Flexible Screen-printed Electrodes Research Articles

An Overview of Biochar Utilization Strategies for Screen-Printed Electrochemical Sensors

In this review, we address the utilization of biochar, a cost-effective material derived from renewable resources (biomass), for the construction of printable electrochemical devices. Key parameters influencing the final properties of biochar, including pyrolysis temperature, pyrolysis duration, heating rate, and activation treatments, are detailed. The role of biochar in the fabrication of electrochemical (bio)sensors is highlighted with emphasis on advancements in screen-printed electrochemical devices. Furthermore, this review showcases examples of using biochar in the construction of portable and flexible screen-printed electrodes, as well as humidity sensors. Future perspectives and challenges in the field of biochar-based electrochemical sensors and biosensors are also discussed, providing a comprehensive outlook on this promising area of research.

Bio-functionalized conductive poly(acrylic acid):poly(3,4-Ethylenedioxythiophene)-Prussian blue hybrid transducer for biosensors and bioelectronics interfaces

This study presents an innovative organic-inorganic hybrid transducer of poly(acrylic acid) (PAA), poly(3,4-ethylenedioxythiophene) (PEDOT) and Prussian blue (PB) nanocatalysts. The transducer demonstrated functionality conducive to enzyme conjugation and exhibited favorable electrochemical properties for biosensor signal transduction. Fabricated by a one-tube chemical redox method, the PAA:PEDOT-PB transducer showed long-term electrocatalytic and structural stability. The performance of the transducer was characterized by high transduction activity and low charge transfer resistance, particularly for H2O2 reduction. It achieves a linear detection range from 1.0 μM to 4.0 mM, with a sensitivity of 494 ± 10 μA mM−1 cm−1 and a LOD of 0.34 μM. The PAA:PEDOT-PB transducer featured a high density of carboxyl groups (DCOOH = 14.64 ± 0.05 μmol cm−2) that promoted the immobilization of the H2O2-dependent oxidase enzyme lactate oxidase (LOx) with an EDC/S–NHS coupling agent. The LOx-PAA:PEDOT-PB transducer was developed for lactate biosensing. The transducer provided high LOx-enzyme affinity (KMapp = 1.47 ± 0.05 mM), and a rapid response time (10 s) for lactate detection across a concentration range of 5.0 μM to 4.0 mM, showing a sensitivity of 223 ± 3 μA mM−1 cm−1 and an LOD of 1.45 μM. The LOx-PAA:PEDOT-PB transducer was integrated with a flexible screen-printed electrode, incorporating a wireless, battery-free near-field communication potentiostat module to measure lactate in artificial sweat on a skin model via smartphone. The PAA:PEDOT-PB transducer could enable connections with multiple bio-recognition molecules through polycarboxylic acid groups, providing potential avenues for the development of advanced biosensors.

Antifouling and antimicrobial wearable electrochemical sweat sensors for accurate dopamine monitoring based on amyloid albumin composite hydrogels

Wearable electrochemical sweat sensors are potentially promising for health monitoring in a continuous and non-invasive mode with high sensitivity. However, due to the complexity of sweat composition and the growth of skin bacteria, the wearable sweat sensors may gradually lose their sensitivity or even fail over time. To deal with this issue, herein, we proposed a new strategy to construct wearable sweat sensors with antifouling and antimicrobial capabilities. Amyloid albumin hydrogels (ABSAG) were doped with two-dimensional (2D) nanomaterial MXene and CeO2 nanorods to obtain the antifouling and antimicrobial amyloid albumin composite hydrogels (ABSACG, CeO2/MXene/ABSAG), and the wearable sensors were prepared by modifying flexible screen-printed electrodes with the ABSACG. Within this sensing system, the hydrophilic ABSAG possesses strong hydration capability, and it can form a hydration layer on the electrode surface to resist biofouling in sweat. The 2D nanomaterial MXene dispersed in the hydrogel endows the hydrogel with good conductivity and electrocatalytic capability, while the doping of CeO2 nanorods further improves the electrocatalytic performance of the hydrogel and also provides excellent antimicrobial capability. The designed wearable electrochemical sensors based on the ABSACG demonstrated satisfying antifouling and antimicrobial abilities, and they were capable of detecting dopamine accurately in human sweat. It is expected that wearable sensors utilizing the antifouling and antimicrobial ABSACG may find practical applications in human body fluids analysis and health monitoring.

