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Open access peer-reviewed chapter

An Overview of the Synergy of Electrochemistry and Nanotechnology for Advancements in Sensing Applications

Written By

Rajni Bais

Submitted: 06 June 2022 Reviewed: 28 June 2022 Published: 27 August 2022

DOI: 10.5772/intechopen.106151

Frontiers in Voltammetry IntechOpen
Frontiers in Voltammetry Edited by Dr. Shashanka Rajendrachari

From the Edited Volume

Frontiers in Voltammetry

Edited by Shashanka Rajendrachari, Kiran Kenchappa Somashekharappa, Sharath Peramenahalli Chikkegouda and Shamanth Vasanth

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Abstract

Electrochemical sensors have been widely employed in diverse domains of electrochemical analysis, biosensing, drug administration, healthcare, agriculture, and so on because of their special potential features that are closely related to their high selectivity, sensitivity and cycling stability. Various electrochemical techniques employed to transduct biological or chemical signal to electrical signal are voltammetry, conductometry, potentiometry and amperometry. Due to the high demand of global market and human interest in having a device to check the concentration of species in different samples that is simple and fast, researchers have been engaged in a fierce competition to design and build new sensors and biosensors in recent years. The performance of the sensors can be considerably improved by modifying the electrode surfaces using diverse nanomaterials. Further, electrochemical biosensors are promising diagnostic tools that can find biomarkers in bodily fluids including sweat, urine, blood or excrement. Nanoparticles have found propitious role in biosensors, because they aid in functions like immobilisation of molecules, catalysis in electrosynthesis, facilitation of electron transfer between electrodes and biomolecules and labelling of biomolecules. The advance in the research amalgamating electrochemistry and nanotechnology for electro (bio) sensing applications is the beginning of a promising future for mankind and global market.

Keywords

  • nanomaterials/ nanoparticles (NPs)
  • electrochemical
  • sensor
  • biosensor

1. Introduction

The information carried by an electrochemical redox reaction (the reaction between electrode and analyte) is converted into an applicable quantitative or qualitative signal by electrochemical sensors. The sensors can generate electronic outputs in the form of digital signals that can be analysed further [1]. Depending on the mechanism involved in recognition, the sensors can be chemical or biological (biosensor). Electrochemistry is found to play a crucial role in medical technology, forensics, food, environmental sciences, defence settings, agriculture, among others [2, 3]. Electrochemical sensors and detectors are very appealing for applications, viz. on-site monitoring of environmental contaminants, addressing varied environmental needs, health monitoring, testing of adulterants in food samples, forensic drug analysis, and many more. Many of the specifications for on-site environmental scanning are met by sensing devices. They are intrinsically sensitive and selective to electroactive species and are fast, reliable, portable, compact and economical [4]. A transducer and a chemical recognition system are the two primary components of an electrochemical sensor, and collectively these two components constitute a sensing electrode. Other electrodes may also be used in electrical measurements like reference and counter electrodes (CEs) [5]. In electrochemical sensors, a potential difference is applied in between working and counter electrodes, and on the basis of redox reactions caused by the analyte at the electrode’s interface, the resulting current response is measured. Voltammetry, conductometry, potentiometry, or amperometry can be used to study the transduction of biological or chemical signal to electrical signal. Since their invention, the electrochemical sensors are being studied extensively for their applications in efficient biosensors, immunosensors, special electrode design automated systems, and microelectrodes, etc. [6]. With the recent advancements in the designing and synthesis of nanomaterials along with the evaluation of intrinsic properties of nanoparticles (NPs) based on carbon [7] and many other types of base materials, the engine of nano-electrochemistry has begun to gain speed in the field of electrosensing.

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2. Electrochemical signal transduction techniques

A transduction process involves efficient capture of biological or chemical recognition signals and their conversion into electrical, gravimetric, optical, electrochemical or acoustic signals. There are four main types of electrochemical signal transduction techniques that can be used in analysis, depending on the reaction under investigation:

  1. Voltammetry

  2. Potentiometry

  3. Amperometry

  4. Conductometry

Each of these techniques is described in the following section in brief.

