Accepted Manuscript

Title: Synthesis and utilisation of carbon nanotubes for

fabrication of electrochemical biosensors

Author: Abdulazeez. T. Lawal

PII: S0025-5408(15)30103-3
DOI: http://dx.doi.org/doi:10.1016/j.materresbull.2015.08.037
Reference: MRB 8390

To appear in: MRB

Received date: 30-3-2015

Revised date: 30-6-2015
Accepted date: 31-8-2015

Please cite this article as: Az.T. Lawal, Synthesis and utilisation of carbon nanotubes
for fabrication of electrochemical biosensors, Materials Research Bulletin (2015),
http://dx.doi.org/10.1016/j.materresbull.2015.08.037

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Synthesis and utilisation of carbon nanotubes for fabrication of electrochemical biosensors
*Abdulazeez. T. Lawala

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Department of Chemical and Geological Science. Al-Hikmah University Ilorin, Nigeria

Abstract

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This review summarises the most recent contributions in the fabrication of carbon nanotubes-

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based electrochemical biosensors in recent years. It discusses the synthesis and application of

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carbon nanotubes to the assembly of carbon nanotube-based electrochemical sensors, its

analytical performance and future expectations. An increasing number of reviews and

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publications involving carbon nanotubes sensors have been reported ever since the first

design of carbon nanotube electrochemical biosensors. The large surface area and good
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electrical conductivity of carbon nanotubes allow them to act as “electron wire” between the

redox centre of an enzyme or protein and an electrode's surface, which make them very
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excellent material for the design of electrochemical biosensors. Carbon nanotubes promote
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the different rapid electron transfers that facilitate accurate and selective detection of

cytochrome-c, β-nicotinamide adenine dinucleotide, haemoglobin and biomolecules, such as

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glucose, cholesterol, ascorbic acid, uric acid, dopamine pesticides, metals ions and hydrogen
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peroxide.
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Keywords Enzymes; DNA biosensor; Immunosensor; Enzyme biosensor; Carbon nanotube;

Glucose; Ascorbic acid;

Corresponding author: Tel: +2348174328856

E-mail address: abdul.lawal@yahoo.com

Content

Abstract 1

1. Introduction 2

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Page 1 of 165
2. Synthesis of carbon nanotube 6

2.1. Chemical vapour deposition (CVD) method 7

2.2Othermethods 9

3. Fuctionalisation

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11

4. Review studies

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17

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4.1. Carbon nanotubes synthesis and production’sreview

19

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4.2. Carbon nanotubes electrochemical reviews

20
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5 Carbon nanotubes nanocomposites

23
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6. Electrochemical sensing
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25
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6.1. Carbon nanotubes electrochemical sensing 25

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6.2. Carbon nanotubes-based-electrochemical enzymatic biosensors

27
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7. Use of electrodes based on carbon nanotubes for sensing different analytes

29

7.1. Glucose biosensor

29

7.2. Haemoglobin (Hb) biosensor 46

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7.3. Hydrogen peroxide biosensor (H2O2)

51

7. 4. NADH 63

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7.5. Cholesterol biosensor 66

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7.6. Electrochemical Immunosensing 71

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7.7. DNA sensors 77

7.9. Cytochrome c (Cyt-c). 83

7.8.Ascobic Acid (AA), Uric

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Acid (UA) andDopamine(DA)
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87
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7.10. Metal ions

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99

7.11. Pesticides
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103
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8. Conclusions .
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111

1. Introduction

Carbon nanotubes (CNTs) have become some of the most attractive nanomaterials in

nanotechnology revolution. With the continuous progress of nanotechnology in material

science, carbon nanomaterials have been given special attention because of their remarkable

mechanical and electrical properties and are being used in many scientific and engineering

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Page 3 of 165
research projects [1, 2]. In recent years, CNTs have received great attention as promising

carbon-based nanoelectronic devices. Because of their exceptional physical, chemical, and

electrical properties, namely, a high surface-to-volume ratio, their enhanced electron transfer

properties and their high thermal conductivity, CNTs can be employed effectively as

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electrochemical sensors. The integration of CNTs with a functional group provides a good

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and solid support for the immobilisation of enzymes and has made CNTs to attract

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considerable attention in electroanalysis and biosensing.

CNTs are rolled up sheets of graphene. These can be single sheet cylinders giving single-

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walled carbon nanotubes (SWCNTs), or multiple concentric cylinders of increasing diameter

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about a common axis separated by 0.34 nm that are known as multi-walled carbon nanotubes

(MWCNTs) [3]. There is also double wall carbon nanotube (DWCNT), but MWCNT have
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shown the most promising appearance to the market place in recent times. Fig.1.

Recently, researchers have focused great attention on CNTs and their derivatives, and they
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are being studied in nearly every field of science [1], medicine [4-6] and engineering [7].
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CNTs-based materials can have a profound impact on electronic and optoelectronic devices

[8], chemical sensors [9, 10], nanocomposites [11-19], optical biosensor [20, 21] and energy
p

storage [16, 22]. New applications of CNT-nanomaterials in electrochemical sensors and

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biosensors are now on the increase with the advent of nanotechnology [23]. There are various

CNT-nanomaterials [24-30], including carbon nanotube metal nanoparticle (NP) [31],

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nanocomposite [14, 19], metal alloy NP [14], magnetic NP [32, 33], nanowires [34-37],

nanofibers [27, 38] and nanorod [39]. CNTs have been used as electrical connectors between

the electrodes and the redox centers of the biomolecules [40-44]. Sensors based on CNTs and

graphene have shown excellent performance in electrochemical detection of metal ions,

pesticides and other pollutants. The properties of CNTs, such as fast electron transportation,

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Page 4 of 165
high thermal conductivity, excellent mechanical flexibility and good biocompatibility, make

it a potential in the fabrication of sensitive electrochemical biosensor [45]

CNTs were discovered in 1991 by Iijima [46] and they have been the goal of numerous

researchers due to their unique structural, electronic and mechanical properties that make

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them a very attractive material for a wide range of applications. Since their discovery in

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1991, study of the properties and applications of CNTs has rapidly increased. The studies

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demonstrated that CNTs can significantly enhance the electrochemical reactivity of important

biomolecules and can promote the direct electron-transfer reaction of proteins. Additionally,

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CNT-modified electrodes can also relieve the surface fouling effects. These properties make

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CNTs extremely attractive for a wide range of electrochemical biosensors. Their unique

structure provides an exceptional electric-current-carrying capacity along their length (1000

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times higher than copper wires) which leads to attractive CNT-based new electrode materials.

CNTs excellent intrinsic properties, such as high surface area, unique physical properties,
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chemical stability and high electrical conductivity, lead to their wide potential applications in
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nanoelectronics, composite materials, energy research and biomedicine [5, 14, 47-56].

Nowadays, CNTs remarkable electronic, optical, mechanical, thermal and electrochemical

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properties have made them suitable electronic materials for electrochemical sensing, as CNTs
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have very good low-noise electronic [57]. Many groups all over the world are doing exciting

works using CNTs and their hybrids in applications such as super capacitors [28, 57-62],
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clinical chemistry [20, 63], medicine [64], fuel cells [28, 65-72], batteries [73-76], biodiesel

[72], photocatalysis [77], photovoltaic [66, 78], chemical and biosensors [10, 76, 79, 80],

greenhouse gas sensor [81], gas sensors [81-90], photonics [21], solar cell [57, 69, 73, 78],

light-emitting diodes (LEDs) [57], optical sensor [91], energy [92, 93] optoelectronics,

photocatalyst, biofuel [94], thin-film transistors and field effect transistor (FET) [1, 20, 57,

95] (Fig. 2). In this review, the recent progress of electrochemical sensors based on

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functionalised CNTs will be discussed, covering synthesis, functionalisation, nanocomposite

electrochemical process and representative examples. It will be demonstrated that

functionalised CNTs as templates, carriers, immobilisers and transducers are suitable

innovations for the construction of sensitive electrochemical sensors Fig.3.

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2.1. Synthesis of CNTs

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A number of different routes to synthesise CNTs have been demonstrated over recent

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years.The three main synthesis techniques for CNTs production are arc discharge [57], laser

ablation [96] and chemical vapour deposition (CVD) [ 57, 97, 98]. Dumisteriscus et al. [99]

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named the techniques as electric arc discharge, laser ablation, high-pressure carbon monoxide

(HiPCO) and catalysed chemical vapour deposition (cCVD) [100]. Baskar et al. [101] named
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the techniques that have been developed to produce nanotubes in sizeable quantities,

including arc discharge, laser ablation, chemical vapor deposition, saline solution method and
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flame synthesis method. CNTs generally obtained by the arc method or hydrocarbon
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pyrolysis are multi-walled, having several graphitic sheets or layers [102].

Single-walled carbon nanohorns (SWCNHs) are horn-shaped single-walled tubules with a

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conical tip. They are generally synthesised by laser ablation of pure graphite without using
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metal catalyst with high production rate and high yield, and typically form radial aggregates.

SWCNHs are essentially metal-free and very pure, which avoids cumbersome purification
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and makes them user-friendly and environmentally benign. Currently, SWCNHs have been

widely studied for various applications, such as gas storage, adsorption, catalyst support, drug

delivery system, magnetic resonance analysis, electrochemistry, biosensing application,

photovoltaic and photo electrochemical cells, photodynamic therapy and fuel cells. Multi-

walled (MWNTs), double-walled (DWNTs) and single-walled (SWNTs) carbon nanotubes

have been synthesised using methods which include arc evaporation of graphite, laser

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ablation, chemical vapour deposition (CVD) and vapour phase decomposition or

disproportionation of carbon-containing molecules.

Depending on the exact technique, it is possible to selectively grow SWNTs or MWNTs. If

SWNTs are required, the anode has to be doped with a metal catalyst based on Fe, Co, Ni, or

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Mo. Several elements and mixtures of elements have been tested and the results vary

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considerably [103]. SWNTs have been produced using the arc discharge process wherein the

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graphite electrodes were modified by transition metal catalysts. They have also been

produced using laser ablation [96] and chemical vapour deposition. Smalley’s group reported

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the synthesis of CNTs by laser vaporization in 1995 [104]. Zhu et al.’s [66] review outlines

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the research progress on SWCNHs, including their properties, functionalization, applications

and outlook. Double-walled carbon nanotubes (DWNTs) have been obtained by arc discharge
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in an atmosphere of Ar and H2 mixture (1:1/v: v) at 350 Torr and in the presence of a catalyst.

DWNTs synthesized from MWNTs carbon nanofibres have higher purity than those from
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graphite powders. Kumar and Ando [105] reviewed the synthesis, growth mechanism and
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mass production of CNTs by CVD. MWNTs and SWNTs have also been prepared by

techniques such as electrochemical synthesis [106] and pyrolysis of precursor organic

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molecules [107].
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2.2. Chemical vapour deposition (CVD) method

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Chemical vapor deposition (CVD) is a chemical process that uses a chamber of reactive gas

to synthesize high-purity, high performance solid materials. The chemical vapor deposition

process allows for gases containing the deposition material to be introduced into a reaction

chamber and subsequently deposited on a substrate to form a coating. CVD is one of the

most used techniques to produce one-dimensional nanomaterials. CVD is also a general

method used to synthesise CNTs branched or encapsulating other ‘‘foreign’ ’components for

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Page 7 of 165
its easy operation and the possibility of mass production of CNTs. Good alignment as well as

positional control nanometer scale are achieved by using CVD [108, 109]. Control over the

diameter, as well as the growth rate of the nanotubes, were also achieved. Use of an

appropriate metal catalyst permits preferential growth of single-walled, rather than multi-

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walled, nanotubes [110]. CVD synthesis of nanotubes is essentially a two-step process,

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consisting of a catalyst preparation step, followed by synthesis of the nanotube. The catalyst

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is generally prepared by sputtering a transition metal onto a substrate, followed by etching by

chemicals such as ammonia, or thermal annealing to induce the nucleation of catalyst

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particles.

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CNTs grown upon a substrate by CVD has emerged as an important method for the

preparation and production of CNTs for various applications since the method was first
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reported in 2008/2009 [111]. Metter et al. [100] reviewed the fabrication of the world’s

smallest electrode, the carbon nanotube, via chemical vapour deposition (CVD) and
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demonstrated how these electrodes are beneficially utilised and tailored towards the
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electrochemical sensing of target analytes. The use of CNTs arrays grown via CVD to

beneficially tailor the arrays to their intended electro-analytical application, was also
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highlighted.
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Park et al. [57] stated that there are generally two methods of depositing SWNTs on flexible

substrates - transferring CVD-grown SWNTs or solution-depositing SWNTs. Since CVD-

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grown SWNTs can be highly aligned, they often out perform solution-processed SWNT films

that are typically in the form of random network. However, solution-based SWNTs can be

printed at a large-scale and at low-cost, rendering them more appropriate for manufacturing.

In either case, the removal of metallic SWNTs in an effective and a scalable manner is

critical, which must still be developed and optimised.

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Sanginario et al. [112] grew self-standing cylinder-shaped blocks of multi-wall CNTs

(MWCNTs) by means of a catalytic chemical vapour deposition system, fed by camphor and

ferrocene gases. The blocks were subsequently back-contacted and encapsulated into epoxy

resin as electrical insulator and sealant for their use as voltammetric electrodes. Jin et al.

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[113] electronically activated CVD–CNT with open-end caps of CNT after coating with

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polyelectrolytes (PEs). Han et al. [114] developed a MWCNT-based electrochemical

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biosensor for monitoring microcystin-LR (MC-LR), a toxic cyanobacterial toxin, in sources

of drinking water supplies. The biosensor electrodes were fabricated using vertically well-

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aligned, dense, millimeter-long MWCNT arrays with a narrow size distribution, grown on

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patterned Si substrates by water-assisted chemical vapor deposition. Taurino et al. [115]

reported on multi-walled carbon nanotubes fabricated on silicon substrate with four different
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orientations via CVD. It is well-known that chemical treatments improve the nanotube

electrochemical reactivity by creating edge-like defects on their exposed sidewalls. Before

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use, Taurino et al performed an acid treatment on carbon nanotubes. Others who recently
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used CVD for CNTs synthesis include Guadarrama-Fernández et al. [116], Choi et al [117],

Chen et al. [118], Feng et al. [119], Maghsoodi et al. [120] , Han [114], Bai et al. [26] and
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Brownson [97].
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2.3. Other methods

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Hsu et al. [121] developed an electrochemical method for the synthesis of multiwalled

nanotubes. This involves the electrolysis of molten lithium chloride, using a graphite cell in

which the anode is a graphite crucible and the cathode a graphite rod immersed in the melt. A

current of about 30 A is passed through the cell for one min, after which the electrolyte is

allowed to cool and then added to water to dissolve the lithium chloride and react with the

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Page 9 of 165
lithium metal. Transmission electron microscopy (TEM) revealed that the material contained

a large numbers of rather imperfect multiwalled nanotubes.

Sen et al. [122, 123] prepared MWNTs using vapour phase growth. In the vapour phase

growth, pyrolysis or the floating catalyst method the carbon vapour and the catalytic metal

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particles are both deposited in the reaction chamber without a substrate. The diameter of the

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carbon nanotubes by vapour phase growth is in the range 2–4nm for SWNTs and 70 and 100

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nm for MWNTs.

Nikolaev et al. [124] obtained SWNTs using a gas-phase catalytic method involving the

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pyrolysis of Fe(CO)5 and CO. Decomposition of CO on a silica-supported-Mo catalyst also

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yields SWNTs [125].The improvised technique ‘‘High-pressure CO’’ disproportionation

process (HiPco) is a technique for catalytic production of SWNTs in a continuous-flow gas

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phase, using CO as the carbon feedstock and Fe(CO)5 as the iron-containing catalyst

precursor. SWNTs are produced by flowing CO mixed with a small amount of Fe(CO)5,
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through a heated reactor.

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Flame synthesis method is based on the use of a controlled flame environment, wherein

carbon atoms are formed from inexpensive hydrocarbon fuels along with aerosols of metal
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catalysts [126]. Zhu and Xu [66] recently reported laser synthesis of SWNT which was
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synthesised by laser ablation of pure graphite without using metal catalyst with high

production rate and high yield. SWCNTs are essentially metal-free and very pure. This
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avoids cumbersome purification and thus makes them user-friendly and environmentally

benign. Gougis et al. [96] used pulsed laser deposited gold nanostructures onto carbon

nanotubes electrodes and Zhu et al. [66] reviewed synthesis on SWCN which are generally

synthesised by laser ablation of pure graphite without using metal catalyst with high

production rate, high yield, and typically form radial aggregate.

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A sonochemical route for producing high-purity SWNTs in liquid solution under ambient

conditions has been reported [127]. This method for SWNT growth begins, typically, with the

preparation of a mixture solution of ferrocene and xylene. Silica powder is then added to this

solution. Ultra sonication is performed under ambient conditions to grow high purity SWNTs.

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3.1. Functionalisation of CNTs surfaces

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The poor solubility of CNTs in most solvents limits their applications. Their poor solubility

in aqueous and organic solvents and limited compatibility with polymer matrices are major

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drawbacks, rendering these materials incapable of achieving their full potential. Hence the

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functionalisation of nanotubes is extremely important, as it increases their solubility and

process ability [128]. Several modification approaches like physical, chemical or combined
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modifications have been exploited for their homogeneous dispersion in common solvents to

improve their solubility and applications. In order to enhance their performance, broaden
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their properties and expand their applications, various chemical and physical approaches have
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been pursued to modify the walls of CNTs. Functionalised CNTs have been used as

electrochemical sensors and many review papers concerning CNTs-electrochemical sensors

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have been highlighted [129-134] and they mainly focused on the discussion of organic
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modification of CNTs for biosensors.

There are different strategies addressing the surface of CNTs, which can be divided into two
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general classes: (1) The supramolecular approach including the self-assembled construction

using non-covalent interactions. (2) The chemical addition of reactive molecules, resulting in

the formation of a new covalent bond. The supramolecular approach comprises the

endohedral filling and non-covalent functionalisation. The chemical approach includes the

defect and covalent side wall functionlisation [24, 135]. A number of methods of organic

functionalisation have been developed, which can be divided into two major approaches: (1)

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Page 11 of 165
non-covalent supramolecular modifications, and (2) covalent functionalisation. In Singh et

al.‘s [128] tutorial review, they studied the covalent modification of SWCNTs with organic

moieties and illustrated the major analytical techniques routinely used to characterise the

functionalised materials.

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However, with the development of CNT chemistry, the concept of its functionalisation

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gradually moved from organic materials to inorganic materials. So far, numerous literatures

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have demonstrated that various inorganic materials such as metal nanoparticles, metal oxides

and semiconductor nanoparticles, have been widely employed to modify CNTs. Furthermore,

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electrochemical activities of these hybrid composites have also been systematically

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investigated. There are few review papers involving electrochemical sensors based on CNTs

modified with inorganic nanomaterials and making a comprehensive highlight about

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functionalised CNTs for electrochemical sensors [24, 136]. Fig.3 shows various

functionalisation processes that include organic, polymer, DNA, enzyme and inorganic
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materials that have been widely employed to modify CNTs.

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3.2. Endohedral functionalisation

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One possibility of CNT functionalisation is the filling of the inner cavity with molecules,
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called endohedral functionalisation, which, especially, is interesting for the development of

nanowires [35], storage applications fuel [73] and nanocontainers. Additionally,

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metallofullerenes were encapsulated in CNTs as well as noble metals (e.g. Au, Ag, Pt, Pd),

yielding metallic nanowires [35, 37]. In opened MWCNTs with an inner diameter of 2-10

nm, bio molecules such as carotene or proteins (lactamase) were also channeled in, showing a

catalytic activity inside the CNTs. Even the polymerisation of conductive polymers inside a

carbon nanotube was achieved.

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 3.3. Non-Covalent functionalisation

One major drawback of CNTs is the poor solubility in organic solvents or water, due to their

strong interfacial π- π -interactions. These properties can also be utilized for a further kind of

functionalisation (non-covalent) which coincidentally results in an efficient debundling.

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Noncovalent couplings are commonly based on hydrophobic interactions between a CNT and

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a biomolecule. For example, various proteins can absorb spontaneously on the sidewalls of

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acid-oxidised CNTs. Electrostatic interactions can also be used for functionalising CNTs with

biomolecules. For example, an elegant way to prepare electrochemical biosensors is to coat

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CNTs with one or multiple enzyme layers via a layer-by-layer (L-B-L) electrostatic process

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[137, 138]. A broad variety of amphiphilic or surfactants, as well as different kinds of

polymers, are also added to a CNT dispersion, yielding significantly individualisation after
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ultra-sonication or stirring [139]. An important benefit of this kind of functionalisation is the

reversibility and the structural integrity of the nanotube, as no covalent bonds between the
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addend molecules and the nanotube surface are formed [140]. Another invaluable advantage
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is the fact that besides the design of the corresponding addend molecules, no special chemical

equipment and knowledge is necessary, making this method very convenient and scalable.
p
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First basic findings in this field exhibited that indeed π - π -interactions are fundamental for

the attaching of addends to the CNT surface, including experiments with small aromatic
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molecules such as cyclohexane, cyclohexene. Further on, classical detergents such as SDS

(Sodium dodecylsulfate) or SDBS (Sodium dodecylbenzenesulfonate) have extensively

become standard surfactants in carbon nanotube chemistry and processing, due to their

unlimited availability and low prices in contrast to other surfactant molecules. As for the

classical surfactants, another substance class successfully attached on the CNT surface

yielding water soluble CNT materials, are ionic liquids. Especially, the detergent molecules

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SDS and SDBS can not only interact via π-π -interactions with the CNT surface, but their

unpolar tail can additionally wrap around the nanotube. This binding motif can be used

wrapping a huge variety of synthetic- and bio-polymers as, for example, DNA around

nanotubes, tailoring the degree of debundling and the solubility in different solvents. The

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DNA functionalised samples could be separated into nanotube batches with different

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diameters, as well as by ion exchange chromatography and density ultra-centrifugation.

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Recently, Zhan et al. [141] noncovalently attached Poly(methacrylic acid-co-acrylamide)

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(P(MAA-co-AAM) unto the surface of multiwalled carbon nanotubes (MWCNTs) through

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hydrophobic interactions and hydrogen bonding or electrostatic attraction. This method was

employed for the first time as a novel matrix for enzyme immobilisation to develop highly
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sensitive amperometric biosensors. Bilalis et al. [142] discussed the non-covalent

functionalisation through various types of interactions between polymers and carbon

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nanotubes as shown in Fig. 4. Recently, various researchers have non-covalently

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fuctionalised various compounds unto CNTs [14, 140, 142-148].

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3.4. Defect functionalization

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A considerable numbers of researchers presumes that the CNT sidewall is inert and that edge-

plane-graphite-like open ends and defect sites are responsible for the electron transfer activity
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observed. In contrast, studies of well characterised single-walled nanotube (SWNT)

electrodes, either as individual tubes or as two-dimensional networks, suggest sidewall

activity. Dumitrescu, et al.’s [99] review highlighted defects as a result of oxidation of

impurities.The fact that nanotubes have two fullerene-like end-caps and in reality are not

perfect sp2 cylinders, additionally results in a partial oxidation of the CNT material. Next to

their end-caps, nanotubes display various disorders from topological, rehybridisation

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Page 14 of 165
incomplete bonding defects, right up to intramolecular junctions and Stone-Wales defects.

