skip to main content


Title: Wearable Organic Electrochemical Transistor Patch for Multiplexed Sensing of Calcium and Ammonium Ions from Human Perspiration
Abstract

Wearable health monitoring has garnered considerable interest from the healthcare industry as an evolutionary alternative to standard practices with the ability to provide rapid, off‐site diagnosis and patient‐monitoring. In particular, sweat‐based wearable biosensors offer a noninvasive route to continuously monitor a variety of biomarkers for a range of physiological conditions. Both the accessibility and wealth of information of sweat make it an ideal target for noninvasive devices that can aid in early diagnosis of disease or to monitor athletic performance. Here, the integration of ammonium (NH4+) and calcium (Ca2+) ion‐selective membranes with a poly(3,4‐ethylenedioxythiophene):poly(styrenesulfonate)‐based (PEDOT:PSS) organic electrochemical transistor (OECT) for multiplexed sensing of NH4+and Ca2+in sweat with high sensitivity and selectivity is reported for the first time. The presented wearable sweat sensor is designed by combining a flexible and stretchable styrene‐ethylene‐butene‐styrene substrate with a laser‐patterned microcapillary channel array for direct sweat acquisition and delivery to the ion‐selective OECT. The resulting dermal sensor exhibits a wide working range between 0.01 × 10−3and 100 × 10−3m, well within the physiological levels of NH4+and Ca2+in sweat. The integrated devices are successfully implemented with both ex situ measurements and on human subjects with real‐time analysis using a wearable sensor assembly.

 
more » « less
Award ID(s):
1804915
NSF-PAR ID:
10458533
Author(s) / Creator(s):
 ;  ;  ;  ;  ;  
Publisher / Repository:
Wiley Blackwell (John Wiley & Sons)
Date Published:
Journal Name:
Advanced Healthcare Materials
Volume:
8
Issue:
24
ISSN:
2192-2640
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. Abstract

    Complex graphene electrode fabrication protocols including conventional chemical vapor deposition and graphene transfer techniques as well as more recent solution‐phase printing and postprint annealing methods have hindered the wide‐scale implementation of electrochemical devices including solid‐state ion‐selective electrodes (ISEs). Herein, a facile graphene ISE fabrication technique that utilizes laser induced graphene (LIG), formed by converting polyimide into graphene by a CO2laser and functionalization with ammonium ion (NH4+) and potassium ion (K+) ion‐selective membranes, is demonstrated. The electrochemical LIG ISEs exhibit a wide sensing range (0.1 × 10−3–150 × 10−3mfor NH4+and 0.3 × 10−3–150 × 10−3mfor K+) with high stability (minimal drop in signal after 3 months of storage) across a wide pH range (3.5–9.0). The LIG ISEs are also able to monitor the concentrations of NH4+and K+in urine samples (29–51% and 17–61% increase for the younger and older patient; respectively, after dehydration induction), which correlate well with conventional hydration status measurements. Hence, these results demonstrate a facile method to perform in‐field ion sensing and are the first steps in creating a protocol for quantifying hydration levels through urine testing in human subjects.

     
    more » « less
  2. Abstract

    Low‐cost biosensors that can rapidly and widely monitor plant nutritional levels will be critical for better understanding plant health and improving precision agriculture decision making. In this work, fully printed ion‐selective organic electrochemical transistors (OECTs) that can detect macronutrient concentrations in whole plant sap are described. Potassium, the most concentrated cation in the majority of plants, is selected as the target analyte as it plays a critical role in plant growth and development. The ion sensors demonstrate high current (170 µA dec−1) and voltage (99 mV dec−1) sensitivity, and a low limit of detection (10 × 10−6 m). These OECT biosensors can be used to determine potassium concentration in raw sap and sap‐like aqueous environments demonstrating a log‐linear response within the expected physiological range of cations in plants. The performance of these printed devices enables their use in high‐throughput plant health monitoring in agricultural and ecological applications.

