Hydrogel-Templated Transfer-Printing of Conductive Nanonetworks for Wearable Sensors on Topographic Flexible Substrates.

Transfer-printing enables the assembly of functional nanomaterials on unconventional substrates with a desired layout in a controllable manner. However, transfer-printing to substrates with complex surfaces remains a challenge. Herein, we show that hydrogels serve as effective template material platforms for the assembly and transfer-printing of conductive nanonetwork patterns for flexible sensors on various topographic surfaces in a very simple yet versatile manner. The non-adherence, nanoporous structure, and molding capability of the hydrophilic hydrogel enable the assembly of conductive nanonetwork patterns on the hydrogel surface and transfer of the nanonetworks onto various flexible and topographic substrates. Flexible strain sensors and pressure sensors that monitor finger motions and arterial pulses are successfully demonstrated using the hydrogel-templated approach. The rich chemistry of polymeric networks, facile molding capability, and biocompatibility of hydrogels could be further combined with additive technology for hydrogels and electronic materials for emerging four-dimensional functional materials and soft bioelectronics.

Bio-fabrication of nanomesh channels of single-walled carbon nanotubes for locally gated field-effect transistors.

Single-walled carbon nanotubes (SWNTs) are one of the promising electronic components for nanoscale electronic devices such as field-effect transistors (FETs) owing to their excellent device characteristics such as high conductivity, high carrier mobility and mechanical flexibility. Localized gating gemometry of FETs enables individual addressing of active channels and allows for better electrostatics via thinner dielectric layer of high k-value. For localized gating of SWNTs, it becomes critical to define SWNTs of controlled nanostructures and functionality onto desired locations in high precision. Here, we demonstrate that a biologically templated approach in combination of microfabrication processes can successfully produce a nanostructured channels of SWNTs for localized active devices such as local bottom-gated FETs. A large-scale nanostructured network, nanomesh, of SWNTs were assembled in solution using an M13 phage with strong binding affinity toward SWNTs and micrometer-scale nanomesh channels were defined using negative photolithography and plasma-etching processes. The bio-fabrication approach produced local bottom-gated FETs with remarkably controllable nanostructures and successfully enabled semiconducting behavior out of unsorted SWNTs. In addition, the localized gating scheme enhanced the device performances such as operation voltage and I on/I off ratio. We believe that our approach provides a useful and integrative method for fabricating electronic devices out of nanoscale electronic materials for applications in which tunable electrical properties, mechanical flexibility, ambient stability, and chemical stability are of crucial importance.

Bionic artificial skin with a fully implantable wireless tactile sensory system for wound healing and restoring skin tactile function.

Tactile function is essential for human life as it enables us to recognize texture and respond to external stimuli, including potential threats with sharp objects that may result in punctures or lacerations. Severe skin damage caused by severe burns, skin cancer, chemical accidents, and industrial accidents damage the structure of the skin tissue as well as the nerve system, resulting in permanent tactile sensory dysfunction, which significantly impacts an individual's daily life. Here, we introduce a fully-implantable wireless powered tactile sensory system embedded artificial skin (WTSA), with stable operation, to restore permanently damaged tactile function and promote wound healing for regenerating severely damaged skin. The fabricated WTSA facilitates (i) replacement of severely damaged tactile sensory with broad biocompatibility, (ii) promoting of skin wound healing and regeneration through collagen and fibrin-based artificial skin (CFAS), and (iii) minimization of foreign body reaction via hydrogel coating on neural interface electrodes. Furthermore, the WTSA shows a stable operation as a sensory system as evidenced by the quantitative analysis of leg movement angle and electromyogram (EMG) signals in response to varying intensities of applied pressures.

M13 phage-functionalized single-walled carbon nanotubes as nanoprobes for second near-infrared window fluorescence imaging of targeted tumors.