These defects occur preferentially on small diameter CNTs and in locations with an increased

reactivity which are oxidised during the purification process. The oxidation mainly yields an

opening of the sp2 carbon lattice and the generation of carboxylic acid or other oxygen

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containing functionalities at the defect sites. There are different oxidation approaches,

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including nitric and sulphuric acid, mixtures of hydrogen peroxide and sulphuric acid,

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gaseous oxygen and ozone, as well as potassium permanganate. Additionally, ultra-sonication

steps further shorten the oxidized nanotubes, yielding an even higher degree of introduced

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oxygen containing functionalities. Materials which were treated in such a fashion, afterwards,

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exhibit increased solubility in polar organic solvents.
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3.5. Covalent sidewall functionalisation

In defect functionalisation, only the ends and the defects of CNTs can be functionalised,
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whereby only a small surface area of the CNT can be addressed [115]. As a consequence, the
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degree of functionalisation is relatively low and the introduction of defect sites deteriorates

the electronic and mechanical properties of the nanotube. By direct covalent sidewall
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functionalisation, the complete CNT surface can be addressed, resulting in a very high degree
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of functionalisation and the preservation of the structural integrity of the CNT framework

[149, 150]. The addition only yields a hybridization of sp2 into sp3 carbon atoms, which has a
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minor influence on the mechanic stability of the CNT. The reactivity of the carbon allotrope

(SWCNT) is by far lower in comparison to the fullerenes, although some reaction sequences

were successfully transferred from fullerene to CNT chemistry. Another opportunity is the

activation of CNTs in combination with subsequently mild reactions, as in the case of

fluorinated ones and other halides.

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Page 15 of 165
Kamil Reza et al. [151] fabricated the chemically functionalized multi-walled carbon

nanotubes (MWCNT) electrophoretically deposited onto indium tin oxide for urea detection.

Urease and glutamate dehydrogenase are attached to MWCNT/ITO electrode surface

covalently using ethyl-dimethylaminopropyl-carbodiimide and N-hydroxysuccinimide

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coupling chemistry. Excellent electrochemical properties of MWCNT and covalent

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functionalisation of dual enzyme improve biosensor stability and sensitivity. Various

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researchers also covalently functionalised various compounds unto CNTs surfaces [143, 152-

161].

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3.6. The chemical modification

It is well-known that chemical treatments improve the nanotube electrochemical reactivity by

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creating edge-like defects on their exposed sidewalls. Before use, Tuarino et al. [115]

performed an acid treatment on carbon nanotubes and to prove the effect of the treatment on
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these nanostructured electrodes, contact angles were measured. The modification protocol
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was generally achieved by attaching specific molecule or entity which imparts chemical

specificity to the substrate material. These chemical modifications can be easily achieved in
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many ways and the modification routes are mainly classified into two namely, surface
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modification and bulk modification. The surface modification includes electrochemical

induced method, polymer grafting and metal nanoparticle deposition. The later includes
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chemical reduction of diazonium salts, using hypo-phosphorous acid as a reducing agent,

thermally activated covalent modification, microwave assisted modification and ball milling

modification.

3.7. Physical functionalisation

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Page 16 of 165
Functionalisation of CNTs using covalent method can provide useful functional groups onto

the CNT surface. However, these methods have two major drawbacks: firstly, during the

functionalisation reaction, especially along with damaging ultra-sonication process, a large

number of defects are inevitably created on the CNT sidewalls and, in some extreme cases,

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CNTs are fragmented into smaller pieces. These damaging effects result in severe

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degradation in mechanical properties of CNTs as well as disruption of p electron system in

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nanotubes. The disruption of p electrons is detrimental to transport properties of CNTs

because defect sites scatter electrons and photons that are responsible for the electrical and

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thermal conductions of CNTs respectively. Secondly, concentrated acids or strong oxidants

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are often used for CNT functionalisation, which are environmentally unfriendly. Therefore,

many efforts have been put forward to develop methods that are convenient to use of low cost
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and less damage to CNT structure. Non-covalent functionalisation is an alternative method

for tuning the interfacial properties of nanotubes. The suspension of CNTs in the presence of
d

polymers, such as poly(phenylenevinylene) [65] or polystyrene [66], leads to the wrapping of

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polymer around the CNTs to form supermolecular complexes of CNTs. The polymer

wrapping process is achieved through the van der Waals interactions and p–p stacking
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between CNTs and polymer chains containing aromatic rings.

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Ac

4. Review studies

Because of the excellent properties of CNTs, such as large surface-to volume ratio, high

conductivity and electron mobility at room temperature, as well as low energy dynamics of

electrons with atomic thickness, robust mechanics and flexibility, makes it to be at the centre

of an ever- growing research. These unique properties have made many researchers to review

synthesis of CNTs and their applications in recent years. Some of the reviews present

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possible technological applications, with focus on the electronic properties and basic physics

of carbon nanotubes.

4.1. Review of CNTs synthesis and production

There are many reviews on CNTs and their applications to various devices. However, few of

t
the review articles connect the intrinsic properties of CNT with its energy. Chaudhary et al.

ip
[162] in their review, discussed the electrochemical sensors and biosensors based on carbon

cr
nanotubes, metal oxide nanoparticles and ionic liquid/composite modified electrodes. The

main thrust of the review was to present an overview of the advantages of the use of RTILs

us
along with nanomaterials for electrochemical sensors and biosensors. Consequently, recent

an
developments and major strategies for enhancing sensing performance have been thoroughly

discussed. Balasubramanian and Burghard [6], in their review, highlighted various design
M
methodologies for CNT-based biosensors and their employment for the detection of a number

of biomolecules. In addition, recent developments in the fields of CNT-based chemiresistors

d

and chemically sensitive field-effect transistors were presented. After a critical discussion of
te

the factors that currently limit the practical use of CNT-based biosensors, the review

concluded with an outline of potential future applications for CNTs in biology and medicine.
p

Balasubramanian [163], in his review, surveyed CNT-based label-free indicator-free

ce

biosensing strategies that have been demonstrated for the sensitive detection of nucleic acids.

After an introduction to CNTs, the fabrication of biosensors and techniques for the
Ac

immobilisation of probe nucleic acids were outlined. Subsequently, two major label-free

strategies, namely: electrochemical transduction and field-effect detection were presented.

The focus was on direct detection methods that avoided labels, indicators, intercalating

agents, mediators, and even secondary receptors. The review concluded with a comparison

between the various biosensors and presented ways of engineering them so that they can be

deployed in realistic diagnostic applications. Agüí et al. [164] in their review, covered recent

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Page 18 of 165
advances in the development of new designs of electrochemical sensors and biosensors that

make use of electrode surfaces modification with CNTs. Applications based on carbon

nanotubes-driven electrocatalytic effects and the construction and analytical usefulness of

new hybrid materials with polymers or other nanomaterials, were treated. Moreover,

t
electrochemical detection using CNTs-modified electrodes as detecting systems in separation

ip
techniques such as high performance liquid chromatography (HPLC) or capillary

cr
electrophoresis (CE), were also considered. Finally, the preparation of electrochemical

biosensors, including enzyme electrodes, immunosensors and DNA biosensors, in which

us
carbon nanotubes play a significant role in their sensing performance, were separately

an
considered. Mittal and Kumar‘s [85] review focused on CNT chemiresistive gas sensing

mechanisms, which make them suitable for the development of next generation sensor
M
technology. The resistance of CNTs decreases when oxidizing gas molecules adsorb on their

surface, whereas, adsorption of reducing gas molecules results in increasing the resistance of
d

CNTs. Sensing ability of CNTs for the gases, namely, NO, NO2, CO, CO2 and SO2, released
te

on burning of fossil fuels was reviewed. This review provided basic understanding of sensing

mechanisms, creation of adsorption sites by chemical processes and charge transfer between
p

adsorbed gas molecules and surface of CNTs. In addition, useful current update on research
ce

and development of CNT gas-sensors were provided. Various groups had earlier reviewed

synthesis of CNTs [24, 99, 134, 165] and some groups recently reviewed the synthesis and
Ac

application of CNTs [7, 8, 24, 77, 78, 101, 118, 165-172].

4.2. CNTs electrochemical reviews

The functionalisation and application of CNTs in electroanalysis [150, 173] have been

extensively reviewed in recent years [174-177]. Walcarius et al. [178], in their review

highlighted the interest of nanomaterials for building biologically modified electrodes.

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Page 19 of 165
Ragavan et al. [179] comprehensively reviewed principles, mechanisms and the performances

of chemical sensors and biosensors available in the literature. They also discussed future

perspectives in developing sensors for the detection of BPA.Over the past few years, much

work has been done in the design and preparation of novel CNTs-based materials for a wide

t
range of applications in photoelectron chemistry, ranging from photo electrochemical solar

ip
cells, photo catalytic decomposition of organic pollutants, photo-catalytic splitting of H2O,

cr
and photo-catalytic conversion to fuels. Taurino et al. [115] reviewed MWCNT fabricated on

silicon substrate with four different orientations via chemical vapor deposition. It is well-

us
known that chemical treatments improve the nanotube electrochemical reactivity by creating

an
edge-like defects on their exposed sidewalls. Chaudhary et al.’s [162] review discussed the

electrochemical sensors and biosensors based on CNTs, metal oxide nanoparticles and ionic
M
liquid/composite modified electrodes. Recent developments and major strategies for

enhancing sensing performance were thoroughly discussed.

d
te

Pisoschi [20] reviewed recent advances in biosensor construction and the development of

modified electrodes based on CNTs. Others were nanocomposite materials and the use of
p

screen printing or sol-gel technique. Potentiometric biosensors make use of ion selective
ce

electrodes, gas sensitive electrodes, redox electrodes, solid state electrodes and ion selective

field effect transistors in order to transduce the biochemical reaction into an analytical signal.
Ac

Amperometric biosensors are based on redox reactions, namely the oxidation/reduction of

electroactive species generated/consumed in an enzyme-reaction. Optical biosensors rely on

the measurement of an optical property that varies as a result of the enzymes’ reaction.

Thermal biosensors rely on the measurement of the thermal effect that follows an enzyme

catalysed reaction. Piezoelectric biosensors are based on the diminution of the vibration

frequency of an oscillator crystal, due to the mass variation which occurs after the adsorption

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Page 20 of 165
of a chemical compound on its surface. The applications of biosensors in the assessment of

key food components, in environmental, pharmaceutical and clinical analysis were also

reviewed. Salavagione et al.’s [80] review provided an overview of recent research on

chemical sensors based on polymer composites with CNTs and graphene (G) for quantitative

t
and qualitative analysis in diverse application fields such as biosensing (DNA, enzymes,

ip
proteins, antigens and metabolites), chemical and gas sensing using electrochemical and

cr
optical detection methods. Both CNTs and G show outstanding electrical, chemical,

electrochemical and optical properties that make them ideal candidates for use in chemical

us
sensors. The incorporation of polymers into the development of this type of sensor not only

an
improved the CNT and G dispersion, but also enhanced some of their properties like redox

behaviour and biocompatibility, and provides additional properties such as photoelectric or

M
swelling capacity. Moreover, unique synergistic effects arising from the combination of the

matrix and nanofiller contributions were described by means of several examples

d

highlighting the most important achievements in this field. Special emphases were placed
te

throughout the review on analysing the role of the polymer in different sensing platforms.

The combination of polymers with carbon nanomaterials for the preparation of chemical
p

sensors opened up exciting areas of research due to their biocompatibility and excellent
ce

sensitivity and selectivity.

Various groups have earlier reviewed CNTs-electrochemical sensors [133, 134, 180-182] and
Ac

other groups have recently reviewed CNTs-electrochemical sensors [55, 67, 80, 91, 163, 183-

190].

4. CNTs nanocomposites

Various hybrid composites based on CNTs with inorganic (metal and metal oxide) [191] and

organic materials [192] have been reported in recent years [56, 141, 170, 192-222]. CNTs, as

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support materials, have been employed for the dispersion and stabilisation of various

inorganic nanomaterials and organic materials owing to their large chemical active surface

and stability. Carbon and noble metal nanomaterials exhibit unique properties that have been

explored over the last few decades for developing electrochemical sensors and biosensors.

t
Hybridisation of nanometals to carbon nanomaterials such as graphene or CNTs produces, a

ip
synergistic effect on the electrocatalytic activity when compared to either material alone.

cr
These hybrid materials formed have shown great potential application in catalysis [75],

electronics [223], optics [223], sensors [224] and energy storage devices [225].

us
CNT-inorganic nanocomposites (metal and metal oxide) [191, 226] have opened up an

an
exciting new field in the science and technology of CNT. CNT-metal nanoparticles have

excellent conductivity and catalytic properties, which make them suitable for acting as
M
‘electronic wires’ to enhance the electron transfer between the redox centres in proteins and

electrode surfaces, and as catalysts to increase electrochemical reaction rates [79, 203]. The
d

conductivity of nanocomposites enhances electron transfer between the active centres of

te

enzymes and electrodes so that the particles act as electron transfer conduits or mediators

[204]. Metal nanoparticles such as Au, Ag, Pt, Pd and metal oxide deposited CNTs as sensing
p

materials have been constructed for excellent electro chemical sensors and biosensors as seen
ce

in Table 1.They improve electrical conductivity and electron transport on the modified

electrode surface.
Ac

Venegas et al. [203] recently embarked on comparative study and investigated the efficacy of

various platinum-carbon hybrid nanostructures for amperometric biosensing. Electroactive

surface area, sensitivity towards hydrogen peroxide (H2O2), response time, limit of detection,

and surface roughness were measured for various hybrid nanomaterial arrangements. Both

design factors (nanocarbon concentration and network arrangement) influenced the

performance of the reduced graphene oxide-based platforms; whereas only nanomaterial

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arrangement affected the performance of the CNTs-composites. The highest sensitivity

towards H2O2 mM-1 was measured for a graphene concentration of 2 mg mL-1 in a

"sandwich" structure nanoplatinum layers enveloping the reduced graphene oxide. Likewise,

the best carbon nanotube performance toward H2O2 (49 +/- 1.4 A mM-1) was measured for a

t
sandwich-type structure with nanoplatinum. The enhanced electrocatalytic activity of this

ip
"sandwich" structure was due to a combined effect of electrical junctions formed amongst

cr
nanocarbon, and nanocomposite soldering to the electrode surface. The top-down carbon-

platinum hybrid nanocomposites in the paper represent a simple, low-cost, approach for

us
formation of high fidelity amperometric sensors with remarkable performance characteristics

an
that are similar to bottom-up fabrication approaches. Yu et al. [204] fabricated poly-

diallyldimethylammonium chloride (PDDA)-capped gold nanoparticles (AuNPs)

M
functionalised G/ MWCNTs nanocomposites. Based on the electrostatic attraction, the

G/MWCNTs hybrid material can be decorated with AuNPs uniformly and densely. The new
d

hierarchical nanostructure can provide a larger surface area and a more favorable
te

microenvironment for electron transfer. The AuNPs/G/MWCNTs nanocomposite was used as

a novel immobilisation platform for glucose oxidase (GOD). Direct electron transfer (DET)
p

was achieved between GOD and the electrode. Field emission scanning electron microscopy
ce

(FESEM), UV and CV were used to characterize the electrochemical biosensor. The glucose

biosensor fabricated based on GOD electrode modified with AuNPs/G/MWCNTs,

Ac

demonstrated satisfactory analytical performance with high sensitivity (29.72mAM-1cm-2)

and low limit of detection (4.8µM). The heterogeneous electron transfer rate constant (ΚS)

and the apparent Michaelis-Menten constant (Km) of GOD were calculated to be 11.18s-1 and

2.09mM respectively. With satisfactory selectivity, reproducibility and stability the

nanostructure we proposed offered an alternative for electrode fabricating and glucose

biosensing. Wang et al. [191] constructed a sensitive and selective imprinted electrochemical

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Page 23 of 165
sensor for the determination of aflatoxin B1 (AFB1) on a glassy carbon electrode by stepwise

modification of functional MCNTs, Au/Pt bimetallic nanoparticles (Au/PtNPs) and a thin

imprinted film. The fabrication of a homogeneous porous poly o-phenylenediamine (POPD)-

grafted Au/Pt bimetallic MWCNT nanocomposite film was conducted by controllable

t
electrodepositing technology. The sensitivity of the sensor was improved greatly because of

ip
the nanocomposite functional layer; the proposed sensor exhibited excellent selectivity

cr
toward AFB1 owing to the porous molecular imprinted polymer (MIP) film.

Xu et al. [88] prepared a novel polyurethane (PU) conducting composite thin films based on

us
tetra hydroxyl-terminated poly(butadiene-co-acrylonitrile) (THTBN) and hydroxyl-

an
functionalized multi-walled carbon nanotubes (MWNTs-OH), via an in-situ coupling reaction

route between hydroxyl groups and isocyanate groups. Wang et al. [227] prepared a
M
biosensor with high stability to determine H2O2. This hydrogen peroxide biosensor was

obtained by modifying glassy carbon electrode (GCE) with a composite film composed of
d

gelatin-MWNTs. Catalase (Cat) was covalently immobilised into gelatin-MWNTs modified

te

GCE through the well-known glutaraldehyde (GAD) chemistry in order to enhance the

stability of electrodes. The enzyme sensor can achieve direct electrochemical response of
p

H2O2. Jaiang et al. [193] employed a nitrogen-doped graphene/carbon nanotubes (NGR-

ce

NCNTs) nanocomposite into the study of the electrochemical sensor via electrodeposition.

The morphology and structure of NGR-NCNTs nanocomposite were investigated by SEM

Ac

and TEM, respectively. Meanwhile, the electrochemical performance of the glassy carbon

electrode (GCE) modified with electrodeposited NGR-NCNTs (ENGR-NCNTs/GCE)

towards caffeine (CAF) and vanillin (VAN) determination was demonstrated by CV and

square wave voltammetry (SWV). Under optimal condition, ENGR-NCNTs/GCE exhibited a

wide linearity of 0.06-50µM for CAF and 0.01-10µM for VAN, with detection limits of

0.02µM and 3.3×10-3µM respectively. Furthermore, the application of the proposed sensor in

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Page 24 of 165
food products was proven to be practical and reliable. The desirable results show that the

ENGR-NCNTs nanocomposite has promising potential in electrocatalytic biosensor

application.

t
Du et al. [228] developed a facile approach for the preparation of nanocomposite based on β-

ip
lactoglobulin (BLG)-functionalised MWCNTs and gold nanoparticles (GNPs). Owing to the

cr
amphipathic nature, BLG can be adopted onto the surface of MWCNTs to form BLG-

MWCNTs with uniform dispersion in water. Taking advantage of sulfhydryl groups on BLG-

us
MWCNTs, GNPs were decorated on the BLG-MWCNTs-modified glassy carbon electrode

an
(GCE) by electrodeposition. The nanocomposite was characterised by TEM, SEM and X-ray

spectroscopy analysis. CV and chronoamperometric method were used to evaluate the

M
electrocatalytic ability of the nanocomposite. Furthermore, a glucose biosensor was

developed based on the immobilisation of glucose oxidase with cross-linking in the matrix of
d

bovine serum albumin (BSA) on the nanocomposite modified GCE. The resulting biosensor
te

exhibited high sensitivity (3.98µAmM-1), wider linear range (0.025-5.5mM), low detection

limit (1.1µM at the signal-to-noise ratio of 3) and fast response time (within 7s) for glucose
p

detection.
ce

6. Electrochemical sensing
Ac

6.1. CNTs electrochemical sensing

Carbon materials possess suitable properties for the design of electrodes used in electro

analytical chemistry because of their relatively wide potential windows in aqueous media,

low cost, and relative chemical inertness in most electrolyte solutions. Carbon nanomaterials

are typically used in electrochemical biosensing applications for their unique properties

[229].There are several available microstructures of carbon materials, such as graphite, glassy

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Page 25 of 165
carbon, carbon fiber, CNTs, amorphous powders and diamond [230]. CNTs have tremendous

potential for electrochemical catalysis, biosensing and as a novel electrode material. CNTs

have been incorporated in electrochemical sensors to decrease overpotential and improve

sensitivity [133]. CNTs have been attracting a lot of interest as electron transfer mediators to

t
enhance electrochemical biosensing [183, 231]. CNT-based electrochemical transducers can

ip
offer substantial improvements in the performance of amperometric enzyme electrodes,

cr
immunosensors or nucleic-acid sensing devices. The superior electronic properties of CNTs,

in conjunction with their size and mechanically robust nature, make these nanomaterial

us
extremely attractive for the development of next generation biosensing platforms [129, 133,

an
232].

Electrochemical detection is highly sensitive to electro active molecules and also offers
M
detection selectivity, as different molecules can be oxidised/reduced at different potentials.

CNT, graphene, graphite and fullerene are often used for electrochemistry due to their low
d

residual current, readily renewable surface and wide potential window. The large over
te

potential for O2 reduction and H2 density of edge-plane defect sites on CNTs provides

multiple active sites for electron transfer to biospecies [133, 233, 234]. CNTs are excellent
p

conductor of electrical charge and the large surface area of CNTs facilitates large number of
ce

electroactive sites. Electrodes made from CNTs have more uniform distribution of

electrochemically active sites than do those made from graphite. Its entire volume is exposed
Ac

to the surroundings due to its 2D structure, making it very good in detecting adsorbed

molecules on the electrode. These properties show that CNTs can be ideal immobilisation

matrixes for biomolecules, at the same time, they can transmit electrochemical signals acting

as transducers. CNTs can be used as electrical bridges that communicate with the enzymes

and the electrodes, leading to the development of various novel biosensors [235]. The

MWCNTs embedded in enzyme were like "conductive wires" connecting enzyme with

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Page 26 of 165
electrode, reduced the distance between them and were propitious to fast direct electron

transfer [41, 236]. Efficient electrochemistry also takes place when metals nanoparticles

(NP) decrease the distance between the redox site of a protein and the electrode surface, as

the rate of the electron transfer (ET) is inversely proportional to the exponential distance

t
between them.

ip
cr
The direct wiring of enzymes to an electrode surface is essential to amplify the

electrochemical signal of the biochemical reaction [13, 68]. CNTs support efficient electrical

us
wiring of the redox centers of several metalloproteins containing heame (cytochrome c,

an
myoglobin, and horseradish peroxidase) to the electrode [68] as shown in Fig. 5. Nanowiring

of redox enzyme can also take place by metal NP [13, 96]. Direct electron transfer (DET)
M
between redox enzymes and the electrode surfaces can be used for the study of enzyme

kinetics and thermodynamics of redox transformation of enzymes’ molecules involving redox

d

transformations [68, 237]. DET can also be used to investigate enzyme catalysed reactions in
te

biological systems. Direct electrochemistry of enzymes involves direct ET between the

electrode and the active centre of the enzymes without the participation of mediators or other
p

reagents. Studies have demonstrated that CNTs can significantly enhance the electrochemical
ce

reactivity of important biomolecules and can promote the DET reaction of proteins [238-

240]. New mediator-free (or reagent less) biosensors [15, 241-243], enzymatic bioreactor,
Ac

and biomedical devices employ DET by immobilising enzymes on conducting substrates.

