Nanoparticle-Structured Highly Sensitive and Anisotropic Gauge Sensors.

The ability to tune gauge factors in terms of magnitude and orientation is important for wearable and conformal electronics. Herein, a sensor device is described which is fabricated by assembling and printing molecularly linked thin films of gold nanoparticles on flexible microelectrodes with unusually high and anisotropic gauge factors. A sharp difference in gauge factors up to two to three orders of magnitude between bending perpendicular (B(⊥)) and parallel (B(||)) to the current flow directions is observed. The origin of the unusual high and anisotropic gauge factors is analyzed in terms of nanoparticle size, interparticle spacing, interparticle structure, and other parameters, and by considering the theoretical aspects of electron conduction mechanism and percolation pathway. A critical range of resistivity where a very small change in strain and the strain orientation is identified to impact the percolation pathway in a significant way, leading to the high and anisotropic gauge factors. The gauge anisotropy stems from molecular and nanoscale fine tuning of interparticle properties of molecularly linked nanoparticle assembly on flexible microelectrodes, which has important implication for the design of gauge sensors for highly sensitive detection of deformation in complex sensing environment or on complex curved surfaces such as wearable electronics and skin sensors.

Label-Free Neuropeptide Detection beyond the Debye Length Limit.

Biosensors with high selectivity, high sensitivity, and real-time detection capabilities are of significant interest for diagnostic applications as well as human health and performance monitoring. Graphene field-effect transistor (GFET) based biosensors are suitable for integration into wearable sensor technology and can potentially demonstrate the sensitivity and selectivity necessary for real-time detection and monitoring of biomarkers. Previously reported DC-mode GFET biosensors showed a high sensitivity for sensing biomarkers in solutions with a low salt concentration. However, due to Debye length screening, the sensitivity of the DC-mode GFET biosensors decreases significantly during operation in a physiological fluid such as sweat or interstitial fluid. To overcome the Debye screening length limitation, we report here alternating current (AC) mode heterodyne-based GFET biosensors for sensing neuropeptide-Y (NPY), a key stress biomarker, in artificial sweat at physiologically relevant ionic concentrations. Our AC-mode GFET biosensors show a record ultralow detection limit of 2 × 10-18 M with an extensive dynamic range of 10 orders of magnitude in sensor response to target NPY concentration. The sensors were characterized for various carrier frequencies (ranging from 30 kHz to 2 MHz) of the applied AC voltages and various salt concentrations (10, 50, and 100 mM). Contrary to DC-mode sensing, the AC-mode sensor response increases with an increase in salt concentration in the electrolyte. The sensor response can be further enhanced by tuning the carrier frequency of the applied AC voltage. The optimum response frequency of our sensor is approximately 400-600 kHz for salt concentrations of 50 and 100 mM, respectively. The salt-concentration- and frequency-dependent sensor response can be explained by an electrolyte-gated capacitance model.

Nano-Filamented Textile Sensor Platform with High Structure Sensitivity.

A key challenge to the creation of chemically responsive electro-functionality of nonconductive, hydrophobic, and free-contacted textile or fibrous network materials is how to impart the 3D structure with functional filaments to enable responsive structure sensitivity, which is critical in establishing the fibrous platform technology for sensor applications. We demonstrate this capability using an electrospun polymeric fibrous substrate embedded with nano-filaments defined by size-tunable gold nanoparticles and structurally sensitive dendrons as crosslinkers. The resulting interparticle properties strongly depend on the assembly of the nano-filaments, enabling an interface with high structure sensitivity to molecular interactions. This is demonstrated with chemiresistive responses to vaporous alcohol molecules with different chain lengths and isomers, which is critical in breath and sweat sensing involving a high-moisture or -humidity background. The sensitivity scales with the chain length and varies with their isomers. This approach harnesses the multifunctional tunability of the nano-filaments in a sensor array format, showing high structure sensitivity to the alcohol molecules with different chain lengths and isomers. The high structure sensitivity and its implications for a paradigm shift in the design of textile sensor arrays for multiplexing human performance monitoring via breath or sweat sensing and environmental monitoring of air quality are also discussed.

Surface-Mediated Interconnections of Nanoparticles in Cellulosic Fibrous Materials toward 3D Sensors.

Fibrous materials serve as an intriguing class of 3D materials to meet the growing demands for flexible, foldable, biocompatible, biodegradable, disposable, inexpensive, and wearable sensors and the rising desires for higher sensitivity, greater miniaturization, lower cost, and better wearability. The use of such materials for the creation of a fibrous sensor substrate that interfaces with a sensing film in 3D with the transducing electronics is however difficult by conventional photolithographic methods. Here, a highly effective pathway featuring surface-mediated interconnection (SMI) of metal nanoclusters (NCs) and nanoparticles (NPs) in fibrous materials at ambient conditions is demonstrated for fabricating fibrous sensor substrates or platforms. Bimodally distributed gold-copper alloy NCs and NPs are used as a model system to demonstrate the semiconductive-to-metallic conductivity transition, quantized capacitive charging, and anisotropic conductivity characteristics. Upon coupling SMI of NCs/NPs as electrically conductive microelectrodes and surface-mediated assembly (SMA) of the NCs/NPs as chemically sensitive interfaces, the resulting fibrous chemiresistors function as sensitive and selective sensors for gaseous and vaporous analytes. This new SMI-SMA strategy has significant implications for manufacturing high-performance fibrous platforms to meet the growing demands of the advanced multifunctional sensors and biosensors.

Rheological characterization of in situ cross-linkable hyaluronan hydrogels.

This report investigates the rheological properties of cross-linked, thiol-functionalized HA (HA-DTPH) hydrogels prepared by varying the concentration and molecular weight (MW) of the cross-linker, poly(ethylene glycol) diacrylate (PEGDA). Hydrogels were subsequently cured for either short-term (hours) or long-term (days) and subjected to oscillatory shear rheometry (OSR). OSR allows the evaluation and comparison of the shear storage moduli (G'), an index of the total number of effective cross-links formed in the hydrogels. While the oscillatory time sweep monitored the evolution of G' during in situ gelation, the stress and frequency sweeps measured the G' of preformed and subsequently cured hydrogels. From stress sweeps, we found that, for the hydrogels, G' scaled linearly with PEGDA concentration and was independent of its MW. Upon comparison with the classical Flory's theory of elasticity, stress sweep tests on short-term cured hydrogels revealed the simultaneous, but gradual, formation of spontaneous disulfide cross-links in the hydrogels. Results from time and frequency sweeps suggested that the formation of a stable, three-dimensional network depended strictly on PEGDA concentration. Results from the equilibrium swelling of hydrogels concurred with those obtained from oscillatory stress sweeps. Such a detailed rheological characterization of our HA-DTPH-PEGDA hydrogels will aid in the design of biomaterials targeted for biomedical or pharmaceutical purposes, especially in applications involving functional tissue engineering.