Juliane R. Sempionatto

Epidermal Microfluidic Electrochemical Detection System: Enhanced Sweat Sampling and Metabolite Detection

Despite tremendous recent efforts, noninvasive sweat monitoring is still far from delivering its early analytical promise. Here, we describe a flexible epidermal microfluidic detection platform fabricated through hybridization of lithographic and screen-printed technologies, for efficient and fast sweat sampling and continuous, real-time electrochemical monitoring of glucose and lactate levels. This soft, skin-mounted device judiciously merges lab-on-a-chip and electrochemical detection technologies, integrated with a miniaturized flexible electronic board for real-time wireless data transmission to a mobile device. Modeling of the device design and sweat flow conditions allowed optimization of the sampling process and the microchannel layout for achieving attractive fluid dynamics and rapid filling of the detection reservoir (within 8 min from starting exercise). The wearable microdevice thus enabled efficient natural sweat pumping to the electrochemical detection chamber containing the enzyme-modified electrode transducers. The fabricated device can be easily mounted on the epidermis without hindrance to the wearer and displays resiliency against continuous mechanical deformation expected from such epidermal wear. Amperometric biosensing of lactate and glucose from the rapidly generated sweat, using the corresponding immobilized oxidase enzymes, was wirelessly monitored during cycling activity of different healthy subjects. This ability to monitor sweat glucose levels introduces new possibilities for effective diabetes management, while similar lactate monitoring paves the way for new wearable fitness applications. The new epidermal microfluidic electrochemical detection strategy represents an attractive alternative to recently reported colorimetric sweat-monitoring methods, and hence holds considerable promise for practical fitness or health monitoring applications.

Detection of vapor-phase organophosphate threats using wearable conformable integrated epidermal and textile wireless biosensor systems

Flexible epidermal tattoo and textile-based electrochemical biosensors have been developed for vapor-phase detection of organophosphorus (OP) nerve agents. These new wearable sensors, based on stretchable organophosphorus hydrolase (OPH) enzyme electrodes, are coupled with a fully integrated conformal flexible electronic interface that offers rapid and selective square-wave voltammetric detection of OP vapor threats and wireless data transmission to a mobile device. The epidermal tattoo and textile sensors display a good reproducibility (with RSD of 2.5% and 4.2%, respectively), along with good discrimination against potential interferences and linearity over the 90-300mg/L range, with a sensitivity of 10.7µA∙cm3∙mg-1 (R2 = 0.983) and detection limit of 12mg/L in terms of OP air density. Stress-enduring inks, used for printing the electrode transducers, ensure resilience against mechanical deformations associated with textile and skin-based on-body sensing operations. Theoretical simulations are used to estimate the OP air density over the sensor surface. These fully integrated wearable wireless tattoo and textile-based nerve-agent vapor biosensor systems offer considerable promise for rapid warning regarding personal exposure to OP nerve-agent vapors in variety of decentralized security applications.

Wearable Ring-Based Sensing Platform for Detecting Chemical Threats

This work describes a wireless wearable ring-based multiplexed chemical sensor platform for rapid electrochemical monitoring of explosive and nerve-agent threats in vapor and liquid phases. The ring-based sensor system consists of two parts: a set of printed electrochemical sensors and a miniaturized electronic interface, based on a battery-powered stamp-size potentiostat, for signal processing and wireless transmission of data. A wide range of electrochemical capabilities have thus been fully integrated into a 3D printed compact ring structure, toward performing fast square-wave voltammetry and chronoamperometric analyses, along with interchangeable screen-printed sensing electrodes for the rapid detection of different chemical threats. High analytical performance is demonstrated despite the remarkable miniaturization and integration of the ring system. The attractive capabilities of the wearable sensor ring system have been demonstrated for sensitive and rapid voltammetric and amperometric monitoring of nitroaromatic and peroxide explosives, respectively, along with amperometric biosensing of organophosphate (OP) nerve agents. Such ability of the miniaturized wearable sensor ring platform to simultaneously detect multiple chemical threats in both liquid and vapor phases and alert the wearer of such hazards offers considerable promise for meeting the demands of diverse defense and security scenarios.

Delayed Sensor Activation Based on Transient Coatings: Biofouling Protection in Complex Biofluids

Transient polymeric coatings with a programmable transiency behavior are used for delayed exposure of fresh surfaces of multi-electrode sensor arrays at preselected times. Such delayed sensor actuation is shown to be extremely attractive for addressing severe biofouling characteristic of electrochemical biosensors in complex biofluids. Controlled coating dissolution and tunable sequential actuation of the individual sensing electrodes are achieved by tailoring the characteristics of the coating (density and thickness). The unique features offered by these delayed sensors allowed direct glucose monitoring in untreated blood and saliva samples over prolonged periods. This attractive delayed-sensor exposure concept, offering time-tunable sequential activation of multiple sensors with remarkable anti-biofouling properties, indicates considerable promise for operating sensors continuously in complex body fluids.

Enzymatic glucose/oxygen biofuel cells: Use of oxygen-rich cathodes for operation under severe oxygen-deficit conditions

A glucose/oxygen biofuel cell (BFC) that can operate continuously under oxygen-free conditions is described. The oxygen-deficit limitations of metabolite/oxygen enzymatic BFCs have been addressed by using an oxygen-rich cathode binder material, polychlorotrifluoroethylene (PCTFE), which provides an internal oxygen supply for the BFC reduction reaction. This oxygen-rich cathode component mitigates the potential power loss in oxygen-free medium or during external oxygen fluctuations through internal supply of oxygen, while the bioanode employs glucose oxidase-mediated reactions. The internal oxygen supply leads to a prolonged energy-harvesting in oxygen-free solutions, e.g., maintaining over 90% and 70% of its initial power during 10- and 24-h operations, respectively, in the absence of oxygen. The new strategy holds considerable promise for energy-harvesting and self-powered biosensing applications in oxygen-deficient conditions.

Simultaneous Monitoring of Sweat and Interstitial Fluid Using a Single Wearable Biosensor Platform

Abstract The development of wearable biosensors for continuous noninvasive monitoring of target biomarkers is limited to assays of a single sampled biofluid. An example of simultaneous noninvasive sampling and analysis of two different biofluids using a single wearable epidermal platform is demonstrated here. The concept is successfully realized through sweat stimulation (via transdermal pilocarpine delivery) at an anode, alongside extraction of interstitial fluid (ISF) at a cathode. The system thus allows on‐demand, controlled sampling of the two epidermal biofluids at the same time, at two physically separate locations (on the same flexible platform) containing different electrochemical biosensors for monitoring the corresponding biomarkers. Such a dual biofluid sampling and analysis concept is implemented using a cost‐effective screen‐printing technique with body‐compliant temporary tattoo materials and conformal wireless readout circuits to enable real‐time measurement of biomarkers in the sampled epidermal biofluids. The performance of the developed wearable device is demonstrated by measuring sweat‐alcohol and ISF‐glucose in human subjects consuming food and alcoholic drinks. The different compositions of sweat and ISF with good correlations of their chemical constituents to their blood levels make the developed platform extremely attractive for enhancing the power and scope of next‐generation noninvasive epidermal biosensing systems.