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Graphene-Based Electrochemical Sensors for Biomolecules

Graphene-Based Electrochemical Sensors for Biomolecules

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Graphene-Based Electrochemical Sensors for Biomolecules

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Lançado em:
Oct 22, 2018


Graphene-Based Electrochemical Sensors for Biomolecules presents the latest on these nanomaterials that have gained a lot of attention based on their unique properties of high mechanical flexibility, large surface area, chemical stability, superior electric and thermal conductivities that render them great choices as alternative electrode materials for electrochemical energy storage and sensor applications. The hybridization of graphene with other nanomaterials induces a synergetic effect, leading to the improvement in electrical conductivity, stability and an enhancement of the electrocatalytic activity of the new nanocomposite material. This book discusses the electrochemical determination of a variety of biomolecules using graphene-based nanocomposite materials.

Finally, recent progress in the development of electrochemical sensors using graphene-based nanocomposite materials and perspectives on future opportunities in sensor research and development are discussed in detail.

  • Covers the importance of detecting biomolecules and the application of graphene and its nanocomposite materials in the detection of a wide variety of bioanalytes
  • Presents easily understood fundamentals of electrochemical sensing systems and the role of graphene-based nanocomposite materials in research and development
Lançado em:
Oct 22, 2018

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Graphene-Based Electrochemical Sensors for Biomolecules - Elsevier Science


Chapter 1

Graphene-Modified Electrochemical Sensors

M. Amal Raj⁎; S. Abraham John†    ⁎ Department of Chemistry, Loyola College, Chennai, India

† Department of Chemistry, Centre for Nanoscience and Nanotechnology, The Gandhigram Rural Institute, Dindigul, India


In the last decade, remarkable advances in the field of electrochemical sensors based on graphene and its composites have been depicted. Graphene, a new 2D nanomaterial with outstanding physical, chemical, and electrochemical properties, is an efficient electrode material for creating new sensing assays due to its large conductivity, fast heterogeneous electron transfer, and large surface area. Graphene-modified electrodes prepared by different methods have been used for the successful determination of various biomolecules with high sensitivity and selectivity in the past few years. In this chapter, after a brief introduction to the properties, synthetic methods of graphene and its derivatives, and the importance of various biomolecules, the current development on graphene-based electrochemical sensors is discussed. The implications of graphene on the development of modern electrochemical sensors are also discussed. Finally, future prospects on graphene as advanced electrocatalysts are highlighted.


Graphene; Biomolecules; Electrocatalysts; Electrode material; Electron transfer

1 Introduction

The development of electrochemical sensors has received a great deal of scientific interest in the past few decades. Due to their high selectivity and sensitivity, researchers have been actively involved in developing cost-effective electrochemical sensors. The recent emergence of nanomaterials and nanotechnology has opened new prospects in designing the nanomaterial-modified electrodes for electrochemical sensor applications. In this respect, efforts have been directed to the modification of electrodes with nanomaterials with controlled assembly onto electrode surfaces for improved bioelectrocatalytic performance [1–7]. Metal/metal oxide nanoparticles, conducting polymers, macrocyclic metal complexes and carbon nanostructures have been widely used as electrode materials [8–11]. Among them, carbon materials are widely used for the design of electrodes used in electroanalytical chemistry because of their relatively wide potential window in aqueous media, low cost, low background current, and relative chemical inertness in most of the electrolyte solutions [12,13]. To date, many carbon nanomaterials including carbon nanotubes (CNTs), fullerenes, diamond, graphite, carbon dots, and graphene have been used for electrode modification. Among these carbon nanostructures, graphene, the mother of all graphitic nanostructures has become an important electrode material due to its conductivity and high surface area [14,15].

