Highly Stretchable and Strain-Insensitive Fiber-Based Wearable Electrochemical Biosensor to Monitor Glucose in the Sweat.

Development of high-performance fiber-shaped wearable sensors is of great significance for next-generation smart textiles for real-time and out-of-clinic health monitoring. The previous focus has been mainly on monitoring physical parameters such as pressure and strains associated with human activities. Development of an enzyme-based non-invasive wearable electrochemical sensor to monitor biochemical vital signs of health such as the glucose level in sweat has attracted increasing attention recently, due to the unmet clinical needs for the diabetic patients. To achieve this, the key challenge lies in the design of a highly stretchable fiber with high conductivity, facile enzyme immobilization, and strain-insensitive properties. Herein, we demonstrate an elastic gold fiber-based three-electrode electrochemical platform that can meet the aforementioned criteria toward wearable textile glucose biosensing. The gold fiber could be functionalized with Prussian blue and glucose oxidase to obtain the working electrode and modified by Ag/AgCl to serve as the reference electrode; and the nonmodified gold fiber could serve as the counter electrode. The as-fabricated textile glucose biosensors achieved a linear range of 0-500 µM and a sensitivity of 11.7 µA mM-1 cm-2. Importantly, such sensing performance could be maintained even under a large strain of 200%, indicating the potential applications in real-world wearable biochemical diagnostics from human sweat.

Real-Time and In-Situ Monitoring of H2O2 Release from Living Cells by a Stretchable Electrochemical Biosensor Based on Vertically Aligned Gold Nanowires.

Traditional electrochemical biosensing electrodes (e.g., gold disk, glassy carbon electrode, etc.) can undergo sophisticated design to detect chemicals/biologicals from cells. However, such electrodes are typically rigid and nonstretchable, rendering it challenging to detect cellular activities in real-time and in situ when cells are in mechanically deformed states. Here, we report a new stretchable electrochemical cell-sensing platform based on vertically aligned gold nanowires embedded in PDMS (v-AuNWs/PDMS). Using H2O2 as a model analyte, we show that the v-AuNWs/PDMS electrode can display an excellent sensing performance with a wide linear range, from 40 µM to 15 mM, and a high sensitivity of 250 mA/cm2/M at a potential of -0.3 V. Moreover, living cells can grow directly on our stretchable high-surface area electrodes with strong adhesion, demonstrating their excellent biocompatibility. Further cell stimulation by adding chemicals induced H2O2 generation, which can be detected in real-time and in situ using our v-AuNWs/PDMS platform for both natural and stretched states of cells. Our results indicate the v-AuNWs/PDMS electrochemical biosensor may serve as a general cell-sensing platform for living organisms under deformed states.

Fractal Gold Nanoframework for Highly Stretchable Transparent Strain-Insensitive Conductors.

Percolation networks of one-dimensional (1D) building blocks (e.g., metallic nanowires or carbon nanotubes) represent the mainstream strategy to fabricate stretchable conductors. One of the inherent limitations is the control over junction resistance between 1D building blocks in natural and strained states of conductors. Herein, we report highly stretchable transparent strain-insensitive conductors using fractal gold (F-Au) nanoframework based on a one-pot templateless wet chemistry synthesis method. The monolayered F-Au nanoframework (∼20 nm in thickness) can be obtained from the one-pot synthesis without any purification steps involved and can be transferred directly to arbitrary substrates like polyethylene terephthalate, food-wrap, polydimethylsiloxane (PDMS), and ecoflex. The F-Au thin film with no capping agents leads to a highly conductive thin film without any post-treatment and can be stretched up to 110% strain without significantly losing conductivity yet with the optical transparency of 70% at 550 nm. Remarkably, the F-Au thin film shows the strain-insensitive behavior up to 20% stretching strain. This originates from the unique fractal nanomesh-like structure which can absorb external mechanical forces, thus maintaining electron pathways throughout the nanoframework. In addition, a semitransparent bilayered F-Au film on 100% prestrained PDMS could achieve to a high stretchability of 420% strain with negligible resistance changes under low-level strains.

