3D‐Printed Biomimetic Super‐Hydrophobic Structure for Microdroplet Manipulation and Oil/Water Separation

Biomimetic functional surfaces are attracting increasing attention for various technological applications, especially the superhydrophobic surfaces inspired by plant leaves. However, the replication of the complex hierarchical microstructures is limited by the traditional fabrication techniques. In this paper, superhydrophobic micro‐scale artificial hairs with eggbeater heads inspired by Salvinia molesta leaf was fabricated by the Immersed surface accumulation three dimensional (3D) printing process. Multi‐walled carbon nanotubes were added to the photocurable resins to enhance the surface roughness and mechanical strength of the microstructures. The 3D printed eggbeater surface reveals interesting properties in terms of superhydrophobilicity and petal effect. The results show that a hydrophilic material can macroscopically behave as hydrophobic if a surface has proper microstructured features. The controllable adhesive force (from 23 μN to 55 μN) can be easily tuned with different number of eggbeater arms for potential applications such as micro hand for droplet manipulation. Furthermore, a new energy‐efficient oil/water separation solution based on our biomimetic structures was demonstrated. The results show that the 3D‐printed eggbeater structure could have numerous applications, including water droplet manipulation, 3D cell culture, micro reactor, oil spill clean‐up, and oil/water separation.     

Hierarchical 3D SERS Substrates Fabricated by Integrating Photolithographic Microstructures and Self‐Assembly of Silver Nanoparticles

Most of the surface‐enhanced Raman scattering (SERS) substrates are 2D planar systems, which limits the SERS active area to a single Cartesian plane. Here, we fabricate 3D SERS substrates with the aim to break the traditional 2D SERS active area limitation, and to extend the SERS hotspots into the third dimension along the z‐axis. Our 3D SERS substrates are tailored with increased SERS hotspots in the z‐direction from tens of nanometers to tens of micrometers, increasing the hotspots in the z‐direction by at least an order of magnitude larger than the confocal volume (～1 μm) of most Raman spectrometers. Various hierarchical 3D SERS‐active microstructures are fabricated by combining 3D laser photolithography with Langmuir‐Blodgett nanoparticle assembly. 3D laser photolithography creates microstructured platforms required to extend the SERS‐active area into 3D, and the self‐assembly of Ag nanoparticles ensures homogeneous coating of SERS‐active Ag nanoparticles over the entire microstructured platforms. Large‐area 3D Raman imaging demonstrates that homogeneous signals can be collected throughout the entire 3D SERS substrates. We vary the morphology, height, and inclination angles of the 3D microstructures, where the inclination angle is found to exhibit strong influence on the SERS signals. We also demonstrate a potential application of this hierarchical 3D SERS substrate in information tagging, storage and encryption as SERS micro‐barcodes, where multiple micro‐barcodes can be created within a single set of microstructures.     

Increasing the Dimensionality of Soft Microstructures through Injection‐Induced Self‐Folding

Devices fabricated using soft materials have been a major research focus of late, capturing the attention of scientists and laypersons alike in a wide range of fields, from microfluidics to robotics. The functionality of such devices relies on their structural and material properties; thus, the fabrication method is of utmost importance. Here, multilayer soft lithography, precision laser micromachining, and folding to establish a new paradigm are combined for creating 3D soft microstructures and devices. Phase‐changing materials are exploited to transform actuators into structural elements, allowing 2D laminates to evolve into a third spatial dimension. To illustrate the capabilities of this new fabrication paradigm, the first “microfluidic origami for reconfigurable pneumatic/hydraulic” device is designed and manufactured: a 12‐layer soft robotic peacock spider with embedded microfluidic circuitry and actuatable features.     