Development of Lab-made Flexible Screen-printed Electrode based on S-Graphene Enriched with AuNPs and CuO for Electrochemical Detection of Tyrosine

Tyrosine (Tyr) is an amino acid that serves as a precursor for the synthesis of numerous neurotransmitters in the human body. This study aimed to design paper-based lab-made screen-printing electrodes (SPE) for tyrosine determination using a flexible electrochemical sensor. To achieve this, conductive inks with this composition were developed for the first time in the literature by incorporating sulfur (S)-doped graphene, synthesized using Yucel’s method, as well as gold nanoparticles and copper oxide (CuO) as conductive fillers, which were then integrated into flexible paper substrates. The optimized electrodes (CuO/S-G/AuNPs/SPE) were used to investigate the best oxidation response to tyrosine. Characterization of CuO/S-G/AuNPs/SPE was performed using electrochemical impedance spectroscopy, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and field emission scanning electron microscopy. The sensor had a limit of detection of 0.024 μM and a limit of quantitation of 0.08 μM. In addition, the sensor’s affordability and ease of use make it advantageous for practical applications. The results demonstrate the sensor’s stability and reproducibility in measuring tyrosine. It is anticipated that the proposed sensor can effectively detect tyrosine in sweat samples and serve as a non-invasive, wearable, flexible sensor in the future.

A nanoplatform-based aptasensor to electrochemically detect epinephrine produced by living cells.

Anovel aptasensor has beendesigned for quantitative monitoring of epinephrine (EP) based on cerium metal-organic framework (CeMOF) loaded gold nanoparticles (AuNPs). The aptamer, specific to EP, is immobilized on a flexible screen-printed electrode modified with AuNPs@CeMOF, enabling highly selective binding to the target biomolecule. Under optimized operational conditions, the peak currents using voltammetric detectionmeasured at voltage of 83mV (vs. Ag/AgCl) for epinephrine exhibit a linear increase within concentration in the range1pM-10nM. Following this detection strategy, a boasted limit of detection of 0.3pM was achieved, surpassing the sensitivity of most reported methods. The developed biosensor showcased exceptional performance in detection ofEP in spiked serum sample, with remarkable recovery range of 95.8-113% and precision reflected by low relative standard deviation (RSD) ranging from 2.23 to 6.19%. These results indicate the potential utility of this biosensor as a valuable clinical diagnostic tool. Furthermore, in vitro experiments were carried out using the presented biosensor to monitor the release of epinephrine from PC12 cells upon extracellular stimulation with K+ ions.

Flexible Miniaturized Electrochemical Sensors Based on Multiwalled Carbon Nanotube-Chitosan Nanomaterial for Determination of Nitrite in Soil Solutions

Flexible screen-printed electrodes (SPE) were modified in a simple manner with different composite nanomaterials based on carbon allotropes, polymers, and metallic nanoparticles, for amperometric detection of nitrites in soil. Multiwalled carbon nanotubes (MWCNT), chitosan (CS), silver nanoparticles (AgNPs), 1,8-diaminonaphthalene (1,8-DAN), and a sol-gel (SG) matrix were used for modification of the carbon paste working electrodes. Sensitive and selective detection of nitrite was achieved by using a MWCNT-CS-modified sensor, in acetate buffer at pH 5, at an applied potential of 0.58 V vs. Ag/AgCl. The MWCNT-CS-based sensor displayed a specific sensitivity of 204.4 mA·M−1·cm−2, with a detection limit of 2.3 µM (S/N = 3) in a linear range up to 1.7 mM, showing good stability, reproducibility, and selectivity towards other interfering species. A miniaturized portable system using the developed flexible electrochemical MWCNT-CS-based sensors was dedicated for the detection of nitrite in different samples of soil solutions extracted by using suction lysimeters.