Second near-infrared (NIR) window light (950-1400 nm) is attractive for in vivo fluorescence imaging due to its deep penetration depth in tissues and low tissue autofluorescence. Here we show genetically engineered multifunctional M13 phage can assemble fluorescent single-walled carbon nanotubes (SWNTs) and ligands for targeted fluorescence imaging of tumors. M13-SWNT probe is detectable in deep tissues even at a low dosage of 2 µg/mL and up to 2.5 cm in tissue-like phantoms. Moreover, targeted probes show specific and up to 4-fold improved uptake in prostate specific membrane antigen positive prostate tumors compared to control nontargeted probes. This M13 phage-based second NIR window fluorescence imaging probe has great potential for specific detection and therapy monitoring of hard-to-detect areas.

Fibriform Organic Electrochemical Diodes with Rectifying, Complementary Logic and Transient Voltage Suppression Functions for Wearable E-Textile Embedded Circuits.

In this study, a fibriform electrochemical diode capable of performing rectifying, complementary logic and device protection functions for future e-textile circuit systems is fabricated. The diode was fabricated using a simple twisted assembly of metal/polymer semiconductor/ion gel coaxial microfibers and conducting microfiber electrodes. The fibriform diode exhibited a prominent asymmetrical current flow with a rectification ratio of over 102, and its performance was retained after repeated bending deformations and washings. Fundamental studies on the electrochemical interactions of polymer semiconductors with ions reveal that the Faradaic current generated in polymer semiconductors by electrochemical reactions results in an abrupt current increase under a forward bias, in which the threshold voltages of the device are determined by the oxidation or reduction potential of the polymer semiconductor. Textile-embedded full-wave rectifiers and logic gate circuits were implemented by simply integrating the fibriform diodes, exhibiting AC-to-DC signal conversion and logic operation functions, respectively. It was also confirmed that the proposed fibriform diode can suppress transient voltages and thus protect a low-voltage operational wearable e-textile circuit.

Graphene sheets stabilized on genetically engineered M13 viral templates as conducting frameworks for hybrid energy-storage materials.

Utilization of the material-specific peptide-substrate interactions of M13 virus broadens colloidal stability window of graphene. The homogeneous distribution of graphene is maintained in weak acids and increased ionic strengths by complexing with virus. This graphene/virus conducting template is utilized in the synthesis of energy-storage materials to increase the conductivity of the composite electrode. Successful formation of the hybrid biological template is demonstrated by the mineralization of bismuth oxyfluoride as a cathode material for lithium-ion batteries, with increased loading and improved electronic conductivity.

An epifluidic electronic patch with spiking sweat clearance for event-driven perspiration monitoring.

Sensory neurons generate spike patterns upon receiving external stimuli and encode key information to the spike patterns, enabling energy-efficient external information processing. Herein, we report an epifluidic electronic patch with spiking sweat clearance using a sensor containing a vertical sweat-collecting channel for event-driven, energy-efficient, long-term wireless monitoring of epidermal perspiration dynamics. Our sweat sensor contains nanomesh electrodes on its inner wall of the channel and unique sweat-clearing structures. During perspiration, repeated filling and abrupt emptying of the vertical sweat-collecting channel generate electrical spike patterns with the sweat rate and ionic conductivity proportional to the spike frequency and amplitude over a wide dynamic range and long time (> 8 h). With such 'spiking' sweat clearance and corresponding electronic spike patterns, the epifluidic wireless patch successfully decodes epidermal perspiration dynamics in an event-driven manner at different skin locations during exercise, consuming less than 0.6% of the energy required for continuous data transmission. Our patch could integrate various on-skin sensors and emerging edge computing technologies for energy-efficient, intelligent digital healthcare.

An Artificial Tactile Neuron Enabling Spiking Representation of Stiffness and Disease Diagnosis.