2 Electrochemical Sensors

A sensor (also called detector) is a converter that measures a physical quantity and converts it into a signal which can be read by an observer or by an instrument (today mostly electronic). The sensor contains a recognition element that enables the selective response to a particular analyte or a group of analytes, thus minimizing interferences from other sample components [16]. Electrochemical sensors have several advantages as the electrodes can sense the materials that are present within the host without doing any damage to the host system with low detection limit and high specificity. These devices contain a recognition element that selectively produces an electrical signal that is related to the concentration of the analyte being studied. The active sensing material on the electrode should act as a catalyst and catalyze the reaction of the chemical and biochemical compounds to obtain the output signals. The combination of biosensors and electrochemical sensors leads to a new type of sensors called electrochemical biosensors, where the electrochemical methods are applied for the construction and working of a biosensor [17]. Scheme 1 shows the schematic illustration of an electrochemical sensor. Several nanomaterials such as gold nanoparticles (AuNPs), conducting polymers, graphene, platinum nanoparticles, CNTs, metal oxides, and composite materials have been utilized as an electrode material for the determination of variety of biomolecules and toxic chemicals [18–21]. In this section, we restrict ourselves to graphene-modified electrodes and their applications toward the determination of biomolecules such as vitamins, amino acids, neurotransmitters, purine bases, nucleobases, nucleosides, and nucleotides (Fig. 1).

Scheme 1 Schematic illustration of an electrochemical sensor.

Fig. 1 Graphene modified electrodes for the determination of various biomolecules.

3 Importance of Biomolecules

Biomolecules carry out various biological functions such as the transformation of genetic information, regulating the physiological and biological activity because the levels in the body fluids are an indication of various disorders. Before discussing the detection of various biomolecules using graphene-modified electrodes, a brief discussion about the significance of few important biomolecules are given below (Fig. 2).

Fig. 2 Structures of important biomolecules.

The balance between the inhibitory and excitatory neurotransmitters is important to how our body functions [22]. Knowing the levels of a particular neurotransmitter can help to identify an imbalance immediately or prevent problems occurring in the future. Hence, the sensitive determinations of inhibitory neurotransmitters are important from a clinical point of view. Dopamine (DA), epinephrine (EP), and norepinephrine (NE) are neurotransmitters that belong to catecholamine family. DA regulates blood flow through the arteries, modulates eating habits, contributes to learning and high cognitive functioning, reinforces behavior, and regulates motor activity. It is also involved in regulating the secretion of hormones from the pituitary gland and contributes to the function of the autonomic nervous system [23,24]. NE plays a central role in controlling alertness, rest cycles, attention, and memory in the central nervous system [25]. Adrenaline, or EP, is a hormone and neurotransmitter produced by the adrenal glands that participates in the sympathetic nervous system's fight-or-flight response (or acute stress response) to situations that are high-stress, dangerous, and/or physically exhilarating [26].

Another important category of biomolecules are vitamins. Vitamin B2 (riboflavin (RB), water-soluble vitamin B) is primarily found as an integral component of the coenzymes (called flavocoenzymes) of flavin adenine dinucleotide (FAD) and flavin mononucleotide. Flavocoenzymes participate in redox reactions in numerous metabolic pathways. Symptoms of RB deficiency include a sore throat, redness and swelling of the lining of the mouth and throat, and/or cracks or sores on the outsides of the lips (cheliosis) [27]. Pyridoxal, pyridoxamine, and pyridoxine are collectively known as vitamin B6. All three compounds are efficiently converted to a biologically active form of vitamin B6, pyridoxal phosphate, which is catalyzed by the enzyme called pyridoxal kinase. It is stored in the muscle and only excreted in urine when intake is excessive [28]. Folic acid (FA) is a water-soluble vitamin and is a member of the vitamin B complex. All forms of this vitamin are readily converted to the coenzyme form called tetrahydrofolate (THFA), which plays a key role in transferring single-carbon methyl units during the synthesis of DNA and RNA, and in interconversions of amino acids. Folate also plays an important role in the synthesis of neurotransmitters. Pregnancy is a time of rapid cell multiplication and DNA synthesis, which increases the need for folate. Seventy percent of folate defects could be avoided by adequate folate status before conception, and it is recommended that all women of childbearing age consume at least 400 μg of folic acid each day from fortified foods and supplements [29,30]. Vitamin C (ascorbic acid, AA) is needed to form and maintain collagen, a fibrous protein that gives strength to connective tissues in skin, cartilage, bones, teeth, and joints. A deficiency of vitamin C causes widespread connective tissue changes throughout the body. Deficiencies may occur in people who eat limited fruits and vegetables, follow restrictive diets, or abuse alcohol and drugs. It has been shown that doses up to 1 g per day may have small effects on duration and severity of the common cold, but not on the prevention of its occurrence [31].