The redox centres of the biomolecules are usually embedded deep in their large three-

dimensional structures. Recent research has shown that CNTs can enhance DET between

enzymes and electrodes [244]. The electron transfer between CNTs and redox active species

occurs at the edges of the CNTs sheet and/or at defects in the basal plane. The high surface

area of CNTs typically provides a large number of electroactive sites that enhance ET and

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Page 27 of 165
promote potential applications in electrochemical sensing [245]. CNTs have shown to be

particularly promising to establish electronic communication with redox enzymes because of

their tiny diameter which can closely approach the redox active sites [246, 247]. The facile

electron transfer between CNTs and a variety of protein redox cofactors, in conjunction with

t
conductive polymers and metallic or semi-conductor nanoparticles, provides the means to

ip
implement highly sensitive electrochemical biosensing protocols [232, 248, 249].

cr
6.2. CNT-based electrochemical enzymatic biosensors

us
Electrochemical sensors have been developing very fast in the last decades due to the

an
possibilities of generating miniaturised and simplified low-cost analytical devices [250].

CNTs can enhance the electrochemical reactivity of important biomolecules and can promote
M
the electron-transfer reactions of proteins (including those where the redox centre is

embedded deep within the glycoprotein shell). In addition to enhanced electrochemical

d

reactivity, CNTs-modified electrodes have been useful when coated with biomolecules (e.g.,
te

nucleic acids) and to alleviate surface fouling effects (such as those involved in the NADH

oxidation process) [40].

p
ce

The first enzymes electrode was proposed by Clark and Lyons [251] and, since then,

electrochemical biosensors based on the use of enzymes have received great attention,
Ac

because of the advantages of the association of the biocatalytic activity of enzymes with the

high sensitivity and versatility of the electrochemical transduction. CNTs have been shown to

be particularly useful to establish electronic communication with redox enzymes. Because of

their tiny diameter, they can closely approach the redox active sites. CNTs can act as

molecular wires to allow efficient electron transfer between the underlying electrode and the

redox centres of enzymes as in Fig. 5. They can promote the direct electron-transfer reaction

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Page 28 of 165
of proteins, and CNT-modified electrodes can also alleviate the surface fouling effects. These

properties make CNTs extremely attractive for a wide range of electrochemical biosensors.

The immobilisation of enzyme is critical, since the enzyme has to remain active to perform

t
efficient bio recognition of the substrate. The transducer where the enzyme is immobilised

ip
has to allow a fast charge transfer to ensure a rapid and sensitive response for a good

cr
biosensor. Several strategies for immobilising redox enzymes and other proteins on CNTs-

modified electrodes have been explored [67, 70, 252]. Proper conjugation between biological

us
molecules such as enzymes, ssDNA, RNA, Ab, receptors and aptamers need to be developed

an
for CNTs-based electrochemical sensing electrodes [44]. Appropriate functionalisation of

CNT and the immobilisation of biomaterials on it are important, as functional groups can
M
create defects on CNTs surfaces [186]. CNTs are excellent materials for use as electrodes in

electrochemical sensors due to fast electron-transfer kinetics from a number of electroactive

d

species. A wide range of sensor architectures have been developed from carbon-nanotube
te

paste electrodes (CNTPE), glassy carbon electrodes (GCE) modified by CNTs, metal

nanoparticle-modified CNT electrodes, to CNTs embedded in a conducting polymer matrix.

p

Many sensing methodologies involve immobilising enzymes at the CNT electrode, either
ce

through electrostatic forces or through covalent attachment. Glucose sensing has been a

major thrust of electrochemical biosensor development. Table 2 shows different types of

Ac

enzymatic CNT-based biosensor.

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Page 29 of 165
7. Use of electrodes based-CNT for electrochemical detection of biomolecules and

metals

7.1.1. Glucose biosensor

The metabolic disorder of diabetes mellitus results in the deficiency of insulin and

t
ip
hyperglycaemia and is reflected by blood glucose concentration higher or lower than the

normal range of 80–120 mg dL−1 (4.4–6.6 mmol L-1). The disease is a leading cause of death

cr
and disability [253, 254]. This is reflected by the multibillion USD glucose sensing markets

us
[255, 256]. Two of the most common diseases in the developed world are cancer and diabetes

[188, 257]. Therefore, the diagnosis and management require close monitoring of blood

an
glucose levels. The application of CNT in highly sensitive and cost-effective biosensors can

aid the monitoring of diabetic diseases [258]. Real-time monitoring of physiological glucose
M
transport is crucial for gaining new understanding of diabetes. The development of various

types of biosensors (e.g. electrochemical, optical sensors) for laboratory and/or clinical
d

applications will provide new insights into the cause(s) and possible treatments of diabetes.
te

There is the need for a powerful diagnostic and monitoring tool for measuring glucose in
p

diabetes research and point of care diagnostics.

ce

Taguchi et al.’s [259] review provided a general overview of the state of the art in
Ac

nanomaterial-mediated biosensors for in vivo and in vitro glucose sensing, and discussed

some of the challenges associated with nanomaterial toxicity. CNTs have recently been

employed in many schemes for sensing glucose [260]. In the determination of glucose levels

using biosensors which detect the glucose molecule by catalysing glucose to gluconic acid

and H2O2 in the presence of oxygen, H2O2 is detected electrochemically. The direct

electrochemistry of CNTs based on redox-active centers was confirmed by CV experiments

in the potential range of 0.8–0 V [204, 261]. DET was achieved between GOD and the

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Page 30 of 165
electrode, making this an analytically valuable signal that has been used in glucose sensing

[41, 204, 242, 245, 262-266], while mediator was used in glucose sensing by Takase et al.

[267], Qiu et al. [268-270], Lin et al. [271] and Kavanagh and Leech [272]. Yu et al. [204]

reported direct electrochemistry of glucose oxidase (GOD) on three-dimensional (3D)

t
interpenetrating porous CNTs electrodes as shown in Fig. 7. Chen et al. [273] reviewed

ip
glucose detection in biomedical applications, principles, methods and recent developments in

cr
electrochemical glucose sensors. They gave attention to the discussion on some problems and

bottlenecks in areas of nonenzymatic and enzymatic (glucose oxidase-based) amperometric

us
glucose sensing. Huang et al. [35] fabricated glucose biosensor with high sensitivity and low

an
detection limit by modifying one-dimensional ultra-long Cu nanowires (Cu NWs) and

MWCNTs hybrid on the surface of glassy carbon electrode (GCE). Cu NWs with uniform
M
diameter were synthesised by a facile approach in large scale and characterized by SEM, X-

ray diffraction (XRD). The electrocatalytic activity of the as-prepared biosensor towards
d

glucose oxidation was investigated by cyclic voltammetry and amperometric measurement in

te

alkaline media. The results showed that the biosensor exhibited a rapid response time of less

than 1 s and high sensitivity of 1995 µAm M−1 cm−2, with a wide linear range (up to 3 mM)
p

and low detection limit (0.26 µM at signal/noise ratio (S/N) = 3). For practical application,
ce

the biosensor was successfully applied to detect glucose in serum and study the relationship

between the glucose concentrations in cultivated cells and the glucose concentrations in
Ac

culture mediums in which the cells were cultivated. All the results of the experiment showed

that the Cu NWs–MWCNTs hybrid had great potential applications in the development of

biosensors for enzyme-free detection of low concentration glucose.

DET from GOD has been reported by several authors [239, 266, 274-284]. Li et al. and others

[204, 238, 262, 285-287] reported DET in some hybrid composite of glucose sensors. Li et al.

[238] reported that the DET of glucose oxidase (GOx) was achieved based on the

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Page 31 of 165
immobilisation of CdSe@CdS quantum dots on glassy carbon electrode by MWNTs-chitosan

(Chit) film. The immobilised GOx displayed a pair of well-defined and reversible redox

peaks with a formal potential (E θ') of -0.459 V (versus Ag/AgCl) in 0.1 M pH 7.0 phosphate

buffer solution. The apparent heterogeneous electron transfer rate constants (k s) of GOx

t
confined in MWNTs-Chit/CdSe@CdS membrane were evaluated as 1.56 s-1 according to

ip
Laviron's equation. The surface concentration (Γ*) of the electroactive GOx in the MWNTs-

cr
Chit film was estimated to be (6.52 ± 0.01) × 10-11 mol cm -2.

us
Meanwhile, the catalytic ability of GOx toward the oxidation of glucose was studied. Its

an
apparent Michaelis-Menten constant for glucose was 0.46 ± 0.01 mM, showing a good

affinity. The linear range for glucose determination was from 1.6 × 10-4 to 5.6 × 10 -3 M with
M
a relatively high sensitivity of 31.13 ± 0.02 µA mM-1 cm-2 and a detection limit of 2.5 × 10 -5

M (S/N=3). Ali et al. [150] fabricated a highly-sensitive glucose biosensor amenable to ultra-
d

miniaturisation by immobilisation of glucose oxidase (GOx), onto a poly(2,6-

te

diaminopyridine)/multi-walled carbon nanotube/glassy carbon electrode (poly(2,6-

DP)/MWNT/GCE). CV was used for both the electrochemical synthesis of poly-(2,6-DP) on

p

the surface of a MWNT-modified GC electrode and characterisation of the polymers

ce

deposited on the GC electrode. The synergistic effect of the high active surface area of both

the conducting polymer, i.e., poly-(2,6-DP) and MWNT gave rise to a remarkable
Ac

improvement in the electrocatalytic properties of the biosensor. The transfer coefficient (α),

heterogeneous electron transfer rate constant and Michaelis-Menten constant were calculated

to be 0.6, 4 s-1 and 0.20 mM at pH 7.4, respectively. The GOx/poly(2,6-DP)/MWNT/GC

bioelectrode exhibited two linear responses to glucose in the concentration ranging from 0.42

µM to 8.0 mM with a correlation coefficient of 0.95, sensitivity of 52.0 µAmM-1 cm-2,

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Page 32 of 165
repeatability of 1.6% and long-term stability, which could make it a promising bioelectrode

for precise detection of glucose in the biological samples.

Various groups have earlier shown that CNTs-based glucose biosensors exhibit good

t
sensitivity, selectivity and reproducibility [12, 14, 111, 150, 239, 271, 274-275, 288-298].

ip
Jose et al. [299] and others employed direct electron transfer in a mediator-free glucose

cr
oxidase-based carbon nanotube-coated biosensor in detection of low concentration glucose.

Bhattacharyya et al. [300] developed a lipid functionalised single walled carbon nanotube-

us
based self-assembly that formed a super-micellar structure. This assemblage has been

an
exploited to trap glucose oxidase in a molecular cargo for glucose sensing. The advantage of

such a molecular trap is that all components of this unique structure (both the trapping shell
M
and the entrapped enzyme) are reusable and rechargeable. The unique feature of this sensing

method lies in the solid state functionalisation of SWCNT that facilitates liquid state
d

immobilisation of the enzyme. The method can be used for soft-immobilisation (a new
te

paradigm in enzyme immobilisation) of enzymes with better thermal stability that is imparted

by the strong hydrophobic environment provided through encapsulation by the nanotubes.

p

Barman et al. [301] employed CNTs and nitrogen-doped carbon nanotubes (CNx) modified
ce

carbon cloth (CCl) materials for the first time for the development of new electrode sensor

materials characterised by CV and electrochemical impedance spectroscopy. The

Ac

voltammetric response of model electroactive species shows a close to reversible

electrochemical behavior under diffusion control, at both functionalised CNT-CCl and CNx-

CCl. Polymerisation of 3,4-ethylenedioxythiophene (EDOT) at CCl based electrodes was

performed in order to decrease the material pore size and decrease sorption. The difference in

charge values of PEDOT-modified CCl-based electrodes indicates that different amounts of

polymer are deposited at each substrate. Glucose biosensors were constructed by

33
Page 33 of 165
immobilising glucose oxidase on top of PEDOT-CNT/CNx-CCl and the analytical properties

together with operational stability were evaluated. Electrochemical impedance spectroscopy

was used to evaluate interfacial and bulk properties of CNT/CNx-CCl, PEDOT-CNT/CNx-

CCl and GOx-PEDOT-CNT/CNx-CCl electrodes, and differences in both capacitance and

t
charge transfer resistance values are seen, revealing the advantages of CNT and CNx

ip
modification of CCl.

cr
Biloivan et al. [302] investigated the possibility of application of MWCT modified with NH2-

us
groups (MWCNT-NH2) for creation of sensitive elements of the amperometric biosensor

an
based on immobilised oxidoreductases, in particular, glucose oxidase (GOD). They studied

electrochemical properties of the membranes obtained. Experiments were carried out with
M
amperometric methods using the MStat 200 device («DropSens», Spain). The enzymes were

immobilised in glutaraldehyde vapour. The method of formation of bioselective matrix based

d

on immobilised GOD with MNP-NH2 on the surface of gold amperometric electrodes was
te

optimised. Optimal working conditions of the biosensor developed were determined. Bai et

al. [26] coated free-standing MWNT films, using chemical vapor deposition method, with a
p

thin layer of nanostructural ZnO. The morphology and crystal structure of the as-grown
ce

products were characterized by SEM, X-ray, XRD and Raman scattering analyses. Field

emission (FE) results demonstrated that the needle-like and spherical ZnO–MWNTs
Ac

composite structure films possessed good performance with a turn-on field of 1.3, 2.2 V µm−1

and a threshold field of 2.6, 4.5 V µm−1 respectively.

The glucose-sensing characteristic has also been studied. The multi-layer electrode

(PDDA/GOx/ZnO/MWNTs) exhibited significant electrocatalysis to the oxidation and

reduction of H2O2 than the PDDA/GOx/MWNTs electrode, which provided wide potential

34
Page 34 of 165
applications in clinical, environmental and food analysis. Antiochia [303] described a new

amperometric biosensor for glucose monitoring. The biosensor was based on the activity of

glucose dehydrogenase (GDH) and diaphoresis (DI) co-immobilized with NAD+ into a

carbon nanotube paste (CNTP) electrode modified with an osmium functionalised polymer.

t
This mediator was demonstrated to shuttle the electron transfer between the immobilised

ip
diaphorase and the CNTP electrode, thus showing a good electrocatalytic activity towards

cr
NADH oxidation at potentials around +0.2 V versus Ag|AgCl, where interfering reactions are

less prone to occur. The biosensor exhibits a detection limit of 10 mol L-1, linearity up to 8

us
10-4 mol L-1, a sensitivity of 13.4 A cm-2 mmol-1 L-1, a good reproducibility (R.S.D. 2.1%, n =

an
6) and a stability of about one week when stored dry at 4 Co.

Finally, the proposed biosensor was applied for the determination of glucose in different
M
samples of sweet wine and validated with a commercial spectrophotometric enzymatic kit.

Salimi et al. [304] fabricated glucose biosensor by immobilising glucose oxidase into a sol-
d

gel composite at the surface of a basal plane pyrolytic graphite (bppg) electrode modified
te

with MCNT. The electrode was subjected to abrasive immobilisation of CNTs by gently

rubbing the electrode surface on a filter paper supporting the CNTs. Secondly, the electrode
p

surface was covered with a thin film of a sol-gel composite containing encapsulated glucose
ce

oxidase. The CNTs offer excellent electrocatalytic activity toward reduction and oxidation of

H2O2 liberated in the enzymatic reaction between glucose oxidase and glucose, enabling
Ac

sensitive determination of glucose.

The amperometric detection of glucose was carried out at 0.3 V (vs. saturated calomel

electrode) in 0.05 M phosphate buffer solution (pH 7.4) with linear response range of 0.2-20

mM glucose, sensitivity of 196 nA/mM and detection limit of 50 M (S/N = 3). The response
oC
time of the electrode was <5 s when it is stored dry at 4 , the sensor showed almost no

35
Page 35 of 165
change in the analytical performance after operation for three weeks. The present carbon

nanotube sol-gel biocomposite glucose oxidase sensor showed excellent properties for the

sensitive determination of glucose with good reproducibility, remarkable stability and rapid

response and in comparison to bulk modified composite biosensors, the amounts of enzyme

t
and CNT needed for electrode fabrication are dramatically decreased.

ip
Cai et al. [280] obtained a stable suspension of CNT by dispersing the CNT in a solution of

cr
surfactant, such as acetyltrimethylammonium bromide (CTAB, a cationic surfactant). CNT

(dispersed in the solution of 0.1% CTAB) has promotion effects on the direct electron

us
transfer of GOx, which was immobilized onto the surface of CNT. The direct electron

an
transfer rate of GOx was greatly enhanced after it was immobilised onto the surface of CNT.

CV results showed a pair of well-defined redox peaks, which corresponded to the direct
M
electron transfer of GOx, with a midpoint potential of about −0.466 V vs SCE (saturated

calomel electrode) in the phosphate buffer solution (PBS, pH 6.9). The electrochemical
d

parameters such as apparent heterogeneous electron transfer rate constant (ks) and the value
te

of midpoint potential (E1/2) were estimated. The dependence of E1/2 on solution pH

indicated that the direct electron transfer reaction of GOx is a two-electron-transfer, coupled
p

with a two-proton-transfer reaction process. The experimental results also demonstrated that
ce

the immobilised GOx retained its bioelectrocatalytic activity for the oxidation of glucose,

suggesting that the electrode may find use in biosensors.

Ac

Ghica and Bret [306] formed Poly(brilliant green) (PBG) and poly(thionine) (PTH) films on

carbon film electrodes (CFEs), modified with CNTs by electropolymerisation using potential

cycling. Voltammetric and electrochemical impedance characterisation were performed.

Glucose oxidase and uricase, as model enzymes, were immobilised on top of PBG/CNT/CFE

and PTH/CNT/CFE for glucose and uric acid (UA) biosensing. Amperometric determination

of glucose and UA was carried out in phosphate buffer pH 7.0 at -0.20 and +0.30 V vs. SCE

36
Page 36 of 165
respectively, and the results were compared with other similarly modified electrodes existing

in the literature. An interference study and recovery measurements in natural samples were

successfully performed, indicating these architectures to be good and promising biosensor

platforms.

t
ip
Goornava et al. [307] reported the improved performance of an electrochemical glucose

cr
sensor based on a glassy carbon electrode (GCE) that has been modified with highly purified

SWCNTs dispersed in polyethyleneimine (PEI), polyethylene glycol (PEG) and polypyrrole

us
(PPy). The SWCNTs were purified by both thermal and chemical oxidation to achieve

an
maximum purity of ~ 98% with no damage to the tubes. The SWCNTs were then dispersed

by sonication in three different organic polymers (1.0 mg/ml SWCNT in 1.0 mg/ml of
M
organic polymer). The stable suspension was coated onto the GCE and electrochemical

characterisation was performed by CV and Amperometry. The electroactive enzyme glucose

d

oxidase (GOx) was immobilised on the surface of the GCE/ (organic polymer–SWCNT)
te

electrode. The amperometric detection of glucose was carried out at 0.7 V versus Ag/AgCl.

The GCE/ (SWCNT–PEI, PEG, PPY) gave a detection limit of 0.2633 µM, 0.434 µM, and
p

0.9617 µM. Sensitivities was 0.2411 ± 0.0033 µA mM− 1, r2 = 0.9984, 0.08164 ± 0.001129
ce

µA mM− 1, r2 = 0.9975, 0.04189 ± 0.00087 µA mM− 1, and r2 = 0.9944 respectively and a

response time of less than 5 s.

Ac

The use of purified SWCNTs has several advantages, including fast electron transfer rate and

stability in the immobilised enzyme. The significant enhancement of the SWCNT modified

electrode as a glucose sensor can be attributed to the superior conductivity and large surface

area of the well dispersed purified SWCNTs. Lui et al. [146] demonstrated a novel and

scalable procedure for facile enzyme immobilisation in which three-dimensional porous Sn-

37
Page 37 of 165
Fe hydrogels were applied to incorporate the enzyme to construct a sensing interface for an

amperometric biosensor. The process was initiated from the electrodeposition of Prussian

Blue (PB) on MWCNT-modified gold electrodes, sequentially capped with tin tetrachloride

(SnCl4) solution, followed by the addition of a freshly-made homogeneous mixture of

t
enzyme and potassium ferrocyanide solution. This lead to instant formation of hydrated

ip
three-dimensional (3D) porous Sn-Fe cyanogel networks, deeply set outside the produced

cr
rough layer of the MWCNT-PB complexes, providing a desirable microenvironment for the

entrapped enzyme. The structural morphology and electrochemical properties of the as-

us
prepared Sn-Fe cyanogels, noncovalently grafted to MWCNTs with functionalities of

an
electrodeposited PB, were well characterized by SEM, UV-vis and CV. The results indicate

that the modified electrode with a multilayer configuration was well-organised, as proposed,
M
and exhibited good electrical conductivity and stable catalytic activity to H2O2 electro-

reduction due to the functional layer of PB.

d
te

When glucose oxidase (GOx) was selected as a model enzyme, the resulting glucose

biosensor exhibited a relatively low detection limit of 0.1 µM (S/N 3) with a good sensitivity
p

of 1.68 µA mM-1 cm -2
and improved stability. Palanisamy et al. [210] developed an
ce

amperometric glucose biosensor based on enhanced and fast DET of glucose oxidase (GOx)

at enzyme dispersed MWCNTs/graphene oxide (MWCNT/GO) hybrid biocomposite. The

Ac

fabricated hybrid biocomposite was characterised by TEM, Raman and infrared spectroscopy

(IR). The TEM image of hybrid biocomposite reveals that a thin layer of GOx was covered

on the surface of MWCNT/GO hybrid composite. IR results validate that the hybrid

biocomposite was formed through the electrostatic interactions between GOx and

MWCNT/GO hybrid composite. Further, MWCNT/GO hybrid composite has also been

characterised by TEM and UV–visible spectroscopy. A pair of well-defined redox peak was

38
Page 38 of 165
observed for GOx immobilised at the hybrid biocomposite electrode than that immobilised at

the MWCNT modified electrode. The electron transfer rate constant (Ks) of GOx at the

hybrid biocomposite was calculated to be 11.22 s− 1. The higher Ks value revealed that fast

DET of GOx occurred at the electrode surface. Moreover, fabricated biosensor showed a

t
good sensitivity towards glucose oxidation over a linear range 0.05–23.2 mM. The limit of

ip
detection (LOD) was estimated to be 28 µM. The good features of the proposed biosensor

cr
could be used for the accurate detection of glucose in the biological samples.

us
Poursi et al. [308] analytically modelled a single-wall carbon nanotube field-effect transistor

an
biosensor for glucose detection. In the proposed model, the glucose concentration was

presented as a function of gate voltage. Subsequently, the proposed model was compared
M
with existing experimental data. A good consensus between the model and the experimental

data was reported. The simulated data demonstrate that the analytical model can be employed
d

with an electrochemical glucose sensor to predict the behaviour of the sensing mechanism in
te

biosensors.

