Recent Advances in Disposable Electrochemical Sensors

Recent Advances in Disposable Electrochemical Sensors

  • Manjushree S. G.
    Manjushree S. G.
    Department of Chemistry, Siddaganga Institute of Technology, Tumkur–572103, Karnataka, India
  •  and 
  • Prashanth S. Adarakatti*
    Prashanth S. Adarakatti
    Department of Chemistry, SVM Arts, Science and Commerce College, Ilkal–587125, India, affiliated to Rani Channamma University, Belagavi, Karnataka, India
    *Email: [email protected]
DOI: 10.1021/bk-2023-1437.ch001
  • Free to Read
Publication Date (Web):February 16, 2023
Copyright © 2023 American Chemical Society. This publication is available under these Terms of Use.
Recent Developments in Green Electrochemical Sensors: Design, Performance, and Applications
Chapter 1pp 1-21
ACS Symposium SeriesVol. 1437
ISBN13: 9780841297227eISBN: 9780841297210

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Abstract

Disposable sensors are becoming increasingly used in the healthcare industry for quick and affordable biomarker screening and monitoring. The electrochemical detection technique makes it simple to scale up and miniaturize inexpensive disposable sensors, can be employed for accurate biomarker measurement at or close to the patient site. The paper-based analytic tools make it easier to sample in situ, search for biomarkers, and detect them multiplexedly. This chapter describes the high-throughput fabrication methods used to create disposable electrodes, such as paper based electrodes, screen-printing, ink jet printing, and laser induced printing, and goes into detail on how they can be utilized for various enzymatic, nonenzymatic, and aptamer-based sensing. The effectiveness of nanostructured materials in enhancing electrochemical sensor performance is outlined. Additionally, current innovations in hybrid wearable devices capable of sensing various analytes.

This publication is licensed for personal use by The American Chemical Society.

1 Introduction

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Anything might be disposable. For many years, the main determinant of disposability has been the question of economic viability. It is currently, however, more closely related to environmental sustainability. This is valid for sensors used in biomedical, industrial, and environmental sensing applications. Disposability often requires that devices be created from small amounts of extremely inexpensive materials that can be produced quickly in huge quantities and are also becoming more and more biodegradable. The most effective commercial breakthroughs in sensors, particularly in the treatment of diabetes (glucose sensing strips) and reproductive health (pregnancy tests), have been largely driven by the capacity to attain extremely low unit prices at extremely high manufacturing volumes.
Despite the fact that no other market has come close to matching the size of the glucose sensing industry, numerous emerging electrochemical sensing technologies frequently use the same concepts of low cost, large quantity fabrication to increase their market potential. As a result, the discipline of developing electrochemical sensors continues to be characterized by research, development, and design ideas that allow disposability. This has an impact on the types of fabrication materials utilized, the processing techniques that may be employed on them, and the types of applications that they are most effectively used for. The development in functional complexity, which is now possible with rising material and production simplicity and affordability, is another important aspect. All of these extra needs must be met while still preserving, enhancing, and extending the devices’ analytic capabilities ( 1).
Because of the enhanced sensitivity with low contact resistance, silicon sensors quickly gained popularity after semiconducting sensors were first introduced almost 20 years ago ( 2), However, these have some drawbacks, like more cost for fabrication, more input power, and less reliability, which promoted researchers to look for substitutes. Flexible sensors ( 3) have grown in popularity as an alternative to rigid sensors because of their improved electrical, mechanical, and thermal properties. The choice to use a processing material is dependent on whether its properties are appropriate for a given application, despite the fact that some polymeric materials have disadvantages in their mechanical and chemical properties. For instance, because of its strong heat and wear resistance, polyimide is frequently chosen in settings involving high temperatures and abrasive conditions, but polydimethylsiloxane (PDMS) is suited in conditions that profit from its hydrophobicity and biocompatibility. Although polymeric materials have significant drawbacks, such as cracking and chemical inertness, the sensors designed for use in healthcare and applications that operate at room temperature outperform their comparable rigid counterparts. As a result, the development of flexible sensors has concentrated on identifying and evaluating these characteristics in a variety of applications. Furthermore, researchers have been employed a variety of polymers to create the substrates, choosing them based on their Young’s modulus, ability to create composites, interfacial bonding with nanofillers, biocompatibility, hydrophobic nature, and resilience to temperature fluctuations. Some of the common substrates employed for forming flexible sensors are polydimethylsiloxane (PDMS) ( 4), polyethylene terephthalate (PET) ( 5) and polyimide (PI) ( 6). The characteristics of the conductive materials must be taken into consideration when producing the sensors’ electrodes, much like with the substrates. The electrodes for flexible sensors are frequently made of poly(3,4-ethylenedioxythiophene) and polystyrene sulfonate (PEDOT: PSS) ( 7), carbon nanotubes (CNTs) ( 8), silver ( 9), gold ( 10), copper ( 11), aluminum ( 12), and graphene ( 13). These conductive materials have been applied as nanoparticles, nanowires, nanopowder, and quantum dots among other forms ( 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28). The conjugation of these polymers and conductive materials are processed with different kinds of fabrication techniques ( 29) to form the sensors. The required dimensions, repeatability, flexibility, stretchability, efficiency in terms of sensitivity, and if it is designed to work in harsh environment are some of the characteristics that determine a sensor’s fabrication technique. Printing technology has been one of these methods that researchers have used regularly recently since printed flexible prototypes have greatly improved properties. Ultrathin, light, and highly conductive sensors may be made quickly and in huge quantities using printing technology. One common method of processing substrates and electrodes with a laser in printing technology is laser cutting. Depending on their unique properties, many laser types have been used to process the sensing prototypes. Prior to being refined recently, laser cutting could only be used on glass, metal, and ceramic materials. It is now also capable of cutting polymeric substrates and electrodes made of nanoparticles. To accurately tune the features of the produced sensor prototypes, the number of parameters has also been expanded. Prior to being refined recently, laser cutting could only be used on glass, metal, and ceramic materials. It is now also capable of cutting polymeric substrates and electrodes made of nanoparticles ( 30). Due to the lack of a need for a mask or template to create the electrode design, laser cutting has a greater value within the noncontact printing category. Additionally, the surface tension and shadow effects of the printed inks on the flexible substrates are prevented in this way. Researchers are working to create laser-printed flexible circuit boards, where — along with the sensors — the full signal conditioning circuit is generated via laser printing. This is being done because of the advantages of laser cutting ( 31).