Another major class of biomolecules of clinical interest is amino acids. The biological role of amino acids includes muscle protein maintenance, potentiation of immune function, affecting neuronal activities in the brain, pain relief effects, lowering blood pressure, modulating cholesterol metabolism, and stimulating insulin or growth hormone secretion [32]. Tryptophan (TRP), an essential amino acid, is the largest of the amino acids. It is also a derivative of alanine, having an indole substituent on the β carbon. It is required for the production of niacin (vitamin B3) [33,34]. Cysteine is 1 of 20 naturally-occurring biogenic amino acids that are linked by peptide bonds to form polypeptides and proteins. Its residues may also play important role in catalytic processes of enzymes, in storage and adjusting the reduction potentials [35]. l-Dopa is an amino acid and a hormone that is made naturally by a number of plants and animals. In humans, it is created via biosynthesis from the amino acid l-Tyrosine. In its pure form, l-Dopa is considered to be a psychoactive chemical, and can also be used for the treatment of Parkinson's disease and a number of other conditions related to lowered levels of the above neurotransmitters [36].

Purine is a heterocyclic aromatic compound which contains a pyrimidine ring fused with an imidazole group. Purines have never been found in nature but their substituted derivatives, nucleosides and nucleotides, are the important heterocyclic compounds that are involved in many metabolic processes as cofactors and play an important role in the functioning of living systems [37]. They act as energy carriers in the cell (adenosine triphosphate [ATP] and guanosine-5′-triphosphate [GTP]), coenzymes (nicotinamide adenine dinucleotide [NAD] and FAD) and as neurotransmitters by acting upon purinergic receptors (adenosine monophosphate [AMP] and guanosine monophosphate [GMP]). They can be excellent probes for elucidation of biochemical mechanisms and biophysical characteristics of nucleic acids. The change in concentration of purine derivative in body fluids is a direct indicator for several diseases [38].

Higher levels of meat and seafood consumption increases the possibility of gout whereas higher consumption of dairy products decreases the risk of gout [39,40]. The metabolism of purine involves the breakdown of ATP to adenosine diphosphate (ADP), AMP, adenosine, inosine monophosphate (IMP), and inosine. Further breakdown of inosine forms hypoxanthine (HXN) which breaks into xanthine (XN) and uric acid (UA). The breakdown of GTP produces guanine which also produces XN. Hence, UA is the final product of purine metabolism. Fig. 3 shows the simple metabolic pathway of purine metabolism [41].

Fig. 3 Metabolism of purine derivatives.

The important purine derivatives (Fig. 4) are purine metabolites (UA, XN, HXN), purine bases (adenine [A], guanine [G]), purine nucleotides (ATP, GMP, β-nicotinamide adenine dinucleotide [NADH]), other methyl xanthine derivatives (theophylline [TP], caffeine [CAF]) and the isomer of HXN (allopurinol [AP]).

Fig. 4 Structures of important purine derivatives.

UA (2,6,8-trihydroxypurine), the endproduct of purine metabolism, is present in blood and urine. It is generated by the xanthine oxidase catalyzed conversion of XN. The detection of UA is of great importance because abnormal levels of UA have been linked to gout, hyperuricemia, leukemia, pneumonia and Lesch–Nyhan syndrome [42–44].

XN is another important biomolecule present in our body. Its concentration level in blood plasma and urine may provide sensitive indicators of certain pathologic states, especially for xanthinuria [45–47]. This is a rare genetic disorder where the lack of xanthine oxidase leads to high concentration of XN in body fluids and can cause health problems such as renal failure.

HXN is an essential metabolite to degrade adenine nucleotide, which is mainly accumulated in biological tissues [48]. The determination of HXN is very important for the quality of fish products in food industries.

The metabolism of purine pathway involves the transformation of HX → XN, XN → UA by xanthine oxidase. XN and HX are intermediates and UA is the terminal product of purine degradation metabolism [49]. Abnormalities of the metabolites concentrations in body fluids such as human serum and urine are sensitive indicators of many pathologic states.