Mechanical properties of biological systems provide useful information about the biochemical status of cells and tissues. Here, an artificial tactile neuron enabling spiking representation of stiffness and spiking neural network (SNN)-based learning for disease diagnosis is reported. An artificial spiking tactile neuron based on an ovonic threshold switch serving as an artificial soma and a piezoresistive sensor as an artificial mechanoreceptor is developed and shown to encode the elastic stiffness of pressed materials into spike frequency evolution patterns. SNN-based learning of ultrasound elastography images abstracted by spike frequency evolution rate enables the classification of malignancy status of breast tumors with a recognition accuracy up to 95.8%. The stiffness-encoding artificial tactile neuron and learning of spiking-represented stiffness patterns hold a great promise for the identification and classification of tumors for disease diagnosis and robot-assisted surgery with low power consumption, low latency, and yet high accuracy.

Dendritic Network Implementable Organic Neurofiber Transistors with Enhanced Memory Cyclic Endurance for Spatiotemporal Iterative Learning.

Dendritic network implementable organic neurofiber transistors with enhanced memory cyclic endurance for spatiotemporal iterative learning are proposed. The architecture of the fibrous organic electrochemical transistors consisting of a double-stranded assembly of electrode microfibers and an iongel gate insulator enables the highly sensitive multiple implementation of synaptic junctions via simple physical contact of gate-electrode microfibers, similar to the dendritic connections of a biological neuron fiber. In particular, carboxylic-acid-functionalized polythiophene as a semiconductor channel material provides stable gate-field-dependent multilevel memory characteristics with long-term stability and cyclic endurance, unlike the conventional poly(alkylthiophene)-based neuromorphic electrochemical transistors, which exhibit short retention and unstable endurance. The dissociation of the carboxylic acid of the polythiophene enables reversible doping and dedoping of the polythiophene channel by effectively stabilizing the ions that penetrate the channel during potentiation and depression cycles, leading to the reliable cyclic endurance of the device. The synaptic weight of the neurofiber transistors with a dendritic network maintains the state levels stably and is independently updated with each synapse connected with the presynaptic neuron to a specific state level. Finally, the neurofiber transistor demonstrates successful speech recognition based on iterative spiking neural network learning in the time domain, showing a substantial recognition accuracy of 88.9%.

Highly Sensitive On-Skin Temperature Sensors Based on Biocompatible Hydrogels with Thermoresponsive Transparency and Resistivity.

The development of electrically responsive sensors that interact directly with human skin and at the same time produce a visual indication of the temperature is in great demand. Here, we report a highly sensitive electronic skin (E-skin) sensor that measures and visualizes skin temperature simultaneously using a biocompatible hydrogel displaying thermoresponsive transparency and resistivity resulting from a temperature dependence of the strength of the hydrogen bonding between its components. This thermoresponsive hydrogel (TRH) showed a temperature dependence of not only the proton conductivity but also of its transmittance of light through a change in polymer conformation. We were able to use our TRH temperature sensor (TRH-TS) to measure temperature in a wide range of temperatures based on a change in its intrinsic resistivity (-0.0289 °C-1 ) and to visualize the temperature due to its thermoresponsive transmittance (from 7% to 96%). The TRH-TS exhibited high reliability upon multiple cycles of heating and cooling. The on-skin TRH-TS patch is also shown to successfully produce changes in its impedance and optical transparency as a result of changes in skin temperature during cardiovascular exercise. This work has shown that our biocompatible TRH-TS is potentially suitable as wearable E-skin for various emerging flexible healthcare monitoring applications.

Spirally Wrapped Carbon Nanotube Microelectrodes for Fiber Optoelectronic Devices beyond Geometrical Limitations toward Smart Wearable E-Textile Applications.

