Wearable Flexible Perspiration Biosensors Using Laser-Induced Graphene and Polymeric Tape Microfluidics.

Wearable biosensors promise real-time measurements of chemicals in human sweat, with the potential for dramatic improvements in medical diagnostics and athletic performance through continuous metabolite and electrolyte monitoring. However, sweat sensing is still in its infancy, and questions remain about whether sweat can be used for medical purposes. Wearable sensors are focused on proof-of-concept designs that are not scalable for multisubject trials, which could elucidate the utility of sweat sensing for health monitoring. Moreover, many wearable sensors do not include the microfluidics necessary to protect and channel consistent and clean sweat volumes to the sensor surface or are not designed to be disposable to prevent sensor biofouling and inaccuracies due to repeated use. Hence, there is a need to produce low-cost and single-use wearable sensors with integrated microfluidics to ensure reliable sweat sensing. Herein, we demonstrate the convergence of laser-induced graphene (LIG) based sensors with soft tape polymeric microfluidics to quantify both sweat metabolites (glucose and lactate) and electrolytes (sodium) for potential hydration and fatigue monitoring. Distinct LIG-electrodes were functionalized with glucose oxidase and lactate oxidase for selective sensing of glucose and lactate across physiological ranges found in sweat with sensitivities of 26.2 and 2.47 × 10-3 µA mM-1 cm-2, detection limits of 8 and 220 µM, and linear response ranges of 0-1 mM and 0-32 mM, respectively. LIG-electrodes functionalized with a sodium-ion-selective membrane displayed Nernstian sensitivity of 58.8 mV decade-1 and a linear response over the physiological range in sweat (10-100 mM). The sensors were tested in a simulated sweating skin microfluidic system and on-body during cycling tests in a multisubject trial. Results demonstrate the utility of LIG integrated with microfluidics for real-time, continuous measurements of biological analytes in sweat and help pave the way for the development of personalized wearable diagnostic tools.

Systematic Design of a Graphene Ink Formulation for Aerosol Jet Printing.

Aerosol jet printing is a noncontact, digital, additive manufacturing technique compatible with a wide variety of functional materials. Although promising, development of new materials and devices using this technique remains hindered by limited rational ink formulation, with most recent studies focused on device demonstration rather than foundational process science. In the present work, a systematic approach to formulating a polymer-stabilized graphene ink is reported, which considers the effect of solvent composition on dispersion, rheology, wetting, drying, and phase separation characteristics that drive process outcomes. It was found that a four-component solvent mixture composed of isobutyl acetate, diglyme, dihydrolevoglucosenone, and glycerol supported efficient ink atomization and controlled in-line drying to reduce overspray and wetting instabilities while maintaining high resolution and electrical conductivity, thus overcoming a trade-off in deposition rate and resolution common to aerosol jet printing. Biochemical sensors were printed for amperometric detection of the pesticide parathion, exhibiting a detection limit of 732 nM and a sensitivity of 34 nA µM-1, demonstrating the viability of this graphene ink for fabricating functional electronic devices.

Enzymatic Laser-Induced Graphene Biosensor for Electrochemical Sensing of the Herbicide Glyphosate.

Glyphosate is a globally applied herbicide yet it has been relatively undetectable in-field samples outside of gold-standard techniques. Its presumed nontoxicity toward humans has been contested by the International Agency for Research on Cancer, while it has been detected in farmers' urine, surface waters and crop residues. Rapid, on-site detection of glyphosate is hindered by lack of field-deployable and easy-to-use sensors that circumvent sample transportation to limited laboratories that possess the equipment needed for detection. Herein, the flavoenzyme, glycine oxidase, immobilized on platinum-decorated laser-induced graphene (LIG) is used for selective detection of glyphosate as it is a substrate for GlyOx. The LIG platform provides a scaffold for enzyme attachment while maintaining the electronic and surface properties of graphene. The sensor exhibits a linear range of 10-260 µ m, detection limit of 3.03 µ m, and sensitivity of 0.991 nA µ m -1. The sensor shows minimal interference from the commonly used herbicides and insecticides: atrazine, 2,4-dichlorophenoxyacetic acid, dicamba, parathion-methyl, paraoxon-methyl, malathion, chlorpyrifos, thiamethoxam, clothianidin, and imidacloprid. Sensor function is further tested in complex river water and crop residue fluids, which validate this platform as a scalable, direct-write, and selective method of glyphosate detection for herbicide mapping and food analysis.

Tuning the Structure, Conductivity, and Wettability of Laser-Induced Graphene for Multiplexed Open Microfluidic Environmental Biosensing and Energy Storage Devices.