2.1 Voltammetry

Voltammetry is an electroanalytical method that obtains information about an analyte by modifying a potential and then measuring the resultant current. Here, the potential sweep is applied between working electrode (WE) and counter electrode (CE) with respect to reference electrode (RE), and the current so produced is measured as an analytical signal. Because the potential can be varied in many ways, many forms of voltammetry are available, such as direct current (DC) polarography, differential pulse polarography (DPP), differential staircase voltammetry, cyclic voltammetry, linear sweep voltammetry, normal pulse, and reverse pulse voltammetry [8, 9, 10]. Cyclic voltammetry is one of the most widely used electroanalytical methods.

2.2 Potentiometry

In potentiometry, the analytical signal is the open-circuit voltage between working electrode and reference electrode. Depending on the concentration of the analyte, this signal can increase or decrease [11]. Here, Nernst equation governs the relationship between concentration and potential. Useful information about ion activity in redox reaction is provided by potentiometry [12]. Ion-selective electrodes (ISEs) are often employed to achieve low detection limits for potentiometric sensors. Also the potentiometric sensors are ideal for measuring low concentrations of analyte in small sample volumes, because they do not chemically influence the sample [13].

2.3 Amperometry

It is similar to voltammetry with the difference that here a constant or stepped potential is employed to measure the current as electric signal, whereas in voltammetry, controlled variation of voltage is done to measure current. In fact, some scientists classify voltammetry as a type of amperometry only, because both these techniques employ measurement of current upon variation of potential. Here, a continuous measurement of current is done, and this current is produced by oxidation or reduction of an analyte in a biochemical reaction [9, 14]. Here, the peak value of the measured current (over a linear range of potential) is a direct indication of the bulk concentration of the electroactive species [15, 16]. Glucose biosensor is one of the most widely employed amperometric sensors. It is often claimed by many scientific practitioners that amperometric sensors are superior to potentiometric sensors when it comes to sensitivity [17].

2.4 Conductometry

Conductometry sensors are used to measure concentrations of electrolyte in aqueous solutions. The recorded electrical resistance of the solution is used to calculate the molar concentration of an identified electrolyte that causes solution conductivity [18]. Conductivity can be measured directly with a conductivity metre or indirectly with conductometric titration. Electrolyte conductometric analysis has long been used. Conductometric methods were used to analyse mineral waters and salt solutions by Henry Cavendish and Andreas Baumgartner [19].

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3. Types of sensors

Sensors can be classified into two broad categories depending on their application or mode of transduction, as follows:

3.1 Types of sensors on the basis of application

  1. Chemical Sensors: A chemical sensor converts an analyte’s physical and/or chemical properties into a measurable signal [20]. The intensity of the measurable signal is normally proportional to concentration of the analyte [21]. The chemical sensors can further be classified as follows:

    1. pH Sensors: These sensors are sensitive to even minute changes in pH of a solution and are used to measure acidity and alkalinity in aqueous and other solutions. When used properly, these devices can guarantee the safety and quality of a product as well as the processes that take place in a wastewater treatment or different manufacturing units in industries [22].

    2. Gas Sensors: These sensors are employed to detect the type and amount or concentration of a gas in a specific environment. Any change in the composition of gas can be linked with electric signals through these sensors [23].

    3. Alcohol Sensors: Technically known as a MQ3 sensor, an alcohol sensor is a non-contact breath sensor that is mostly used to detect ethanol in the air. When a drunk person breathes near an alcohol sensor, the sensor detects the ethanol in his breath and provides an output based on the concentration of alcohol [24].

    4. Ion-selective Sensors: Ion-selective electrodes are a type of potentiometric devices. Many electrode systems exhibit a Nernstian relationship between the activity of a redox species in solution and measured electrode potential. The affinity of surface of the membrane for a typical redox species as well as minimum ion conductivity over the membrane are important requirements for the advancement of ion-selective electrodes [25].