Microstructural and Interfacial Designs of Oxygen‐Permeable Membranes for Oxygen Separation and Reaction–Separation Coupling

Mixed ionic–electronic conducting oxygen‐permeable membranes can rapidly separate oxygen from air with 100% selectivity and low energy consumption. Combining reaction and separation in an oxygen‐permeable membrane reactor significantly simplifies the technological scheme and reduces the process energy consumption. Recently, materials design and mechanism investigations have provided insight into the microstructural and interfacial effects. The microstructures of the membrane surfaces and bulk are closely related to the interfacial oxygen exchange kinetics and bulk diffusion kinetics. Therefore, the permeability and stability of oxygen‐permeable membranes with a single‐phase structure and a dual‐phase structure can be adjusted through their microstructural and interfacial designs. Here, recent advances in the development of oxygen permeation models that provide a deep understanding of the microstructural and interfacial effects, and strategies to simultaneously improve the permeability and stability through microstructural and interfacial design are discussed in detail. Then, based on the developed high‐performance membranes, highly effective membrane reactors for process intensification and new technology developments are highlighted. The new membrane reactors will trigger innovations in natural gas conversion, ammonia synthesis, and hydrogen‐related clean energy technologies. Future opportunities and challenges in the development of oxygen‐permeable membranes for oxygen separation and reaction–separation coupling are also explored.     

Shape‐Shifting 3D Protein Microstructures with Programmable Directionality via Quantitative Nanoscale Stiffness Modulation

The ability to shape‐shift in response to a stimulus increases an organism's survivability in nature. Similarly, man‐made dynamic and responsive “smart” microtechnology is crucial for the advancement of human technology. Here, 10–30 μm shape‐changing 3D BSA protein hydrogel microstructures are fabricated with dynamic, quantitative, directional, and angle‐resolved bending via two‐photon photolithography. The controlled directional responsiveness is achieved by spatially controlling the cross‐linking density of BSA at a nanometer lengthscale. Atomic force microscopy measurements of Young's moduli of structures indicate that increasing the laser writing distance at the z‐axis from 100–500 nm decreases the modulus of the structure. Hence, through nanoscale modulation of the laser writing z‐layer distance at the nanoscale, control over the cross‐linking density is possible, allowing for the swelling extent of the microstructures to be quantified and controlled with high precision. This method of segmented moduli is applied within a single microstructure for the design of shape‐shifting microstructures that exhibit stimulus‐induced chirality, as well as for the fabrication of a free‐standing 3D microtrap which is able to open and close in response to a pH change.     

All‐Silicon Broadband Ultraviolet Metasurfaces

Featuring high photon energy and short wavelength, ultraviolet (UV) light enables numerous applications such as high‐resolution imaging, photolithography, and sensing. In order to manipulate UV light, bulky optics are usually required, and hence do not meet the fast‐growing requirements of integration in compact systems. Recently, metasurfaces have shown unprecedented control of light, enabling substantial miniaturization of photonic devices from terahertz to visible regions. However, material challenges have hampered the realization of such functionalities at shorter wavelengths. Herein, it is experimentally demonstrated that all‐silicon (Si) metasurfaces with thicknesses of only one‐tenth of the working wavelength can be designed and fabricated to manipulate broadband UV light with efficiencies comparable to plasmonic metasurface performance in infrared (IR). Also, for the first time, photolithography enabled by metasurface‐generated UV holograms is shown. Such performance enhancement is attributed to increased scattering cross sections of Si antennas in the UV range, which is adequately modeled via a circuit. The new platform introduced here will deepen the understanding of light–matter interactions and introduce even more material options to broadband metaphotonic applications, including those in integrated photonics and holographic lithography technologies.     

Biotinylated Photopolymers for 3D‐Printed Unibody Lab‐on‐a‐Chip Optical Platforms

The present work reports the first demonstration of straightforward fabrication of monolithic unibody lab‐on‐a‐chip (ULOCs) integrating bioactive micrometric 3D scaffolds by means of multimaterial stereolithography (SL). To this end, a novel biotin‐conjugated photopolymer is successfully synthesized and optimally formulated to achieve high‐performance SL‐printing resolution, as demonstrated by the SL‐fabrication of biotinylated structures smaller than 100 µm. By optimizing a multimaterial single‐run SL‐based 3D‐printing process, such biotinylated microstructures are incorporated within perfusion microchambers whose excellent optical transparency enables real‐time optical microscopy analyses. Standard biotin‐binding assays confirm the existence of biotin‐heads on the surfaces of the embedded 3D microstructures and allow to demonstrate that the biofunctionality of biotin is not altered during the SL‐printing, thus making it exploitable for further conjugation with other biomolecules. As a step forward, an in‐line optical detection system is designed, prototyped via SL‐printing and serially connected to the perfusion microchambers through customized world‐to‐chip connectors. Such detection system is successfully employed to optically analyze the solution flowing out of the microchambers, thus enabling indirect quantification of the concentration of target interacting biomolecules. The successful application of this novel biofunctional photopolymer as SL‐material enables to greatly extend the versatility of SL to directly fabricate ULOCs with intrinsic biofunctionality.     