Hwa et al. [309] demonstrated synthesis of zinc oxide nanoparticles incorporated graphene-
p

carbon nanotubes hybrid (GR-CNT-ZnO) through a simple, one-pot method. The as-
ce

synthesized GR-CNT-ZnO composite is applied to fabricate an enzyme based glucose

biosensor. The GOx immobilized on GR-CNT-ZnO composite exhibits well-defined redox

Ac

peaks, with a peak potential separation (δEp) of about 26mV with enhanced peak currents,

indicating a fast electron transfer at the modified electrode surface. The CV measurements

revealed that the modified film has high electrocatalytic ability towards glucose detection in

the presence of oxygen. The proposed sensor has a wide linear detection range from 10µM to

6.5mM of glucose, with a limit of detection (LOD) of 4.5 (±0.08) µM. In addition, the sensor

possessed appreciable repeatability, reproducibility and remarkable stability for the sensitive

39
Page 39 of 165
determination of glucose. The practicality of this sensor has been demonstrated in human

serum samples, with results being in good agreement with those determined using a standard

photometric method.

t
Tang et al. [41] fabricated a novel glucose biosensor. The first layer of the biosensor was

ip
polythionine, which was formed by the electrochemical polymerisation of the thionine

cr
monomer on a glassy carbon electrode. The remaining layers were coated with chitosan-

MWCNTs, GOx and chitosan-PTFE film in sequence. The MWCNTs embedded in FAD

us
were like conductive wires connecting FAD with electrode, reduced the distance between

an
them and were propitious to fast direct electron transfer. Combining with good electrical

conductivity of PTH and MWCNTs, the current response was enlarged. The sensor was a
M
parallel multi-component reaction system (PMRS) and excellent electrocatalytic performance

for glucose could be obtained without a mediator. The glucose sensor had a working voltage
d

of -0.42 V, an optimum working temperature of 25°C, an optimum working pH of 7.0, and

te

the best percentage of polytetrafluoroethylene emulsion (PTFE) in the outer composite film

was 2%. Under the optimised conditions, the biosensor displayed a high sensitivity of 2.80
p

µA mM -1 cm-2 and a low detection limit of 5 µM (S/N = 3), with a response time of less than
ce

15 s and a linear range of 0.04 mM to 2.5 mM. Furthermore, the fabricated biosensor had a

good selectivity, reproducibility and long-term stability, indicating that the novel
Ac

CTS+PTFE/GOx/MWCNTs/PTH composite is a promising material for immobilisation of

biomolecules and fabrication of third generation biosensors.

Wang et al. [310] studied a novel glucose biosensor with an immobilised mediator, using

electrochemical impedance spectroscopy (EIS) and amperometry measurements. The

biosensor has a characteristic ultrathin form and is composed of a self-assembled monolayer

anchoring GOx, covered with Langmuir–Blodgett (LB) films of Prussian blue (PB). The

40
Page 40 of 165
immobilised PB in the LB films acts as a mediator and enables the biosensor to work under a

low potential (0.0 V vs. Ag/AgCl). In the EIS measurements, a dramatic decrease in charge

transfer resistance (Rct) was observed with sequential addition of glucose, which can be

attributed to enzymatic activity. The linearity of the biosensor response was observed by the

t
variation of the sensor response (1/Rct) as a function of glucose concentration in the range 0

ip
to 25 mM. The sensor also showed linear amperometric response below 130 mM glucose.

cr
The organic–inorganic system of GOx and PB nanoclusters demonstrated bifunctional

sensing action, both amperometry and EIS modes, as well as long sensing stability for 4 days.

us
7.1.2. Non-enzymatic glucose sensing
an
M
The number of people requiring glucose sensors has significantly increased over the last

decade, so there is overwhelming demand for the development and improvement of glucose
d

sensors. There is also the need to make sensors which are both biocompatible and have
te

increased sensing capabilities as compared to current technologies. To meet these needs, a

move towards nonenzymatic glucose sensors has begun [311]. These new sensors have
p

attracted significant interest due to their capacity to achieve continuous glucose monitoring,
ce

their high stability compared to traditional glucose sensors, and the ease of their fabrication.

Research has been extensively geared towards the preparation of these nonenzymatic glucose
Ac

sensors from novel materials, often with unique micro- or nano-structures, which possess

ideal properties for electrochemical biosensor applications. A variety of materials, including

noble metals, metal oxides, CNTs, graphene, polymers and composites have been explored in

recent years for their electrocatalytic response to the oxidation of glucose.

Recently, Singh et al. [312] demonstrated an efficient approach for nanoparticle decoration of

carbon nanochips and carbon nanotubes, together with effective utilisation of Pt for direct

41
Page 41 of 165
glucose determination. The synthesised materials were investigated using morphological,

compositional, structural and electrochemical characterisations. TEM data indicated the

successful nanoparticles decoration with average particle sizes in the range of 2.5 ± 0.4 nm

for all the synthesised nanomaterials. The overall aim was to reduce precious Pt content in

t
addition to improving the Pt surface utility, via using multicomponent catalytic system and

ip
effective particles dispersion on carbon-based supports. Amperometry was employed for

cr
non-enzymatic glucose determination and the best response among the bi/tri-metallic

nanomaterials was achieved for Pt2Au1Pd1/f-CNC (sensitivity = 11.24 µA mM−1 cm−2 at

us
Eapp = 0.43 V vs Ag/AgCl), over the range 0–10 mM glucose, in neutral pH conditions.

an
Chen et al. [313] developed a nonenzymatic electrochemical method for glucose detection

using an electrode modified with palladium nanoparticles (PdNPs)-functional carbon

M
nanotubes (FCNTs). PdNPs were homogeneously modified on FCNTs through a facile

spontaneous redox reaction and characterised by TEM. Based on the voltammetric and
d

amperometric results, PdNPs efficiently catalysed the oxidation of glucose at 0.40V in the
te

presence of 0.2M NaCl and showed excellent resistance towards poisoning from such

interfering species as ascorbic acid, uric acid, and p-acetamidophenol. This anti-poisoning
p

ability was investigated using analysis of the electrocatalytic products by in situ subtractively
ce

normalised interfacial Fourier transform infrared reflection spectroscopy. The results

indicated that no strongly adsorbed species could be found in the oxidation products, which
Ac

was obviously different from the results obtained using Pt-based electrodes. In order to verify

the sensor reliability, it was applied to the determination of glucose in urine samples. Tian et

al. [311] reviewed most recent advances in nonenzymatic glucose sensors, with their focus

being on the recent years of research glucose sensing.

Choi et al. [314] fabricated carbon-nanotube-nickel (CNT-Ni) nanocomposites through

atomic layer deposition (ALD) of Ni and chemical vapour deposition (CVD) of

42
Page 42 of 165
functionalised CNTs and various techniques, including SEM, TEM and X-ray photoelectron

spectroscopy (XPS) were used to characterise the morphology and the structure of as-

prepared samples. It was confirmed that the products possess uniform Ni nanoparticles that

are constructed by finely controlled deposition of Ni onto oxygen or bromine functionalised

t
CNT surface. Electrochemical studies indicate that the CNT-Ni nanocomposites exhibit high

ip
electrocatalytic activity for glucose oxidation in alkaline solutions, which enables the

cr
products to be used in enzyme-free electrochemical sensors for glucose determination. It was

demonstrated that the CNT-Ni nanocomposite-based glucose biosensor offers a variety of

us
merits, such as a wide linear response window for glucose concentrations of 5µM-2mM,

an
short response time (3s), a low detection limit (2µM), high sensitivity (1384.1µAmM-1cm-2),

and good selectivity and repeatability.

M
Gougis et al. [96] described the non-enzymatic cyclic and pulse voltammetric detection of
d

glucose, using pulsed laser deposited gold nanostructures onto CNTs electrodes. Several
te

synthesis conditions have been considered in order to obtain various morphologies for the Au

film. Among all the synthesised Au nanostructures, it is found that an Au film deposited
p

under vacuum with 10,000 laser pulses displays a high electroactive surface area of 6.55 cm2
ce

and a roughness factor of 13.2. In addition, this electrode exhibits a low onset potential of

−0.28 V vs. Ag/AgCl for glucose oxidation. A linear square-wave voltammetric response for
Ac

oxidation of glucose was observed up to a glucose concentration of 50 mM, with a sensitivity

of 25 µA cm−2 mM−1 and a detection limit of 0.1 mM. Finally, owing to its versatile

capabilities such as robust control of the surface morphology, control of the stoichiometry

and ultra-low loading of noble catalyst, it can be expected that the pulsed laser deposition

(PLD) technique will emerge as a fabrication tool for on chip miniature-sized sensors in the

near future.

43
Page 43 of 165
Gao et al. [315] fabricated a nonenzymatic sensor based on Ni(OH)2/electro-reduced

graphene oxide (ERGO)–MWNT nanocomposites via convenient electrodeposition of

Ni(OH)2 nanoparticles on ERGO–MWNT film modified glass carbon electrode (GCE).

t
Graphene oxide (GO) sheets can serve as surfactants to stabilise the dispersion of pristine

ip
MWNTs in aqueous solution, rendering a fine coverage of ERGO–MWNT film on GCE

cr
during the fabrication process. MWNTs perform as conducting bridges between ERGO

sheets to enhance the electron transfer rate in the substrate. By combining the advantages of

us
ERGO and MWNTs, together with electrocatalytic effect of Ni(OH)2 nanoparticles, the well-

an
designed nanocomposites exhibit excellent sensing behavior towards glucose and H2O2. The

linear detection ranges for glucose and H2O2 are 10–1500 µM and 10 µM–9050 µM, while
M
the detection limits are 2.7 µM and 4.0 µM respectively. Furthermore, a very high sensitivity

is achieved with 2042 µAm M−1 cm−2 estimated for glucose and 711 µAm M−1 cm−2 for
d

H2O2. These results suggest that Ni(OH)2/ERGO–MWNT nanocomposites thus easily

te

prepared through a green electrochemical method, are promising electrode materials for

biosensing. Additionally, good recoveries of analytes in real samples, like urine and milk,
p

confirm the reliability of the prepared sensor in practical applications.

ce

Pilan and Raincapol [316] investigated a new selective and stable glucose biosensor based on

polyaniline (PANI)/functionalised SWCNTs)/Prussian Blue (PB) composite films. For

Ac

biosensor synthesis, they combined two widely used techniques to produce modified

electrodes that are the electroreduction of diazonium salts and the electropolymerisation.

Thus, in a first step, SWCNTs deposited at a PB-modified glassy carbon (GC) electrode were

functionalised with p-nitrophenyl group by electrochemical reduction of p-

nitrobenzenediazonium salt in nonaqueous media. Then, the nitro group was reduced

electrochemically to amine functionality. The enzyme doped PANI film can easily be grafted

44
Page 44 of 165
onto the surface of such obtained aminophenyl-modified SWCNTs electrodes. The marked

synergistic electrocatalytic activity of SWCNTs and PB film toward H2O2 produced during

enzymatic reaction of glucose oxidation, permitted effective low-potential amperometric

measurement of glucose.

t
Xing et al. [317] fabricated a nano composite film by dispersing nano scale Ni(OH)2 and

ip
CNTs into polyvinylidene fluoride (PVDF). The morphology of the film was examined by

cr
SEM. The electrocatalytic oxidation of glucose in alkaline medium on the Ni(OH)2-CNT-

PVDF (NCP) composite modified glass carbon electrode had been investigated. The stability

us
of the composite is confirmed by cyclic voltammetry measurements in sodium hydroxide

an
solution (0.50 M, scan rate 100 mV s -1). The NCP composite film maintains the

electrocatalytic activity of the nano scale Ni(OH)2 and is used to fabricate a nonenzymatic
M
biosensor for electrochemical detection of glucose. Amperometric measurements were done

with different concentrations of glucose. The NCP glucose sensor has good anti-interference
d

performance toward maltose, fructose, urea and ascorbic acid. It has wide concentration
te

ranges to glucose. It shows a detection limit of 0.023 mM (S/N = 3) with a wide linear range

from 0.25 to 39.26 mM, which is comparable with commercial glucose test strip. In real
p

serum sample, it has a RSD of 2.5%.

ce

Zhu et al. [318] fabricated a highly sensitive nonenzymatic amperometric glucose sensor by

using Ni nanoparticles homogeneously dispersed within and on the top of a vertically aligned
Ac

CNT forest (CNT/Ni nanocomposite sensor), which was directly grown on a Si/SiO2

substrate. The surface morphology and elemental analysis were characterised using SEM and

energy dispersive spectroscopy, respectively. CV and chronoamperometry were used to

evaluate the catalytic activities of CNT/Ni electrode. The CNT/Ni nanocomposite sensor

exhibited a great enhancement of anodic peak current after adding 5 mM glucose in alkaline

solution. The sensor can also be applied to the quantification of glucose content with a linear

45
Page 45 of 165
range covering from 5 µM to 7 mM, a high sensitivity of 1433 µA mM−1 cm−2 and a low

detection limit of 2 µM. The CNT/Ni nanocomposite sensor exhibits good reproducibility and

long-term stability. Moreover, it was also relatively insensitive to commonly interfering

species, such as uric acid, ascorbic acid, acetaminophen, sucrose and d-fructose.

t
Jiang et al. [319] fabricated an improved nonenzymatic glucose sensor of Ni(OH)2 on carbon

ip
nanotube/polyimide (PI/CNT) membrane by a simple electrochemical method. Three

cr
different morphologies of Ni(OH)2 were formed by changing the conditions used in synthesis

process. The formation mechanism for Ni(OH)2 nanospheres was studied to provide a deep

us
understanding of crystal growth. The electrochemical behaviors of different Ni(OH)2

an
nanostructures were investigated by CV and chronoamperometry in alkaline solution. At an

applied potential of +0.60 V, the sensor based on PI/CNT–Ni(OH)2 nanospheres shows a

M
high sensitivity of 2071.5 µA mM−1 cm−2 and a detection limit of 0.36 µM (signal/noise = 3).

The proposed sensor exhibits high sensitivity, long-term stability and good reproducibility,
d

and performs well for the detection of glucose in human blood serums. Therefore, this novel
te

fabrication method for glucose sensor is promising for the future development of

nonenzymatic glucose sensors. Various researchers have used CNTs-biosensor and CNTs-
p

non enzymic sensor for sensitive determination of glucose [17, 41, 117, 119, 263, 278, 281,
ce

300, 301, 305, 316-318, 320-336]. Table 3 shows summary of the various CNT-based

glucose sensors based on nanotubes reported in the literature, along with their important
Ac

parameters.

7.2. Haemoglobin (Hb) biosensor

Haemoglobin is the most important part of blood and is responsible for transporting O2

throughout the circulatory system. Change of Hb concentration in blood can cause several

46
Page 46 of 165
diseases, such as anaemia and even death. Therefore, accurate determination of Hb content in

blood is medically very essential.

Batra et al. [337] described a method for the construction of a highly sensitive

electrochemical biosensor for the detection of acrylamide, based on covalent immobilisation

t
ip
of haemoglobin (Hb) onto carboxylated multiwalled carbon nanotube/copper

nanoparticle/polyaniline (c-MWCNT/CuNP/PANI) composite deposited onto pencil graphite

cr
(PG) electrode. The enzyme electrode was characterised by CV, SEM, XRD, TEM, Fourier

us
transform infrared (FTIR) spectroscopy and EIS. The biosensor showed an optimal response

at pH 5.5 (0.1 M sodium acetate buffer) and 35 °C when operated at 20 mV s-1. The

an
biosensor exhibited low detection limit (0.2 nM) with high sensitivity (72.5 µA/nM/cm2), fast

response time 2 s and wide linear range (5 nM to 75 mM). Analytical recovery of added
M
acrylamide was 95.40 to 97.56%. Within and between batches coefficients of variation were

2.35 and 4.50%, respectively. The enzyme electrode was used 120 times over a period of 100
d

days, when stored at 4 °C.

te

Wang et al. [221] applied new composite films composed of diblock weak polyelectrolyte
p

poly(2-hydroxyethyl methacrylate)-b-poly(2-(dimethylamino)ethyl methacrylate) (PHEMA-

ce

b-PDMAEMA) and MWCNTs to immobilise Hb for biosensor fabrication. The

characterisation of Hb/PHD/MWCNTs films was demonstrated by UV spectra, SEM, EIS,

Ac

CV and typical amperometric response (i-t) measurements. The immobilised Hb maintains its

bioactivities and displays an excellent electrochemical behaviour. The modified electrode

exhibited good electrocatalytic activity to the reduction of hydrogen peroxide (H2O2). The

linear response range of the H2O2 biosensor was from 1.0 × 10-6 to 1.5 × 10-3 M with a
-7
detection limit of 3.5 × 10 M. The apparent Michaelis-Menten constant of Hb on the

PHD/MWCNTs film was estimated to be 0.51 mM. These results indicated that the

47
Page 47 of 165
composite films have potential applicability of new types third-generation biosensors or

bioreactors based on direct electrochemistry of the proteins.

Bagayeri et al. [338] investigated the direct electron-transfer reactivity of immobilised Hb on

a biocompatible poly(styrene-alternative-maleic acid) (PSMAC) copolymer/MWCNTs) blend

t
ip
for biosensor designs. The copolymer possesses good biocompatibility, uniformity,

conformability and is ready for protein immobilisation. On the other hand, electrochemical

cr
measurements show that the presence of MWCNTs provides a unique structure for

us
interaction of Hb and copolymer and facilitate the direct electron transfer between the

immobilised Hb and the surface conductivity. The immobilised Hb maintains its bioactivities

an
and displays an excellent electrochemical behaviour. The proposed method opens a way to

develop biosensors by using nanostructured materials mixed with low electrical conductivity
M
matrixes. The biosensor was used to catalyse the reduction of hydrogen peroxide. The

electrocatalytic response showed a linear dependence on the H2O2 concentration, ranging

d

widely from 1.0 to 56.0 µM, with a detection limit of 0.38 µM at 3σ. [339].
te

Baghayeri et al. [205] applied a nanocomposite films based on poly(styrene-alternative-

p

maleic anhydride) grafted to 3-aminobenzoic acid (PSMA-g-3ABA) and MWCNTs to

ce

immobilise Hb for biosensor fabrication (PSMA-g-3ABA/MWCNTs). Electrochemical

impedance spectroscopy was used to confirm the adsorption of Hb onto the surface of
Ac

PSMA-g-3ABA/MWCNTs. The immobilised Hb maintains its bioactivities and displays an

excellent electrochemical behaviour. The biosensor was used to catalyse the reduction of

H2O2. The electrocatalytic response showed a linear dependence on the H2O2 concentration,

ranging widely from 1.0 × 10- 6 M to 5.0 × 10- 4 M with a detection limit of 3.2 × 10- 7 M. The

apparent Michaelis-Menten constant of Hb on the modified electrode was estimated to be

48
Page 48 of 165
0.22 mM. The proposed method opens a way to develop biosensors by using nanostructured

materials with low electrical conductivity.

Chekin et al. [340] developed a novel biosensor based on immobilisation of Hb on chitosan-

sodium dodecyl sulfate-carbon nanotube composite modified glassy carbon electrode

t
ip
(Hb/CS-SDS-CNT/GCE). The surface morphologies of the modified electrode were

characterised by SEM and direct electrochemistry of Hb on Hb/CS-SDS-CNT/GCE was

cr
investigated by CV and EIS. UV-vis spectroscopic results indicated that Hb molecules in the

us
composite film retained the native structure. The results indicate that Hb immobilised on the

surface of the modified electrode could keep its bioactivity, exhibiting a surface-controlled

an
electrochemical process. The kinetic parameters for the electrode reaction, such as the formal

potential (E), the electron transfer rate constant (ks), the apparent coverage and Michaelis-
M
Menten constant (Km), were evaluated. Moreover, the immobilised Hb also displayed its

good electrocatalytic activity for the reduction of hydrogen peroxide, with a low detection
d

limit of 4.2 M and good stability and reproducibility. The results demonstrated that porous
te

CS-SDS-CNT composite can improve the Hb loading with retention of its bioactivity, and
p

greatly promote the direct electron transfer, which can be attributed to its high specific
ce

surface area, uniform ordered porous structure, suitable pore size and biocompatibility.

Chen and Lu [341] developed a novel hydrogen peroxide biosensor based on the
Ac

encapsulation of Hb in the composite film of carboxylic carbon nanotubes and

polyelectrolyte-surfactant polymer. The direct electron transfer of the Hb entrapped in the

composite film was observed. The formal potential of the encapsulated Hb was −0.287 V

versus SCE and the heterogeneous electron transfer rate constant was 0.4 s−1 in a 0.1 M

phosphate buffer solution (pH 7.0). An FT-IR spectroscopy study confirmed that the

secondary structure of Hb encapsulated in the composite film still retains the original

49
Page 49 of 165
arrangement. It was suggested that the achieved faradic response of the Hb could be due to

the promotion properties of carbon nanotube in electron transfer in biomembrane-like

polyelectrolyte-surfactant polymer. The entrapped Hb exhibited excellent electrocatalytic

activity to reduce H2O2. The properties of functional composite film, together with the

t
bioelectrochemical catalytic activity, could make them useful in the development of

ip
bioelectronic devices and investigation of protein electrochemistry at functional interface.

cr
Hong et al. [342] realised direct electron transfer of Hb by immobilizing Hb on a carboxyl

us
functionalised multi-walled carbon nanotubes (FMWCNTs) and gold nanoparticles (AuNPs)

nanocomplex-modified glassy carbon electrode. The UV, TEM and FTIR methods were

an
utilised for additional characterisation of the AuNPs and FMWCNTs. The CV of the

modified electrode has a pair of well-defined quasi-reversible redox peaks, with a formal
M
potential of -0.270 ± 0.002 V (vs. Ag/AgCl) at a scan rate of 0.05 V/s. The heterogeneous

electron transfer constant (ks) was evaluated to be 4.0 ± 0.2 s (-1). The average surface
d

concentration of electro-active Hb on the surface of the modified glassy carbon electrode was
te

calculated to be 6.8 ± 0.3 × 10(-10) mol cm-2. The cathodic peak current of the modified
p

electrode increased linearly with increasing concentration of H2O2 (from 0.05 nM to 1 nM),
ce

with a detection limit of 0.05 ± 0.01 nM. The apparent Michaelis-Menten constant (K (m)

(app)) was calculated to be 0.85 ± 0.1 nM. Thus, the modified electrode could be applied as a
Ac

third generation biosensor with high sensitivity, long-term stability and low detection.

Pakapongpan et al. [343] developed effective electrochemical sensors for Hb and myoglobin

(Mb) detection using a simple procedure of self-assembled methylene blue-multiwalled

carbon nanotubes (MB-MWNTs) nanohybrid modified, on glassy carbon electrode without

using any enzymes immobilisation. The direct electrochemical and electrocatalytic behaviors

of the modified electrode were studied, using CV and FIA with amperometry. The

50
Page 50 of 165
performance of the sensor was investigated and optimized and the system was evaluated by

monitoring Hb and Mb concentrations. The developed MB-MWNTs nanohybrid modified

electrode showed excellent electrocatalytic activity for reduction of Hb and Mb with good

stability, sensitivity and reproducibility (RSD = 3.05% and 4.5% for 50 successive injections

t
of Hb and Mb respectively). Under optimal conditions, the catalytic currents are linearly

ip
proportional to the concentrations of Hb and Mb in the wide range from 5 nM to 2 µM and

cr
0.1 to 3 µM, and the corresponding detection limits are 1.5 nM and 20 nM (S/N = 3),

respectively. This approach provides improved detection limit over other previous works and

us
may provide a novel and efficient platform for the fabrication of sensors for other heme

an
proteins.