    5. Humidity Sensors: A humidity sensor is a device that detects, measures, and reports the relative humidity (RH) of air or the amount of water vapour present in a gas mixture (air) or pure gas. Humidity sensing is associated with the adsorption and desorption of water. Industrial and agricultural products are both monitored by humidity sensors. Incubators, sterilisers, and pharmaceutical processing plants all use humidity sensors [26].

  2. Biosensors: Biosensor is a powerful, efficient, and innovative analytical device that incorporates a biological sensing element and has a wide range of applications, like, environmental monitoring, diagnosis, biomedicine, food safety and processing, drug discovery, defence, and security [27, 28, 29]. In a biosensor, an electron exchange takes place in between layer of bioreceptor and an electrode, and this exchange of electrons (because of reduction or oxidation of the analyte) can be transduced into a readable signal [30].

3.2 Types of sensors on the basis of mode of transduction

  1. Amperometric Sensors: The working of amperometric sensor is based on measuring current generated because of an electrochemical reaction at the electrode surface when a constant working potential is applied with respect to the reference electrode [31]. The amperometric set-up may consist of either two-electrode (WE and RE) or three-electrode (WE, RE, and CE) assembly.

  2. Potentiometric Sensors: These sensors are used to measure difference in potential applied between two electrodes when there is no current flowing between them. This measured potential is then used to detect or quantify the analyte of interest in the solution. In a general potentiometric sensor, the signal obeys Nernst Eq. [32].

  3. Optical Sensors: These are light-based sensors, which work on the principle of studying the change in wavelength of a particular light when the photosensitive analyte in the medium interacts with the recognition element [33]. Position-sensitive diode, phototransistor, photoresistor, photodiode, and diode array are some commonly used light sensors [34].

  4. Piezoelectric Sensors: In these sensors, environmental or mechanical energy changes are converted into electric signals or vice versa. The environmental or mechanical energy changes may include alteration in strain, vibration, pressure, force, etc. [35]. Piezoelectric sensors can be of two types, i.e. passive or active.

  5. Thermal or Calorimetric Sensors: In these sensors, the concentration of analyte is correlated to amount of heat produced during a molecular recognition reaction. The working principle of calorimetric sensors is to detect the presence or measure the concentration of an analyte by studying the changes in enthalpy produced as a result of any physisorption process or chemical reaction in the medium under observation [36]. Calorimetric sensors are also known as chemoresistors, and the two types of chemoresistors are low-temperature chemoresistors and high-temperature chemoresistors.

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4. Types of nanoparticles used in electrosensing

A nanoparticle has diameter approximately one lakh times smaller than that of a human hair strand. Nanomaterials, like in many other technological or scientific segments, have demonstrated their applicability and worthiness for electrochemical/biosensing applications. The astute use of such nanomaterials has resulted in clearly improved performance, with enhanced specificity, sensitivity, and extremely lowered limits of detection. Further, the high specific surface area of all nano-objects allows for the immobilisation of an increased number of bioreceptor units (in biosensors) [37]. The direct functionalisation of nanomaterials (during their synthesis) or coating of nanomaterials with specific functional polymers results in nanomaterials equipped with desired functions without altering their specific properties [38]. The commonly used nanoparticles in electrosensing applications are of following types:

  1. Gold nanoparticles (AuNPs)

  2. Quantum dots (QDs)

  3. Magnetic nanoparticles (MNPs)

  4. Carbon nanotubes (CNTs)

A brief description of these nanoparticles is given as follows.

4.1 Gold nanoparticles

  1. Properties: The characteristics of AuNPs, such as their optical and electronic properties, their biocompatibility, and their comparatively simple production and modification, make them of high priority and utility among the class of noble metal nanoparticles [38, 39]. The electrons of AuNPs when irradiated with light of a specific wavelength oscillate in the conduction band (resonant surface plasmons), and this optical behaviour of AuNPs makes them of immense applicability in the field of optical sensing. The use of surface plasmons resonance (SPR) transduction for sensing applications of gold nanoparticles is based on studying the changes in environment of gold films with reference to dielectric constant of propagating surface plasmons. Here, variation in intensity, angle or phase of the reflected light is used to monitor the analyte [40]. Phyto-AuNPs that are phytosynthesised with the aid of green chemistry approach are catalytically and biologically active, biocompatible, and stable. But despite their potent applications, these have not been explored sufficiently [41].