The other important purine derivatives are DNA purine bases A and G which are two important building blocks of both DNA and RNA that play a vital role in genetic information storage and are involved in processes such as energy transduction, metabolic cofactors, and cell signaling [50,51]. They have widespread effects on coronary and cerebral circulation, prevention of cardiac arrhythmias and inhibition of neurotransmitter release [52]. Indeed, G and A in physiological fluids, tissues, and cells are related to the catabolism of nucleic acids, enzymatic degradation of tissues, dietary habits, and various salvage pathways. Purine bases, including A, XN, HXN, and G, as catabolic intermediates of nucleotide catabolism, are closely related to many physiological functions of cells and show different metabolic levels for noncancerous and cancer cells.

8-Azaguanine is a purine analog. It exerts a strong action on human tumor cells by inhibiting the protein synthesis as a result of its incorporation in mRNA [53]. It has been successful in treating leukemia and uterine and breast cancers. On the other hand, 8-hydroxy-2′-deoxyguanosine (8-OH-dG), one of the major products of oxidative base damage, has received considerable attention as a consequence of its demonstrated mutagenic potential [54,55]. 8-OH-dG is believed to be excreted unchangeably in the urine and the urinary level of 8-OH-dG is regarded as an important biomarker of endogenous oxidative damage to DNA and its precursors [56,57].

ATP is a multifunctional purine nucleotide and is often called the molecular unit of currency for the intracellular energy transfer [58]. ATP can be produced by photophosphorylation with the functions such as biosynthetic reactions, motility, and cell division.

GMP is a type of purine nucleotide which can be synthesized in the human body and plays a crucial role in many functions related to normal cellular metabolism and cardiac activities [59,60]. It is very important to determine the level of GMP in order to elucidate its physiological function in the organism.

NADH is an important cofactor present in oxidase- and dehydrogenase-based enzymes. Quantitative assessment of NADH could be very promising for assembly of dehydrogenase-based biosensors [61,62].

TP (1,3-dimethylxanthine) is a methylated derivative of XN [63], a purine base that can be found in food products such as tea and cocoa beans. A high dose of TP may cause insomnia, anorexia, and heartburn tachycardia due to its narrow therapeutic index [64]. CAF (3,7-dihydro-1,3,7-trimethyl-1H-purine-2,6-dione or 1,3,7-trimethylxanthine) is the active alkaloid component, together with other trace purines of coffee, cola nuts, cocoa beans, tea leaves, yerba mate, guarana berries, among many varieties of plants, in which it acts as a natural pesticide [65]. It is a stimulant of the central nervous system, affecting alertness and wakefulness [66]. It also acts as a vasoconstrictor, increasing blood pressure and increasing respiration cycles, but may also cause emesis and dehydration, being a powerful diuretic and is considered a risk factor for cardiovascular diseases.

AP (4-hydroxypyrazolo[3,4-d] pyrimidine), an isomer of HXN, is a radical scavenging clinical drug commonly used for the treatment of chronic gout or hyperuricemia associated with leukemia and diuretic conditions [67]. The inhibiting action of AP on xanthine oxidase indirectly decreases the protein synthesis by increasing the concentration of nucleoribotides. Therefore, it is recommended for urate lowering therapy.

4 Graphene

Among the available carbon materials, graphene, a one-atom thick and two-dimensional closely packed honeycomb lattice, has been the focus of several explorations in recent years due to its unique electronic, mechanical, and thermal properties since its discovery in 2004 by Geim and Novoselov [68,69]. The emerging potential of graphene-based devices was innovatively utilized in numerous fields, for example in transistors, transducers, chemical sensors, DNA sequencing, solar cells, batteries, capacitors, and rust prevention [70–72]. The electrochemical properties of graphene are also of high contemporary interest. It is potentially the world's thinnest electrode material which finds potential application in electrochemistry due to its high surface area and high electrical conductivity [73–75]. Its main electrochemical utility is also based on a wide electrochemical potential window, low charge resistance (in comparison to glassy carbon) [76] and well defined redox peaks [77].