Fiber optoelectronics technology has recently attracted attention as enabling various form factors of wearable electronics, and the issue of how to control and optimize the configuration and physical properties of the electrode micropatterns in the microfiber devices has become important. Here, spirally wrapped carbon nanotube (CNT) microelectrodes with a controlled dimension are demonstrated for high-performance fiber optoelectronic devices. Inkjet-printed CNT microelectrodes with the desired dimension on an agarose hydrogel template are rolling-transferred onto a microfiber surface with an efficient electrical interface. A fiber organic field-effect transistor with spirally wrapped CNT microelectrodes verifies the feasibility of this strategy, where the transferred microelectrodes intimately contact the organic semiconductor active layer and the output current characteristics are simply controlled, resulting in characteristics that exceed the previous structural limitations. Furthermore, a fiber organic photodiode with spirally wrapped CNT microelectrodes, when used as a transparent electrode, exhibits a high Ilight/Idark ratio and good durability of bending. This fiber photodiode can be successfully incorporated into a textile photoplethysmography bandage for the real-time monitoring of human vital signals. This work offers a promising and efficient strategy to overcome the geometric factors limiting the performance of fiber-optic optoelectronic devices.

All-Inkjet-Printed Flexible Nanobio-Devices with Efficient Electrochemical Coupling Using Amphiphilic Biomaterials.

Nanostructured flexible electrodes with biological compatibility and intimate electrochemical coupling provide attractive solutions for various emerging bioelectronics and biosensor applications. Here, we develop all-inkjet-printed flexible nanobio-devices with excellent electrochemical coupling by employing amphiphilic biomaterial, an M13 phage, numerical simulation of single-drop formulation, and rational formulations of nanobio-ink. Inkjet-printed nanonetwork-structured electrodes of single-walled carbon nanotubes and M13 phage show efficient electrochemical coupling and hydrostability. Additive printing of the nanobio-inks also allows for systematic control of the physical and chemical properties of patterned electrodes and devices. All-inkjet-printed electrochemical field-effect transistors successfully exhibit pH-sensitive electrical current modulation. Moreover, all-inkjet-printed electrochemical biosensors fabricated via sequential inkjet-printing of the nanobio-ink, electrolytes, and enzyme solutions enable direct electrical coupling within the printed electrodes and detect glucose concentrations at as low as 20 µM. Glucose levels in sweat are successfully measured, and the change in sweat glucose levels is shown to be highly correlated with blood glucose levels. Synergistic combination of additive fabrication by inkjet-printing with directed assembly of nanostructured electrodes by functional biomaterials could provide an efficient means of developing bioelectronic devices for personalized medicine, digital healthcare, and emerging biomimetic devices.

High-Performance Transparent Quantum Dot Light-Emitting Diode with Patchable Transparent Electrodes.

Patchable electrodes are attractive for applications in optoelectronic devices because of their easy and reliable processability. However, development of reliable patchable transparent electrodes (TEs) with high optoelectronic performance is challenging; till now, optoelectronic devices fabricated with patchable TEs have been exhibiting limited performance. In this study, Ag nanowire (AgNW)/poly(methyl methacrylate) (PMMA) patchable TEs are developed and the highly efficient transparent quantum dot light-emitting diodes (QLEDs) using the patchable TEs are fabricated. AgNWs with optimized optoelectronic properties (figure of merit ≈ 3.3 × 10-2) are coated by an ultrathin PMMA nanolayer and transferred to thermal release tapes that enable physical attachment of TEs on the QLEDs without a significant damage to the adjacent active layer. The transparent QLEDs using patchable transparent top electrodes display excellent performance, with the maximum total luminance and current efficiency of 27 310 cd·m-2 and 45.99 cd·A-1, respectively. Fabricated by all-solution-based processes, these QLEDs exhibit the best performance to date among devices adopting patchable top electrodes.

Wearable Piezoresistive Sensors with Ultrawide Pressure Range and Circuit Compatibility Based on Conductive-Island-Bridging Nanonetworks.