  2. Recent Research Trends: Owing to the aforementioned properties, the use of AuNPs for the development of novel sensing techniques holds significant promises when it comes to research related to: drug determination [42, 43, 44]; anticancer and other biomedical applications [45, 46]; immuno-PCR (Polymerase Chain Reaction) assay and ELISA (Enzyme-Linked Immunosorbent Assay) [47, 48], and so on.

4.2 Quantum dots

  1. Properties: QDs are nanoscale crystals created by scientists which are capable of electron transport. These semiconducting QDs show the property of emitting a variety of colours when UV light strikes them. These semiconductor nanoparticles have found varied applications in fluorescent biological labels, electrochemical sensing, solar cells and composites. The optical properties of a particle can be altered by controlling their size, and so, these particles can also be tuned or regulated in a way that they can absorb or emit light (colours) of specific wavelength [49]. Further, the shape (hollow/ solid), composition and structure are other crucial parameters of QDs that can affect their various properties. Another important application of QDs is as single-electron transistors. But studies have shown that these semiconductor nanoparticles may exert harmful effects on living systems in some cases [50].

  2. Recent Research Trends: When carbon QDs are doped with heteroatoms [51], such as nitrogen [52], both sulphur and nitrogen [53], zinc [54], lanthanum [55] and CuInS2 [56], then their optical/photoluminescent properties are found to improve prominently for sensing applications.

4.3 Magnetic nanoparticles

  1. Properties: MNPs can be assimilated into transducer materials or scattered in the sample prior to being attracted to the active recognition surface of the sensor by an external magnetic field [57]. Because of the reduced number of magnetic domains in nanosized MNPs, these exhibit magnetic behaviours different than the bulk material, resulting in superparamagnetic behaviour. This means that in a very short time, magnetisation can rapidly and randomly flip directions, and when an external magnetic field is absent, the magnetisation denotes to be average zero. This is a temperature-dependent phenomenon which disappears when the magnetic moments are aligned by the application of an external magnetic field [58]. MNPs offer a highly sensitive technique of transduction in biosensors, optical sensors and electrochemical sensors [57, 58].

  2. Recent Research Trends: In the recent times, the utility of MNPs has increased multifold. Some advanced sensing applications of MNPs are as follows: diagnosis of anticancer drug 6-mercaptopurine using cerium-based MNP as a fast-response and efficient fluorescence quenching sensor [59], Ihlamur leaves [60] and saffron flowers [61]-based biosynthesis of magnetic nanoparticles for antibacterial applications, use of silver MNPs to enhance the surface plasmon resonance signal for determination of leukocyte cell-derived chemotaxin-2 which is an important biomarker for the diagnosis of liver fibrosis [62], green synthesis of Fe3O4 nano-flakes and its utility as an electrocatalyst for the voltammetric determination of ascorbic acid [63], diversified biomedical applications of multifunctional MNPs [64], and many more.

4.4 Carbon nanotubes

  1. Properties: Owing to the distinctive electronic properties (high conductivity and large surface-to-volume ratios) of CNTs, in recent years these have been widely investigated for their utility as electrosensing devices. Non-functionalised CNTs are not very selective for many chemicals, but functionalisation with different chemical moieties can be done to surpass this drawback. For their electrosensing applications, the CNTs can be functionalised with specific metals or functional groups [65]. The adsorption and binding of specific molecules on the surface of carbon nanotubes result in change in potential– current curves, and this forms the working principle of these devices [66]. The properties of CNTs as sensors are mainly dependent on their shape. The diameter of CNTs is of one to several nanometres, and their length may be of several microns. Well-ordered hexagonal carbon cycles or graphite rolls constitute their surface [67]. One to multilayered tubulenes (with closed or open terminations) may be formed, depending on the conditions of synthesis of these nanotubes.