4.1 Structure and Properties of Graphene

Graphene is often categorized by the number of stacked layers: single layer, few-layer (2–10 layers) and multilayer, which is also known as thin graphite [78]. Graphene constitutes a single layer of sp²-hybridized carbon atoms packed into a dense honeycomb two-dimensional lattice (Fig. 5). A single two-dimensional (2D) sheet of graphene has a hexagonal structure with each atom forming three σ-bonds with each of its nearest neighbors [79]. Due to the delocalized out-of-plane π bonds arising from the sp² hybridization carbon atoms, an unprecedented high carrier mobility of ∼ 200,000 cm² V− 1 s− 1 has been achieved for suspended graphene [80]. The theoretical surface area of graphene is reported to be ~ 2630 m² g− 1 which is higher than the surface areas of single walled carbon nanotubes (SWCNTs) (1315 m² g− 1) and graphite material (10 m² g− 1) [81]. The electrical conductivity of graphene is reported to be 64 mS cm− 1, which is 60 times higher than that of SWCNTs and remains stable over a vast range of temperatures [82]. It appears to be one of the strongest materials ever tested. Measurements have shown that graphene has a breaking strength over 100 times greater than a hypothetical steel film of the same thickness with a tensile modulus of 1 TPa (150,000,000 psi) [83]. The thermal conductivity of graphene was measured to be between (4.84 ± 0.44) × 10³ and (5.30 ± 0.48) × 10³ W m− 1 K− 1. Graphene's unique optical properties produce an unexpectedly high opacity for an atomic monolayer in vacuum. It absorbs πα ≈ 2.3% of white light, where α is the fine-structure constant. Electrons in graphene move at an effective speed of light, 300 times less than the speed of light in a vacuum [84].

Fig. 5 Structure of a graphene.

4.2 Synthesis of Graphene

The synthesis of graphene can be categorized into two main approaches: top-down and bottom-up methods (Fig. 6) [85].

Fig. 6 Synthesis of graphene by different methods.

4.2.1 Top-Down Methods

Micromechanical cleavage of graphite leads to the formation of high quality graphene films reported by Geim and coworkers in 2004 [86]. In contrast to manual mechanical exfoliation, the ball milling method provides a much higher yield of few-layer graphene [87]. On the other hand, chemical reduction of exfoliated graphene oxide (GO), the precursor of graphene, was historically the first method for the synthesis of graphene reported by Boehm and coworkers in 1962 [88]. Chemical oxidation which produces the precursor compound GO can be the most popular route to graphene because it achieves large quantities in one-time preparation [89]. The GO is an insulator which is absolutely different from its parent material [90]. It can be synthesized by oxidizing the natural graphite by the use of a strong oxidizing agent that leads to the interruption of aromatic nature which is confirmed by the increase in interlayer spacing from 0.335 nm from graphite to more than 0.625 nm for GO [91]. The synthesis of GO was first demonstrated by Brodie in 1859 by adding potassium chlorate to a slurry of graphite in fuming HNO3[92]. Staudenmaier improved this method by using concentrated H2SO4 and HNO3 and adding chlorate over the course of the reaction [93]. In 1958, Hummers used KMnO4 and NaNO3 in concentrated H2SO4 for the production of GO and this method is now the most commonly used [94]. Recently, Tour et al. reported the synthesis of GO using 9:1 mixture of H2SO4/H3PO4 that improves the efficiency of the oxidation process [95].

To retain the aromatic backbone, the oxygen functional groups of GO must be removed from the surface of GO which yields a product that is denoted reduced graphene oxide (rGO) [96,97]. The reduction of GO is generally accomplished by high temperature treatments [98], electrochemical reduction (ERGO) [99] and using various reducing agents (CRGO) [100,101]. Recently, interest has been focused on graphene nanoribbons by unzipping CNTs. In this method, the side walls of CNTs are etched by either plasma [101] or potassium permanganate [102].

4.2.2 Bottom-Up Approach

For the preparation of graphene thin films on transition metal substrates such as nickel, copper and palladium, the chemical vapor deposition (CVD) method was used. The advantage of CVD is its self-limiting nature, i.e., it automatically stops after the formation of a single layer of graphene [103]. Ultrathin graphene sheets were also grown on silicon carbide by vacuum graphitization which finds application in electronics [104]. The graphene synthesized by these methods are suitable for graphene electronics, yet the low yields and inconvenient transfer processes restrict this process in wide electrochemical applications [105].