7.3.1. Hydrogen peroxide biosensor (H2O2)

M
Hydrogen peroxide (H2O2) is a general enzymatic product of oxidases and a substrate of
d

peroxidases, which is important in biological processes and biosensor development [344,

te

345]. H2O2 is an important analyte in chemistry, biology, biochemical and food industry,

clinical control and environmental protection. Thus, the rapid and accurate analysis of H2O2
p

is of great importance [346]. The high level of H2O2 is closely associated with cancer and
ce

progressive neurodegenerative diseases, such as Parkinson's disease. High level of oxidative

stress is involved in the formation of incipient tumour and carcinomatous cells. Various
Ac

groups have earlier shown that CNTs-based H2O2 biosensors exhibit good sensitivity,

selectivity and reproducibility and recent studies have shown that CNTs-based H2O2

biosensors exhibit good sensitivity, selectivity and reproducibility [13, 203, 347-358].

Recently, Zhang et al. [359] reported on an experimental study of flexible nanocomposite

film for electrochemical detection of H2O2 based on bacterial cellulose (BC) and MWCNTs

in combination with microperoxidase-11 (MP-11). MWCNTs are used to functionalise BC

51
Page 51 of 165
and provide a flexible conductive film. On the other hand, BC can improve MWCNTs'

biocompatibility. The investigation shows that MP-11 immobilised on the flexible film of

MWCNTs-BC can easily present a pair of well-defined and quasi-reversible redox peaks,

revealing a direct electrochemistry of MP-11 on the nanocomposite film. The apparent

t
heterogeneous electron-transfer rate constant ks is estimated to be 11.5 s -1. The resulting

ip
flexible electrode presents appreciated catalytic properties for electrochemical detection of

cr
H2O2, compared to traditional electrodes (such as gold, glassy carbon electrode) modified

with MP-11. The proposed biosensor exhibited a low detection limit of 0.1 µM (at a signal-

us
to-noise ratio of 3) with a linear range of 0.1-257.6 µM, and acquires a satisfactory stability.

an
Wang et al. [360] prepared a biosensor with high stability to determine H2O2. This H2O2

biosensor was obtained by modifying glassy carbon electrode (GCE) with a composite film
M
composed of gelatin-MWCNT. Catalase (Cat) was covalently immobilised into gelatin-

MWCNT- modified GCE through the well-known glutaraldehyde (GAD) chemistry in order
d

to enhance the stability of electrodes. The enzyme sensor can achieve direct electrochemical
te

response of H2O2. The CV at different scan rates, EIS and SEM tests indicateed that the

enzyme sensor performs positively on increasing permeability, reducing the electron transfer
p

resistance and improving the electrode performance. The linear response of standard curve
ce

for H2O2 is in the range of 0.2 to 5.0 mM, with a correlation coefficient of 0.9972, and the

detection limit of 0.001 mM. A high operational and storage stability was demonstrated for
Ac

the biosensor. The peak potential at room temperature in two consecutive weeks stays almost

consistent, and the enzyme activity was kept stable even after 30 days in further study.

Wang et al. [361] also prepared carbon nanodots and CoFe-layered double hydroxide

composites (C-Dots/LDHs) via simply mixing C-Dots and CoFe-LDHs. The as-prepared

composites were used for the immobilisation of horseradish peroxidase (HRP) on the glass

carbon (GC) electrode. The electrochemical behaviour of the HRP/C-Dots/LDHs/GC

52
Page 52 of 165
electrode and its application as an H2O2 biosensor were investigated. The results indicated

that HRP immobilised by C-Dots/LDHs retained the activity of enzyme and displayed quasi-

reversible redox behaviour and fast electron transfer with an electron transfer rate constant ks

of 8.46 s−1. Under optimum experimental conditions, the HRP/C-Dots/LDHs/GC electrode

t
displayed good electrocatalytic reduction activity and excellent analytic performance toward

ip
H2O2. The H2O2 biosensor showed a linear range of 0.1–23.1 µM (R2=0.9942) with a

cr
calculated detection limit of 0.04 µM (S/N=3). In addition, the biosensor exhibited high

sensitivity, good selectivity, acceptable reproducibility and stability. The superior properties

us
of this biosensor are attributed to the synergistic effect of HRP, C-Dots and CoFe-LDHs,

an
which has been proved by investigating their electrochemical response to H2O2. Thus the C-

Dots and LDHs composites provide a promising platform for the immobilisation of redox
M
enzymes and construction of sensitive biosensors.

Bai et al. [347] developed a new amperometric biosensor for H2O2, based on adsorption of
d

horseradish peroxidase at the glassy carbon electrode modified with zinc oxide nanoflowers
te

produced by electrodeposition onto MWNTs film. The morphology of the MWNTs/nano-

p

ZnO electrode was investigated by SEM, and the electrochemical performance of the
ce

electrode was also studied by amperometric method. The resulting electrode offered an

excellent detection for hydrogen peroxide at −0.11 V with a linear response range of 9.9 ×
Ac

10−7 to 2.9 × 10−3 mol/L with a correlation coefficient of 0.991 and response time of 5 s. The

biosensor displays rapid response and expanded linear response range and excellent stability.

Denesh et al. [362] described the fabrication of an amperometric biosensor based on

cytochrome c (Cyt c) immobilized graphene oxide-multiwalled carbon nanotube (GO-

MWCNT) composite on a nano Au modified glassy carbon electrode for trace level detection

of H2O2. Morphology and surface characterization of the nanocomposite reveal the successful

53
Page 53 of 165
formation of a highly conducting MWCNT network on the GO surface. EIS indicated a lower

charge transfer resistance compared to the bare electrode. CV studies clearly demonstrated an

enhanced direct electrochemistry of Cyt c with a high electron transfer rate constant (k s)

value of 3.4 s-1. An amperometric H2O2 biosensor has been fabricated with an excellent

t
current sensitivity of 0.533 µA pM-1 cm-2 and a very low detection limit of 27.7 pM. The

ip
fabricated sensor showed exceptional selectivity to H2O2 in the presence of a high

cr
concentration of some likely interferents. Moreover, the sensor exhibited high stability with

appreciable repeatability and reproducibility.

us
Ensafi et al. [206] prepared a new hybrid chitosan derivatives (chitosan (Chit), amine group

an
grafted chitosan (N-Chit) and thiol group grafted chitosan (S-Chit) modified-carbon (carbon

nanotubes or graphite) and they were used as supports for Cu-nanoparticles. The synthesised
M
materials were characterised with different methods such as TEM, Brunauer-Emmett-Teller

and CV. The electrocatalytic effect of the nanohybrid was investigated in the reduction of
d

H2O2 and the oxidation of glucose. It was found that the Cu nanoparticles decorate on the
te

modified chitosan-CNT (Cu@M-Chit-CNT) exhibited a remarkable catalytic performance for

p

H2O2 reduction and glucose oxidation. Hydrodynamic amperometry was used for the
ce

electrochemical determination of H2O2 and glucose. The linear range for H2O2 was from 0.1

to 1000 µmol L-1 , with a detection limit of 0.025 µmol L-1, whereas the linear range for
Ac

glucose was from 0.5 to 1000 µmol L-1 with a detection limit of 0.05 µmol L -1. In addition,

Cu@N-Chit-CNT/GCE and Cu@Chit-CNT/GCE showed a good selectivity for H2O2 and

glucose detection in the presence of dopamine, ascorbic acid and uric acid. The kinetic

parameters such as the electron transfer coefficient and the catalytic reaction rate constant

were also determined for glucose and H2O2. Finally, the modified electrode is the most

sensitive probe ever reported and can be used to achieve the real-time quantitative detection

of H2O2 and glucose for biological applications.

54
Page 54 of 165
Ezhil Vilian et al. [363, 364] reported a novel third-generation H2O2 biosensor, which was

fabricated by loading catalase (CAT) onto l-lysine/multiwalled carbon nanotube (PLL/f-

MWCNT) film modified glassy carbon electrode (GCE). The UV and FTIR spectra show that

the catalase encapsulated in the PLL/f-MWCNT film can effectively retain its bioactivity.

t
The immobilised CAT retained its bioactivity with a high protein loading of 4.072×10-

ip
10
molcm-2, thus exhibiting a surface-controlled reversible redox reaction, with a fast

cr
heterogeneous electron transfer rate of 5.48 s-1. The immobilised CAT showed a couple of

reversible and well-defined CV peaks with a formal potential (E0) of -0.471V (vs. Ag/AgCl)

us
in a pH 6.5 phosphate buffer solution (PBS). Moreover, the modified film exhibited high

an
electrocatalytic activity for the reduction of H2O2. It exhibited a wide linear response to H2O2

in the concentration range of 1×10-6-3.6×10-3, with higher sensitivity (392mAcm-2M-1) and a

M
lower Michaelis-Menten constant (0.224mM). It provided high-catalytic activity towards

H2O2 in a shorter time (5s), with a detection limit of 8 nM. These results indicated great
d

improvement in the electrochemical and electrocatalytic properties of the CAT/PLL/f-

te

MWCNT biosensor, offering a new idea for the design of third-generation electrochemical

biosensors.
p
ce

Han et al. [365] prepared a MWCNT grafted Poly(lactic acid) (MWCNT-g-PLA) by

intercalative polymerisation of poly(lactic acid) in the presence of MWCNT functionalised

Ac

with hydroxyl groups. The functionalised MWCNT was obtained from the treatment of

methylene diphenyl diisocyanate (MDI) with MWCNT, and then the reaction with 1,4-

butanediol (BD) to create functional hydroxyl groups. MWCNT-g-PLA-Pd and MWCNT-g-

PLA-Pt were prepared from the MWCNT-g-PLA and metal precursors. The synthesised

materials were characterised by 1H-NMR, FT-IR, Raman spectroscopy, X-ray photoelectron

spectroscopy (XPS), TEM. The MWCNT-g-PLA-Pd was employed for electrochemical

detection of H2O2. Electrocatalytic activities were verified from CV and amperometric

55
Page 55 of 165
response in 0.1 M phosphate buffer solution (PBS). The biosensor provided good stability

and selectivity towards interferences such as UA, AA and glucose.

Hasmenia and Eskaneri [366] investigated the use of a mixture MWCNT and thionine (Th)

dye in designing a thionine-based electrochemical biosensor containing catalase (Ct) enzyme

t
ip
(MWCNT-Nafion-Th/Ct) onto a glassy carbon electrode (GCE). The effects of pH, MWCNT

concentration and thionine concentration on electrochemical response were explored for

cr
optimum analytical performance. The modified electrode exhibited a pair of well-defined,

us
quasi-reversible peaks at formal potential (Eo) = -0.218 ± 0.017 V vs. Ag/AgCl

corresponding to the Thox/Thred redox couples in the presence of MWCNT, Nafion, and Ct.

an
The electrochemical parameters, including charge-transfer coefficient (0.36), and apparent

heterogeneous electron transfer rate constant (4.28 ± 0.26 s -1) were determined. Using
M
differential pulse voltammetry, the prepared enzyme electrode exhibited a linear response to

H2O2 in the range of 10.0-100.0 µM with a detection limit 8.7 µM and a sensitivity of 6051.0
d

µA mM-1 cm -2.
te

Husman et al. [355] modified carbon nanotubes paste electrodes with Prussian blue (PB) and
p

used it as a sensor for H2O2 at low concentration. These electrodes were characterised by
ce

Raman spectroscopy and SEM to attest the modification. Influence of pH, storage conditions

and numbers of cycles were studied and related to the amount of PB deposited and its
Ac

behaviour on H2O2 detection. The electrode modified by 500 cycles and maintained in air

obtained the best H2O2 responses, with high electrochemical stability, good repeatability,

reproducibility and a linear range, with limit of detection and sensitivity of 4.74 × 10−9 mol

L−1 and 31.4 A cm−2/mol L−1 respectively. Interference tests were made with six different

species, with four of them showing less than 1% of deviation in H2O2 detection. Lin et al.

[367] described a facile and effective polymer-assisted route to synthesis of structurally

56
Page 56 of 165
uniform and electrochemically active single-walled carbon nanotubes–poly(dopamine)–silver

particles nanocomposite (SWCNTs–PDA–AgNPs). Poly(dopamine) used here serves as a

multifunctional molecule for: (1) dispersing SWCNTs into an aqueous system, tethering Ag+

precursor onto SWCNT surfaces (2) reducing Ag+ to Ag to eventually on-spot grow AgNPs

t
nanoparticles onto SWCNT and (3) promoting the nanocomposite adhesion ability. The

ip
synthetic nanocomposite was found to possess a good electrocatalytic activity toward H2O2

cr
reduction by remarkably enhancing the current response and decreasing H2O2 reduction over

potential at −0.23 V vs. Ag/AgCl, which is positive than most other electrocatalysts for H2O2

us
reduction. The excellent performance of H2O2 sensor can be ascribed to the synergy effects of

an
the large surface-to-volume ratio and excellent electrocatalytic properties of SWCNTs and

AgNPs, as well as the dispersing ability, reductive properties, together with excellent
M
adhesive of PDA.

Mani et al. [208] described the preparation of a novel nanobiocomposite, reduced graphene
d

oxide- multiwalled carbon nanotubes-platinum nanoparticles/myoglobin (RGO-MWCNT-

te

Pt/Mb) for the direct electrochemistry of myoglobin and its application towards
p

determination of H2O2 and nitrite (NO2-1). RGO-MWCNT-Pt nanocomposite was prepared

ce

by simple solution based approach and its structure was characterised. RGO-MWCNT-Pt/Mb

nanobiocomposite was prepared and it attained the direct electrochemistry of Mb with pair of
Ac

well-defined redox peaks with the formal potential of -0.33V and peak-to-peak separation of

22mV. Amount of electroactive protein (G) and heterogeneous electron transfer rate constant

(ks) were calculated to be 1.04×10-9molcm-2 and 9.47s-1. The sensor displayed lowest

detection limit (LOD) of 6 pM, which is the lowest LOD ever achieved for the detection of

H2O2. Two linear ranges were observed for the detection of H2O2: (1) 10pM-0.19 nM with

sensitivity of 1.99 (±0.058) µA pM-1cm-2 and (2) 0.25 nM-2.24 µM with sensitivity of 0.037

(±0.081) µAnM-1cm-2. In addition, the biosensor offered good analytical parameters towards

57
Page 57 of 165
determination of NO2 - with wide linear range of 1µM to 12mM and high sensitivity of

0.1651 (±0.026) µAµM-1cm-2. The sensor acquired good selectivity, repeatability,

reproducibility and stability. The practical feasibility of the sensor has been addressed.

Moyo et al. [209] used a novel H2O2 biosensor derived from maize tassel (MT) and

t
ip
multiwalled carbon nanotube (MWCNT) composite to adsorb horseradish peroxidase (HRP)

onto the surface of a glassy carbon electrode through electrostatic interactions. The

cr
morphology and structure of the products were characterised by SEM, FTIR and UV-visible

us
spectroscopy. The electrochemical and electrocatalytic performance of the HRP/MT-

MWCNT/GCE was studied using voltammetric and amperometric methods. The

an
amperometric response of the biosensor varied linearly with concentration of H2O2 from 9 M

to 1 mM with detection limit of 4.0 M (S/N = 3). Furthermore, the biosensor exhibited good
M
reproducibility and stability. Zhan et al. [356] employed Poly(methacrylic acid-co-

acrylamide) (P(MAA-co-AAM)), noncovalently attached on the surface of MWCNTs

d

through hydrophobic interactions, hydrogen bonding or electrostatic attraction, as a novel

te

matrix for enzyme immobilisation to develop highly sensitive amperometric biosensors. The
p

effective interaction between P(MAA-co-AAM) and MWCNTs, and the structural

ce

morphology of the as-prepared P(MAA-co-AAM)-MWCNTs nanocomposite were

characterised by FT-IR spectroscopy, XPS, SEM and TEM. Further experimental results
Ac

show that the solubility and stability of as-prepared P(MAA-co-AAM)-MWCNTs

nanocomposites in water are better than that of pristine MWCNTs, and no significant

electronic and structural change was observed after functionalisation. When myoglobin (Mb)

was selected as a model protein, studies by UV and Circular dichroism (CD) spectroscopy

indicated that the encapsulated Mb in the as-prepared P(MAA-co-AAM)-MWCNTs

nanocomposites, was kept in a near-native state, indicating that the P(MAA-co-AAM)-

MWCNTs nanocomposites have good biocompatibility for protein/enzyme immobiliation.

58
Page 58 of 165
The fabricated electrochemical biosensor based on the immobilised Mb reveals fast response

of less than 3 s, wide linear range from 1.47 × 10-6 M to 4.76 × 10-3 M and good detection

limit as low as 7.60 × 10-7 M towards the electro-determination of H2O2 under optimal

experimental conditions.

t
ip
7.3.2. Nonenzymatic hydrogen peroxide sensor

cr
Luo et al. [368] synthesised Cu2O/Cu NC nanocomposite catalysts on glass carbon electrodes

us
by electrochemical deposition at -0.2 V versus silver/silver chloride and used them for

constructing an electrochemical sensor for detection of H2O2. The effects of deposition time

an
and pH were investigated in detail. In 0.1 M phosphate buffer saline (PBS, pH = 6.5), the

Cu2O/Cu NC modified electrode exhibits a wide linear dependence (R = 0.996) at a

M
concentration of H2O2 from 4.0 ×10-7 M to 1.0 ×10-2 M, a high sensitivity of 870.4 A mM-1

cm-2 and a detection limit of 2.0 ×10-7 M. Additionally, the sensor was applied for the
d

determination of H2O2 in milk, showing its potential for practical applications.

te

Abdelwahab and Shim [369] proposed a novel method for highly sensitive H2O2 sensor using
p

silver nanoparticles (AgNPs) modified oxidised poly-2,2′:5′,2′′-terthiophene-3-p-benzoic

ce

acid/multi wall carbon nanotube (Ox-pTTBA/MWCNT). The Ox-pTTBA/MWCNT

nanocomposite film was prepared via electropolymerisation of a TTBA monomer and

Ac

MWCNT mixture solution, followed by in situ electrooxidation of the pTTBA/MWCNT

film. Then, AgNPs were formed on the Ox-pTTBA/MWCNT layer through immersing the

freshly prepared Ox-pTTBA/MWCNT electrode in AgNPs solution. The characterisation of

sensor probe and experimental parameters affecting its activity were investigated employing

UV, TEM, SEM, EIS, XPS, and CV. The AgNPs/Ox-pTTBA/MWCNT nanocomposite

showed an excellent electrocatalytic activity to H2O2 by significantly increasing the reduction

peak current and completely inhibiting the effect of other interfering species. The sensor

59
Page 59 of 165
probe displayed a fast response time less than 5 s with a linear range from 10 to 260 µM and

detection limit of 0.24 µM. The sensitive, stable and specific response to H2O2 demonstrated

that the sensor is potentially suitable for monitoring H2O2 concentrations in biological

system. The sensor was used for the determination of H2O2 in human urine real samples.

t
ip
Zhu et al. [323] reported the doping of ionic liquid (IL) into Prussian blue-multiwalled carbon

nanotubes (PB-MWCNTs) modified screen-printed carbon electrodes (SPCE) to fabricate a

cr
nonenzymatic H2O2 sensor with enhanced analytical performance. The enzyme-free

us
electrochemical sensor (Nafion-PB-MWCNTs/SPCE-IL) was prepared by home-printing the

disposable carbon electrode using a 1-butyl-3-methylimidazolium tetrafluoroborate

an
([Bmim]BF4) doped commercial graphite-based ink, followed by drop-casting the

synthesised cubic PB-MWCNTs hybrid and Nafion onto the sensing surface. CV and
M
chronoamperometry were employed to comparatively characterise the features of sensors

with and without IL doping for enzymeless H2O2 determination. The results demonstrated
d

that the doping of [Bmim] BF4 can significantly improve the detection performance of the
te

PB-MWCNTs modified SPCE for H2O2 monitoring, mainly due to the promoted electron
p

transfer. It was found that, under optimised conditions, the fabricated sensor provides linear
ce

amperometric responses for H2O2 in the concentration range from 5 to 1645 µM, with a

sensitivity of 0.436 mA cm−2 mM−1 and a detection limit of 0.35 µM (S/N = 3). In addition,
Ac

the IL-doped electrode exhibits excellent selectivity, good reproducibility and favorable long-

term stability for H2O2 detection. It was found that the proposed H2O2 sensor can be used as

an effective tool to measure the analyte in practical samples.

Heli and Pishang [370] synthesised Cobalt (II) dicobalt (III) oxide nanoparticles anchored to

MWCNTs by a microwave decomposition method, using cobalt nitrate as a precursor and

MWCNTs as a scaffold. The nanostructure was then employed as the modifier of a carbon

60
Page 60 of 165
paste electrode. The kinetics of the charge transfer process across the modified

electrode/solution interface was studied. The modified electrode was then applied to fabricate

an enzyme-less H2O2 biosensor. The mechanism and kinetics of the electrocatalytic reduction

and oxidation reactions of H2O2 on the modified electrode surface were studied by CV and

t
chronoamperometry. The catalytic rate constants of the H2O2 electroreduction and

ip
electrooxidation processes by an active cobalt species and the diffusion coefficient of H2O2

cr
were reported. An amperometric method was developed for determination of H2O2 based on

its electrocatalytic reduction with a sensitivity of 1002.8 mA mol−1 dm3 cm−2 and a limit of

us
detection of 2.46 µmol dm−3. The sensor had the advantages of high electrocatalytic activity

an
and sensitivity with a simple fabrication method, without complications of immobilisation

steps and without using any enzyme or reagent.

M
Habibi et al. [371] reported the synthesis and characterisation of a novel nanohybrid

composed of mesoporous carbon (MC) and silver nanoparticles (MC/AgNPs) to use in

d

amperometric sensing of H2O2. In this process, the MC was synthesised by using the
te

mesoporous silica as a template and glucose as a carbon source. The AgNPs were produced
p

by in situ chemical reduction of silver nitrate through glucose as a reducing and stabilising
ce

agent in the presence of MC to give the desired MC/AgNPs nanohybrid. It was investigated

by FESEM, TEM, X-ray diffraction and electrochemical measurements. The obtained

Ac

nanohybrid was used to modify a glassy carbon electrode and to fabricate an amperometric

sensor for H2O2 determination at a working potential of −200 mV vs. silver/silver chloride

electrode in aqueous 0.1 M phosphate buffer solution (pH 7.0). The resulted sensor can detect

H2O2 in the concentration range of 0.1–41 µM, with a detection of limit 50 nM at a signal-to-

noise ratio of 3.