Wearable pressure sensors with wide operating pressure ranges and enhanced wearability via seamless integration with circuits can greatly improve the fields of digital healthcare, prosthetic limbs, and human-machine interfaces. Herein, we report an approach based on a conductive-island-bridging nanonetwork to realize wearable resistive pressure sensors that are operative over ultrawide pressure ranges >400 kPa and are circuit-compatible. The sensor has a simple two-layered structure, where nanonetworks of single-walled carbon nanotubes selectively patterned on a surface-modified elastomeric film interface and bridge conductive Au island patterns on printed circuit boards (PCBs). We show that varying the design of the Au islands and the conductivity of the nanonetworks systematically tunes the sensitivity, linearity, and the operation range of the pressure sensor. In addition, introducing microstructured lead contacts into the sensor based on a Au-island-bridging nanonetwork produces a record-high sensitivity of 0.06 kPa-1 at 400 kPa. Furthermore, the PCB that serves as the bottom layer of the pressure sensor and contains embedded interconnects enables facile integration of the sensor with measurement circuits and wireless communication modules. The developed sensor enables the monitoring of wrist pulse waves. Moreover, an insole-shaped PCB-based pressure-sensing system wirelessly monitors pressure distributions and gait kinetics during walking. Our scheme can be extended to other nanomaterials and flexible PCBs and thus provides a simple yet powerful platform for emerging wearable applications.

Hydrodynamic Layer-by-Layer Assembly of Transferable Enzymatic Conductive Nanonetworks for Enzyme-Sticker-Based Contact Printing of Electrochemical Biosensors.

Realizing high-performance electrochemical biosensors in a simple contact-printing-based approach significantly increases the applicability of integrated flexible biosensors. Herein, an enzyme-sticker-based approach that enables flexible and multielectrochemical sensors via simple contact-transfer printing is reported. The enzyme sticker consists of an enzymatic conductive network film and a polymeric support. The enzyme-incorporated nanostructured conductive network showing an efficient electrical coupling was assembled via the hydrodynamic layer-by-layer assembly of redox enzymes, polyelectrolytes, single-walled carbon nanotubes, and a biological glue material, M13 phage. The enzymatic conductive network on a polymeric membrane support was facilely wet contact-transfer printed onto integrated electrode systems by exploiting varying degrees of hydrophilicity displayed by the enzymatic electronic film, polymeric support, and receiving electrodes of the sensor system. The glucose sensors fabricated using the enzyme sticker detected glucose at a concentration of as low as 35 µM and showed high selectivity and stability. Furthermore, a flexible dual-sensor array capable of detecting both glucose and lactate was demonstrated using the versatile enzyme sticker concept. This work presents a new route toward assembling and integrating hybrid nanomaterials with efficient electrochemical coupling for high-performance biosensors and health-monitoring devices as well as for emerging bioelectronics and electrochemical devices.

Ultrasensitive and Highly Stable Resistive Pressure Sensors with Biomaterial-Incorporated Interfacial Layers for Wearable Health-Monitoring and Human-Machine Interfaces.

Flexible piezoresistive sensors have huge potential for health monitoring, human-machine interfaces, prosthetic limbs, and intelligent robotics. A variety of nanomaterials and structural schemes have been proposed for realizing ultrasensitive flexible piezoresistive sensors. However, despite the success of recent efforts, high sensitivity within narrower pressure ranges and/or the challenging adhesion and stability issues still potentially limit their broad applications. Herein, we introduce a biomaterial-based scheme for the development of flexible pressure sensors that are ultrasensitive (resistance change by 5 orders) over a broad pressure range of 0.1-100 kPa, promptly responsive (20 ms), and yet highly stable. We show that employing biomaterial-incorporated conductive networks of single-walled carbon nanotubes as interfacial layers of contact-based resistive pressure sensors significantly enhances piezoresistive response via effective modulation of the interlayer resistance and provides stable interfaces for the pressure sensors. The developed flexible sensor is capable of real-time monitoring of wrist pulse waves under external medium pressure levels and providing pressure profiles applied by a thumb and a forefinger during object manipulation at a low voltage (1 V) and power consumption (<12 µW). This work provides a new insight into the material candidates and approaches for the development of wearable health-monitoring and human-machine interfaces.