Cell Sheet-Like Soft Nanoreactor Arrays.

Tissues, which consist of groups of closely packed cell arrays, are essentially sheet-like biosynthesis plants. In tissues, individual cells are discrete microreactors working under highly viscous and confined environments. Herein, soft polystyrene-encased nanoframe (PEN) reactor arrays, as analogous nanoscale "sheet-like chemosynthesis plants", for the controlled synthesis of novel nanocrystals, are reported. Although the soft polystyrene (PS) is only 3 nm thick, it is elastic, robust, and permeable to aqueous solutes, while significantly slowing down their diffusion. PEN-associated palladium (Pd) crystallization follows a diffusion-controlled zero-order kinetics rather than a reaction-controlled first-order kinetics in bulk solution. Each individual PEN reactor has a volume in the zeptoliter range, which offers a unique confined environment, enabling a directional inward crystallization, in contrast to the conventional outward nucleation/growth that occurs in an unconfined bulk solution. This strategy makes it possible to generate a set of mono-, bi-, and trimetallic, and even semiconductor nanocrystals with tunable interior structures, which are difficult to achieve with normal systems based on bulk solutions.

Plasmene nanosheets as optical skin strain sensors.

Skin-like optoelectronic sensors can have a wide range of technical applications ranging from wearable/implantable biodiagnostics, human-machine interfaces, and soft robotics to artificial intelligence. The previous focus has been on electrical signal transduction, whether resistive, capacitive, or piezoelectric. Here, we report on "optical skin" strain sensors based on elastomer-supported, highly ordered, and closely packed plasmonic nanocrystal arrays (plasmene). Using gold nanocubes (AuNCs) as a model system, we find that the types of polymeric ligands, interparticle spacing, and AuNC sizes play vital roles in strain-induced plasmonic responses. In particular, brush-forming polystyrene (PS) is a "good" ligand for forming elastic plasmenes which display strain-induced blue shift of high-energy plasmonic peaks with high reversibility upon strain release. Further experimental and simulation studies reveal the transition from isotropic uniform plasmon coupling at a non-strained state to anisotropic plasmon coupling at strained states, due to the AuNC alignment perpendicular to the straining direction. The two-term plasmonic ruler model may predict the primary high-energy peak location. Using the relative shift of the averaged high-energy peak to the coupling peak before straining, a plasmene nanosheet may be used as a strain sensor with the sensitivity depending on its internal structures, such as the constituent AuNC size or inter-particle spacing.

Self-assembly and characterization of 2D plasmene nanosheets.

Freestanding plasmonic nanoparticle (NP) superlattice sheets are novel 2D nanomaterials with tailorable properties that enable their use for broad applications in sensing, anticounterfeit measures, ionic gating, nanophotonics and flat lenses. We recently developed a robust, yet general, two-step drying-mediated approach to produce freestanding monolayer, plasmonic NP superlattice sheets, which are typically held together by holey grids with minimal solid support. Within these superlattices, NP building blocks are closely packed and have strong plasmonic coupling interactions; hence, we termed such freestanding materials 'plasmene nanosheets'. Using the desired NP building blocks as starting material, we describe the detailed fabrication protocol, including NP surface functionalization by thiolated polystyrene and the self-assembly of NPs at the air-water interface. We also discuss various characterization approaches for checking the quality and optical properties of the as-obtained plasmene nanosheets: optical microscopy, spectrophotometry, transmission/scanning electron microscopy (TEM/SEM) and atomic force microscopy (AFM). With regard to different constituent building blocks, the key experimental parameters, including NP concentration and volume, are summarized to guide the successful fabrication of specific types of plasmene nanosheets. This protocol, from initial NP synthesis to the final fabrication and characterization, takes ~33.5 h.

Covalent-Cross-Linked Plasmene Nanosheets.