Fabrication of Hybrid Electrodes by Laser-Induced Forward Transfer for the Detection of Cu2+ Ions

Composites based on poly(3,4-ethylenedioxythiophene): poly(styrene sulfonate) (PEDOT:PSS)-graphene oxide (GO) are increasingly considered for sensing applications. In this work we aim at patterning and prototyping microscale geometries of PEDOT:PSS: GO composites for the modification of commercially available electrochemical sensors. Here, we demonstrate the laser-induced forward transfer of PEDOT:PSS: GO composites, a remarkably simple procedure that allows for the fast and clean transfer of materials with high resolution for a wide range of laser fluences (450-750 mJ/cm2). We show that it is possible to transfer PEDOT:PSS: GO composites at different ratios (i.e., 25:75 %wt and 50:50 %wt) onto flexible screen-printed electrodes. Furthermore, when testing the functionality of the PEDOT:PSS: GO modified electrodes via LIFT, we could see that both the PEDOT:PSS: GO ratio as well as the addition of an intermediate release layer in the LIFT process plays an important role in the electrochemical response. In particular, the ratio of the oxidation peak current to the reduction peak current is almost twice as high for the sensor with a 50:50 %et PEDOT:PSS: GO pixel. This direct transfer methodology provides a path forward for the prototyping and production of polymer: graphene oxide composite based devices.

Flexible electrochemical sensor for highly sensitive and selective non-enzymatic detection of creatinine via electrodeposited copper over polymelamine formaldehyde.

A non-enzymatic electrochemical biosensor was developed for highly sensitive detection of creatinine using copper nanoparticles supported over polymelamine formaldehyde. The synergy between the electrodeposited copper nanoparticles over the highly porous polymer (eCu-PMF) provided a greener platform to boost up the electron transport at the electrode electrolyte interface by eliminating the role of redox species as well as interference of major interferents like glucose, dopamine, and ascorbic acid in physiological media 0.1 M PBS (pH 7.4). The proposed sensor exhibited a wide detection range of 100 fM-60 mM with high sensitivities of 0.320 mA nM-1 cm-2 and 3.8 mA nM-1 cm-2. Moreover, the sensor was applied to real samples of serum creatinine and recoveries of 97 to 114% were found. Additionally, a paper-based flexible screen-printed electrode was fabricated which displayed an excellent activity with the same detection range of 100 fM-60 mM and long-term storage stability of 15 days.

A Flexible Iontronic Capacitive Sensing Array for Hand Gesture Recognition Using Deep Convolutional Neural Networks.

Hand gesture recognition, one of the most popular research topics in human-machine interaction, is extensively used in visual and augmented reality, sign language translation, prosthesis control, and so on. To improve the flexibility and interactivity of wearable gesture sensing interfaces, flexible electronic systems for gesture recognition have been widely studied. However, these systems are limited in terms of wearability, stability, scalability, and robustness. Herein, we report a flexible wearable hand gesture recognition system that is based on an iontronic capacitive pressure sensing array and deep convolutional neural networks. The entire capacitive array is integrated into a flexible silicone wristband and can be comfortably and conveniently wrapped around the wrist. The pressure sensing array, which is composed of an iontronic film sandwiched between two flexible screen-printed electrode arrays, exhibits a high sensitivity (775.8 kPa-1), fast response time (65 ms), and high durability (over 6000 cycles). Image processing techniques and deep convolutional neural networks are applied for sensor signal feature extraction and hand gesture recognition. Several contexts such as intertrial test (average accuracy of 99.9%), intersession rewearing (average accuracy of 93.2%), electrode shift (average accuracy of 83.2%), and different arm positions during measurement (average accuracy of 93.1%) are evaluated.

A Flexible Dual-Analyte Electrochemical Biosensor for Salivary Glucose and Lactate Detection.

Electrochemical biosensors have been widely applied in the development of metabolite detection systems for disease management. However, conventional intravenous and fingertip blood tests are invasive and cannot track dynamic trends of multiple metabolites. Among various body fluids, saliva can be easily accessed and is regarded as a promising candidate for non-invasive metabolite detection. Recent works on the development of electrochemical biosensors for monitoring salivary metabolites have demonstrated high sensitivity and wide linear range. However, most of this research has been focused on salivary detection of a single metabolite. Here, we present a dual-channel electrochemical biosensor for simultaneous detection of lactate and glucose in saliva based on a flexible screen-printed electrode with two working electrodes. The sensitivities of glucose and lactate channels were 18.7 μA/(mM·cm2) and 21.8 μA/(mM·cm2), respectively. The dual-channel biosensor exhibited wide linear ranges of 0–1500 μM for the glucose channel and 0–2000 μM for the lactate channel and the cross-talk between the two detection channels was negligible, which made it adequately suitable for sensing low-level salivary metabolites. Such attractive characteristics demonstrate the potential of this dual-analyte biosensor in the development of wearable devices for monitoring disease progression and fitness.