High‐Throughput Phase‐Field Design of High‐Energy‐Density Polymer Nanocomposites

Understanding the dielectric breakdown behavior of polymer nanocomposites is crucial to the design of high‐energy‐density dielectric materials with reliable performances. It is however challenging to predict the breakdown behavior due to the complicated factors involved in this highly nonequilibrium process. In this work, a comprehensive phase‐field model is developed to investigate the breakdown behavior of polymer nanocomposites under electrostatic stimuli. It is found that the breakdown strength and path significantly depend on the microstructure of the nanocomposite. The predicted breakdown strengths for polymer nanocomposites with specific microstructures agree with existing experimental measurements. Using this phase‐field model, a high throughput calculation is performed to seek the optimal microstructure. Based on the high‐throughput calculation, a sandwich microstructure for PVDF–BaTiO₃ nanocomposite is designed, where the upper and lower layers are filled with parallel nanosheets and the middle layer is filled with vertical nanofibers. It has an enhanced energy density of 2.44 times that of the pure PVDF polymer. The present work provides a computational approach for understanding the electrostatic breakdown, and it is expected to stimulate future experimental efforts on synthesizing polymer nanocomposites with novel microstructures to achieve high performances.     

Nanomolar Synthesis in Droplet Microarrays with UV‐Triggered On‐Chip Cell Screening

Miniaturization and parallelization of combinatorial organic synthesis is important to accelerate the process of drug discovery while reducing the consumption of reagents and solvents. This work presents a miniaturized platform for on‐chip solid‐phase combinatorial library synthesis with UV‐triggered on‐chip cell screening. The platform is based on a nanoporous polymer coating on a glass slide, which is modified via photolithography to yield arrays of hydrophilic (HL) spots surrounded by superhydrophobic (SH) surface. The combination of HL spots and SH background enables confinement of nanoliter droplets, functioning as miniaturized reactors for the solid‐phase synthesis. The polymer serves as support for nanomolar solid‐phase synthesis, while a photocleavable linker enables the release of the synthesized compounds into the droplets containing live cells. A 588 compound library of bisamides is synthesized via a four‐component Ugi reaction on the chip and products are detected via stamping of the droplet array onto a conductive substrate and subsequent matrix‐assisted laser desorption ionization mass spectrometry. The light‐induced cleavage shows high flexibility in screening conditions by spatial, temporal, and quantitative control.     

Large‐Area Direct Laser‐Shock Imprinting of a 3D Biomimic Hierarchical Metal Surface for Triboelectric Nanogenerators

Ongoing efforts in triboelectric nanogenerators (TENGs) focus on enhancing power generation, but obstacles concerning the economical and cost‐effective production of TENGs continue to prevail. Micro‐/nanostructure engineering of polymer surfaces has been dominantly utilized for boosting the contact triboelectrification, with deposited metal electrodes for collecting the scavenged energy. Nevertheless, this state‐of‐the‐art approach is limited by the vague potential for producing 3D hierarchical surface structures with conformable coverage of high‐quality metal. Laser‐shock imprinting (LSI) is emerging as a potentially scalable approach for directly surface patterning of a wide range of metals with 3D nanoscale structures by design, benefiting from the ultrahigh‐strain‐rate forming process. Here, a TENG device is demonstrated with LSI‐processed biomimetic hierarchically structured metal electrodes for efficient harvesting of water‐drop energy in the environment. Mimicking and transferring hierarchical microstructures from natural templates, such as leaves, into these water‐TENG devices is effective regarding repelling water drops from the device surface, since surface hydrophobicity from these biomicrostructures maximizes the TENG output. Among various leaves' microstructures, hierarchical microstructures from dried bamboo leaves are preferable regarding maximizing power output, which is attributed to their unique structures, containing both dense nanostructures and microscale features, compared with other types of leaves. Also, the triboelectric output is significantly improved by closely mimicking the hydrophobic nature of the leaves in the LSI‐processed metal surface after functionalizing it with low‐surface‐energy self‐assembled‐monolayers. The approach opens doors to new manufacturable TENG technologies for economically feasible and ecologically friendly production of functional devices with directly patterned 3D biomimic metallic surfaces in energy, electronics, and sensor applications.     