2 Types of Electrodes

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Due to their wide potential window, minimal background current, low cost, chemical inertness, and appropriateness for a variety of sensing applications, carbon-based solid electrodes are currently used extensively in electroanalysis. The following discussion covers the characteristics of various carbon electrode types.

2.1 Glassy Carbon Electrode

A type of carbon known as glassy carbon is produced by carefully controlling the thermal degradation of polymeric resins, such as polyacrylonitrile or phenol/formaldehyde, at high temperatures, or between 1000 and 3000 °C. It is more resilient and durable than graphite because of the ribbon-like structure in which the graphitic sheets are cross-linked ( 32). It has the benefit of having outstanding mechanical and electrical qualities and often a large working potential window including both anodic and cathodic processes, making it one of the most commonly employed electrochemical devices in electroanalytical chemistry. The surface morphology of GCE, which is linked to surface pretreatment techniques, is widely acknowledged to play a major role in the electron transfer reactions on its surface ( 33).
Numerous processing techniques, including chemical, electrochemical, thermal, and laser irradiation, were described in the literature. The most popular and widely used approach, in addition to these methods, is mechanically polishing the surface with an alumina slurry of various particle sizes until it resembles a shiny mirror, accompanied by ultrasonic treatment in demineralized water or cyclohexane. It is possible to attribute the increased electron transport to the fresh surface being exposed and contaminants being removed ( 34).

2.2 Carbon Paste Electrodes

The main components of carbon paste electrodes are graphite powder and binders like organic solvents like Nujol, mineral oil, paraffin oil, silicone grease, and bromonaphthalene. In electroanalysis, the carbon paste electrodes (CPEs) provide easily reusable surfaces at low cost and with minimal background current. A modifier substance, graphite powder, and binder material can also be combined to create CPEs, which serve as working electrodes for electrochemical measurements. Although these electrodes are advantageous in terms of surface renewability, their stability is compromised by the ongoing draining of modifier particles during extended measurement. Additionally, the availability of a binder impairs the electrode kinetics, which would in turn reduces their suitability for long-term use, storage, and reliability ( 35).

2.3 Basal and Edge Plane Pyrolytic Graphite Electrodes

Pyrolytic graphite is an electrode material which has both basal plane and edge plane interfaces; the size of the graphite nanocrystals as well as the basal/edge ratios rely upon that caliber of the pyrolytic graphite utilized ( 36). The basal plane surface of highly ordered pyrolytic graphite (HOPG) electrodes ((Figure 1)) is composed of layers of graphite that are spaced 3.35 Å apart and parallel to the surface ( 37). Steps that reveal the borders of the graphite layers are a type of surface imperfection. The two planes, edge and basal, might display entirely distinct electrochemical properties because of the type of chemical bonding in graphite. It has been discovered that the electron-transfer rate constants at edge plane graphite are over 103 times faster than for basal plane graphite for a wide range of redox couples. In contrast to electrodes made of glassy carbon, boron-doped diamond, basal plane pyrolytic graphite, or basal plane pyrolytic graphite enhanced with carbon nanotubes, the edge plane pyrolytic graphite electrode produces low background currents and superior electrocatalytic signals ( 38).

Figure 1

Figure 1. Various types of electrodes and their structures used for modification in sensing applications.
Adapted with permission from ref. ( 36). Copyright 2019 Royal Society of Chemistry.

2.4 Disposable Electrodes

In the discipline of electroanalysis, screen-printed electrodes (SPEs) have been widely used. Working, counter, and reference electrodes are the three electrodes that make up a SPE. The fact that all three electrodes were printed on a single strip allows a large potential window, quick fabrication at a low cost, and assessment with a small sample size. For the creation of reference, counter, and working electrodes, a variety of commercially available inks may also be used to produce the target-specific electrodes. SPEs additionally offer the benefit of being single-use disposable sensor strips and do not frequently need the electrode surface to be polished or smoothened, unlike more traditional solid electrodes ( 39). (Figure 1) illustrates the many procedures required in building SPEs. The thixotropic fluid, which contains graphite, carbon black, solvents, and polymeric binder, is printed through a mesh screen during the constriction of SPEs. The preceding step determines the size and shape of the manufactured electrode. For building, ceramic and plastic substrate materials are two different types that can be used. It was discovered that plastic components were less expensive, and that carbon ink sticks well to plastic surfaces rather than ceramic surfaces ( 40). Various types of disposable sensors and their fabrication techniques have been discussed below.

