Fibrillar Elastomeric Micropatterns Create Tunable Adhesion Even to Rough Surfaces

Biologically inspired, fibrillar dry adhesives continue to attract much attention as they are instrumental for emerging applications and technologies. To date, the adhesion of micropatterned gecko‐inspired surfaces has predominantly been tested on stiff, smooth substrates. However, all natural and almost all artificial surfaces have roughnesses on one or more different length scales. In the present approach, micropillar‐patterned PDMS surfaces with superior adhesion to glass substrates with different roughnesses are designed and analyzed. The results reveal for the first time adhesive and nonadhesive states depending on the micropillar geometry relative to the surface roughness profile. The data obtained further demonstrate that, in the adhesive regime, fibrillar gecko‐inspired adhesive structures can be used with advantage on rough surfaces; this finding may open up new applications in the fields of robotics, biomedicine, and space exploration.     

Controllable Anisotropic Dry Adhesion in Vacuum: Gecko Inspired Wedged Surface Fabricated with Ultraprecision Diamond Cutting

Gecko adhesion has inspired the fabrication of various dry adhesive surfaces, most of which are developed to be used under atmospheric conditions. However, applications of gecko‐inspired surfaces can be expanded to vacuum and even space environment due to the characteristics of van der Waals interactions, which are always present between materials regardless of the surrounding environment. In this paper, a controllable, anisotropic dry adhesion in vacuum is demonstrated with gecko‐inspired wedged dry adhesive surfaces fabricated using an ultraprecision diamond cutting mold. The adhesion and friction properties of the wedge‐structured surfaces are systematically characterized in loading–pulling mode and loading–dragging–pulling mode. The surfaces show significant anisotropic adhesion (P_ad ≈ 10.5 kPa vs P_ad ≈ 0.7 kPa) and friction (P_f ≈ 50 kPa vs P_f ≈ 30 kPa) when actuated in gripping and releasing direction, respectively. The wedge‐structured surfaces in vacuum show comparable properties as exposed in atmosphere. A three‐legged gripper is designed to pick up, hold, and release a patterned silicon wafer in vacuum. The study demonstrates a green, high‐yield, and low‐cost method to fabricate a reliable and durable mold for gecko inspired anisotropic dry adhesive surfaces and the potential application of dry adhesive surface in vacuum.     

Carbon and Graphene Quantum Dots for Optoelectronic and Energy Devices: A Review

As new members of carbon material family, carbon and graphene quantum dots (CDs, GQDs) have attracted tremendous attentions for their potentials for biological, optoelectronic, and energy related applications. Among these applications, bio‐imaging has been intensively studied, but optoelectronic and energy devices are rapidly rising. In this Feature Article, recent exciting progresses on CD‐ and GQD‐based optoelectronic and energy devices, such as light emitting diodes (LEDs), solar cells (SCs), photodetctors (PDs), photocatalysis, batteries, and supercapacitors are highlighted. The recent understanding on their microstructure and optical properties are briefly introduced in the first part. Some important progresses on optoelectronic and energy devices are then addressed as the main part of this Feature Article. Finally, a brief outlook is given, pointing out that CDs and GQDs could play more important roles in communication‐ and energy‐functional devices in the near future.     

Multifunctional Hybrid Polymer‐Based Porous Materials

Polymer‐based porous hybrid materials (PHMs) carrying inorganic nanoparticles on the surface of pores have important applications in chemical and biological sensing, in chromatography, and in heterogeneous catalysis. This Feature Article provides an overview of the recent developments in the synthesis and fabrication of multifunctional PHMs using polymerization‐induced phase separation. Exemplary applications of a PHM coated with gold nanorods were demonstrated for the simultaneous detection of different analytes using surface enhanced Raman scattering (SERS) spectroscopy and fluorescence microscopy.     