  2. Recent Research Trends: The characteristic properties of CNTs allow nanotechnology to provide promising platforms for sensing applications. Some of the emerging researches done in this field are as follows: designing of terahertz metasurface-based single-walled CNT [68], synthesis of sensing piezoresistive materials with carbon nanotubes [69], diagnosis of pancreatic and liver cancer employing CNTs [70], etc.

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5. Role or functions of nanoparticles in (bio) sensing techniques

The various roles of NPs in (bio) sensing techniques are as follows.

  1. Immobilisation of molecules: Chemical functional groups or biomolecules (antibody, DNA, enzymes, and cells) that are immobilised on transducer surface during the construction of a (bio) sensor decide for its stability, sensitivity, selectivity and reproducibility [71]. Hence, a number of methods are employed for immobilisation of desired (bio) molecules onto solid support materials. Some of these methods are adsorption, covalent bonding, entrapment, copolymerisation or crosslinking and encapsulation [72].

  2. Catalysis in electrosynthesis/electrochemical reactions: The use of solid nanoparticles as heterogeneous catalysts during electrosynthesis reactions has increased in recent times. Under green chemistry conditions, nanocatalysts can be employed efficiently to promote electrochemical reactions [73]. The incorporation of catalytic nanoparticles into electrochemical (bio) sensors can reduce overpotentials in many analytically crucial electrochemical reactions. Also the reversibility of some otherwise irreversible redox reactions (at traditional unmodified electrodes) can be enabled by nanocatalysts [74]. Production of hydrogen through splitting of water by renewable electricity [75], reduction of carbon dioxide into hydrocarbon products [73] and conversion of biomass products to high-value chemicals [73] are some of the commercially or energetically important electrochemical reactions that use nanocatalysts. Nanoparticles of metals like platinum, gold, silver, palladium, copper, nickel and iridium and also some oxide NPs have been used as catalysts in electrochemical reactions [74].

  3. Enhancement of electron transfer between electrode surfaces and proteins:

    The conductivity properties of metallic nanoparticles make them suitable for facilitating electron transfer between electrodes and active centres of proteins/enzymes, thereby ascertaining their role as ‘electrical wires’ or ‘mediators’ [74].

  4. Labelling of biomolecules: The use of NPs for labelling biomolecules aids in retaining their interaction with cellular/molecular counterparts and also in maintaining their bioactivity. Stripping voltammetric technique is commonly used to measure the trace amounts of dissolved nanoparticle labels (usually semiconductor or metal NPs), which in turn is an indication of the concentration of biomolecule under investigation [74]. The NP labels can be introduced either actively (targeted) or passively (non-targeted) into cells under investigation [76]. The incorporation of nanoparticles in cells as labels allows enhanced visualisation of these cells in vivo using a variety of molecular imaging modalities, such as optical imaging, radionuclide imaging (positron emission tomography or PET), magnetic resonance imaging (MRI) and single-photon emission computed tomography (SPECT)) [77, 78].

  5. Acting as reactant: In some cases, significant difference is observed in chemical properties of bulk material and nanoparticles made from it because of high surface-to-volume ratio in case of NPs. This enhanced surface energy of NPs provides them amplified chemical activity. As a result, the nanoparticles have found significant applications in novel electrochemical analysis systems as special reactants [74]. For example, the high reactivity of manganese oxide NPs (react directly with H2O2) in comparison with bulk MnO2 (catalyses decomposition of H2O2) has made these NPs an important component of some electrochemical systems [79].