5 Electrode Fabrications With Graphene

As graphene has a large electrochemical potential window (~ 2.5 V in 0.1 mM phosphate buffer solution) [106], detection of molecules in a wide potential range is possible for the electrodes modified with graphene. In addition, the edges and defects on graphene provide a high electron transfer rate [107], which makes the graphene a suitable candidate for electrode material. Nevertheless, the surface coverage, orientation, and possible interaction from the exposed areas of the underlying electrode are the major challenges in understanding the electrochemistry of graphene [108]. The major problem in utilizing graphene as an electrode material is electrically wiring the graphene to the electrode surface for the efficient electron transfer [97]. Mostly, the dropcast method was used by researchers for the immobilization of graphene nanosheets onto the electrode surface [99,109,110]. Although most of the researchers used the dropcast method, the reproducibility of this method is still questionable. To overcome this problem, researchers used CVD-produced graphene for studying the electrochemical and electrocatalytic properties [111]. Although CVD graphene exhibits great electrocatalytic activity, the tedious transfer process limits the application of CVD graphene in electrocatalytic applications [111].

As GO is soluble in water and other polar solvents [112], a solution-based process such as inkjet printing, electrostatic assembly, spray coating, or microfludic patterning can be employed followed by its reduction to fabricate rGO thin films [71,113–115]. Compared to chemical reduction of GO, electrochemical reduction of GO has received considerable attention due to its green approach [116]. Another important method is self-assembly which is one of the elegant methods for the fabrication of nanomaterials on conducting substrates [117]. Only a very few researchers have used the self-assembly method for the fabrication of graphene-modified electrodes [118–124]. Graphene was self-assembled on Au electrode via n-octadecylmercaptanself-assembled monolayer by the strong hydrophobic interaction between SAM of mercaptan and graphene nanosheets (Fig. 7) [119,120]. Ramesha and Sampath reported the self-assembly of GO on Au substrate through cystamine SAM by electrostatic interaction between amine terminal of SAM and GO [121]. Similar interaction was also utilized by Viinikanoja et al. to study the spectroelectrochemical characterization of GO on Au electrode using a mercaptoethylamine linker [122]. Zhang et al. reported the self-assembly of GO on 3-aminopropyltriethoxysilanepre-assembled on activated GCE followed its electrochemical reduction [118,123]. Kim and coworkers reported the self-assembly of GO using amine-terminated grafted surface of ITO followed by the electrochemical reduction of GO for the immobilization of horseradish peroxidase for the determination of hydrogen peroxide [124]. The preactivation of GCE as well the possible cleavage of thiol SAM on the Au electrode was the major limitation of the above mentioned self-assembly methods besides the limited potential window of Au electrode. By considering the above issues, Raj and John developed a simple self-assembly method using 1,6-hexadiamine (HDA) SAM on GCE for the immobilization of GO on amine terminal of HDA via electrostatic assembly followed by the electrochemical reduction and utilize the resulting graphene modified electrode for electrocatalytic applications (Fig. 8) [125].

Fig. 7 Graphical illustration of the protocol for the fabrication of a graphene/SAM modified Au electrode. Reprinted with permission from X. Xie, K. Zhao, X. Xu, W. Zhao, S. Liu, Z. Zhu, M. Li, Z. Shi, Y. Shao, Study of heterogeneous electron transfer on the graphene/self-assembled monolayer modified gold electrode by electrochemical approaches, J. Phys. Chem. C 114 (2010) 14243. Copyright 2010 American Chemical Society.

Fig. 8 Schematic illustration for the modification of ERGO on GCE. Reprinted with permission from M.A. Raj, S.A. John, Fabrication of electrochemically reduced graphene oxide films on glassy carbon electrode by self-assembly method and their electrocatalytic application, J. Phys. Chem. C 117 (2013) 4326. Copyright 2009 American Chemical Society.

Graphene modified electrodes have been reported to show not only excellent electrocatalytic activity toward H2O2, O2, NADH and other important electroactive species but also greatly improved the performance in enzyme based biosensing [126,127]. This chapter highlights the electrochemical applications of graphene toward various biomolecules.

6 Electrochemical Determination of Neurotransmitters, Vitamins, and Amino Acids

Neurotransmitters play a significant role in the function of human metabolism. Therefore, it is important to develop sensitive sensor for the determination of different neurotransmitters without any interferences. The determinations of vitamins and amino acids are also vital in the clinical point of view while diagnosing various diseases.