2.4.1 Paper-Based Disposable Electrochemical Sensors (PES) for Point-of-Care Testing

The user has access to a number of paper materials, but the decision is primarily determined by the manufacturing stages necessary to produce a device and by the particular application area. Due to its capacity to wick liquid, filter paper has been widely used in the creation of sensors and microfluidic technologies in recent years ( 41). The Whatman® cellulose range is especially well-liked, and the key characteristics that distinguish the various varieties of filter paper are porosity, particle retention, and flow rate. Whatman® filter paper No. 1, a standard grade filter paper with medium retention and flow rate, was used in the work of several groups ( 41). However, Li, et al. ( 42) employed Whatman® No. 4 filter paper and coated it with a cellulose hydrophobisation agent as a basis for etch printing of hydrophilic channels to maximize liquid penetration. Because the solvent-induced swelling of the cellulose fibers can constrict the capillary pores and prevent liquid penetration, this form of filter paper has bigger holes than the ordinary grade.
Despite its widespread use, filter paper occasionally lacks the desired physical properties, hence different types of paper or paper modifications have been investigated. For instance, hydrophobic nitrocellulose membranes are well suited for immobilizing enzymes, proteins, and DNA due to their high level of nonspecific binding toward biomolecules. To build a paper-based sensor, Lu, et al. ( 43, 44) studied the use of a nitrocellulose membrane as the substrate, first creating a wax barrier on the membrane via printing and heating, then depositing an enzyme for a colorimetric assay. Wax penetration is slower than with filter paper, despite the smoothness and relatively uniform pore size (0.45 μm) of nitrocellulose membranes, which leads to a more stable and repeatable liquid flow within the paper. Utilizing cellulose fibers that have undergone chemical modification is another possibility to investigate. Ion exchange cellulose papers and composite papers made of cellulose and polyester are readily accessible on the market.
Other forms of paper, such as glossy paper, have been described as a viable platform in sensor technologies instead of filter paper as the principal material to develop paper-based sensing devices. Glossy paper is a flexible substrate comprised of inorganic filler and cellulose fiber. Glossy paper was utilized by Arena, et al. ( 45) to create a flexible paper-based sensor for the detection of ethanol using multiwaled carbon nanotubes as electrodes and indium tin oxide nanoparticulate powder as a sensing material. Glossy paper is a good alternative to filter paper since it is nondegradable and has a surface that is generally smooth, especially when it is necessary to adjust nanomaterials on the surface rather than within the fiber matrix.
On a variety of paper substrates, electrodes can be created using a wide range of conducting inks, from carbon, the most basic electrode, to various metallic and nanostructured materials. Given their availability, stability, and cost considerations, silver/silver chloride ink is frequently used to fabricate working and counter electrodes, while carbon-based electrodes can be modified with a variety of synthetic or naturally occurring/biologically derived chemicals for the reference electrode ( 46). In this article, we discuss screen printing, which has lately gained popularity among other electrode fabrication methods such as pencil/lead drawing, stencil printing, inkjet printing, and microwire placement that have been tested for PESs and supplied with examples.
Dungchai, and his colleagues ( 47) presented the first screen-printed electrodes (SPEs) method of electrode manufacturing on paper for PESs for the simultaneous detection of glucose, lactate, and uric acid (UA), which was a milestone for PESs. In this particular ground-breaking study, hydrophobic patterns were created using photolithography on Whatman® Grade 1 filter paper, and electrodes were screen-printed there. The working and counter electrodes were prepared from carbon ink having Prussian Blue, and the reference electrode wasprepared from Ag/AgCl ink. The carbon paste that acts as a catalyst for hydrogen-peroxide reduction was doped with a modest amount of Prussian Blue (PB). To reduce current resistance in the circuit, the counter electrode’s shape was created to be larger than the working and reference electrodes. Using glucose oxidase, lactate oxidase, and uricase solutions, respectively, along with potassium phosphate as a buffer solution and Prussian Blue as a mediator, each test zone was spotted with a different enzyme for the specific analytes (glucose, lactate, and UA) in order to detect the analytes through the reduction of hydrogen peroxide that is produced by the enzymatic reaction. More specifically, the oxidase enzyme catalyzes the oxidation of the analyte in the presence of oxygen to generate H2O2, which is subsequently reduced and quantified using chronoamperometry at the interface of the working electrode. Finally, under ideal experimental conditions, this electrochemical detection system was successfully evaluated for the simultaneous measurement of the target analytes from undiluted serum samples employing oxidase enzymes.