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Page 61 of 165
Li et al. [372] developed a very efficient, simple approach to fabricate a high Pt

nanoparticles-loading multiwall carbon nanotube (MWCNTs) amperometric sensor for H2O2

determination. In this strategy, MWCNTs were first functionalised with an anionic surfactant,

sodium dodecyl sulfate (SDS). Then, the Pt nanoparticles (NPs) were loaded on MWCNTs-

t
SDS by electrodepositing. The large amounts of Pt nanoparticles could be well deposited on

ip
the surface of the MWCNTs-SDS modified electrode, as revealed by SEM. In addition, the

cr
PtNPs/MWCNTs-SDS composite was also characterised by electrochemical methods

including, CV and EIS. The experimental results demonstrated that the constructed electrode

us
exhibited good catalytic activity towards the H2O2, and obtained a wide linear range from

an
5.8×10-9 to 1.1×10-3M with a limit of detection (LOD) of 1.9×10-9 M, which was superior to

that obtained with other H2O2 electrochemical sensors reported previously. Moreover, it can
M
also be applied to real samples analysis. The excellent performance of H2O2 sensor was

ascribed to the MWCNTs-SDS composites being used as effective load matrix for the
d

deposition of PtNPs and the synergistic amplification effect of the two kinds of
te

nanomaterials-PtNPs and MWCNTs.

p

Yang et al. [373] developed a simple sonochemical route for the preparation of gold
ce

nanoparticles/boron nitride sheets (AuNPs/BNS) nanocomposites without using reducing or

stabilising agents. TEM, SEM, XRD and UV absorption spectra were used to characterise the
Ac

structure and morphology of the nanocomposites. The experimental results showed that

AuNPs with approximately 20 nm were uniformly attached onto the BNS surface. It was

found that the AuNPs/BNS nanocomposites exhibited good catalytic activity for the

reduction of H2O2. The modified electrochemical sensor showed a linear range from 0.04 to

50 mM with a detection limit of 8.3 µM at a signal-to-noise ratio of 3. The findings provide a

low-cost approach to the production of stable aqueous dispersions of nanoparticles/BNS

nanocomposites.

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Han et al. [374] obtained a novel composite of cobalt hexacyanoferrate nanoparticles (CoNP)

and platinum nanoparticles (Pt) on carbon nanotubes (CNTs) by ultrasonically mixing CoNP

synthesised in a microemulsion with CNTs chemically modified with platinum nanoparticles

(Pt/CNTs). CV and aerometric measurements on a glass carbon electrode showed that the

t
composite (called CoNP-Pt/CNTs) exhibits a well-defined pair of redox peaks and a

ip
prominent electrocatalytic activity toward H2O2 reduction. Besides, the current response of

cr
CoNP-Pt/CNTs is 2 orders of magnitude higher than the response of CoNP alone and 1 order

of magnitude higher than the response of Pt/CNTs or CoNP/CNTs alone. This higher

us
efficiency can be attributed to a remarkable synergistic effect between CoNP, Pt and CNTs.

an
This sensor showed a linear response to H2O2 concentrations ranging from 0.2 M to 1.25 mM

with a detection limit of 0.1 M, a maximum sensitivity of 0.744 A M-1 and a fast response
M
time below 2 s. Nayak et al. [375] reported the fabrication of nonenzymatic H2O2 biosensor

using multiwalled carbon nanotubes-solar exfoliated graphene hybrid nanocomposite

d

(MWCNTs-sG) as a transducer candidate. The hybrid material has been synthesised by solar
te

reduction technique from a mixture of MWCNTs and graphite oxide (GO). The fabricated

MWCNTs-sG based biosensor shows a high catalytic response towards H2O2 reduction at a
p

low potential of -0.4 V and good linearity over a wide range of concentration from 2 mM to
ce

344 mM. Various groups [12, 339, 357, 376-380] have earlier shown that CNTs-based- H2O2

biosensors exhibit good sensitivity, selectivity and reproducibility and recent studies have
Ac

shown that CNTs-based H2O2 biosensors exhibited good sensitivity, selectivity and

reproducibility towards detection of H2O2 [79, 173, 203, 205, 206, 208, 215, 283, 315, 323,

338, 347-350, 363, 367, 368, 372, 381-394].

7. 4. β-nicotinamide adenine dinucleotide (NADH)

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Nicotinamide adenine dinucleotide (NAD+) is an important cofactor of redox reactions inside

living cells. The NADH generated can be detected by electrochemical oxidation at

appropriate electrodes. The electrochemical detection of NADH is one of the most studied

areas of bioelectroanalysis because of the importance of NAD(P)H-based enzymatic reactions

t
in nature [395, 396]. NADH is involved as a cofactor in over 300 enzymatic reactions of

ip
NAD+/NADH dependent dehydrogenases [189]. The application of amperometric NADH

cr
sensors has evolved to provide a promising measurement technique for detection of substrate

or enzymatic activity. However, the direct oxidation of NADH at ordinary electrodes often

us
requires high overpotential and suffers from low sensitivity and the fouling of the electrode

an
surface by its oxidation products. In recent years, CNTs are attracting growing attention in

decreasing the high overpotential for NADH oxidation and minimising the surface fouling.
M
The attractive low-potential anodic detection of H2O2 and NADH at CNT-modified

electrodes, [397-399] along with the minimal surface passivation during the oxidation of
d

NADH, makes CNTs extremely attractive for a variety of oxidase- and dehydrogenase-based
te

enzyme electrodes for various important analytes. The fast heterogeneous charge transfer

reactions of CNTs have been attributed to edge plane like sites [399].
p
ce

Recently, Zhu et al. [400] investigated the electrodeposition of pyrocatechol violet (PCV) by

the electrochemical surface plasmon resonance (ESPR) technique. Subsequently, PCV was
Ac

used as redox-mediator and was electrodeposited on the surface of pencil graphite electrode

(PGE) modified with single-wall carbon nanotubes (SWCNTs). Owing to the remarkable

synergistic effect of SWCNTs and PCV, PGE/SWCNTs/PCV exhibited excellent

electrocatalytic activity towards NADH oxidation at low potential (0.2 V vs. SCE) with fast

amperometric response 10 s, broad linear range (1.3-280 µM), good sensitivity (146.2 µA

mM-1 cm-2) and low detection limit (1.3 µM) at signal-to-noise ratio of 3. Thus this

PGE/SWCNTs/PCV could be further used to fabricate a sensitive and economic ethanol

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biosensor, using alcohol dehydrogenase (ADH) via a glutaraldehyde/BSA cross-linking

procedure. Yu et al. [204] introduced the research progress of the NADH electrochemical

sensors based on CNT-modified electrodes, and foretells its application prospect. Li et al.

[401] demonstrated that the electrocatalytic oxidation of NADH can be enhanced by the

t
hybrid composites of polyluminol and functionalised MWCNTs. The hybrid composites can

ip
be easily prepared by the electropolymerisation of luminol and the adsorption of

cr
functionalised MWCNTs. The modified electrode exhibits two redox couples which can

show two electrocatalytic peaks at about 0.1 and 0.3 V (vs.Ag/AgCl) to NADH oxidation.

us
The kinetic constant, kkin, for the electrocatalytic oxidation of NADH, evaluated by

an
chronoamperometry and voltammetry using a rotating disk electrode (RDE), provided values

close to 105 M-1 s-1. At an applied potential of 0.1 V, the sensor provides a linear response
M
range for NADH from 5 ×10-6 up to 1.5 ×10-4 M with a sensitivity of 183.9 A mM-1 cm-2 and

detection and quantification limits of 0.6 and 5 M (S/N = 3) respectively. Ge et al. [402]
d

synthesised novel nanocomposite of glutaraldehyde crosslinked chitosan (CS)–dopamine

te

(DA) composite with MWCNTs for low-potential and sensitive amperometric sensing of

NADH. The composite was characterised by FT-IR spectrophotometry. The nanocomposite

p

modified Au electrode showed well-defined quinone/phenol redox peaks of the dopamine

ce

moieties and was able to effectively mediate the oxidation of NADH in pH 7.0 phosphate

buffer, with an overpotential decrease by ca. 450 mV (vs. bare Au). The NADH
Ac

electrochemical sensor showed a linear range of 0.1–600 µM, a limit of detection of 12 nmol

L−1, good antiinterferent ability and long-term stability. It was also found that the use of

acidified MWCNTs showed better performance than that of the nonacidified MWCNTs. Both

CS and DA being biomaterials, the CS–DA/MWCNTs system should be of interest and

potential for developing in vivo NAD+ (the oxidised form of NADH)-dependent

dehydrogenase enzymes based biosensors. Goran et al. [403] observed that nitrogen-doped

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carbon nanotubes (N-CNTs) substantially lower the overpotential necessary for NADH

oxidation, compared to nondoped CNTs or traditional carbon electrodes such as GC. They

observed a 370 mV shift in the peak potential (E p) from GC to CNTs and another 170 mV

shift from CNTs to 7.4 atom % N-CNTs in a sodium phosphate buffer solution (pH 7.0) with

t
2.0 mM NADH (scan rate 10 mV/s). The sensitivity of 7.4 atom % N-CNTs to NADH was

ip
measured at 0.30 ± 0.04 A M-1 cm-2, with a limit of detection at 1.1 ± 0.3 µM and a linear

cr
range of 70 ± 10 µM poised at a low potential of -0.32 V (vs Hg/Hg2SO4). NADH fouling,

known to occur to the electrode surface during NADH oxidation, was investigated by

us
measuring both the change in Ep and the resulting loss of electrode sensitivity. NADH

an
degradation, known to occur in phosphate buffer, was characterised by absorbance at 340 nm

and correlated with the loss of NADH electroactivity. N-CNTs are further demonstrated to be
M
an effective platform for dehydrogenase-based biosensing by allowing glucose

dehydrogenase to spontaneously adsorb onto the N-CNT surface and measuring the resulting
d

electrode's sensitivity to glucose. The glucose biosensor had a sensitivity of 0.032 ± 0.003 A
te

M-1 cm-2, a limit of detection at 6 ± 1 µM, and a linear range of 440 ± 50 µM.
p

Huang et al. [404] performed electrochemical sensing using conductive carbon composite
ce

films containing reduced graphene oxide (rGO) and SWCNTs as electrode modifiers on

GCEs. Raman spectroscopy, TEM, AFM and SEM all suggested that the rGO acted as a
Ac

surfactant, covering and smoothening out the surface, and that the SWCNTs acted as a

conducting bridge to connect the isolated rGO sheets, thereby (i) minimising the barrier for

charge transfer between the rGO sheets and (ii) increasing the conductivity of the film. They

used the rGO/SWCNT-modified GCE as a sensor to analyse H2O2 and NADH, obtaining

substantial improvements in electrochemical reactivity and detection limits relative to those

obtained from rGO- and SWCNT-modified electrodes, presumably because of the higher

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conductivity and greater coverage on the GCE, due to π-π interactions originating from the

graphitic structures of the rGO and SWCNTs.

Chiang et al. [405] performed hybridisation of poly(luminol) (PLM) and poly(neutral red)

(PNR) further enhanced by a conductive and steric hybrid nanotemplate using graphene

t
ip
oxide (GO) and MWCNTs. The morphology of the PLM-PNR-MWCNT-GO mycelium-like

nanocomposite is studied by SEM and AFM and it is found to be electroactive, pH-

cr
dependent, and stable in the electrochemical system. It shows electrocatalytic activity

us
towards NADH with a high current response and low overpotential. Using amperometry, it

has been shown to have a high sensitivity of 288.9 A mM-1 cm-2 to NADH (Eapp. = +0.1 V).

an
Linearity is estimated in a concentration range of 1.33 ×10-8 to 1.95 ×10-4 M with a

detection limit of 1.33 ×10-8 M (S/N = 3). Particularly, it also shows another linear range of
M
2.08 ×10-4 to 5.81 ×10-4 M with a sensitivity of 151.3 A mM-1 cm-2. The hybridisation and

activity of PLM and PNR can be effectively enhanced by MWCNTs and GO, resulting in an
d

active hybrid nanocomposite for determination of NADH. Deng et al. [406] reported a
te

NADH and glucose biosensor based on thionine cross-linked MWCNTs and Au

p

nanoparticles (Au NPs) multilayer functionalised indium-doped tin oxide (ITO) electrode.
ce

The effect of light irradiation on the enhancement of bioelectrocatalytic processes of the

biocatalytic systems by the photovoltaic effect was investigated. This bioelectrode exhibited
Ac

excellent catalytic activity of the oxidation towards NADH. Most interestingly, the

performance of this NADH sensor could be tuned by the visible light. When the biosensor

was performed in the dark, the anodic current increased linearly with NADH concentration

over the range of 0.5 to 237 µM, with detection limit 0.1 µM and sensitivity 17 nA µM−1. The

sensitivity became 115 nA µM−1 with detection limit 0.05 µM with the light irradiation.

Compared with the reaction in the dark, the sensitivity increased around 7 folds while the

detection limit decreased 2 folds. Various groups have earlier on shown that CNTs-based-

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NADH biosensors exhibited good sensitivity [34, 407] and in recent years, most researchers

have shown that CNTs-based NADH biosensor exhibited good sensitivity, selectivity and

reproducibility [397, 408, 409].

7.5. Cholesterol biosensor

t
ip
Increases in cholesterol levels can cause life-threatening coronary heart diseases, cerebral

cr
thromboses and artherosclerosis [410]. Therefore, accurate detection of cholesterol level is

us
medically very important. Various groups have previously shown that CNTs-based-

cholesterol biosensors exhibit good sensitivity [411-418] and in recent years, most

an
researchers have shown that CNTs-based cholesterol biosensor exhibits good sensitivity,

selectivity and reproducibility [5, 419-423]. Recently, Molaei et al. [424] established the
M
electrochemical behaviour of gold electrodes modified with gold nanoparticles, acetone-

extracted propolis, MWCNTs and cholesterol oxidase (ChOx) for the detection of hydrogen
d

peroxide by using CV and amperometric techniques. The obtained results confirmed that the
te

current enzymatic biosensor exhibits a fast, highly sensitive and cost-effective detection of

cholesterol. Cholesterol in the concentration range of 0.15-0.55 mmol l-1 was determined with
p

a detection limit of 4.9 × 10-5 mol l-1 by the amperometric method, and the sensitivity of the
ce

proposed method was found to be 17.38 µA/mmol l-1. Normal electroactive species such as

ascorbic acid and glucose in the presence of the constant concentration of cholesterol in the
Ac

samples, do not interfere with the determination.

Cai et al. [425] fabricated a bienzyme biosensor for the detection of cholesterol, based on

functionalised carbon nanotubes (CNTs) through layer-by-layer (LBL) assembly technique.

Being wrapped with cationic poly(allylamine hydrochloride) (PAH), the nanocomposite,

MCNTs mixed with gold nanoparticles (GNPs) was water soluble and positively charged.

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Based on reliably electrostatic interaction, bienzyme biosensor was then fabricated by LBL

assembly of the positively charged nanocomposite and the negatively charged enzymes, HRP

and ChOx. The fabricated process and the electrochemical behaviors of the biosensor were

investigated by SEM, EIS and CV. Under the optimal conditions, the bienzyme biosensor

t
obtained the linear range from 0.18 to 11 mM, with a detection limit of 0.02 mM. The

ip
proposed biosensor exhibited good sensitivity, stability, and controllability for the detection

cr
of cholesterol.

Karimi et al. [426] prepared an electrochemical biosensor by immobilising cholesterol ChOx

us
on a nanocomposite consisting of amine functionalised MWCNT and a room temperature

an
ionic-liquid (1-butyl-3-methylimidazolium tetrafluoroborate). The biosensor was examined

for cholesterol quantification in clinical serum samples. ChOx on the modified electrode
M
exhibited a couple of quasi-reversible redox peaks corresponding to the direct electron

transfer of FAD/FADH2 buried in the enzyme structure. A formal potential of -400 mV was
d

obtained for the immobilised enzyme in phosphate buffer solution (0.1 M, pH 7.4). Under the
te

optimised experimental conditions, the biosensor exhibited a linear response towards

cholesterol concentration from 26 nM to 3.4M, with a sensitivity of 540 A mM-1and a

p

detection limit of 12 nM.

ce

Kakhki et al. [419] developed a new enzyme biosensor for cholesterol detection based on a
Ac

recently developed transduction platform constituted of a GCE modified with polymer redox

mediator poly(methylene blue) (PMB) and conducting polymer poly(3,4-

ethylenedioxythiophene) (PEDOT) were prepared and evaluated. The enzyme ChOx was

immobilised by simple adsorption, the ChOx/PEDOT/PMB/GCE biosensor being applied for

amperometric determination of cholesterol by monitoring the peroxide reduction produced by

the enzymatic reaction at -0.4 V vs. SCE. Amperometric studies at fixed potential reveal that

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Page 69 of 165
almost interference-free cholesterol determination can be achieved at the newly developed

biosensor in a range between 10 and 220 M with a sensitivity of 79.0 A cm-2 mM-1 and a

detection limit of 1.6 M. The recovery and storage stability of the biosensor were evaluated

and the biosensor was applied to cholesterol detection in whole cow milk and chicken egg

t
yolk.

ip
cr
Tong et al. [422] reported monolithic molecular imprinting sensor based on ceramic carbon

electrode (CCE). The sensor can be renewed simply by smoothning. It was fabricated by

us
thoroughly mixing MWCNT molecularly imprinted polymer (MWCNT@MIP), graphite

an
powder, and silicon alkoxide, and then packing the resulting complex mixture of components

firmly into the electrode cavity of a Teflon sleeve. The incorporated MWCNT@MIP in CCEs
M
functioned as a recognition element for cholesterol determination. The MWCNT@MIP-

CCEs were tested in the presence or absence of cholesterol by CV and linear sweep
d

voltammetry. The cholesterol sensor has excellent sensitivity, with a linear range of 10-300.
te

nM and a detection limit of 1 nM (S/N=3). The monolithic molecular imprinting sensor

exhibits good stability, high sensitivity and user-friendly reusability for cholesterol
p

determination.
ce

Zhu et al. [421] fabricated an electrochemical cholesterol biosensor based on the direct
Ac

electron transfer of ChOx immobilised on gold nanoparticles-decorated multiwalled carbon

nanotubes (GNPs-MWCNTs). GNPs-MWCNTs were prepared based on the reduction of

HAuCl4 in the presence of carboxyl group functionalised MWCNTs. Transmission electron

microscopy image shows that rounded gold nanoparticles with diameters of 6-10 nm were

decorated on CNTs surfaces. ChOx was directly adsorbed on the nanocomposite modified

glassy carbon electrode and protected by a Nafion film. Direct electrochemistry of ChOx on

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Page 70 of 165
the electrode surface was obtained, proved by one pair of well-defined, quasi-reversible redox

peaks in phosphate buffered saline. Under optimised conditions, the fabricated electrode

displayed a linear response in the cholesterol concentration range from 0.0100 to 5.00 mmol
-1
L , with a detection limit of 4.3 µmol L-1 estimated at a signal-to-noise ratio of 3. The

t
apparent Michaelis-Menten constant was measured to be 0.29 mmol L-1, indicating that the

ip
immobilised ChOx on GNPs-MWCNTs matrix retained its native activity. The developed

cr
biosensor presented good selectivity, repeatability, reproducibility and stability. The

concentration of free cholesterol in a human serum sample, detected by using the developed

us
biosensor, is in good agreement with that determined by the well-established

an
spectrophotometric method. Researchers who previously fabricated sensitive cholesterol

biosensor include Dhand et al. [427], Gopalan et al. [428], Guo et al. [429] and Li et al. [417].
M
d
p te

7.6. Electrochemical Immunosensing

ce

Immunosensing is based on the high affinity reactions antigen/antibody. Several strategies

can be used to immobilise the recognition element, either the antibody or the antigen,
Ac

depending on the selected scheme. The detection of the recognition event uses the same

principle as the enzymatic immunoassay. In general, an enzyme is coupled to the recognition

layer (the antigen or antibody) and the enzymatic reaction is developed once the

antigen/antibody interaction occurs and after the addition of the substrate and electrochemical

detection of the product [430, 431]. Electrochemical immunosensors provide a specific and

simple analytical alternative, as evidenced by their brief analysis times, inexpensive

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Page 71 of 165
instrumentation, lower assay cost, as well as good portability and amenability to

miniaturisation [30].