Improvement of Biological Organisms Using Functional Material Shells

Biomineralization brings inorganic materials into biological organisms and it plays an important role in natural evolution. Inspired by biomineralized eggs and diatoms with protective shell structures, scientists have artificially endowed organisms with functional materials. The resulting organism–material hybrids become more robust and even evolve new functions. This feature article reviews recent achievements of organism improvements by various material shells and related applications in cell protection, storage, thermal stability, biological stealth, photosynthesis and biocatalysis, etc. Different from the previous understanding of biomineralization, the regulation effects of materials on organism functions are highlighted in these biomineralization‐inspired biological improvements, which present an artificial evolution strategy by using material techniques. We suggest that rationally designed organism–materials with optimized functions can shed light on solving global problems such as energy crisis and environmental pollution, as well as on improving medical treatment and intricate material designing. More generally, the studies of material‐based organism improvement can combine biological and material sciences together for a closer integration.     

Bioinspired Material Approaches to Sensing

Bioinspired design is an engineering approach that involves working to understand the design principles and strategies employed by biology in order to benefit the development of engineered systems. From a materials perspective, biology offers an almost limitless source of novel approaches capable of arousing innovation in every aspect of materials, including fabrication, design, and functionality. Here, recent and ongoing work on the study of bioinspired materials for sensing applications is presented. Work presented includes the study of fish flow receptor structures and the subsequent development of similar structures to improve flow sensor performance. The study of spider air‐flow receptors and the development of a spider‐inspired flexible hair is also discussed. Lastly, the development of flexible membrane based infrared sensors, highly influenced by the fire beetle, is presented, where a pneumatic mechanism and a thermal‐expansion stress‐mediated buckling‐based mechanism are investigated. Other areas that are discussed include novel biological signal filtering mechanisms and reciprocal benefits offered through applying the biology lessons to engineered systems.     

Functional Porous Polymers by Emulsion Templating: Recent Advances

Porous materials are currently of great scientific as well as technological interest. A strategy that is increasingly employed to prepare highly porous and well defined macroporous polymers is emulsion templating, whereby the droplets of a high internal phase emulsion are used to create pores in a solid material by curing or polymerization of the emulsion continuous phase. This Feature Article covers recent work in this area, focusing on: the preparation of such materials from new precursors and via novel approaches; the chemical modification of existing materials; and the application of the resulting porous structures in diverse areas of science and technology.     

In Situ Observation Reveals Local Detachment Mechanisms and Suction Effects in Micropatterned Adhesives

Fibrillar adhesion pads of insects and geckoes have inspired the design of high‐performance adhesives enabling a new generation of handling devices. Despite much progress over the last decade, the current understanding of these adhesives is limited to single contact pillars and the behavior of whole arrays is largely unexplored. In the study reported here, a novel approach is taken to gain insight into the detachment mechanisms of whole micropatterned arrays. Individual contacts are imaged by frustrated total internal reflection, allowing in situ observation of contact formation and separation during adhesion tests. The detachment of arrays is found to be governed by the distributed adhesion strength of individual pillars, but no collaborative effect mediated by elastic interactions can be detected. At the maximal force, about 30% of the mushroom structures are already detached. The adhesive forces decrease with reduced air pressure by 20% for the smooth and by 6% for the rough specimen. These contributions are attributed to a suction effect, whose strength depends critically on interfacial defects controlling the sealing quality of the contact. This dominates the detachment process and the resulting adhesion strength.     

Designing Bio‐Inspired Adhesives for Shear Loading: From Simple Structures to Complex Patterns

The gecko has inspired numerous synthetic adhesive structures, yet under shear loading conditions, general design criteria remains underdeveloped. To provide guidance for bio‐inspired adhesives under shear, a simple scaling theory is used to investigate the relevant geometric and material parameters. The total compliance of an elastic attachment feature is described over many orders of magnitude in aspect ratio through a single continuous function using the superposition of multiple deformation modes such as bending, shear deformation, and tensile elongation. This allows for force capacity predictions of common geometric control parameters such as thickness, aspect ratio, and contact area. This superposition principal is extended to develop criteria for patterned interfaces under shear loading. Importantly, the adhesive patterns under shear are controlled through the compliance in the direction of loading. These predictions are confirmed experimentally using macroscopic building blocks over an extensive range of aspect ratio and contact area. Over 25 simple and complex patterns with various contact geometries are examined, and the effect of geometry and material properties on the shear adhesion behavior is discussed. Furthermore, all of these various attachment features are described with a single scaling parameter, offering control over orders of magnitude in adhesive force capacity for a variety of applications.     

