Our data and algorithms are publicly available to encourage further exploration.