CNT-based transducers have been shown to be useful for enhancing the sensitivity of

bioaffinity assays. CNT has been used for electrochemical immunosensing. The direct

t
ip
electrochemical detection of antibody antigen recognition is usually not possible and

electrochemically active labels must typically be used [432]. Recently, Liu et al. [433]

cr
developed a novel multianalyte electrochemical immunosensor based on the assembly of

us
patterned SWNTs on glassy carbon (GC) substrates for simultaneous detection of endosulfan

and paraoxon. Based on aryldiazonium salt chemistry, forest of SWNTs can be patterned on

an
GC substrates by C3C bonding using micro contact printing (MCP), which provides an

interface showing efficient electron transfer between biomolecules and electrodes. Then
M
redox molecules FDMA and PQQ can be attached to the SWNTs, respectively, followed by

the attachment of specific epitopes and antibodies. The modified sensing surfaces were
d

characterized by XPS, SEM, AFM and electrochemistry. Based on the current change of
te

specific redox probes, the fabricated immunosensor array can be used for simultaneous
p

detection of endosulfan and paraoxon by a displacement assay. In phosphate buffer solution

ce

(50. mM, pH 7.0), there is a linear relationship between electrochemical signal of FDMA and

the concentration of endosulfan over the range of 0.05-100. ppb, with a detection limit of
Ac

0.05. ppb. The linear range between electrochemical signal of PQQ and the concentration of

paraoxon is 2-2500 ppb, with a detection limit of 2 ppb. The immunosensor array

demonstrates high repeatability, reproducibility, stability and selectivity for the detection of

endosulfan and paraoxon. Recently, Zhang et al. [434] reported in their studies on a label-

free electrochemical immunosensor for α-fetoprotein (α-FP). It was based on the use of a

glassy carbon electrode that was first modified with conducting poly(5-formylindole) and

single-SWCNTs (P5FIn/SWNTs), and then coated with gold nanoparticles and the respective

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antibody. The presence of aldehyde groups warrants direct immobilisation of the antibody

and results in a convenient method for the fabricating of the immunosensor. Gold

nanoparticles (GNPs) were deposited on the P5FIn/SWNTs composite material, and the

modified electrode was applied to the detection of α-FP. The analytical signal was obtained

t
by measuring the change of amperometric response at a typical working voltage of 100 mV

ip
before and after the immunoreaction. The detection limit was 200 fg mL-1. The

cr
immunosensor is simple, sensitive, specific and reproducible. It has the potential for reliable

point-of-care diagnosis of tumor or other diseases. Various groups have recently shown that

us
CNTs-based immunosensor exhibit good sensitivity, selectivity and reproducibility [95, 326,

an
335-340, 424, 432, 435-439] while other earlier researchers have shown that CNTs-based

immunosensor are sensitive and selective with good reproducibility [5, 21, 95, 440-442].
M
Rusling's group illustrated that SWCNT electrodes provide high surface areas for

immobilising antibody receptors. This team described a number of SWCNT ‘forest’

d

platforms for enzyme-linked amperometric protein immunosensors [443]. Such devices were
te

prepared by chemically attaching secondary antibodies to the carboxylated ends of CNT

forests in connection with EDC coupling [444]. The sensitivity of these sandwich
p

immunosensors can thus be greatly amplified by conjugating both the secondary antibody and
ce

the horseradish-peroxidase (HRP) enzyme label onto the CNTs as shown in Fig. 7.
Ac

In another contribution from Rusling's team, SWCNTs were incorporated into polylysine

(PLL)–antibodyassemblies towards improved enzyme-based amperometricimmunoassays of

biotin [445]. Sequential coating of MWCNTs and gold nanoparticles on the gold electrode

transducer was shown by Akter et al. [446] to further increase the area on which the antibody

is immobilised and to amplify the amperometric detection of cancer biomarkers. Justino et

al. [188]’s review also addressed the synthesis, the properties, the areas of application of

CNTs, the characteristics and the clinical importance of POC testing. Zhang et al. [447]

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developed a simple and green method for in situ assembly of gold nanoparticles on nitrogen-

doped carbon nanotubes, and the resulting Au/nitrogen-doped carbon nanotubes

nanocomposite was used as an immobilisation scaffold of antibody for sensitive

immunosensing of microcystin-LR.

t
ip
Arugula and Simonia [21] focused mainly on recent developments in affinity-based

biosensors such as immunosensors, DNA sensors, emphasising apta sensors and phage-based

cr
biosensors based on novel electrochemical, optical and mass sensitive detection techniques.

us
They also addressed enzyme inhibition-based biosensors and the current problems associated

with the above sensors and their future perspectives. Azav and Senitinguf [448] developed a

an
specific and sensitive biosensor successfully for quantitative detection of human epidermal

growth factor receptor by electrochemical impedance spectroscopy. Anti-human epidermal

M
growth factor receptor antibody was covalently immobilised onto a screen-printed carbon

electrode modified with a CNT. Immobilisation steps were characterised by CV, EIS and
d

SEM. After human epidermal growth factor receptor ligates with anti-human epidermal
te

growth factor receptor immobilised onto an electrode surface, charge transfer resistance
p

changed considerably. This electrochemical response was correlated with human epidermal
ce

growth factor receptor concentration. Under optimal conditions, the proposed biosensor could

detect human epidermal growth factor receptor 2. fg/mL with a linear range from 2 to 14.
Ac

fg/mL, showing high sensitivity. Tran et al. [436] designed an electrochemical immunosensor

for miRNA detection, based on screen-printed gold electrodes modified with reduced

graphene oxide and carbon nanotubes. An original immunological approach is followed,

using antibodies directed to DNA.RNA hybrids. An electrochemical ELISA-like

amplification strategy was set up using a secondary antibody conjugated to horseradish

peroxidase (HRP). Hydroquinone is oxidised into benzoquinone by the HRP/H2O2 catalytic

system. In turn, benzoquinone is electroreduced into hydroquinone at the electrode. The

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Page 74 of 165
catalytic reduction current is related to HRP amount immobilised on the surface, which itself

is related to miRNA.DNA surface density on the electrode. This architecture, compared to

classical optical detection, lowers the detection limit down to 10 fM. Two miRNAs were

studied: miR-141 (a prostate biomarker) and miR-29b-1 (a lung cancer biomarker).

t
ip
Teixeira et al. [435] fabricated a sensor device for detection of hCG, using a CNT screen

cr
printed electrode (SPE). Human chorionic gonadotropin (hCG) is a key diagnostic marker of

pregnancy. The CNT working electrode was first electrochemically oxidised to yield a

us
hydroxyl terminated surface, which was subsequently silanised to produce an amine

an
terminated CNT. The aminated surface allowed oriented binding of an antibody (Ab)

bioreceptor, targeted against hCG (anti-hCG), to the CNT-SPE. This was achieved by
M
activating the -COOH group at the Fc terminal of the antibody and incubating the SPE-CNT-

NH2 electrode in the activated Ab solution. EIS and Raman Spectrometry with Confocal
d

Microscopy studies were performed at each stage of the chemical modification process in
te

order to confirm the resulting surface changes associated with each functionalisation process.

The SPE-CNT-NH2-Ab devices displayed linear responses to hCG in EIS assays in the
p

concentration range from 0.01 × 10-9 g cm -3

to 100 × 10-9 g cm-3. High specificity was
ce

observed with respect to hCG detected in solutions containing urine components with the

components producing a negligible change in the sensor readout relative to changes induced
Ac

by hCG. Successful hCG detection was also achieved using real urine samples from a

pregnant woman. Overall, the immunosensor developed is a promising tool for detecting hCG

in a point-of-care diagnosis (POC), due to the excellent detection capability, simplicity of

fabrication, low cost, high sensitivity and selectivity.

Cui et al. [449] described the combination of electrochemical immunosensor using gold

nanoparticles (GNPs)/CNTs) hybrids platform with HRP-functionalised gold nanoparticle

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label for the sensitive detection of human IgG (HIgG) as a model protein. The GNPs/CNTs

nanohybrids covered on the glass carbon electrode (GCE) constructed an effective antibody

immobilisation matrix and made the immobilised biomolecules hold high stability and

bioactivity. Enhanced sensitivity was obtained by using bioconjugates featuring HRP labels

t
and secondary antibodies (Ab2) linked to GNPs at high HRP/Ab2 molar ratio. The approach

ip
provided a linear response range between 0.125 and 80 ng/mL, with a detection limit of 40

cr
pg/mL. The immunosensor showed good precision, acceptable stability and reproducibility

and could be used for the detection of HIgG in real samples, which provided a potential

us
alternative tool for the detection of protein in clinical laboratory.

an
Dai et al. [219] developed a new biosensing platform based on electrospun carbon nanotubes
M
nanofibers composite, which provided strong electrochemiluminescent emission of

peroxydisulfate, for immunoassay with favorable analytical performances, and was then
d

utilised to evaluate the interaction between antibody and antigen in vitro. Moreover, the
te

obvious ECL image of peroxydisulfate on the prepared sensing platform was firstly recorded

in this report. In order to expand the application of peroxydisulfate ECL, the specific
p

recognisation biomolecules, α-fetoprotein (AFP) antibody was bound to the functionalised

ce

film via electrostatic interaction for fabricating label-free ECL immunosensor to detect α-

AFP. Based on the ECL change resulting from the specific immunoreaction between antigen
Ac

and antibody, the quantitative analysis for AFP with wide dynamic response in the range

from 0.1 pg mL−1 to 160 ng mL−1 was realized, while the limit of detection was estimated to

be 0.09 pg mL−1. Therefore, the flexible sensing platform not only acted as the sensitised

sensing element, but also offered a suitable carrier for immobilisation of biological

recognition elements with low-toxicity and eco-friendliness, which opened a promising

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approach to developing further electrospun nanofiber based amplified ECL biosensor with

favorable analytical performances.

Fayazfar et al. [450] developed a new platform based on electrochemical growth of Au

t
nanoparticles on aligned MWCNT (A-MWCNT) for sensitive lable-free DNA detection of

ip
the TP53 gene mutation, one of the most popular genes in cancer research. EIS was used to

cr
monitor the sequence-specific DNA hybridisation events related to TP53 gene. Compared to

the bare Ta or MWCNT/Ta electrodes, the synergistic interactions of vertically aligned

us
MWCNT array and gold nanoparticles at modified electrode could improve the density of the

an
probe DNA attachment and increase the sensitivity of the DNA sensor greatly. Using EIS,

over the extended DNA concentration range, the change of charge transfer resistance was
M
found to have a linear relationship in respect to the logarithm of the complementary

oligonucleotides sequence concentrations in the wide range of 1.0×10-15-1.0×10-7M, with a

d

detection limit of 1.0×10-17M (S/N=3). The prepared sensor also showed good stability (14
te

days), reproducibility (RSD=2.1%) and could be conveniently regenerated via

dehybridisation in hot water. The significant improvement in sensitivity illustrates that

p

combining gold nanoparticles with the on-site fabricated aligned MWCNT array represents a
ce

promising platform for achieving sensitive biosensor for fast mutation screening related to

most human cancer types. Various groups have previously shown that CNTs-based-
Ac

imunosensors exhibit good sensitivity [449, 451] and in recent years, most researchers have

shown that CNTs-based immunosensor exhibits good sensitivity, selectivity and

reproducibility [30, 241,432- 434, 437- 438, 447, 452, 453].

7.7. DNA sensors

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Electrochemical DNA sensors offer high sensitivity, high selectivity and low cost for the

detection of selected DNA sequences or mutated genes associated with human disease and

promise to provide a simple, accurate and inexpensive platform of patient diagnosis. Various

research groups have demonstrated that CNTs-based DNA biosensors exhibit good

t
sensitivity, selectivity and reproducibility [160, 164, 434, 454-477]. CNTs can enhance

ip
greatly the performance of electrochemical DNA hybridization biosensors [232, 476, 478-

cr
483]. Recently, Fernades et al. [484] reported the construction of new high sensitive

electrochemical genosensor based on MWCNT–chitosan–bismuth complex (MWCNT–Chi–

us
Bi) and Lead sulfide nanoparticles for the detection of pathogenic Aeromonas. Lead sulfide

an
nanoparticles capped with 5′-(NH2) oligonucleotides provided amide bond which was used

as signalising probe DNA (sz-DNA) and thiol-modified oligonucleotides sequence was used
M
as fixing probe DNA (fDNA). The two probes hybridise with target Aeromonas DNA

(tDNA) sequence (fDNA–tDNA–szDNA). The signal of hybridisation is detected by

d

differential pulse voltammetry (DPV) after electrodeposition of released lead nanoparticles

te

(PbS) from sz-DNA on the surface of glass carbon electrode decorated with MWCNT–Chi–

Bi, which improves the deposition and traducing electrical signal. The optimisation of
p

incubation time, hybridisation temperature, deposition potential, deposition time and the
ce

specificity of the probes were investigated. Results showed the highest sensibility to detect

the target gene when compared with related biosensors and polymerase chain reaction (PCR).
Ac

The detection limit for this biosensor was 1.0×10−14 M. They could detect lower than 102

CFU mL−1 of Aeromonas in spiked tap water. This method is rapid and sensitive for the

detection of pathogenic bacteria and would become a potential application in biomedical

diagnosis, food safety and environmental monitoring.

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Quian et al. [485] designed a new strategy to combine Zn2+ assistant DNA recycling

followed with hybridisation chain reaction dual amplification for highly sensitive

electrochemical detection of target DNA. A gold electrode was used to immobilise molecular

beacon (MB) as the recognition probe and perform the amplification procedure. In the

t
presence of the target DNA, the hairpin probe 1 was opened and the DNAzyme was liberated

ip
from the caged structure. The activated DNAzyme hybridised with the MB and catalysed its

cr
cleavage in the presence of Zn2+ cofactor, resulting in a free DNAzyme strand. This novel

cascade signal amplification strategy can detect target DNA down to the attomolar level with

us
a dynamic range spanning 6 orders of magnitude. This highly sensitive and specific assay has

an
a great potential to become a promising DNA quantification method in biomedical research

and clinical diagnosis. Sun et al. [481] constructed peanut allergen Ara h1 detection. The
M
biosensor was constructed by coating a glassy carbon electrode with a chitosan-MWCNT-

nanocomposite and then adding a spongy gold film via electro-deposition to increase the
d

effective area. The probe switched from an “on” to an “off” state in the presence of target
te

DNA, which detached biotin from the electrode surface. This also detached streptavidin–

horseradish peroxidase (HRP-SA), which was bound to the electrode via specific interaction
p

with biotin. The HRP-SA catalysed chemical oxidation of hydroquinone by H2O2 to form
ce

benzoquinone, and when it was detached, electrochemical reduction of the signal of

benzoquinone could be used to monitor DNA hybridization via chronoamperometry. Under

Ac

optimum conditions, a wide dynamic detection range (3.91×10−17–1.25×10−15 mol L−1) and a

low detection limit (1.3×10−17 mol L−1) were achieved for the complementary sequence.

Furthermore, the DNA biosensor exhibited an excellent ability to discriminate between a

complementary target and a one-base mismatch or non-complementary sequence. The sensor

was successfully applied to Ara h 1 analysis in peanuts.

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Wu et al. [463] summarised the latest developments in the application of nanomaterials as

signal amplification elements in ultrasensitive DNA-based electrochemical detection. Braman

et al. [486] developed a novel electrochemical biosensor for the determination of vitamin B1.

The interaction of vitamin B1 with DNA based on the decreasing of the oxidation signal of

t
guanine and adenine bases was studied electrochemically with a pretreated MWCNT paste

ip
electrode (PMWCNTPE) using differential pulse voltammetry. The decrease in the intensity

cr
of the guanine and adenine oxidation signals after interaction with vitamin B1, was used as

indicator signals for the sensitive determination of vitamin B1. Under optimum conditions, a

us
linear dependence of the guanine and adenine oxidation signals was observed for the vitamin

an
B1 concentration in the range of 1.0-80 µg mL-1, with a detection limit of 0.44 µg mL-1 at ds-

DNA modified PMWCNTPE. The reproducibility and applicability of the analysis to serum,
M
plasma and urine sample were also investigated. Vitamin B1 was also determined on a

pretreated MWCNT paste electrode by means of adsorptive stripping differential pulse

d

voltammetry. The peak current was linearly dependent on Vitamin B1 concentration over the
te

range of 0.0025-0.80 µg mL-1, with a detection limit of 1.1 ng mL-1 Vitamin B1. Both ds-

DNA-modified MWCNPTE and PMWCNTPE were applied to analyse Vitamin B1 in real

p

samples.
ce

Fayazfar et al. [450] developed a new platform based on electrochemical growth of Au

Ac

nanoparticles on aligned multi-walled carbon nanotubes (A-MWCNT) for sensitive lable-free

DNA detection of the TP53 gene mutation, one of the most popular genes in cancer research.

EIS was used to monitor the sequence-specific DNA hybridization events related to TP53

gene. Compared to the bare Ta or MWCNT/Ta electrodes, the synergistic interactions of

vertically aligned MWCNT array and gold nanoparticles at modified electrode could improve

the density of the probe DNA attachment and the sensitivity of the DNA sensor greatly.

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Page 80 of 165
Using EIS over the extended DNA concentration range, the change of charge transfer

resistance was found to have a linear relationship in respect to the logarithm of the

complementary oligonucleotides sequence concentrations in the wide range of 1.0×10-15-

1.0×10-7 M, with a detection limit of 1.0×10-17 M (S/N=3). The prepared sensor also showed

t
good stability (14 days), reproducibility (RSD=2.1%) and could be conveniently regenerated

ip
via dehybridisation in hot water. The significant improvement in sensitivity illustrates that

cr
combining gold nanoparticles with the on-site fabricated aligned MWCNT array represents a

promising platform for achieving sensitive biosensor for fast mutation screening related to

us
most human cancer types.

an
Kim et al. [487] developed a microfluidic-assisted electrochemical (EC) biosensing platform
M
based on vertically aligned multi-walled carbon nanotubes (MWCNTs) embedded in SiO2,

using multi-scale manufacturing techniques. The MWCNT-EC sensor was fabricated using
d

electron beam (E-beam) nanolithography, thin-film metal deposition and

te

reactive/electrochemical etching. The MWCNT-EC sensor was integrated with a microfluidic

EC cartridge including the counter and reference electrodes and a PDMS microfluidic
p

channel on a glass substrate. After packaging the MWCNT chip and microfluidic EC
ce

cartridge into a manifold which included sample inlet/outlet, electrical connectors and a

miniaturised potentiostat, the platform was characterised with differential pulse voltammetry
Ac

(DPV) using ferrocyanide and ruthenium (II) solutions. The DPV measurement results were

consistent with commercial EC systems. Microfluidic nucleic acid hybridisation was

demonstrated, using the MWCNT chip on which the MWCNT tips were functionalised with

single-stranded DNA (ssDNA) probes. The synthetic complementary ssDNA targets were

input through the microfluidic channel and hybridised with the functionalised ssDNA probes.

The relative DPV peak magnitude linearly correlated with the target DNA concentration.

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This platform provides a simple way to integrate a MWCNT biosensor with microfluidics as

an electronic system for a variety of possible nucleic acid analyses. Niu et al. [488] developed

a novel and sensitive electrochemical DNA biosensor for the detection of DNA hybridisation.

The biosensor was proposed by using imidazo[4,5-f]1,10-phenanthroline iron(III)

t
(Fe(phen)2IP· 3ClO4·2H2O, abbreviated as [Fe(phen) 2IP]3+), as an electroactive indicator

ip
based on multi-walled carbon nanotubes/platinum nanoparticles (MWCNTs/Ptnano)

cr
modified glassy carbon electrode (GCE). The interaction between [Fe(phen)2IP]3+ and

double-stranded DNA (dsDNA) was investigated by CV. The experiment results showed that

us
[Fe(phen)2IP]3+ presented an excellent electrochemical activity on GCE and could intercalate

an
into the double helix of double-stranded DNA. The target ssDNA of the human hepatitis B

virus (HBV) was quantified in a linear range from 1.13 × 10-11-1.13 × 10-9 M (r = 0.9892) with
M
a detection limit of 5.56 × 10-12 M (3S, n = 11).

Abdel-Hamid and Naweir [489] used MWCNTs-modified glassy carbon electrode biosensor
d

for electrochemical studies of caffeic acid-dsDNA interaction in phosphate buffer solution at

te

pH 2.12. Caffeic acid, CAF, shows a well-defined CV wave. Its anodic peak current

decreases and the peak potential shifts positively on the addition of dsDNA. This behaviour
p

was ascribed to an interaction of CAF with dsDNA, giving CAF-dsDNA complex by

ce

intercalative binding mode. The apparent binding constant of CAF-dsDNA complex was

determined using amperometric titrations. The oxidative damage caused to DNA was
Ac

detected using the biosensor. The damage caused by the reactive oxygen species, hydroxyl

radical (OH) generated by the Fenton system on the DNA-biosensor was detected. It was

found that CAF has the capability of scavenging the hydroxide radical and protecting the

DNA immobilised on the GCE surface.

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Erdem et al. [483] developed SWCNT-chitosan (CHIT) modified pencil graphite electrodes

(PGEs) for monitoring of DNA hybridisation. SWCNT-chitosan modified PGE (CNT–

CHIT–PGE), Chitosan modified PGE (CHIT–PGE) and unmodified PGE (bare-PGE) were

firstly characterised by using SEM, and their electrochemical behaviors were investigated

t
using EIS. The concentrations of CHIT, CNT and also amino linked DNA probe etc. were

ip
respectively optimised in order to obtain the better working conditions of CNT–CHIT

cr
modified PGE in DNA analysis. The sequence selective DNA hybridisation related to

Hepatitis B virus (HBV) was then explored in the case of hybridisation between amino linked

us
HBV probe and its complementary (target), or noncomplementary (NC), or mismatch (MM)

an
sequences, and also hybridisation in mixture sample. Huang et al. [490] developed an

amplified chemiluminescence turn-on sensing platform that relies on SWCNT for

M
ultrasensitive DNA detection. This new type of assay exhibits higher detection sensitivity

over traditional biosensors by three orders of magnitude and high specificity for the target
d

molecules.
te

Tian et al. [161] constructed a biosensor by a covalent self-assembly process to detect the

DNA sequences of genetically modified corn, based on electrochemical detection. This novel
p

detection system consisted of the sulfhydryl- functionalised MWCNT, gold nanoparticles,

ce

DNA sequences and gold electrodes. The self-assembly processes and DNA detection were

analysed by CV and different pulse voltammetry. The results showed that the DNA biosensor
Ac

offered a higher selectivity and sensitivity with the detection limit of 4.03 × 10-10 mol/L.

Moreover, the biosensor has great potential to provide a general method for detecting DNA

sequences of many other genetically modified organisms. Huang et al. [194] synthesised a

novel 2-dimensional graphene analog molybdenum disulfide/MWCNT (MoS2/MWCNT) by

a simple hydrothermal method to achieve excellent electrochemical properties. An

ultrasensitive electrochemical DNA biosensor was subsequently constructed by assembling a

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Page 83 of 165
thiol-tagged DNA probe on a MoS2/MWCNT and gold nanoparticle (AuNP)-modified

electrode that has already been coupled with glucose oxidase (GOD). They used GOD as a

redox marker. The hetero-nanostructure formed on the biosensor surface appeared a relatively

good conductor for accelerating the electron transfer, while the modification of GOD and

t
AuNPs provided multiple signal amplification for electrochemical biosensing. The multiple

ip
signal amplification strategy produced an ultrasensitive electrochemical detection of DNA,

cr
down to 0.79 fM with a linear range from 10fM to 107 fM, and high selectivity to

differentiate three-base mismatched DNA and one-base mismatched DNA. The developed

us
approach provided a simple and reliable method for DNA detection with high sensitivity and

an
specificity and would open new opportunities for sensitive detection of other biorecognition

events. Various groups have earlier shown that CNTs-based-DNA biosensors exhibit good
M
sensitivity, selectivity and reproducibility [154, 459, 465, 469, 471, 491-497] and recent

studies have shown that CNTs-based DNA biosensors exhibit good sensitivity [153, 454,
d

455, 460, 473, 475, 489, 498]

te

7.8. Cytochrome c (Cyt-c)

p

Cytochromes form a large family of heme enzymes that catalyse a diversity of chemical
ce

reactions such as epoxidation, hydroxylation and heteroatom oxidation. Denesh et al. [382]

described the fabrication of an amperometric biosensor based on cytochrome c (Cyt c)

Ac

immobilised graphene oxide-multiwalled carbon nanotube (GO-MWCNT) composite on a

nano Au modified glassy carbon electrode for trace level detection of H2O2. Morphology and

surface characterisation of the nanocomposite reveal the successful formation of a highly

conducting MWCNT network on the GO surface. Electrochemical impedance studies

indicate a lower charge transfer resistance compared to the bare electrode. CV studies clearly

demonstrated an enhanced direct electrochemistry of Cyt c with a high electron transfer rate

84
Page 84 of 165
constant (ks) value of 3.4 s-1. An amperometric H2O2 biosensor has been fabricated with an

excellent current sensitivity of 0.533 A pM-1 cm-2 and a very low detection limit of 27.7 pM.

The fabricated sensor showed exceptional selectivity to H2O2 in the presence of a high

concentration of some likely interferents. Moreover, the sensor exhibits high stability with

t
appreciable repeatability and reproducibility.

ip
cr
Batra et al. [499] fabricated an amperometric biosensor for determination of Cytochrome c

(Cyt c) by immobilising Cytochrome c oxidase (COx) onto nickel oxide nanoparticles (NiO-

us
NPs) decorated carboxylated multiwalled carbon nanotubes/polyaniline (NiO-NPs/cMWCNT

an
/PANI) film, electrodeposited on the surface of a gold (Au) electrode. The electrochemical

characteristics of immobilised COx were investigated by CV, EIS, SEM and FTIR. CV
M
studies of the electrode at different stages of construction of enzyme electrode demonstrated

that the modified Au electrode had enhanced electrochemical oxidation of H2O2, which offers
d

a number of attractive features to develop amperometric biosensors based on split of H2O2.

te

There was a good linear relationship between the current (mA) and Cyt c concentration in the

range of
p

5×10-12 M to 5×10-7 M. The sensor had a detection limit of 5×10-12 M (S/N = 3) with a high
ce

sensitivity of 3.7 mA cm-2 nM-1. The sensor gave accurate and satisfactory results when

employed for determination of Cyt c in different serum samples.