Stretchable,Skin‐Mountable,and Wearable Strain Sensors and Their Potential Applications: A Review

There is a growing demand for flexible and soft electronic devices. In particular, stretchable, skin‐mountable, and wearable strain sensors are needed for several potential applications including personalized health‐monitoring, human motion detection, human‐machine interfaces, soft robotics, and so forth. This Feature Article presents recent advancements in the development of flexible and stretchable strain sensors. The article shows that highly stretchable strain sensors are successfully being developed by new mechanisms such as disconnection between overlapped nanomaterials, crack propagation in thin films, and tunneling effect, different from traditional strain sensing mechanisms. Strain sensing performances of recently reported strain sensors are comprehensively studied and discussed, showing that appropriate choice of composite structures as well as suitable interaction between functional nanomaterials and polymers are essential for the high performance strain sensing. Next, simulation results of piezoresistivity of stretchable strain sensors by computational models are reported. Finally, potential applications of flexible strain sensors are described. This survey reveals that flexible, skin‐mountable, and wearable strain sensors have potential in diverse applications while several grand challenges have to be still overcome.     

Cover Picture: Direct Ink Writing of 3D Functional Materials (Adv. Funct. Mater. 17/2006)

The direct ink writing of three‐dimensional functional materials is detailed in the Feature Article by Lewis on p. 2193. The left side of the cover image displays schematic images that show the conversion of a direct‐write polymer woodpile to a silicon hollow‐woodpile structure. The 3 × 3 image matrix showcases the resulting silicon photonic crystal (center) surrounded by a higher‐magnification view of a representative hollow silicon feature (ca. 1 μm in diameter). The figure was prepared by F. Garcia‐Santamaria, G. M. Gratson, and P. V. Braun. The ability to pattern materials in three dimensions is critical for several technological applications, including composites, microfluidics, photonics, and tissue engineering. Direct‐write assembly allows one to design and rapidly fabricate materials in complex 3D shapes without the need for expensive tooling, dies, or lithographic masks. Here, recent advances in direct ink writing are reviewed with an emphasis on the push towards finer feature sizes. Opportunities and challenges associated with direct ink writing are also highlighted.     

Tailored Assembly of Carbon Nanostructures: Tailored Assembly of Carbon Nanotubes and Graphene (Adv. Funct. Mater. 8/2011)

This Feature Article reviews recent progress in the tailored assembly of carbon nanotubes and graphene into three‐dimensional architectures with particular emphasis on our own research employing self‐assembly principles. Carbon nanotubes and graphene can be assembled into macroporous films, hollow spherical capsules, or hollow nanotubes, via directed assembly from solvent dispersion. This approach is cost‐effective and beneficial for large‐scale assembly, but pre‐requests stable dispersion in a solvent medium. Directed growth from a nanopatterned catalyst array is another promising approach, which enables the control of morphology and properties of graphitic materials as well as their assembly. In addition, the aforementioned two approaches can be synergistically integrated to generate a carbon hybrid assembly consisting of vertical carbon nanotubes grown on flexible graphene films. Tailored assembly relying on scalable self‐assembly principles offer viable routes that are scalable for mass production towards the ultimate utilization of graphitic carbon materials in nanoelectronics, displays, sensors, energy storage/conversion devices, and so on, including future flexible devices.     

Bio‐Inspired Synthesis of Minerals for Energy,Environment, and Medicinal Applications

Biomineralization, the natural pathway of assembling biogenic inorganic compounds, inspires us to exploit unique, effective strategies to fabricate functional materials with intricate structures. In this article, the recent advances in bio‐inspired synthesis of minerals—with a focus on those of calcium‐based minerals—and their applications to the design of functional materials for energy, environment, and biomedical fields are reviewed. Biomimetic mineralization is extending its application range to unconventional area such as the design of component materials for lithium‐ion batteries and elaborately structured composite materials utilizing carbon dioxide gas. Materials with highly enhanced mechanical properties are synthesized through emulating the nacre structure. Studies of bioactive minerals‐carbon hybrid materials show an expansion of potential applications to fields ranging from interdisciplinary science to practical engineering such as the fabrication of reinforced bone‐implantable materials.     