Thiol-polystyrene (SH-PS)-capped plasmonic nanoparticles can be fabricated into free-standing, one-nanoparticle-thick superlattice sheets (termed plasmene) based on physical entanglement between ligands, which, however, suffer from irreversible dissociation in organic solvents. To address this issue, we introduce coumarin-based photo-cross-linkable moieties to the SH-PS ligands to stabilize gold nanoparticles. Once cross-linked, the obtained plasmene nanosheets consisting of chemically locked nanoparticles can well maintain structural integrity in organic solvents. Particularly, arising from ligand-swelling-induced enlargement of the interparticle spacing, these plasmene nanosheets show significant optical responses to various solvents in a specific as well as reversible manner, which may offer an excellent material for solvent sensing and dynamic plasmonic display.

A General Approach to Free-Standing Nanoassemblies via Acoustic Levitation Self-Assembly.

Droplets suspended by acoustic levitation provide genuine substrate-free environments for understanding unconventional fluid dynamics, evaporation kinetics, and chemical reactions by circumventing solid surface and boundary effects. Using a fully levitated air-water interface by acoustic levitation in conjunction with drying-mediated nanoparticle self-assembly, here, we demonstrate a general approach to fabricating free-standing nanoassemblies, which can totally avoid solid surface effects during the entire process. This strategy has no limitation for the sizes or shapes of constituent metallic nanoparticle building blocks and can also be applied to fabricate free-standing bilayered and trilayered nanoassemblies or even three-dimensional hollow nanoassemblies. We believe that our strategy may be further extended to quantum dots, magnetic particles, colloids, etc. Hence, it may lead to a myriad of homogeneous or heterogeneous free-standing nanoassemblies with programmable functionalities.

2D Freestanding Janus Gold Nanocrystal Superlattices.

2D freestanding nanocrystal superlattices represent a new class of advanced metamaterials in that they can integrate mechanical flexibility with novel optical, electrical, plasmonic, and magnetic properties into one multifunctional system. The freestanding 2D superlattices reported to date are typically constructed from symmetrical constituent building blocks, which have identical structural and functional properties on both sides. Here, a general ligand symmetry-breaking strategy is reported to grow 2D Janus gold nanocrystal superlattice sheets with nanocube morphology on one side yet with nanostar on the opposite side. Such asymmetric metallic structures lead to distinct wetting and optical properties as well as surface-enhanced Raman scattering (SERS) effects. In particular, the SERS enhancement of the nanocube side is about 20-fold of that of the nanostar side, likely due to the combined "hot spot + lightening-rod" effects. This is nearly 700-fold of SERS enhancement as compared with the symmetric nanocube superlattices without Janus structures.

Cat-Tail-Like Mesostructured Silica Fibers Decorated with Gold Nanowires: Synthesis, Characterization, and Application as Stretchable Sensors.

Gold-nanowires (AuNWs)-coated mesostructured silica fibers that have the appearance of a cat's tail have been successfully designed and synthesized. The silica fibers had a Brunauer-Emmett-Teller (BET) surface area of 347 m2 g-1 and Barret-Joyner-Halenda (BJH) pore size of 3.8 nm. Negatively charged gold seeds could be anchored onto the surface of mesoporous silica fibers through electrostatic attraction. Further treatment with growth solution (including HAuCl4 , 4-mercaptobenzoic acid, and ascorbic acid) enabled successful growth of vertically aligned AuNWs with controllable lengths on the silica fiber surfaces. These coaxial mesostructured silica microfibers conjugated with AuNWs exhibit excellent stability and real-time response with high durability (≥2500 cycles) as a sensitive flexible microelectronic material. The fabricated device is able to detect the human pulse (measured at the wrist), as well as small-amplitude finger motion.

Cat-Tail-Like Mesostructured Silica Fibers Decorated with Gold Nanowires: Synthesis, Characterization, and Application as Stretchable Sensors.