Tape‐Imprinted Hierarchical Lotus Seedpod‐Like Arrays for Extraordinary Surface‐Enhanced Raman Spectroscopy

A novel two‐side‐activatable high‐performance surface‐enhanced Raman spectroscopy (SERS) substrate is developed based on the tape‐imprinting method. It features 3D full‐space‐distributed hot spots originating from the hierarchical lotus seedpod‐like silver arrays, which offer ultrasensitive, uniform, reproducible, and reliable quantitative measurements with an inherent internal standard. This excellent SERS substrate also holds great promise in practical in situ molecule detection on curved surfaces, such as pesticides on fruit, which is not yet possible with the traditional rigid or flexible material‐based SERS counterparts.     

Fabrication of Micropatterned Self‐Oscillating Polymer Brush for Direction Control of Chemical Waves

The propagation control of chemical waves via a pentagonal patterned structure in a self‐oscillating polymer brush composed of N‐isopropylacrylamide and a metal catalyst for the Belousov–Zhabotinsky (BZ) reaction is reported. The patterned self‐oscillating polymer brush is prepared by combining surface‐initiated atom transfer radical polymerization and maskless photolithography. Surface modification is confirmed by X‐ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, 3D measuring laser microscopy, and fluorescence microscopy. The polymer brush patterns are fabricated with gaps between the pentagonal regions, and investigations on the effect of the gap distance on the BZ reaction reveal that at the appropriate distance, chemical waves propagate across the array from the plane to the corner between the patterns. Unidirectional control is achieved not only in the 1D array, but also in a 2D curved array. This patterned self‐oscillating polymer brush is a novel and advantageous approach for creating an autonomous dynamic soft interface.     

An Unprecedented Stimuli‐Controlled Single‐Crystal Reversible Phase Transition of a Metal–Organic Framework and Its Application to a Novel Method of Guest Encapsulation

The flexibility and unexpected dynamic behavior of a third‐generation metal–organic framework are described for the first time. The synthetic strategy is based on the flexibility and spherical shape of dipyridyl‐based carborane linkers that act as pillars between rigid Co/BTB (BTB: 1,3,5‐benzenetricarboxylate) layers, providing a 3D porous structure ( 1 ). A phase transition of the solid can be induced to generate a new, nonporous 2D structure ( 2 ) without any loss of the carborane linkers. The structural transformation is visualized by snapshots of the multistep single‐crystal‐to‐single‐crystal transformation by single‐crystal and powder X‐ray diffraction. Poor hydrogen bond acceptors such as MeOH, CHCl₃ or supercritical CO₂ induce such a 3D to 2D transformation. Remarkably, the transformation is reversible and the 2D phase 2 is further converted back into 1 by heating in dimethylformamide. The energy requirements involved in such processes are investigated using periodic density functional theory calculations. As a proof of concept for potential applications, encapsulation of C₆₀ is achieved by trapping this molecule during the reversible 2D to 3D phase transition, whereas no adsorption is observed by straight solvent diffusion into the pores of the 3D phase.     

2D Porous TiO2 Single‐Crystalline Nanostructure Demonstrating High Photo‐Electrochemical Water Splitting Performance

Porous single crystals are promising candidates for solar fuel production owing to their long range charge diffusion length, structural coherence, and sufficient reactive sites. Here, a simple template‐free method of growing a selectively branched, 2D anatase TiO₂ porous single crystalline nanostructure (PSN) on fluorine‐doped tin oxide substrate is demonstrated. An innovative ion exchange–induced pore‐forming process is designed to successfully create high porosity in the single‐crystalline nanostructure with retention of excellent charge mobility and no detriment to crystal structure. PSN TiO₂ film delivers a photocurrent of 1.02 mA cm^?2 at a very low potential of 0.4 V versus reversible hydrogen electrode (RHE) for photo‐electrochemical water splitting, closing to the theoretical value of TiO₂ (1.12 mA cm^?2). Moreover, the current–potential curve featuring a small potential window from 0.1 to 0.4 V versus RHE under one‐sun illumination has a near‐ideal shape predicted by the Gartner Model, revealing that the charge separation and surface reaction on the PSN TiO₂ photoanode are very efficient. The photo‐electrochemical water splitting performance of the films indicates that the ion exchange–assisted synthesis strategy is effective in creating large surface area and single‐crystalline porous photoelectrodes for efficient solar energy conversion.     