2.4.2 Screen-Printed Disposable Sensors

The process of screen-printing is now well known as a dependable way to create electrochemical sensors and biosensors. Numerous research facilities have created prototype devices and used them in numerous application fields. The personal glucose biosensor, which is frequently used by diabetics, is a prime example of the potential of this fabrication technique for the creation of commercial devices. This product has a sizable market, which has led to several further endeavors in numerous different fields.
Thick-film technology has been around since SPEs’ inception, and it is used in their production. It is widely believed that it originated in China and left marks on both the Great Wall of China and the designs of ancient Egyptian textiles. Researchers have used the screen-printing method to build electrode devices on a variety of substrates to address the expanding demand for dependable, stable, and disposable electrode devices that are suitable for mass production. SPEs typically consist of an inert substrate with three electrode systems printed on it: the working electrode (WE), reference electrode (RE), and counter electrode (CE). The electrode produced using the screen-printing approach has therefore aroused the interest of many researchers. There is a long history of using screen-printing to create many types of sensors. Three to four processes make up the entire fabrication process: creating the screen-printed electrode, designing its surface, and applying it to sensing. In the process of screen printing, ink or paste is squeezed onto the surface of the substrate and then printed onto a solid surface. The ink composition, curing temperature, pretreatment methods, and surface roughness are just a few of the factors that affect the sensor’s sensitivity and selectivity, as recently documented for thick-film technology ( 48).
Enzymes are the biological components that are most frequently utilized in the creation of biosensors, despite the high costs associated with their extraction, separation, and purification. This is because they quickly and thoroughly form selective connections with the substrate. Proteins called enzymes (polypeptide structures) catalyze particular chemical reactions in living organisms. They speed up certain chemical reactions in particular. The earliest biocatalysts used in biosensors were enzymes, which are still by far the most often used today. The discovery that an enzyme might be inserted into an electrode to create a biosensor for the measurement of glucose was made by pioneers Clark and Lyons ( 49). Since then, building biosensors has made great use of enzymes.
A crucial characteristic that can be used in biosensor technology is enzyme specificity. Because of the restrictions the active site environment places on the substrate molecule, enzymes exhibit a substantially higher level of substrate selectivity when compared to chemical catalysts. The molecular size, stereochemistry, polarity, functional groups, and relative bond energies are among the elements that have a role in this fact. Disposable biosensors based on enzyme immobilization on SPEs have been widely used for the analysis of several analytes.
It is the most popular recognition system in which a single or many enzymes are immobilized in a thin layer at the surface of the transducer using various immobilization methods. This immobilized enzyme used the substrate or analyte and any cosubstrates it encountered to produce the desired product. The next step is to determine the biosensor response by either monitoring cosubstrate consumption or product yield. This is called Direct monitoring of analytes as reported in determination of glucose ( 50), cholesterol ( 51), Urea ( 52, 53), and organophosphate pesticides ( 54). Although these biosensors offer the benefits of being straightforward, portable, and configured for continuous operation, they have certain drawbacks when used for environmental monitoring. The few environmental contaminants that can serve as the enzyme’s substrate and the high detection limits are the main limitations.
If an enzyme is immobilized, indirect monitoring refers to the evaluation of substances or inhibitors that specifically interact with it and reduce its biocatalytic abilities. These inhibitors further obstruct enzymatic processes by attaching to the enzyme or the enzyme—substrate complex. Indirect monitoring has the advantage that most enzymes are sensitive to relatively low concentrations of inhibitors, increasing the sensitivity of the biosensor. The inclusion of other forms of inhibitors in the assay sample, however, may impede the enzyme activity and lead to unexpected results. These kinds of biosensors also need a substrate in addition to the analyte to be tested, which complicates the biosensor’s overall design. Reversible inhibition of an enzyme occurs when the binding of an inhibitor can be undone by lowering the inhibitor concentration, whereas irreversible inhibition occurs when the binding of the inhibitor leads in permanent inhibition of enzyme activity.
Theoretically, nonenzymatic (or enzyme-free) disposable electrochemical sensors are based on the reaction of an analyte catalysed by the electrode or electrode material itself, which facilitates rapid electron transfer kinetics at a lower voltage than that of a normal electrode material. For instance, the potential at 0.2–0.6 V (depending on the kind of catalyst) was adequate for most nonenzymatic transducers ( 54), whereas the oxidation of glucose at GCE in alkaline medium needed the potential of approx. 1.0–1.4 V to obtain a noticeable anodic peak ( 55). There have been studies on a wide range of electrocatalysts for nonenzymatic disposable sensors, including metals, metal composites, metal oxides, nanocarbon, and its derivatives.
The electrocatalytic process for transition metals involves the analyte being adsorbed onto the electrode surface, a bond being broken, and the product then going through desorption. Among the several analyte species, glucose has received the most attention thanks to two electrocatalytic model mechanisms that have been put forth. The first model, as proposed by Pletcher ( 56), primarily relies on active chemisorption. However, this model fails to consider the oxidative activity of hydroxyl radicals, which has been demonstrated in numerous studies ( 57) and is responsible for the electro-oxidation of organic compounds like glucose at adsorbed hydroxyl groups (OHads). As a result Burke ( 58) subsequently presented the “Incipient Hydrous Oxide Adatom Mediator” hypothesis (IHOAM).
Bioanalytical tests, such as immunoassays (IAs), which rely on particular antigen—antibody complexation, are crucial in a variety of sectors, including forensic science, drug and pesticide testing, biological and medical research, and diagnostic medicine. In contrast to their optical counterparts, IAs with electrochemical detection can provide improved sensitivities and lower instrumentation costs. Over the past decade, more and more efforts have been made to connect the specificity of bioaffinity assays with the sensitivity and low detection limits provided by contemporary electrochemical techniques. For the creation of portable instruments that may be used for point-of-care evaluations, Warsinke, et al. ( 59) have previously demonstrated electrochemical IAs as promising alternatives to currently available immunochemical testing. In this way, SPE helps to create economical, dependable, easy-to-handle IAs devices that may produce results in only a few minutes. Because their interaction is only accompanied by minor physico-chemical changes, antigen or antibody labeling is necessary for electrochemical immunosensing. When Yalow and Berson created the first radioimmunoassay using a radioactive substance as a label in 1956, labels were first used. The best enzyme labels, according to research, include peroxidases, phosphatases, ureases, and glucose oxidases. Similarly, IAs have been used to apply fluorophors, redox chemicals, cofactors, fluorescence quenchers, chemiluminescence metals, latex particles, and liposomes. Here, we review current works in IAs based on SPEs with an emphasis on the final analytic use.