Invited for this month's cover are the collaborating groups of Prof. Xiaojun Han from Harbin Institute of Technology, China and Prof. Wenlong Cheng from Monash University, Australia. The cover picture shows how a stretchable sensor made from a 3D structure comprising mesostructured silica fibers decorated with gold nanowires exhibits reliable resistance signals for real-time response to radial artery blood pulses. This work reinforces the idea of smart material hybridization and may offer flexible materials for real-time, in situ health monitoring applications. Read the full text of the article at 10.1002/cplu.201900043.

Two-dimensional gold trisoctahedron nanoparticle superlattice sheets: self-assembly, characterization and immunosensing applications.

Nanoparticles were called "artificial atoms" about two decades ago due to their ability to organize into regular lattices or supracrystals. Their self-assembly into free-standing, two-dimensional (2D) nanoparticle arrays enables the generation of 2D metamaterials for novel applications in sensing, nanophotonics and energy fields. However, their controlled fabrication is nontrivial due to the complex nanoscale forces among nanoparticle building blocks. Here, we report a new type of 2D plasmonic superlattice from high-index gold trisoctahedron (TOH) nanoparticles. TOH is an anisotropic polyhedron with 24 facets and 14 vertices. By using polymer ligands in conjunction with drying-mediated self-assembly, we obtained highly ordered 2D superlattices as quantified by synchrotron based grazing-incidence small-angle X-ray scattering (GISAXS). The plasmonic properties were optimized by adjusting the ligand length and particle size. The excellent surface-enhanced Raman scattering (SERS) performance enables us to demonstrate TOH superlattices as uniform SERS immunosubstrates with a detection limit down to 1 pg ml-1 and a dynamic range from 1 pg ml-1 to 100 ng ml-1.

Shape Transformation of Constituent Building Blocks within Self-Assembled Nanosheets and Nano-origami.

Self-assembly of nanoparticles represents a simple yet efficient route to synthesize designer materials with unusual properties. However, the previous assembled structures whether by surfactants, polymer, or DNA ligands are "static" or "frozen" building block structures. Here, we report the growth of transformable self-assembled nanosheets which could enable reversible switching between two types of nanosheets and even evolving into diverse third generation nanosheet structures without losing pristine periodicity. Such in situ transformation of nanoparticle building blocks can even be achieved in a free-standing two-dimensional system and three-dimensional origami. The success in such in situ nanocrystal transformation is attributed to robust "plant-cell-wall-like" ion-permeable reactor arrays from densely packed polymer ligands, which spatially define and confine nanoscale nucleation/growth/etching events. Our strategy enables efficient fabrication of nanocrystal nanosheets with programmable building blocks for innovative applications in adaptive tactile metamaterials, optoelectronic devices, and sensors.

2D Binary Plasmonic Nanoassemblies with Semiconductor n/p-Doping-Like Properties.

The electronic, optical, thermal, and magnetic properties of an extrinsic bulk semiconductor can be finely tuned by adjusting its dopant concentration. Here, it is demonstrated that such a doping concept can be extended to plasmonic nanomaterials. Using two-dimensional (2D) assemblies of Au@Ag and Au nanocubes (NCs) as a model system, detailed experimental and theoretical studies are carried out, which reveal collective semiconductor n/p-doping-like plasmonic properties. A threshold doping concentration of Au@Ag NCs is observed, below which p-doping dominates and above which n-doping prevails. Furthermore, Au@Ag NC dopants can be converted into corresponding Au seed "voids" dopants by selectively removing Ag without changing the overall structural integrity. The results show that the plasmonic doping concept may serve as a general design principle guiding synthesis and assembly of plasmonic metamaterials for programmable optoelectronic devices.

Highly Stretchable Fiber-Shaped Supercapacitors Based on Ultrathin Gold Nanowires with Double-Helix Winding Design.