Electrolyte‐Dependent Sodium Ion Transport Behaviors in Hard Carbon Anode

A comprehensive study is conducted on hard carbon (HC) series samples by tuning the graphitic local microstructures systematically as an anode for SIBs in both carbonate‐ (CBE) and glyme‐based electrolytes (GBE). The results reveal more detailed charge storage characters of HCs on the LVP section. 1) The LVP capacity is closely related to the prismatic surface area to the basal plane as well as the bulk density, regardless of electrolyte systems. 2) The glyme‐sodium ion complex can facilitate sodium ion delivery into the internal closed pores of the HCs along with not well‐ordered graphitic structures. 3) The glyme‐mediated sodium ion‐storage behavior causes significant decreases in both surface film resistance and charge transfer resistance, leading to enhanced rate capability. 4) The LVP originates from the formation of pseudo‐metallic sodium nanoclusters, which are the same in a CBE and GBE. These results provide insight into the sodium ion‐storage behaviors of HCs, particularly on the interrelationship between graphitic local microstructures and electrolyte systems. In addition, a high‐performance HC anode with a plateau capacity of ≈300 mA h g^?1 is designed based on the information, and its workability is demonstrated in a full‐cell SIB device.     

Solid‐State Diffusional Behaviors of Functional Metal Oxides at Atomic Scale

Metal/metal oxides have attracted extensive research interest because of their combination of functional properties and compatibility with industry. Diffusion and thermal reliability have become essential issues that require detailed study to develop atomic‐scaled functional devices. In this work, the diffusional reaction behavior that transforms piezoelectric ZnO into magnetic Fe₃O₄ is investigated at the atomic scale. The growth kinetics of metal oxides are systematically studied through macro‐ and microanalyses. The growth rates are evaluated by morphology changes, which determine whether the growth behavior was a diffusion‐ or reaction‐controlled process. Furthermore, atom attachment on the kink step is observed at the atomic scale, which has important implications for the thermodynamics of functional metal oxides. Faster growth planes simultaneously decrease, which result in the predominance of low surface energy planes. These results directly reveal the atomic formation process of metal oxide via solid‐state diffusion. In addition, the nanofabricated method provides a novel approach to investigate metal oxide evolution and sheds light on diffusional reaction behavior. More importantly, the results and phenomena of this study provide considerable inspiration to enhance the material stability and reliability of metal/oxide‐based devices.     

Single‐Particle Cryo‐EM and 3D Reconstruction of Hybrid Nanoparticles with Electron‐Dense Components

Single‐particle cryo‐electron microscopy (cryo‐EM), accompanied with 3D reconstruction, is a broadly applicable tool for the structural characterization of macromolecules and nanoparticles. Recently, the cryo‐EM field has pushed the limits of this technique to higher resolutions and samples of smaller molecular mass, however, some samples still present hurdles to this technique. Hybrid particles with electron‐dense components, which have been studied using single‐particle cryo‐EM yet with limited success in 3D reconstruction due to the interference caused by electron‐dense elements, constitute one group of such challenging samples. To process such hybrid particles, a masking method is developed in this work to adaptively remove pixels arising from electron‐dense portions in individual projection images while maintaining maximal biomass signals for subsequent 2D alignment, 3D reconstruction, and iterative refinements. As demonstrated by the success in 3D reconstruction of an octahedron DNA/gold hybrid particle, which has been previously published without a 3D reconstruction, the devised strategy that combines adaptive masking and standard single‐particle 3D reconstruction approach has overcome the hurdle of electron‐dense elements interference, and is generally applicable to cryo‐EM structural characterization of most, if not all, hybrid nanomaterials with electron‐dense components.     