3 Indirect Electrochemical Immunoassays

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Comparatively, using portable instruments and estradiol-ALP, Volpe et al. establish a low-cost, single-use electrochemical immunosensor for a quick and easy assessment of picogram levels of 17-estradiol in nonextracted bovine serum ( 60).
To measure the hormone human chorionic gonadotropin, Bagel, et al. created a disposable electrochemical sensor based on an ion exchange film-coated SPE fitted to the bottom of a polystyrene micro well. In this instance, the monoester phosphate salt of [(4-hydroxyphenyl) amino carbonyl]-cobaltocenium was hydrolyzed using the ALP label. This anionic substrate is converted into a cationic electroactive product, which is subsequently collected at the electrode surface by ion exchange to produce an intensified electrochemical reaction ( 61).
Disposable screen-printed gold electrodes are used in an electrochemical genosensor that can identify certain DNA sequences. Using a streptavidin-ALP conjugate and biotinylated target sequences, an enzyme-amplified detection method was used. Alpha-naphthyl phosphate was hydrolyzed by the enzyme into alphanaphthol, which is electroactive and detectable by DPV. The findings demonstrated that the genosensor enabled sensitive and accurate detection of GMO-related sequences, making it a valuable tool for the investigation of bioengineered food samples during screening ( 62).
Salmonella-specific antibodies found in patient serum warrant special consideration. To find S. Typhi antibodies, an indirect ELISA (enzyme-linked immunosorbant test) was performed. The capacity of these electrodes to detect 1-naphthol, a by-product of the hydrolysis of the substrate 1-naphthyl phosphate by the enzyme ALP, was investigated. These electrodes were blocked with BSA and coated with recombinant flagellin fusion protein created by recombinant DNA technology. Additionally, patient serum and goat anti-human ALP conjugate were added to the incubation process. Amperometric technology was used for the immunosensing ( 63).
The approach created by Keay and McNeil ( 64) and Grennan, et al. ( 65) is used to detect atrazine. The first uses a competitive ELISA using single-use atrazine immune membranes and disposable screen-printed HRP modified electrodes as the detector element. Recombinant single-chain antibody fragments and a conductive polymer are used by Grennan to create a direct mediator-less interaction between the electrode surface and the redox centers of antigen-labeled HRP.

3.1 Direct Electrochemical Immunoassays

As noted above, most of the literature on the creation of electrochemical immunosensors describes systems based on the employment of enzyme labels that necessitate modifying antigen/antibody activity. Additionally, reports on labeless detection have begun to appear.
Due to the magnitude of food pathogens, labeling are not necessary in this situation ( 66). The measurement of a redox probe’s diffusion serves as the foundation for this immunosensor. To quantify the diffusion of a potassium hexacyanoferrate redox probe after antibody immobilization, the diffusion coefficient (D) was computed both before and after the addition of the analyte. Chronocoulometry was used to determine how the diffusion coefficient of the redox probe changed because of the creation of the bacteria-antibody immunocomplex, which creates a barrier for interfacial electron transfer. Diffusion coefficient and the quantity of analyte introduced were found to be linearly related.

3.2 Ink-Jet Printed Disposable Sensors

A fast developing method for direct patterning using material deposition based on a layout created in software is inkjet printing, which first appeared in the 1970s. A print head carrying an ink-filled cartridge swings back and forth horizontally during the inkjet printing process, firing small ink droplets through a nozzle head with a diameter of a few micrometers ( 67). The materials that need to be deposited are frequently in the form of chemical solutions or colloidal dispersions. The inkjet nozzle head has three main actuation mechanisms: thermal, piezoelectric, and electro hydrodynamic. A flexible printing method known as inkjet printing lowers both the cost and the number of manufacturing steps. Elastomer compatibility, high efficiency, maskless printing, and additive printing are additional appealing aspects of inkjet printing ( 68). Inkjet printing technologies are contrasted, and it is underlined that inexpensive inkjet printing is a good option for research projects and for evaluating the viability of novel ideas ( 69). Low cost inkjet printing is a good option for “small-cheap-disposable” sensors in addition to the obvious benefits for military applications ( 69).