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6. Recent advances in nanotechnology-based biosensors

Recently, techniques that are sensitive, selective, and cost-effective are being developed for detecting diseases and underlying medical issues. In this context, biosensors as nano-electroanalytical tools have taken the centre stage. Progress in the health sector enabled by nanotechnology has facilitated in the management of a number of diseases at an early stage [80]. When studying the electrosensing applications of NPs, transfer of electrons between substrate and active site of enzyme (biocatalyst) forms the basis for the functioning of enzymatic biosensors, and this transfer in turn is transduced to produce an electroanalytical signal [81]. Carbon nanostructures, nanotubes, nanorods, ceramic or polymeric matrices, derivatives of graphene, and other functionalised nanoparticles are some of the materials that have been explored and investigated widely by researchers for their electrosensing/ biosensing properties and applications [82, 83, 84]. The following recent researches further ascertain the efficiency and remarkable role of NPs in biosensors:

  1. Shen et al. [85] showed that the DNA nanostructures can be used in a variety of biomedical applications such as biosensors and cancer therapy as these can interact with small biomolecules and cancer cells due to their specific engineering, unparalleled programmability, and innate biocompatibility and can also serve as nanocarriers for various therapeutic agents.

  2. Outstanding physicochemical properties of nanoscaled polyaniline have captured the interest of scientists in the field of medical, as reported by Kazemi et al. [86]. These nanocomposites have shown the ability to immobilise enzymes, nucleic acids and antigen-antibodies on their surface and thus act as bioreceptors or biocatalysts.

  3. A polydimethylsiloxane-based nanostructured immunosensor for the investigation of cortisol in human sweat was fabricated by Liu et al. [87].

  4. The electrocatalytic and electrochemical features of nickel-cobalt nanoparticles (chemically reduced on functionalised multi-walled carbon nanotubes) were investigated voltametrically against glucose oxidation by Arikan et al. [88].

  5. Polyaniline was sequentially electropolymerised on the surface of the functionalised gold electrode followed by electrodeposition of gold nanoparticles to design a nano-biosensor for rapid and ultrasensitive detection of insulin antibodies against diabetes antigens by Farrokhnia at al [89].

  6. Electrochemical immunosensing properties of zirconium oxide nanoflowers integrated with quantum dots were investigated by Gupta et al. [90].

  7. Recently Farzin et al. [91] have reviewed the biosensing applications of nanoparticles for early and accurate diagnosis of lentivirus HIV that leads to AIDS.

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7. Conclusion

An extra advantage of the extensive use of nanoparticles in electrosensing techniques can be owed to their exceptional attributes, like remarkable selectivity and sensitivity, high surface energy, capability to show morphological as well as functional diversity, portability, cost-effectiveness, ease-of-construction and easy-to-operate. Thus, the merger of electrochemistry and nanotechnology has attributed to a wide range of electro (bio) sensing applications for the detection and quantification of chemical as well as biological target molecules. The role of electrode materials in high-performance electrosensing platforms is crucial and evident. Furthermore, when the simple electrode materials are functionalised with nanostructured and/or nanoengineered materials, significant improvement and enhancement in their conductivity, catalytic activity, biocompatibility, amplification of biorecognition events, acceleration of transduction signal, selectivity, specificity and sensitivity has been observed. Almost every passing day, some new innovation is reported in the field of nano-electrosensing, viz. incorporation of CNTs with metallic NPs aids in the development of highly improved nanocomposites for biosensing applications [86], a dramatic enhancement is observed in the electrical conductivity of rGO (reduced graphene oxide) by incorporation of AgNPs [92], nanowires have an exceptional potential as electrosensing probes because of their high surface-to-volume ratios, reproducibility and extraordinary optical, electrical, and magnetic properties [93], and successful designing of dye-sensitised solar cells based on green zinc oxide nanoparticles [94]. The field of nano-electrochemistry seems to expand its horizon continuously, and despite a significant amount of research done in this field, it just seems to be a new start.

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Written By

Rajni Bais

Submitted: 06 June 2022 Reviewed: 28 June 2022 Published: 27 August 2022

© 2022 The Author(s). Licensee IntechOpen. This chapter is distributed under the terms of the Creative Commons Attribution 3.0 License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

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