A flexible electrochemical biosensor based on functionalized poly(3,4-ethylenedioxythiophene) film to detect lactate in sweat of the human body

Conductive polymers with good flexibility, conductivity and film-forming ability attract a lot of attention. In this work, a large-area and ordered structure poly(3,4-ethylenedioxythiophene) (PEDOT) film is fabricated at the air-water interface through interface synthesis method. The PEDOT film can be directly placed on a flexible screen-printed electrode, but also has good adhesion between them. The surface of the PEDOT film is relatively smooth, and has good electrical conductivity and flexibility. Lactate oxidase is immobilized on the surface of PEDOT film through a combination of cross-linking and adsorption method to enhance the lactate sensitive performances. The results show that the PEDOT film sensor has excellent stability and reproducibility. The PEDOT film sensor shows a good response to lactate, the working range is 0.25–40 mmol L−1, and the detection limit is 0.083 mmol L−1 (S/N = 3). Moreover, the electrochemical sensor has potential application in detecting lactate in sweat of the human body.

Fully-printed electrochemical sensors made with flexible screen-printed electrodes modified by roll-to-roll slot-die coating

The manufacture of sensors using large-scale production techniques, such as roll-to-roll (R2R) processing, may fulfill requirements of low-cost disposable devices. Herein, we report the fabrication of fully-printed electrochemical sensors using screen-printed carbon electrodes coated with carbon black inks through slot-die coating within an R2R process. As a proof of concept, sensors were produced to detect the neurotransmitter dopamine with high reproducibility and low limit of detection (0.09 μmol L−1). Furthermore, fully-printed biosensors made with a tyrosinase-containing ink were used to detect catechol in natural water samples. Since slot-die deposition enables printing enzymes without significant activity loss, the biosensors exhibited high stability over a period of several weeks. Even more important, R2R slot-die coating may be extended to any type of sensors and biosensors with the possibility of large-scale manufacturing.

Sensor system based on flexible screen-printed electrodes for electrochemical detection of okadaic acid in seawater

The monitoring of marine dinophysistoxin okadaic acid in seawater can serve as an early alert system for preventing the potential negative effects this toxin can have on the food industry and human health in general. A disposable sensor system for electrochemical detection of this toxin has been developed using screen-printed electrodes. The method described is based on the inhibition of protein phosphatase type 2A by okadaic acid, evaluating the enzyme activity. p-Nitrophenyl phosphate, 4-methylumbelliferyl phosphate and phenyl phosphate have been tested as substrates achieving good limits of detection of 2.7·10–12 M of okadaic acid. The proposed method has been successfully applied to okadaic acid determination in seawater samples. A study of divalent cations present in seawater that can interfere with the measurement has been carried out. The electrode systems were printed on both rigid and textile backing materials to observe the influence of those materials on the final performance of the sensor.

3D Printed Microfluidic Device with Microporous Mn2O3-Modified Screen Printed Electrode for Real-Time Determination of Heavy Metal Ions.

Fabricating portable devices for the determination of heavy metal ions is an ongoing challenge. Here, a 3D printing approach was adopted to fabricate a microfluidic electrochemical sensor with the desired shape in which the model for velocity profiles in microfluidic cells was built and optimized by the finite element method (FEM). The electrode in the microfluidic cell was a flexible screen-printed electrode (SPE) modified with porous Mn2O3 derived from manganese containing metal-organic framework (Mn-MOF). The microfluidic device presented superior electrochemical detection properties toward heavy metal ions. The calibration curves at the modified SPE for Cd(II) and Pb(II) covered two linear ranges varying from 0.5 to 8 and 10 to 100 μg L-1, respectively. The limits of detection were estimated to be 0.5 μg L-1 for Cd(II) and 0.2 μg L-1 for Pb(II), which were accordingly about 6 and 50 times lower than the guideline values proposed by the World Health Organization. Furthermore, the microfluidic device was connected to iPad via a USB to enable real-time household applications. Additionally, the sensing system exhibited a better stability and reproducibility compared with traditional detecting system which offered a promising prospect for the detection of heavy metal ions especially in household and resource-limited occasions.