Ultralow voltage operation of biologically assembled all carbon nanotube nanomesh transistors with ion-gel gate dielectrics.

The demonstration of field-effect transistors (FETs) based entirely on single-walled carbon nanotubes (SWNTs) would enable the fabrication of high-on-current, flexible, transparent and stretchable devices owing to the excellent electrical, optical, and mechanical properties of SWNTs. Fabricating all-SWNT-based FETs via simple solution process, at room temperature and without using lithography and vacuum process could further broaden the applicability of all-SWNT-FETs. In this work, we report on biologically assembled all SWNT-based transistors and demonstrate that ion-gel-gated network structures of unsorted SWNTs assembled using a biological template material enabled operation of SWNT-based transistors at a very low voltage. The compatibility of the biologically assembled SWNT networks with ion gel dielectrics and the large capacitance of both the three-dimensional channel networks and the ion gel allowed an ultralow operation voltage. The all-SWNT-based FETs showed an I on /I off value of >102, an on-current density per channel width of 2.16 × 10-4 A/mm at VDS = 0.4 V, and a field-effect hole mobility of 1.12 cm2/V · s in addition to the low operation voltage of <-0.5 V. We envision that our work suggests a solution-based simple and low-cost approach to realizing all-carbon-based FETs for low voltage operation and flexible applications.

Micro- and nano-patterned conductive graphene-PEG hybrid scaffolds for cardiac tissue engineering.

A lack of electrical conductivity and structural organization in currently available biomaterial scaffolds limits their utility for generating physiologically representative models of functional cardiac tissue. Here we report on the development of scalable, graphene-functionalized topographies with anisotropic electrical conductivity for engineering the structural and functional phenotypes of macroscopic cardiac tissue constructs. Guided by anisotropic electroconductive and topographic cues, the tissue constructs displayed structural property enhancement in myofibrils and sarcomeres, and exhibited significant increases in the expression of cell-cell coupling and calcium handling proteins, as well as in action potential duration and peak calcium release.

Biologically templated assembly of hybrid semiconducting nanomesh for high performance field effect transistors and sensors.

Delicately assembled composites of semiconducting nanomaterials and biological materials provide an attractive interface for emerging applications, such as chemical/biological sensors, wearable health monitoring devices, and therapeutic agent releasing devices. The nanostructure of composites as a channel and a sensing material plays a critical role in the performance of field effect transistors (FETs). Therefore, it is highly desirable to prepare elaborate composite that can allow the fabrication of high performance FETs and also provide high sensitivity and selectivity in detecting specific chemical/biological targets. In this work, we demonstrate that high performance FETs can be fabricated with a hydrodynamically assembled composite, a semiconducting nanomesh, of semiconducting single-walled carbon nanotubes (S-SWNTs) and a genetically engineered M13 phage to show strong binding affinity toward SWNTs. The semiconducting nanomesh enables a high on/off ratio (~104) of FETs. We also show that the threshold voltage and the channel current of the nanomesh FETs are sensitive to the change of the M13 phage surface charge. This biological gate effect of the phage enables the detection of biologically important molecules such as dopamine and bisphenol A using nanomesh-based FETs. Our results provide a new insight for the preparation of composite material platform for highly controllable bio/electronics interfaces.

Direct Electron Transfer of Enzymes in a Biologically Assembled Conductive Nanomesh Enzyme Platform.

Nondestructive assembly of a nanostructured enzyme platform is developed in combination of the specific biomolecular attraction and electrostatic coupling for highly efficient direct electron transfer (DET) of enzymes with unprecedented applicability and versatility. The biologically assembled conductive nanomesh enzyme platform enables DET-based flexible integrated biosensors and DET of eight different enzyme with various catalytic activities.