3.3 Construction of Inkjet-Printed Sensors

The creation of electrochemical sensors by inkjet printing is schematically shown in (Figure 2). The procedure involves patterning and stacking layers of conductive and dielectric materials on a substrate, much like other additive processes like microfabrication or screen printing. However, inkjet printing is a purely digital approach, therefore print designs can be modified with little financial consequence, unlike other manufacturing methods that use photomasks, stencils, or other tangible aids to allow patterning. As a result, inkjet is appealing for use in production settings as well as being excellent for research and prototyping. Inkjet also has the benefit of using extremely little material, which results in the production of layers that are just where they are needed and are less than 1 µm thin. In contrast, screen printing uses ink that must be used in vast quantities and has coatings that are just a few microns thick.
Silver, gold, carbon nanomaterials, including graphene, and conducting polymers like poly (3,4-ethylene dioxythiophene)-poly(styrenesulfonate) (PEDOT:PSS) and polyaniline are the most often employed conducting materials in (inkjet-printed) electrochemical sensors (PANI). SU-8, a common photoresist used in MEMS, is one of the dielectric materials commonly utilized to cover conducting tracks and designate electrode active zones. Finally, most of the selective coatings that have been reported so far are based on conducting polymers and enzymes. When it comes to substrates, inkjet printing is most frequently employed on flexible ones like paper, polyethylene naphthalate (PEN), polyethylene terephthalate (PET), Kapton (a polyimide), and silicon. However, it can also be utilized on rigid ones like glass or 3D constructions ( 71). Contrarily, inkjet printing inks must adhere to very strict rheological specifications, with viscosity and surface tension limits of 1–30 cP and 25–40 mN reciprocal meters, respectively. These are the key barriers preventing widespread use of technology today, together with the high cost of research equipment. Commercial functional inks are expensive, difficult to find, and have a very short shelf life. As a result, almost all the works that have been reported so far have involved creating one or more inks internally.

Figure 2

Figure 2. A schematic showing how inkjet printing is used to create electrochemical sensors. The transducers must be produced using a minimum of two inks, and frequently an additional ink is necessary to enhance sensor performance.
Adapted with permission from ref. ( 70). Copyright 2017 Elsevier.

3.4 Laser-Induced Graphene (LIG) Based Disposable Sensors

An effective electrode substance for electrochemical point-of-care diagnostics is laser-induced graphene (LIG). With its low cost, quick fabrication process without the use of binders, and huge specific surface area, LIG is well suited for large-scale manufacturing outside of cleanrooms. The laser power, scribing speed, and laser pulse density all provide excellent control over energy input. Once the requisite energy input threshold is attained, a wide range of conditions result in LIG with micro morphologies ranging from delicate irregular brush structures produced at rapid, high energy input to smoother and more wall-like materials that are yet porous. Only a small percentage of these LIG structures offered the high conductance needed for effective electroanalytical performance. Here, it was discovered that low, frequent energy input — that is, low levels of power and speed combined with high spatial pulse density — provided the optimum electroanalytical material. For instance, by switching the manufacturing parameters from 60% power and 100% speed to 10% power and 10% speed, the sensitivity for the lowering of K3[Fe(CN)6] was nearly doubled. Independent of the devices used, these general findings can be applied to any LIG production technique. LIG electrodes are ideal and inexpensive transducers for electrochemical (bio)sensors, with the potential to replace the screen-printed systems that are predominating in on-site sensor use due to their straightforward fabrication process, a range of (bio)analytically important compounds, such as ascorbic acid, dopamine, uric acid, p-nitrophenol, and paracetamol, were used to show good electroanalytical activity.
In recent years, there has been a lot of interest in the 2014 discovery of LIG made from polymers. Numerous uses have been investigated, including batteries, catalysis, sterilization, and separation. The advantages of LIG technology over traditional methods for synthesizing graphene are obvious, and include controlled morphologies, programmable compositions, designable patterning, and environmental friendliness. Additionally, LIG has outstanding electric and thermal conductivity, high porosity, tremendous flexibility, and mechanical toughness. The pattern able and printable manufacturing method opens up a new route for creating miniature graphene devices, as do the beneficial characteristics of LIG. It has quickly evolved from a single detection component to an integrated smart detection system in sensing applications.

3.5 Fabrication and Engineering of LIG

The vector graphics program CorelDRAW was used to create electrode designs. LIG electrodes on Kapton foil were produced using a model VLS2.30 laser cutter (Universal Laser Systems, Scottsdale, AZ) outfitted with a 30 W CO2-laser (10.6 µm) and focused beam diameter of approximately 125 µm. The foil was divided into sheets of the proper thickness, and the borders were adhered with tape straight to the engraving table of the machine, which had been brought into focus. The accurate focus distance was determined to be the z-distance that produced the lowest laser spot mark on a test material, with an absolute value of around 5.1±0.1 cm ( 72). A fabrication scheme and two examples for electrode designs are shown in (Figure 3).
The machine software was used to adjust the power setting (1 to 100% of 30 W), lens carriage movement speed (1 to 100% of 50 inches/s), and spatial laser pulse density (with fixed combinations of 500 by 500, 1000 by 1000, or 1000 by 2000 PPI (pulses per inch in x- and y-direction)). Here, power and speed settings are reported in percent values rather than physical units (e.g., "1% power" rather than "0.3 W") because measured power and percent power scale linearly only roughly, making a straight conversion into physical quantities sometimes inaccurate. The following shorthand was used to write circumstances in order to save space. For instance, "1/10/10002000" stands for "1% power, 10% speed, 1000 PPI in the x-direction, and 2000 PPI in the y-direction." The distinction between the x- and y-directions, shown in (Figure a3), is significant because the lens carrier will only move quickly in the former and more slowly in the latter, which is unavoidable due to the design of the positioning system. This is because the laser moves at the set speed and frequency along the x-axis, then moves in the y-direction to continue the scan at the set speed and frequency back along the x-axis. Nevertheless, the gadget fulfils its promise.
PPI going both ways. Throughout operation, air was continuously withdrawn from the scribing chamber to remove soot and any developing gases ( 72).
To control the atmosphere, pure argon and nitrogen gas could be delivered directly to the processing chamber. The gases were immediately discharged at the lasing point through the air assist cone. The supplied gases were, however, invariably diluted with air that was continuously pulled into the (nonairtight) scribing chamber by the extraction mechanism, unlike Li’s and others’ trials with controlled-atmosphere chambers. As a result, the lasing environment was enriched in Ar or N2, but there are no measured statistics on the composition of the gases. After being scribed, electrodes were washed with isopropanol and water before being dried under a spray of nitrogen. Transparent nail polish was placed over the leads to ensure that only the electrode surface was in contact with the electrolyte solution. The provided video files allow you to see the postscribing procedures. Until they were utilized, electrodes were kept in the laboratory at room temperature in nonairtight boxes.