     
    more » « less
  3. Abstract

    Although increasing efforts have been devoted to the development of non‐invasive wearable electrochemical sweat sensors for monitoring physiological and metabolic information, most of them still suffer from poor stability and specificity over time and fluctuating temperatures. This study reports the design and fabrication of a long‐term stable and highly sensitive flexible electrochemical sensor based on nanocomposite‐modified porous graphene by facile laser treatment for detecting biomarkers such as glucose in sweat. The laser‐reduced and patterned stable conductive nanocomposite on the porous graphene electrode provides the resulting glucose sensor with an excellent sensitivity of 1317.69 µA mm−1cm−2and an ultra‐low limit of detection of 0.079 µm. The sensor can also detect pH and exhibit extraordinary stability to maintain more than 91% sensitivity over 21 days in ambient conditions. Taken together with a temperature sensor based on the same material system, the dual glucose and pH sensor integrated with a flexible microfluidic sweat sampling network further results in accurate continuous on‐body glucose detection calibrated by the simultaneously measured pH and temperature. The low‐cost, highly sensitive, and long‐term stable platform could facilitate the early identification and continuous monitoring of different biomarkers for non‐invasive disease diagnosis and treatment evaluation.

     
    more » « less
  4. Abstract

    This work reports the process of sensor development, optimization, and characterization before the transition to on-body measurements can be made. Sensors using lactate oxidase as a sensing mechanism and tetrathiafulvalene as a mediator were optimized for sporting applications. Optimized sensors show linear range up to 24 mM lactate and sensitivity of 4.8μA/mM which normalizes to 68 μA*cm−2/mM when accounting for surface area of the sensor. The optimized sensors were characterized 3 different ways: using commercially available reference and counter electrodes, using printed reference and counter electrodes, and using a printed reference electrode with no counter electrode. Sensors intended for measuring sweat must be selective in the presence of sweat constituents. Thus, in addition to traditional characterization in pH 7.0 buffer, we characterized sensor performance in solutions intended to approximate sweat. Sensor performance in pH 7.0 buffer solution was not reflective of sensor performance in artificial sweat, indicating that further characterization is necessary between sensor measurement in pH 7.0 buffer and on-body measurements. Furthermore, we performed enzyme activity measurements and sensor measurements concurrently in five different salts individually, finding that while NH4Cl and MgCl2do not affect enzyme activity or sensor performance in physiologically relevant ranges of salt concentration, NaCl concentration or KCl concentration decreases enzyme activity and sensor current. On the other hand, CaCl2induced a nonlinear change in sensor performance and enzyme activity with increasing salt concentration.

     
    more » « less
  5. Wearable sweat biosensors offer compelling opportunities for improved personal health monitoring and non-invasive measurements of key biomarkers. Inexpensive device fabrication methods are necessary for scalable manufacturing of portable, disposable, and flexible sweat sensors. Furthermore, real-time sweat assessment must be analyzed to validate measurement reliability at various sweating rates. Here, we demonstrate a “smart bandage” microfluidic platform for cortisol detection and continuous glucose monitoring integrated with a synthetic skin. The low-cost, laser-cut microfluidic device is composed of an adhesive-based microchannel and solution-processed electrochemical sensors fabricated from inkjet-printed graphene and silver solutions. An antibody-derived cortisol sensor achieved a limit of detection of 10 pM and included a low-voltage electrowetting valve, validating the microfluidic sensor design under typical physiological conditions. To understand effects of perspiration rate on sensor performance, a synthetic skin was developed using soft lithography to mimic human sweat pores and sweating rates. The enzymatic glucose sensor exhibited a range of 0.2 to 1.0 mM, a limit of detection of 10 μM, and reproducible response curves at flow rates of 2.0 μL min −1 and higher when integrated with the synthetic skin, validating its relevance for human health monitoring. These results demonstrate the potential of using printed microfluidic sweat sensors as a low-cost, real-time, multi-diagnostic device for human health monitoring. 
    more » « less