Wang et al. reported the fabrication of GCE with graphene and demonstrated the selective determination of DA in the presence of AA (Fig. 9). The modified electrode showed greater sensitivity to DA due to the enhanced π–π interaction between graphene layers and DA [4]. The similar enhancement is also observed for DA oxidation at ERGO-modified GCE fabricated by self-assembly method reported by Raj and John [125]. Rivas and coworkers fabricated a CRGO paste electrode and used it for the determination of DA in the presence of AA and serotonin. The proposed sensor was sensitive to determine DA in nanomolar level concentrations [128]. Multi-nanoporegraphene-modified GCE was fabricated by Nan and coworkers and used for the simultaneous determination of AA, DA, and UA. The enhanced activity of modified electrode compared to bare GCE is due to the presence of carboxylic acid and hydroxyl groups, defects due to hydrothermal treatment and edge plane such as defective sites at multi-nanopore graphene [129]. Aneesh et al. reported the determination of DA in the presence of AA and UA at partially reduced graphene modified electrode prepared by drop casting method (Fig. 10). The limit of detection (LOD) of 8 × 10− 9 M was achieved at this electrode for DA [130]. Banks and coworkers fabricated a graphene-modifiedscreen-printed electrode and studied the electrochemical behavior AA, UA, DA, and NADH. They concluded that the electrocatalytic properties are highly dependent on the surface morphology, composition, and the density states (coverage of edge plane like sites/defects) and the method of fabrication [131]. Hou et al. reported the synthesis of EDTA-modified graphene by silanization and fabricated them on GCE using Nafion as the binder by the dropcast method for the determination of DA. The modified electrode was successfully used for the determination of DA even in the presence of 1000-fold interferences [132].

Fig. 9 (A) DPVs of the blank (a), 1 mM AA (b) and 5, 10, 15, 20, 50, 75, 100, 125, 150, 175 μM DA (from c to m) on graphene-modified GCE in the presence of 1 mM AA in the 0.1 M PBS (pH 7.0). DPV, pulse period, 0.2 s; amplitude, 50 mV. Inset : linear relationship between the reduction peak current and the concentration of DA. (B) Current–time responses for successive addition of 500 μM AA, 500 μM UA, 5 μM DA, 50 μM DA, and 100 μM DA at the graphene modified GCE. Applied potential, 380 mV. Reproduced from Y. Wang, Y. Li, L. Tang, J. Lu, L. Jinghong, Application of graphene-modified electrode for selective detection of dopamine, Electrochem. Commun. 11 (2009) 889 with permission from Elsevier.

Fig. 10 Fabrication of electrochemically reduced graphene oxide modified glassy carbon electrode by the dropcast method for sensing AA, DA, and UA. Reproduced from P.K. Aneesh, S.R. Nambiar, T.P. Rao, A. Ajayaghosh, Electrochemically synthesized partially reduced graphene oxide modified glassy carbon electrode for individual and simultaneous voltammetric determination of ascorbic acid, dopamine and uric acid, Anal. Methods 6 (2014) 5322 with permission of the Royal Society of Chemistry.

Electrochemical determination of DA and acetaminophen was reported by Kim et al. with graphene-modified GCE using Nafion as a binder. The modified electrode showed excellent sensitivity and was used for the determination of DA in real sample analysis (diluted human urine) [133]. Electrochemically-modified graphene oxide-modified GCE was fabricated and used for the simultaneous determination of AA, UA, and DA. The modified electrode showed high sensitivity toward the determination of DA [134]. Kim et al. reported the preparation of graphene oxide by modified Hummer's method, fabricated some graphene-modified electrodes and utilized them for the determination of DA. They achieved a LOD of 2.64 μM [135]. Valentini et al. prepared functionalized graphene nanoribbons by unzipping SWCNTs and then assembled them into a screen-printed electrode. They investigated the electrochemical behavior of modified electrodes by taking various biomolecules such as l-tyrosine, l-DOPAC, AA, UA, DA, epinephrine, guanine, NADH, serotonin, and H2O2. The authors concluded that the modified electrode showed higher electrocatalytic activity toward NADH and DA

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