Figure 3

Figure 3. Electrode fabrication scheme (a), drawings of the electrode designs that were employed (WE working electrode, CE counter electrode, RE reference electrode), top=simple design, bottom=3-electrode design (b), photo of prepared LIG electrodes (c).
Adapted from ref. ( 72). Copyright 2021 Springer publishers.
(Tables 1)-(4) give the summary of previous works on Disposable Electrochemical Sensors.
Table 1. Paper Based Sensors
Paper SubstrateTargetTypes of Electrochemical Analysis
Ref.
Whatman RC60 generated membrane filterBromide, Iodide, ChlorideCyclic voltammetry( 73)
Nitrocellulose membraneAcetomenophenCyclic voltammetry and differential pulse voltammetry( 74)
Filter papers (qualitative, 102, 15 mm)GlucoseCyclic voltammetry and chronopotentiometry( 75)
Whatman chromatography paper 3mmStaphylococc aureususDifferential pulse voltammetry( 76)
Table 2. Screen-Printed Electrodes
AnalyteModifierDetectionLinear rangeDetection limitRef.
L or D Amino acidsrhodinized carbonAmperometric0.1–1.0 mM0.15–0.47 mM( 77)
Secreted Placental alkaline phosphate (SPAP)2-Naphthol OsteryoungSquare wave voltammetry 10 pfu/cell
Herpes simplex virus or 20 mM
( 78)
Cu2+Cation exchanger, Dowex 50W-X8 (H+ form, 20–50 mesh)DPASV0–110 ng/mL0.5 ng/m( 79)
Pb2+, Cd2+Hg thin filmDPASV20–100 ng/mLCd2+ 50 ng/l, Pb2+ 30 ng/l( 80)
DopamineGO/Fe3O4@SiO2DPV0.1–600.0 μM8.9×10−8 M( 81)
Ascorbic acidPhenylenediamineSWV0.45–409.10 μM0.11 μM( 82)
Table 3. Ink-Jet Printed Disposable Sensors
AnalyteSensor featurePrinterInkSubstrateRef.
Dissolved oxygenFully ink get
Range 0–8 mgL-1
Detection limit- 0.11 mgL-1
Dimatix DMP (piezo)Gold, Silver and dielectric (commercial)PEN( 83)
H2O2Clark-type electrode
Range 0–200 mgL-1
Detection limit- 0.05 mgL-1
Dimatix DMP (piezo)GraphenePaper( 84)
Thyroid stimulating hormone (TSH) and atrazine (ATR)Fully-inkjet
Detection limit:
ATR: 0.01 μg×L−1.
TSH: 0.5μIU×L−1.
X-series Cera Printer (Piezo)Carbon nanotubes, silver and dielectric (commercial)PET( 85)
GlucoseInkjet on printed circuit board.
Range: 0−40 mg×dL−1.
Detection Limit 0.3 mgdL−1
Homemade printer (Piezo)Graphene (Commercial)Polyimide( 86)
Iron ion (Fe2+) and dopamine (DA)Fully-inkjet. Range: 10–200 μM (Fe2+). 10 μM - 100 μM (DA).HP deskjet (Thermal)Dielectric commercial and carbon nanotubePaper( 87)
CholesterolScreen printing+inkjet.
Range: 0−15 mM.
Sensitivity: 2.1 μA×mM−1 cm−2.
Detection limit: 0.02 mM
Dimatix DMP (piezo)Prussian blue nanoparticlesPolyester( 88)
Table 4. Laser-Induced Graphene Based Disposable Sensors
AnalyteSensor configurationModifierLinear rangeLODRef.
Glucose, lactate, alcoholThe enzyme/Ti3C2Tx/PB/NLSGEnzyme‘10 μM - 5.3
mM’, ‘0–20 mM’, ‘0–50 mM’
‘0.3 μM’,
‘0.5 μM’
-
( 89)
AA, UA, DAPt/LSGElectrodepositionAA: 10–680
DA: 0.5–32.5 μM
UA: 0.5–19.5 μM
AA:6.1
DA:0.07
UA:0.22
( 90)
Salmonella typhimuriumLIG-based sensorAntibody25–105 CFU/mL13±7 CFU/
mL
( 91)
Cd+2 and Pd+2PANI/N-LEG/GCEPolymerization and laser scribingCd2+
4.4×10−2−3.38
Pb+2:
2.4×10−3−1.
Cd2+: 9.6×10−3 Pb+2: 7.7×10−4( 92)
ChloramphenicolEBT MIP/Amine/ PEDOT/LIGElectropolymerization10–3 μM –10000 μM6.2×10−4 μM( 93)
NitriteMWNT/AuNP/LSGDrop casting10–90 μM6.75 μM( 94)