A novel procedure for fabricating flexible screen-printed electrodes with improved electrochemical performance

Screen-printed electrodes (SPEs) with improved electrochemical performance were fabricated in this study. The SPEs on hydrophilic surface of polyethylene ethylene terephthalate (PET) film showed better electrochemical behaviour than that on hydrophobic surface. The optimal condition of pretreating fresh SPEs was that alternately dealt with chemical treatment (soaked in 3M NaOH solutions for 1h) and high temperature curing (heated at 120 °C for 15 min) for two times. After chemical treatment, the electrochemical performance of self-made SPEs was better than the commercial three electrodes system. By analyzing cyclic voltammetry (CV) curves, we found that the oxidation peak currents and peak to peak separation reached 407.65 μA and 111.16 mV, which mean the sensitivity and electron transfer rate improved 1.9 times and 3.8 times compared with fresh SPEs, and 2 times and 3 times compared with commercial DropSens (DS) electrodes. The obtained SPEs were stable, convenient and inexpensive, which could be extensively applied for developing novel electrochemical sensors.

Amperometric Hydrogen Peroxide Biosensor Based on Horseradish Peroxidase Entrapped in Titania Sol-Gel Film on Screen-Printed Electrode

We report the fabrication of disposable and flexible Screen-Printed Electrodes (SPEs). This new type of screen-printed electrochemical platform consists of Ag nanoparticles (AgNPs) and graphite composite. For this purpose, silver nanoparticles were first synthesized by a chemical reduction method. The morphology and structure of the AgNPs were analyzed using a Scanning Electron Microscope (SEM) and UV-Visible spectroscopy. Graphite was chosen as the working electrode material for the fabrication of a thick-film. The fabrication of a screen-printed hydrogen peroxide biosensor consisting of three electrodes on a polyethylene terephthalate (PET) substrate was performed with a spraying approach (working, counter and reference: enzyme electrode, graphite, pseudo reference: Ag/AgCl). This biosensor was fabricated by immobilizing the peroxidase enzyme (HRP) in a Titania sol-gel membrane which was obtained through a vapor deposition method. The biosensor had electrocatalytic activity in the reduction of H2O2 with linear dependence on H2O2 concentration in the range of 10－5 to 10－3 M; the detection limit was 4.5 × 10－6 M.

Strip-based amperometric detection of myeloperoxidase

The development of a screen-printed strip-based amperometric biosensor for the determination of myeloperoxidase (MPO) levels is reported. The biosensor utilizes 3,3′,5,5′-tetramethylbenzidine (TMB) as a redox mediator to enable high-sensitivity quantification of physiological levels of MPO. A multivariate parameter optimization was performed. Under the optimal conditions, physiological levels of MPO between 3 and 18 U/L were detected in both acetate buffer (pH 4.5) and human serum using flexible screen-printed electrodes (SPE). The potential interference generated by common serum-based electroactive compounds and a similar peroxidase enzyme was also investigated. The proposed detection methodology offers a simpler, more rapid, and cost-effective alternative to conventional MPO immunoassays, thereby leading to further development in point-of-care testing of acute cardiac events.

Flexible thick-film electrochemical sensors: Impact of mechanical bending and stress on the electrochemical behavior

The influence of the mechanical bending, rolling and crimping of flexible screen-printed electrodes upon their electrical properties and electrochemical behavior has been elucidated. Three different flexible plastic substrates, Mylar, polyethylene naphthalate (PEN), and Kapton, have been tested in connection to the printing of graphite ink working electrodes. Our data indicate that flexible printed electrodes can be bent to extremely small radii of curvature and still function well, despite a marginal increase the electrical resistance. Below critical radii of curvature of ∼8 mm, full recovery of the electrical resistance occurs upon strain release. The electrochemical response is maintained for sub-mm bending radii and a 180° pinch of the electrode does not lead to device failure. The electrodes appear to be resistant to repeated bending. Such capabilities are demonstrated using model compounds, including ferrocyanide, trinitrotoluene (TNT) and nitronaphthalene (NN). These printed electrodes hold great promise for widespread applications requiring flexible, yet robust non-planar sensing devices.