Tailored Assembly of Carbon Nanotubes and Graphene

This Feature Article reviews recent progress in the tailored assembly of carbon nanotubes and graphene into three‐dimensional architectures with particular emphasis on our own research employing self‐assembly principles. Carbon nanotubes and graphene can be assembled into macroporous films, hollow spherical capsules, or hollow nanotubes, via directed assembly from solvent dispersion. This approach is cost‐effective and beneficial for large‐scale assembly, but pre‐requests stable dispersion in a solvent medium. Directed growth from a nanopatterned catalyst array is another promising approach, which enables the control of morphology and properties of graphitic materials as well as their assembly. In addition, the aforementioned two approaches can be synergistically integrated to generate a carbon hybrid assembly consisting of vertical carbon nanotubes grown on flexible graphene films. Tailored assembly relying on scalable self‐assembly principles offer viable routes that are scalable for mass production towards the ultimate utilization of graphitic carbon materials in nanoelectronics, displays, sensors, energy storage/conversion devices, and so on, including future flexible devices.     

A Photoresponsive Red‐Hair‐Inspired Polydopamine‐Based Copolymer for Hybrid Photocapacitive Sensors

Inspired by the powerful photosensitizing properties of the red hair pigments pheomelanins, a photoresponsive cysteine‐containing variant of the adhesive biopolymer polydopamine (pDA) is developed via oxidative copolymerization of dopamine (DA) and 5‐S‐cysteinyldopamine (CDA) in variable ratios. Chemical and spectral analysis indicate the presence of benzothiazole/benzothiazine units akin to those of pheomelanins. p(DA/CDA) copolymers display ­impedance properties similar to those of biological materials and a marked photoimpedance response to light stimuli. The use of the p(DA/CDA) copolymer to implement a solution‐processed hybrid photocapacitive/resistive metal‐insulator‐semiconductor (MIS) device disclosed herein is the first example of technological exploitation of photoactive, red‐hair‐inspired biomaterials as soft enhancement layer for silicon in an optoelectronic device. The bio‐inspired materials described herein may provide the active component of new hybrid photocapacitive sensors with a chemically tunable response to visible light.     

Hierarchical Nanocomposites Derived from Nanocarbons and Layered Double Hydroxides ‐ Properties,Synthesis, and Applications

The combination of one‐dimensional and two‐dimensional building blocks leads to the formation of hierarchical composites that can take full advantages of each kind of material, which is an effective way for the preparation of multifunctional materials with extraordinary properties. Among various building blocks, nanocarbons (e.g., carbon nanotubes and graphene) and layered double hydroxides (LDHs) are two of the most powerful materials that have been widely used in human life. This Feature Article presents a state‐of‐the‐art review of hierarchical nanocomposites derived from nanocarbons and LDHs. The properties of nanocarbons, LDHs, as well as the combined nanocomposites, are described first. Then, efficient and effective fabrication methods for the hierarchical nanocomposites, including the reassembly of nanocarbons and LDHs, formation of LDHs on nanocarbons, and formation of nanocarbons on LDHs, are presented. The as‐obtained nanocomposites derived form nanocarbons and LDHs exhibited excellent performance as multifunctional materials for their promising applications in energy storage, nanocomposites, catalysis, environmental protection, and drug delivery. The fabrication of LDH/carbon nanocomposites provides a novel method for the development of novel multifunctional nanocomposites based on the existing nanomaterials. However, knowledge of their assembly mechanism, robust and precise route for LDH/nanocarbon hybrid with well designed structure, and the relationship between structure, properties, and applications are still inadequate. A multidisciplinary approach from the scope of materials, physics, chemistry, engineering, and other application areas, is highly required for the development of this advanced functional composite materials.     