The ability of developing highly durable fiber-shaped electronic devices is crucial for next-generation smart textile electronics. Past several years have witnessed encouraging progress made in stretchable fiber-shaped supercapacitors using carbon materials, transition metal oxides, and conducting polymers. Here, we report a dry-spun strategy to produce scalable ultrathin gold nanowire-based fibers, which can lead to highly stretchable fiber-based supercapacitors using a double-helix winding design. Hildebrand's and Hansen's solubility parameters of gold nanowire-binding oleylamine ligands match those of styrene-ethylene/butylene-styrene and tetrahydrofuran, enabling the formation of high-quality dry-spun fibers. In conjunction with conductivity enhancement by electroless plating and pseudocapacitance by polyaniline, we obtained fiber-shaped supercapacitors stretchable up to 360% with a capacitance of 16.80 mF cm-2. The capacitance retention is about 85% after 2000 cycles of 0-200-0% stretching/releasing. Our fiber capacitors can be woven into an everyday glove, with negligible capacitance changes for normal finger movements.

Self-assembled gold nanorime mesh conductors for invisible stretchable supercapacitors.

Thin, skin-conformal, transparent and stretchable energy devices are ideal for powering future wearable and implantable electronics. However, it is difficult to achieve such "unfeelable" and "invisible" devices with traditional materials and design methodologies because of the challenge of simultaneously achieving high optical transparency, high electrical conductivity and high mechanical stretchability. Here, we report a two-step nanowire growth approach for fabricating gold nanorime mesh conductors, enabling skin-thin, transparent and stretchable supercapacitors. Solution-state oleylamine-capped 2 nm-thin gold nanowires self-assemble into highly transparent nanomeshes, which then serve as templates for growing highly conductive vertically aligned nanowires. This two-step solution-plus-surface nanowire growth strategy leads to elastic gold nanorime mesh conductors with an optical transparency up to 90.3% at 550 nm, a low sheet resistance as low as 1.7 ± 0.8 Ω sq-1, and a stretchability of over 100% strain. Such elastic conductors are successfully used to construct symmetrical supercapacitors that can simultaneously achieve high areal capacitance and high stretchability, demonstrating the potential to power future bio-integratable electronics.

A location- and sharpness-specific tactile electronic skin based on staircase-like nanowire patches.

Human skin can sense an external object in a location-specific manner, simultaneously recognizing whether it is sharp or blunt. Such tactile capability can be achieved in both natural and stretched states. It is impractical to mimic this tactile function of human skin by designing pixelated sensor arrays across our whole curvilinear human body. Here, we report a new tactile electronic skin sensor based on staircase-like vertically aligned gold nanowires (V-AuNWs). With a back-to-back linear or spiral assembly of two staircase structures into a single sensor, we are able to recognize pressure in a highly location-specific manner for both non-stretched and stretched states (up to 50% strain); with a concentric design on the fingertip, we can identify the sharpness of an external object. We believe that our strategy opens up a new route to highly specific second-skin-like tactile sensors for electronic skin (E-skin) applications.

Standing Enokitake-like Nanowire Films for Highly Stretchable Elastronics.

Stretchable electronics may enable electronic components to be part of our organs-ideal for future wearable/implantable biodiagnostic systems. One of key challenges is failure of the soft/rigid material interface due to mismatching Young's moduli, which limits stretchability and durability of current systems. Here, we show that standing enokitake-like gold-nanowire-based films chemically bonded to an elastomer can be stretched up to 900% and are highly durable, with >93% conductivity recovery even after 2000 stretching/releasing cycles to 800% strain. Both experimental and modeling reveal that this superior elastic property originates from standing enokitake-like nanowire film structures. The closely packed nanoparticle layer sticks to the top of the nanowires, which easily cracks under strain, whereas the bottom part of the nanowires is compliant with substrate deformation. This leads to tiny V-shaped cracks with a maintained electron transport pathway rather than large U-shaped cracks that are frequently observed for conventional metal films. We further show that our standing nanowire films can serve as current collectors in supercapacitors and second skin-like smart masks for facial expression detection.