Abbreviations: pfu- plaque forming units per volume; DPASV- Differential pulse anodic stripping voltammetry; DPV- Differential pulse voltammetry; GO/Fe3O4@SiO2-Graphene oxide/Iron oxide/ Silicon oxide; DMP- Dimatix material printer; HP- Hewlett-Packard; Ti3C2Tx/PB/NLSG- MXene/Prussian Blue/ nitrogen-doped laser-scribed graphene; Pt/LSG- Platinum/ Laser Scribed Graphene; PANI/N-LEG/GCE- Polyaniline Nitrogen doped Laser Engraved Graphene; LIG-Laser Induced Graphene; EBT MIP/Amine/ PEDOT/LIG-Eriochrome Black-T Molecularly Imprinted Polymer Poly(3,4-ethylenedioxythiophene)/ Laser Induced Graphene; MWNT/AuNP/LSG- Multi walled Carbon Nano Tubes/Gold nanoparticles/Laser Scribed Graphene; AA, UA, DA- Ascorbic acid, Uric acid, Dopamine; CFU- Colony Forming Unit.

4 Conclusion and Future Perspectives

CHAPTER SECTIONS
Jump To

The development of disposable sensors and the expansion of the availability of ever-more complicated sensing and diagnostic devices will be driven by the constant need to access sensory data. This will be accomplished using a broader variety of cutting-edge materials, manufacturing techniques, and levels of functional integration. The range and style of applications will continue to be expanded to meet unmet demands thanks to this ever improved combination of affordability and functionality. Access to better healthcare in areas with limited resources and less invasive or noninvasive alternatives to present technologies in areas with abundant resources are key motivations. Greater functional integration will be made possible by smart functional nanomaterials combined with print processing while still reaching mass production. Cost will still be the main factor, but environmental sustainability and the “greening” of technology will become more significant.
Disposable electrodes with appropriate activation have significantly increased analytic systems’ sensitivity and selectivity, particularly toward biological targets. They have also made it much easier to identify some analytes that would otherwise be difficult to detect. Future applications may greatly benefit from the screen printing of high performance nanocomposite materials and the coordination of chemical modification with more advanced electrode designs.

Acknowledgments

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Jump To

Manjushree SG is grateful for the financial assistance provided by the Department of Science and Technology through the Women Scientists Scheme-A (WOS-A) SR/WOS-A/CS-153/2018. Prashanth SA expresses his gratitude to SVM Arts, Science and Commerce College, ILKAL for their unwavering support and encouragement as well as to Karnataka Science and Technology Academy (KSTA) for their financial assistance.

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  • Figure 1

    Figure 1. Various types of electrodes and their structures used for modification in sensing applications.
    Adapted with permission from ref. ( 36). Copyright 2019 Royal Society of Chemistry.

    Figure 2

    Figure 2. A schematic showing how inkjet printing is used to create electrochemical sensors. The transducers must be produced using a minimum of two inks, and frequently an additional ink is necessary to enhance sensor performance.
    Adapted with permission from ref. ( 70). Copyright 2017 Elsevier.

    Figure 3

    Figure 3. Electrode fabrication scheme (a), drawings of the electrode designs that were employed (WE working electrode, CE counter electrode, RE reference electrode), top=simple design, bottom=3-electrode design (b), photo of prepared LIG electrodes (c).
    Adapted from ref. ( 72). Copyright 2021 Springer publishers.
  • References

    CHAPTER SECTIONS
    Jump To

    This chapter references 94 other publications.

    1. 1
      Killard A. J. Disposable sensors Current Opinion in Electrochemistry 2017 3 57 62
    2. 2
      Beebe D. J. Denton D. D. Radwin R. G. Webster J. G. A silicon-based tactile sensor for finger-mounted applications IEEE Transactions on Biomedical Engineering 1998 45 151 159
    3. 3
      Han T. Nag A. Afsarimanesh N. Mukhopadhyay S. C. Kundu S. Xu Y. Laser-assisted printed flexible sensors: a review Sensors 2019 19 1462
    4. 4
      Jung H.-C. Moon J.-H. Baek D.-H. Lee J.-H. Choi Y.-Y. Hong J.-S. Lee S.-H. CNT/PDMS composite flexible dry electrodesfor long-term ECG monitoring IEEE Transactions on Biomedical Engineering 2012 59 1472 1479
    5. 5
      El-Saftawy A. Elfalaky A. Ragheb M. Zakhary S. Electron beam induced surface modifications of PET film Radiation Physics and Chemistry 2014 102 96 102
    6. 6
      Yoo K.-P. Lim L.-T. Min N.-K. Lee M. J. Lee C. J. Park C.-W. Novel resistive-type humidity sensor based on multiwall carbon nanotube/polyimide composite films Sensors and Actuators B: Chemical 2010 145 120 125
    7. 7
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