Fluorescent Conjugated Polyelectrolytes for Bioimaging

This Feature Article summarizes the recent advances of water‐soluble fluorescent conjugated polyelectrolytes (CPEs) in bioimaging. Apart from a brief overview of traditional linear CPEs, a special emphasis is placed on CPEs that can self‐assemble into or are born with three‐dimensional nano‐architectures, including grafted CPEs, hyperbranched CPEs, and polyhedral oligomeric silsesquioxanes(POSS)‐based CPE derivatives. These CPEs naturally form nanoparticles with sizes ranging from 3 to 100 nm in aqueous media, and possess reactive functional groups for bioconjugation or complexation with desired biorecognition elements. The tunable size, low cytotoxicity, good photostability, and ease of surface modification ultimately enable these CPEs with wide applications in in vitro intracellular protein sensing, cell detection, in vivo cell imaging and drug tracking. Moreover, traditional linear CPEs can be transformed into uniform nanoparticles by complexation with oppositely charged biomolecules to allow for cell detection and in situ drug release monitoring. The work featured herein not only reveals the important molecular design principles of CPEs for different imaging tasks, but also highlights the promising directions for the further development of CPE‐based imaging materials.     

Electrical Properties of Carbon Nanotube Based Fibers and Their Future Use in Electrical Wiring

The production of continuous fibers made purely of carbon nanotubes has paved the way for new macro‐scale applications which utilize the superior properties of individual carbon nanotubes. These wire‐like macroscopic assemblies of carbon nanotubes were recognized to have a potential to be used in electrical wiring. Carbon nanotube wiring may be extremely light and mechanically stronger and more efficient in transferring high frequency signals than any conventional conducting material, being cost‐effective simultaneously. However, transfer of the unique properties of individual CNTs to the macro‐scale proves to be quite challenging. This Feature Article gives an overview of the potential of using carbon nanotube fibers as next generation wiring, state of the art developments in this field, and goals to be achieved before carbon nanotubes may be transformed into competitive products.     

Biomimetic Bidirectional Switchable Adhesive Inspired by the Gecko

The gecko adhesive system has attracted significant attention since the discovery that van der Waals interactions, which are always present between surfaces, are predominantly responsible for their adhesion. The unique anisotropic frictional–adhesive capabilities of the gecko adhesive system originate from complex hierarchical structures and just as importantly, the anisotropic articulation of the structures. Here, by cleverly engineering asymmetric polymeric microstructures, a reusable switchable gecko‐like adhesive can be fabricated yielding steady high adhesion ( ≈ 1.25 N/cm²) and friction ( ≈ 2.8 N/cm²) forces when actuated for “gripping”, yet release easily with minimal adhesion ( ≈ 0.34 N/cm²) and friction (≈ 0.38 N/cm²) forces during detachment or “releasing”, over multiple attachment/detachment cycles, with a relatively small normal preload of 0.16 N/cm² to initiate the adhesion. These adhesives can also be used to reversibly suspend weights from vertical (e.g., walls), and horizontal (e.g., ceilings) surfaces by simultaneously and judiciously activating anisotropic friction and adhesion forces. This design opens the way for new gecko‐like adhesive surfaces and articulation mechanisms that do not rely on intensive nanofabrication in order to recover the anisotropic tribological property of gecko adhesive pads, albeit with lower adhesive forces compared to geckos.     

Covalent Organic Frameworks: Structures,Synthesis, and Applications

Covalent organic frameworks (COFs) are crystalline porous polymers formed by a bottom‐up approach from molecular building units having a predesigned geometry that are connected through covalent bonds. They offer positional control over their building blocks in two and three dimensions. This control enables the synthesis of rigid porous structures with a high regularity and the ability to fine‐tune the chemical and physical properties of the network. This Feature Article provides a comprehensive overview over the structures realized to date in the fast growing field of covalent organic framework development. Different synthesis strategies to meet diverse demands, such as high crystallinity, straightforward processability, or the formation of thin films are discussed. Furthermore, insights into the growing fields of COF applications, including gas storage and separations, sensing, electrochemical energy storage, and optoelectronics are provided.