Thread‐Like Radical‐Polymerization via Autonomously Propelled (TRAP) Bots

Micromotor‐mediated synthesis of thread‐like hydrogel microstructures in an aqueous environment is presented. The study utilizes a catalytic micromotor assembly (owing to the presence of a Pt layer), with an on‐board chemical reservoir (i.e., polymerization mixture), toward thread‐like radical‐polymerization via autonomously propelled bots (i.e., TRAP bots). Synergistic coupling of catalytically active Pt layer, together with radical initiators (H₂O₂ and FeCl₃ (III)), and PEGDA monomers preloaded into the TRAP bot, results in the polymerization of monomeric units into elongated thread‐like hydrogel polymers coupled with self‐propulsion. Interestingly, polymer generation via TRAP bots can also be triggered in the absence of hydrogen peroxide for cellular/biomedical application. The resulting polymeric hydrogel microstructures are able to entrap living cells (NIH 3T3 fibroblast cells), and are easily separable via a centrifugation or magnetic separation (owing to the presence of a Ni layer). The cellular biocompatibility of TRAP bots is established via a LIVE/DEAD assay and MTS cell proliferation assay (7 days observation). This is the first study demonstrating real‐time in situ hydrogel polymerization via an artificial microswimmer, capable of enmeshing biotic/abiotic microobjects in its reaction environment, and lays a strong foundation for advanced applications in cell/tissue engineering, drug delivery, and cleaner technologies.     

Rapid,Controllable Fabrication of Regular Complex Microarchitectures by Capillary Assembly of Micropillars and Their Application in Selectively Trapping/Releasing Microparticles

A simple strategy to realize new controllable 3D microstructures and a novel method to reversibly trapping and releasing microparticles are reported. This technique controls the height, shape, width, and arrangement of pillar arrays and realizes a series of special microstructures from 2‐pillar‐cell to 12 cell arrays, S‐shape, chain‐shape and triangle 3‐cell arrays by a combined top down/bottom up method: laser interference lithography and capillary force‐induced assembly. Due to the inherent features of this method, the whole time is less than 3 min and the fabricated area determined by the size of the laser beam can reach as much as 1 cm², which shows this method is very simple, rapid, and high‐throughput. It is further demonstrated that the ‘mechanical hand’‐like 4‐cell arrays could be used to selectively trap/release microparticles with different sizes, e.g., 1.5, 2, or 3.5 μm, which are controlled by the period of the microstructures from 2.5 to 4 μm, and 6 μm. Finally, the ‘mechanical hand’‐like 4‐cell arrays are integrated into 100 μm‐width microfluidic channels prepared by ultraviolet photolithography, which shows that this technique is compatible with conventional microfabrication methods for on‐chip applications.     

Self‐regularized pseudo time‐marching schemes for structural system identification with static measurements

We explore the application of pseudo time marching schemes, involving either deterministic integration or stochastic filtering, to solve the inverse problem of parameter identification of large dimensional structural systems from partial and noisy measurements of strictly static response. Solutions of such non‐linear inverse problems could provide useful local stiffness variations and do not have to confront modeling uncertainties in damping, an important, yet inadequately understood, aspect in dynamic system identification problems. The usual method of least‐square solution is through a regularized Gauss–Newton method (GNM) whose results are known to be sensitively dependent on the regularization parameter and data noise intensity. Finite time, recursive integration of the pseudo‐dynamical GNM (PD‐GNM) update equation addresses the major numerical difficulty associated with the near‐zero singular values of the linearized operator and gives results that are not sensitive to the time step of integration. Therefore, we also propose a pseudo‐dynamic stochastic filtering approach for the same problem using a parsimonious representation of states and specifically solve the linearized filtering equations through a pseudo‐dynamic ensemble Kalman filter (PD‐EnKF). For multiple sets of measurements involving various load cases, we expedite the speed of the PD‐EnKF by proposing an inner iteration within every time step. Results using the pseudo‐dynamic strategy obtained through PD‐EnKF and recursive integration are compared with those from the conventional GNM, which prove that the PD‐EnKF is the best performer showing little sensitivity to process noise covariance and yielding reconstructions with less artifacts even when the ensemble size is small. Copyright © 2009 John Wiley & Sons, Ltd.