The integration of microfluidics and electrochemical cells is at the forefront of emerging sensors and energy systems; however, a fabrication scheme that can create both the microfluidics and electrochemical cells in a scalable fashion is still lacking. We present a one-step, mask-free process to create, pattern, and tune laser-induced graphene (LIG) with a ubiquitous CO2 laser. The laser parameters are adjusted to create LIG with different electrical conductivity, surface morphology, and surface wettability without the need for postchemical modification. Such definitive control over material properties enables the creation of LIG-based integrated open microfluidics and electrochemical sensors that are capable of dividing a single water sample along four multifurcating paths to three ion selective electrodes (ISEs) for potassium (K+), nitrate (NO3-), and ammonium (NH4+) monitoring and to an enzymatic pesticide sensor for organophosphate pesticide (parathion) monitoring. The ISEs displayed near-Nernstian sensitivities and low limits of detection (LODs) (10-5.01 M, 10-5.07 M, and 10-4.89 M for the K+, NO3-, and NH4+ ISEs, respectively) while the pesticide sensor exhibited the lowest LOD (15.4 pM) for an electrochemical parathion sensor to date. LIG was also specifically patterned and tuned to create a high-performance electrochemical micro supercapacitor (MSC) capable of improving the power density by 2 orders of magnitude compared to a Li-based thin-film battery and the energy density by 3 orders of magnitude compared to a commercial electrolytic capacitor. Hence, this tunable fabrication approach to LIG is expected to enable a wide range of real-time, point-of-use health and environmental sensors as well as energy storage/harvesting modules.

Electrochemical Sensing of Neonicotinoids Using Laser-Induced Graphene.

Neonicotinoids are the fastest-growing insecticide accounting for over 25% of the global pesticide market and are capable of controlling a range of pests that damage croplands, home yards/gardens, and golf course greens. However, widespread use has led to nontarget organism decline in pollinators, insects, and birds, while chronic, sublethal effects on humans are still largely unknown. Therefore, there is a need to understand how prevalent neonicotinoids are in the environment as there are currently no commercially available field-deployable sensors capable of measuring neonicotinoid concentrations in surface waters. Herein, we report the first example of a laser-induced graphene (LIG) platform that utilizes electrochemical sensing for neonicotinoid detection. These graphene-based sensors are created through a scalable direct-write laser fabrication process that converts polyimide into LIG, which eliminates the need for chemical synthesis of graphene, ink formulation, masks, stencils, pattern rolls, and postprint annealing commonly associated with other printed graphene sensors. The LIG electrodes were capable of monitoring four major neonicotinoids (CLO, IMD, TMX, and DNT) with low detection limits (CLO, 823 nM; IMD, 384 nM; TMX, 338 nM; and DNT, 682 nM) and a rapid response time (∼10 s) using square-wave voltammetry without chemical/biological functionalization. Interference testing exhibited negligible responses from widely used pesticides including the broad-leaf insecticides parathion, paraoxon, and fipronil, as well as systemic herbicides glyphosate (roundup), atrazine, dicamba, and 2,4-dichlorophenoxyacetic acid. These scalable, graphene-based sensors have the potential for wide-scale mapping of neonicotinoids in watersheds and potential use in numerous electrochemical sensor devices.

All-graphene-based open fluidics for pumpless, small-scale fluid transport via laser-controlled wettability patterning.

Open microfluidics have emerged as a low-cost, pumpless alternative strategy to conventional microfluidics for delivery of fluid for a wide variety of applications including rapid biochemical analysis and medical diagnosis. However, creating open microfluidics by tuning the wettability of surfaces typically requires sophisticated cleanroom processes that are unamenable to scalable manufacturing. Herein, we present a simple approach to develop open microfluidic platforms by manipulating the surface wettability of spin-coated graphene ink films on flexible polyethylene terephthalate via laser-controlled patterning. Wedge-shaped hydrophilic tracks surrounded by superhydrophobic walls are created within the graphene films by scribing micron-sized grooves into the graphene with a CO2 laser. This scribing process is used to make superhydrophobic walls (water contact angle ∼160°) that delineate hydrophilic tracks (created through an oxygen plasma pretreatment) on the graphene for fluid transport. These all-graphene open microfluidic tracks are capable of transporting liquid droplets with a velocity of 20 mm s-1 on a level surface and uphill at elevation angles of 7° as well as transporting fluid in bifurcating cross and tree branches. The all-graphene open microfluidic manufacturing technique is rapid and amenable to scalable manufacturing, and consequently offers an alternative pumpless strategy to conventional microfluidics and creates possibilities for diverse applications in fluid transport.