Ac

Lee et al. [500] immobilised Cytochrome c (cyt c) into a matrix consisting of polyaniline

(PANI) and multi-walled carbon nanotubes (MWNT) by a new strategy. First, PANI chains

were grafted onto MWNT through electropolymerisation. Secondly, the amine groups in

PANI chains were oxidised at an applied potential of +0.80 V to acquire positive charges that

would effectively immobilise negatively charged cyt C. The ITO/MWNT-g-PANI(O)/cyt c

electrode exhibited a pair of redox peaks with a peak potential separation (anodic to cathodic)

85
Page 85 of 165
of 0.25 V (vs Ag/AgCl) in 0.1 M phosphate buffer (pH 7.0). The results demonstrated that

ITO/MWNT-g-PANI(O)/cyt c promoted direct electron transfer between cyt c and electrode

with a high electron transfer rate constant (17 s-1). The ITO/MWNT-g-PANI(O)/cyt c

electrode catalyses the reduction of H2O2. The ITO/MWNT-g-PANI(O)/cyt c biosensor

t
displays an amperometric response to H2O2 with a linear concentration range from 0.5 M to

ip
1.5 mM (r = 0.99, n = 12), a high sensitivity (32.2 Am M-1) and fast response (9 s) and

cr
detection limit of 0.3 M (S/N = 3).

us
Liu et al. [173] reported on a new approach for the electrochemical detection of H2O2) based

an
on Cyt c immobilised ionic liquid (IL)-functionalised MWCNTs modified glass carbon

electrode (GCE). Functionalisation of multi-walled carbon nanotube with amine-terminated

M
ionic liquid materials was characterised using FTIR, UV spectra and electrochemical

impedance spectroscopy (EIS), and the results showed that the covalent modification of
d

MWCNTs with ILs exhibited a high surface area for enzyme immobilisation and provided a
te

good microenvironment for Cyt c to retain its bioelectrocatalytic activity toward H2O2.

Amperometry was used to evaluate the catalytic activity of the cyt c towards H2O2. The
p

proposed biosensor exhibited a wide linear response range nearly 4 orders of magnitude of
ce

-8
H2O2 (4.0×10 M-1.0×10-4 M) with a good linearity (0.9980) and a low detection limit of

1.3×10-8 M (based on S/N=3). Furthermore, the biosensor also displayed some other excellent
Ac

characteristics, such as high selectivity, good reproducibility and long-term stability. Song et

al. [501] developed a glucose biosensor based on Cyt c and glucose oxidase (GOD) co-

entrapped on gold nanoparticles (AuNPs)-chitosan (CHIT) nanocomposites which were

constructed on glassy carbon electrode (GCE) by one-step electrodeposition. The surrounding

Cyt c around GOD provided a biocompatible microenvironment to keep GOD's biological

activity. Simultaneously, the AuNPs-CHIT nanocomposites provided a roughened surface

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with large surface-to-volume ratio to greatly amplify the surface coverage of GOD-Cyt c

molecules and good conductivity to realise the DET of GOD. The biosensor showed a wide

detection range, low detection limit, good stability and high sensitivity.

t
Boussaad et al. [502] reported on the in situ detection of Cyt adsorption onto individual

ip
SWNT transistors via the changes in the electron transport properties of the transistors.

cr
Pandiaraj et al. [503] presented a novel approach for the detection of mitochondrial cyt c

release for the first time, using cytochrome c reductase (CcR) immobilised on nanoparticles

us
decorated electrodes. Two kinds of nanomaterial-based biosensor platforms were used: (a)

an
carbon nanotubes (CNT) incorporated polypyrrole (PPy) matrix on Pt electrode and (b) self-

assembled monolayer (SAM) functionalised gold nanoparticles (GNP) in PPy-Pt. SEM was
M
used to characterise the surface morphologies of the nanomaterial modified electrodes. CV of

both the biosensors showed reversible redox peaks at - 0.45 and - 0.34. V vs Ag/AgCl,
d

characteristic of CcR. In comparison, the CcR-CNT biosensor gave a detection limit of 0.5 ±
te

0.03. µM cyt c, which was 4-fold better than the CcR-GNP biosensor (2 ± 0.03. µM).

Moreover, the CcR-CNT biosensor achieved a much larger linear range (1-1000. µM) over
p

the CcR-GNP biosensor (5-600. µM) with 2-fold better sensitivity. The CcR-CNT-PPy-Pt
ce

biosensor was further applied to quantify the mitochondrial cyt c released in cytosol of A549

cells upon induction of apoptosis with doxorubicin, the results agreed well with standard
Ac

western blot analysis.

7.9. Ascorbic Acid (AA), Uric Acid (UA) and Dopamine (DA)

Dopamine is a known biomarker that plays an important role in transporting and modulating

nervous impulses in the synapse [53]. Ascorbic acid, also known as vitamin C, is an

antioxidant that modulates impulse flow in striatal neurons [504]. Uric acid is the major

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Page 87 of 165
metabolite of purines, formed from the breakdown of hypoxanthine by hypoxanthine-guanine

phosphoribosyl transferase (HGPT) [505]. Determination of AA is a problem in analytical

neuro-chemistry and bio-chemistry. Recently, CNTs-based electrodes have been used for

simultaneous detection and determination of AA, DA and UA [39, 43, 506-510],

t
determination of DA and paracetamol [511], determination of DA in the presence of AA and

ip
UR [512, 513] and determination of AA in the presence of rutin (Ru) [514].

cr
Huang et al. [515] prepared carbon paste electrodes (CPEs) modified by the addition of

us
amino-functionalised MWCNT/electroactive polyimide (AF-MWCNT/EPI) composites (AF-

an
MWCNT/EPI-CPE) and these were applied to the electrochemical sensing of ascorbic acid

(AA). MWCNTs were grafted with 4-aminobenzoic acid in a medium of polyphosphoric

M
acid/phosphorus pentoxide to obtain MWCNTs functionalised with 4-aminobenzoyl groups

(AF-MWCNTs). The amino functional groups on the AF-MWCNTs reacted with an

d

oligoaniline by oxidative coupling polymerization to yield the AF-MWCNT/EPI composites.

te

FTIR spectra and UV absorption spectra revealed that the quinoid rings present on the EPI

graft interacted with the AF-MWCNTs. CV studies indicated improved electrochemical

p

properties of the AF-MWCNT/EPI composites, demonstrating the occurrence of efficient

ce

electron/charge transfer between the AF-MWCNTs and the EPI graft. The concentration of

the added AA and the change in the peak current obtained showed a linear relationship. In
Ac

addition, the calibration curve of the amperometric response of the AF-MWCNT/EPI-CPE

sensors against the concentration of AA was also linear. The detection limit and the

sensitivity of the AF-MWCNT/EPI-CPE AA sensors were 4.1 µM at a S/N (signal to noise

ratio) of 3 and 27.5 µA mM-1 respectively.

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Xia et al. [516] reported that Cu4(OH)6SO4 nanoparticles in fact possess an intrinsic

electrocatalytic activity, which is explored as a biosensing material to oxidise AA.

Cu4(OH)6SO4 (brochantite) is an undesirable oxidation product of copper-bearing sulfides,

and it is seldom considered to be biologically and electrochemically active. The

t
Cu4(OH)6SO4 nanorod modified biosensor exhibits excellent performance for the

ip
determination of l-ascorbic acid with a response time of less than 8 s, a linear range between

cr
0.017 and 6 mM and a sensitivity of 17.53 A mM-1. A high selectivity towards the oxidation

of AA in the presence of dopamine (DA) and acetyl aminophenol (AP) was also observed at

us
their maximum physiological concentrations. The good analytical performance and long-term

an
stability, low cost and straightforward fabrication method made the Cu4(OH)6SO4

nanomaterials promising for the development of effective electrochemical sensors for a wide
M
range of potential applications in medicine, biotechnology and environmental chemistry.
d

Liu et al [517] developed a stable sandwich-type amperometric biosensor based on poly(3,4-

te

ethylenedioxythiophene) (PEDOT)–single walled carbon nanotubes (SWCNT)/ascorbate

oxidase (AO)/Nafion films for detection of l-ascorbic acid (AA). PEDOT–SWCNT

p

nanocomposite and Nafion films were used as inner and outer films, respectively. AO was
ce

immobilised between these two films. The sensitivity of the biosensor was found to be 28.5

mA M−1 cm−2. Its experimental detection limit was 0.7 µM (S/N = 3) and the apparent
Ac

Michaelis–Menten constant (Km) was calculated to be 18.35 mM. Beitollahi et al. [518]

fabricated a novel carbon paste electrode modified with carbon nanotubes and 5-amino-2',4'-

dimethoxy-biphenyl-2-ol (5ADMB) and described the electrochemical study of the modified

electrode, as well as its efficiency for electrocatalytic oxidation of ascorbic acid. CV was

used to investigate the redox properties of this modified electrode at various scan rates. The

apparent charge transfer rate constant, ks, and transfer coefficient, α, for electron transfer

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Page 89 of 165
between 5ADMB and carbon nanotubes paste electrode were calculated as 7.94 s-1 and 0.5,

respectively. The electrode was also employed to study the electrocatalytic oxidation of

ascorbic acid, using CV, chronoamperometry and square wave voltammetry as diagnostic

techniques. It has been found that the oxidation of ascorbic acid at the surface of modified

t
electrode occurs at a potential of about 250 mV less positive than that of an unmodified CPE.

ip
The diffusion coefficient, electron transfer coefficient and heterogeneous rate constant for

cr
oxidation of ascorbic acid at the modified electrode surface were also determined. Square

wave voltammetry (SWV) exhibits a linear dynamic range from 1.0×10-6 to 7.5×10-4 M and

us
detection limit of 0.1 µM for ascorbic acid. Finally, this modified electrode was used for the

an
determination of ascorbic acid in real samples. Olivé-Monllauet al [519] used MWCNT and

resin epoxy to fabricate a composite electrode for electroanalytical purposes. The optimum
M
composite proportions for high electrode sensitivity, low limit of detection and fast response

were investigated. Compositions were characterised by percolation theory, EIS, CV and SEM
d

and chronoamperometry. They found that around the optimum composite proportion, the
te

electrode performance is less affected by small variations in the composition of the

composite. These composite electrodes provided easy surface renewal, low background
p

current and an efficient mass transport suitable for chemical modification. The potentiality of
ce

this approach in terms of electroanalytical response is demonstrated by means of the

amperometric detection of ascorbic acid in water solution.

Ac

Kul et al. [520] prepared a new type of modified electrode sensor for AA by deposition of

MWCNT and poly(Nile blue A) on the surface of glassy carbon electrodes. Arvand and

Hassannezhad. [521] prepared a new type of nanocomposite based on MWCNT decorated

with magnetic core-shell Fe3O4@SiO2 nanoparticles (Fe3O4@SiO2/MWCNTs), which was

used to fabricate a modified carbon paste electrode (CPE). The nanocomposite was

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characterised by TEM, SEM, EDX and FT-IR techniques. Electrochemical behaviour of uric

acid (UA) was investigated on Fe3O4@SiO2/MWCNTs-CPE by CV and square wave

voltammetry (SWV) in phosphate buffer solution (pH 6.0). Under the optimized conditions,

the peak currents increased linearly with the concentration of UA in the range from 0.60 to

t
100.0 µM, with a detection limit of 0.13 µM. The proposed sensor was successfully applied

ip
for the determination of UA in biological fluids.

cr
Arora et al. [522] electrochemically deposited MWCNT doped polyaniline (Pani)

us
nanocomposite onto indium tin oxide (ITO)-coated glass substrate for fabrication of UA

an
biosensor. To achieve this, uricase (from Bacillus fastidiosus) has been covalently

immobilised onto glutaraldehyde-modified CNT-Pani/ITO and characterised using CV, SEM,

M
FTIR spectroscopy and EIS. CV studies of CNT-Pani/ITO electrode revealed that the system

obeys quasi-reversible electron transfer behavior with diffusion coefficient of 2.3346 × 10-8
d

cm s-1 in K3FeCN6. Fabricated uricase-CNT-Pani/ITO electrodes were tested for UA

te

detection in buffer and spiked serum samples electrochemically. It was found that fabricated

electrode was able to detect 0.01-1.0 mM UA, using CV and 0.02-0.8 mM UA and using
p

differential pulse voltammetry (DPV). The enhanced electrochemical performance of this

ce

biosensor is due to the high enzyme loading synergistically connected to CNT-Pani

nanocomposite leading to improved enzyme characteristics such as Km value of 4.85 × 10-3

Ac

mM L-1 (about 70 times less than the free enzyme), sensitivity of 43.2 µA mM-1 for CV-based

detection and 8.38 µA mM-1 for DPV-based detection within response time of 60 s.

Fabricated electrodes were able to maintain their electrochemical activity with 60 times

analysis.

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Recently, Pisoschi et al. [523] reviewed electrochemical methods for ascorbic acid

assessment. They also reviewed the occurrence, role, biological importance of vitamin C, as

well as the non-electrochemical methods for its assessment. The electrochemical behaviour of

AA was then illustrated, followed by a description of the potentiometric, voltametric and

t
amperometric methods for vitamin C content estimation in various media. Different methods

ip
for the development of electrochemical sensors were reviewed, from unmodified electrodes

cr
to different composites incorporating carbon nanotubes, ionic liquids or various mediators.

From this perspective, the interaction between the functional groups of the sensor's material

us
and the analyte molecule were discussed. The analytical performances of the potentiometric,

an
voltammetric or amperometric chemical and biochemical sensors (linear range of analytical

response, sensitivity, precision, stability, response time etc) are highlightened. They
M
presented numerous applications of ascorbic acid electrochemical sensors in fields like food,

pharmaceutical or clinical analysis, where vitamin C represents a key analyte.

d
te

Mohamadi et al. [524] proposed a simple and sensitive label-free electrochemical DNA

biosensor for the rapid determination of uric acid (UA), using a carbon nano tube paste
p

electrode (CNTPE) modified with salmon sperm dsDNA. At first, the interaction between
ce

UA and the DNA was studied, using differential pulse voltammetry (DPV). The addition of

the DNA to UA solution resulted in a decrease in the peak current of UA and at the same
Ac

time, a positive shift in the peak potential indicating an intercalative interaction. Then, the

voltammetric response of a DNA-immobilised CNTPE was investigated for the determination

of UA. The immobilisation of the DNA was carried out using acid-functionalised carbon
4-
nanotubes and Fe(CN)6 3-/Fe(CN)6 was used as redox indicator. Compared with

unmodified CNTPE, the oxidation signal of UA showed a significant increase at the DNA-

coated electrode and shifted to more positive potentials attributed to the pre-concentration of

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UA at the electrode surface due to interaction with the surface-confined DNA layer. This

interaction was used for the fabrication of a simple and sensitive biosensor for determining

UA. After the optimisation of operational parameters, a linear dependence of the peak current

on the UA concentration was observed in the range of 7.0×10-7 to 1.1×10-4molL-1, with the

t
detection and quantification limits of 1.8×10-7 and 5.8×10-7molL-1, respectively. The

ip
proposed biosensor was successfully applied to validate its capability for the analysis of UA

cr
in human serum and urine samples.

us
Ghica and Brett [306] formed Poly(brilliant green) (PBG) and poly(thionine) (PTH) films on

an
carbon film electrodes (CFEs) modified with CNTs by electropolymerisation using potential

cycling. Voltammetric and electrochemical impedance characterisation were performed.

M
Glucose oxidase and uricase, as model enzymes, were immobilised on top of PBG/CNT/CFE

and PTH/CNT/CFE for glucose and UA biosensing. Amperometric determination of glucose

d

and UA was carried out in phosphate buffer pH 7.0 at -0.20 and +0.30 V vs. SCE,
te

respectively, and the results were compared with other similarly modified electrodes existing

in the literature. Shi et al. [525] designed and synthesised a sensitive electrochemical sensor
p

for AA. The novel tetra-β- isoheptyloxyphthalocyanine cobalt (II) (PcCo) spontaneously
ce

adsorbs on the surface of acid-treated MWCNTs. Then, the aMWCNT/PcCo composite was

immobilised on the glassy GCE. The results of UV, FT-IR, TG, XPS, SEM and TEM
Ac

revealed the successful self-assembly between PcCo and aMWCNTs via the π-π stacking

interaction, and the aMWCNT/PcCo composite appears to have a uniform network-like

structure on the GCE surface due to the four peripheral isoheptyl substituents of PcCo. Such a

structure can effectively increase the electrode area, facilitate the mass transport of analytes

and provide continuous conducting pathways for the transportation of electrons.

Synchronously, benefitting from the synergistic effect between PcCo and aMWCNTs, the

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Page 93 of 165
obtained electrochemical sensor has a high current and low potential for the oxidation of AA.

The linear range for the AA detection was from 10 µM to 1.2 mM and the detection limit is

as low as 4.0 µM. The developed biosensor exhibited good reproducibility and acceptable

stability, providing a simple method for the analysis of AA.

t
ip
Beiotolahi et al. [518] fabricated a novel carbon paste electrode modified with carbon

cr
nanotubes and 5-amino-2',4'- dimethoxy-biphenyl-2-ol (5ADMB). The group studied the

electrochemical behaviour of the modified electrode, as well as its efficiency for

us
electrocatalytic oxidation of AA. Yang et al. [526] developed an electrochemical biosensor

an
based on [Co (phen)3]2+ (phen = 1,10-phenanthroline) and multi-walled carbon nanotubes

(MWCNTs) for the determination of dopamine (DA) by using a GCE. The electrochemical
M
properties of the composite film were investigated by EIS and CV, and the electrooxidation

behaviour of DA on [Co(phen)3]2+/MWCNTs/GCE was studied by amperometry. Under the

d

optimum experimental conditions, the linear calibration curve was obtained in the range from
te

5 to 453 µmol L-1, with a low detection limit of 1.76 µmol L-1 (at a signal-to-noise ratio of 3).

The experimental results also proved that several co-existing substances, including K +, Na+,
p

etc., had no significant interference on the determination of DA. The validity of using this
ce

modified electrode to determine DA in dopamine hydrochloride injection was also

demonstrated.
Ac

Herrasti et al. [527] exploited the combination of magnetic particles (MP) and carbon

nanotubes (CNT) in biosensor development. It has been recently suggested that combining

MP binding of electroactive molecules with CNT wiring of the MP surface could provide

novel sensing formats. They demonstrated the validity of this approach using as a model DA.

They showed that DA can be electrostatically bound and concentrated using commercially

available streptavidin-coated MP. Electrochemical detection of MP-bound DA is then

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Page 94 of 165
accomplished by CNT wiring using cheap and disposable screen printed electrodes of

different sizes and materials. The parameters potentially affecting DA binding, CNT wiring

and electrochemical detection have been studied and optimised. The resulting assay takes 45

min, displays LOD of 2 nM DA in saline solution, is unaffected by AA, UA and can be

t
operated in diluted urine human samples.

ip
Gopal et al. [528] prepared a polymerised film of glycine (Gly) on the surface of carbon paste

cr
electrode (CPE) through the CV technique. A novel biosensor for the determination of DA

has been constructed based on HRP and MWCNTs immobilising on Poly (Gly)/CPE through

us
silica sol-gel (SiSG) entrapment. CV measurements were employed in order to understand

an
the feasibility of poly (Gly) as an electron carrier between the immobilised peroxidase and

the surface of CPE. By using DPV the calibration curves of DA was obtained in the range of
M
15-865 µM. The limit of detection (LOD) and limit of quantification (LOQ) of DA was found

to be 6×10-7M and 2×10-6M, respectively. The apparent Michaelis-Menten constant (Kmapp)

d

was found to be 0.5mM and illustrated the good biological activity of the fixed enzyme. EIS
te

results confirmed the rapid electron transfer and also the immobilisation of enzyme on the

electrode surface. The biosensor showed high sensitivity, selectivity and reproducibility. This
p

method has been used to determine DA in the presence of various interferences and in
ce

clinical preparations.
Ac

Qianet al. [529] proposed a novel electrochemical sensor using the molecularly imprinted

(MIP) oxygen-containing polypyrrole (PPy) decorated CNTs composite for in vivo detection

of DA. The prepared sensor exhibits a remarkable sensitivity of (16.18µA/µM) with a linear

range of 5.0×10-11-5.0×10-6 M and limit of detection as low as 1.0×10-11M in the detection of

DA, which might be due to the plenty cavities for binding DA through π-π stacking between

aromatic rings and hydrogen bonds between amino groups of DA and oxygen-containing

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Page 95 of 165
groups of the novel PPy. de Souza Ribeiro et al. [530] proposed the development of an

enzymatic biosensor for DA determination based on functionalised MWCNTs and HRP

obtained from the crude extract of zucchini (Cucurbita pepo L.). The biosensor was

developed by means of the immobilisation of the enzyme by covalent bonding to carrier

t
MWCNTs functionalised. In the presence of H2O2, HRP catalyses the oxidation of DA to o-

ip
dopaquinone and the reduction of o-dopaquinone, which requires a low potential difference.

cr
The influence on the response of analytical parameters of biosensor such as enzyme

concentration, 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide (EDC) concentration, H2O2

us
concentration, pH and phosphate buffer solution concentration, as well as the

an
electroanalytical technique, CV, SWV and DPV, were investigated. The analytical

parameters obtained, including the sensitivity, linearity, precision, accuracy and stability,
M
were investigated and were within the recommended guidelines. The validated method

proved to be efficient for DA determination in pharmaceutical formulation and presented

d

good selectivity even in the presence of UA and AA.

te

Noorsifa et al. [531] constructed a novel biosensor by incorporating modified nanosized

p

natural zeolite and 3-hydroxypropanaminium acetate (HPAA) as a novel room temperature

ce

ionic liquid, supported on MWCNTs and employed for the simultaneous determination of

DA and UA. A detailed investigation by TEM and electrochemistry is performed in order to

Ac

elucidate the preparation process and properties of the composites. The voltammetric studies,

using the modified carbon paste electrode, show two well-resolved anodic peaks for DA and

UA, with a potential difference of 160 mV, revealing the possibility of the simultaneous

electrochemical detection of these compounds. The modified carbon paste electrode shows

good conductivity, stability and extraction effect due to the synergic action of HPAA,

MWCNTs, and iron ion-doped natrolite zeolite. Under optimised conditions, the peak

96
Page 96 of 165
currents are linear from 8.12 × 10-7 to 3.01 × 10-4 mol L-1, and from 9.31 × 10-7 to 3.36 × 10-4

mol L-1 with detection limits of 1.16 × 10-7 and 1.33 × 10-7 mol L-1 for DA and UA using the

differential pulse voltammetric method respectively. Finally, the modified carbon paste

electrode proved to have good sensitivity and stability and is successfully applied for the

t
simultaneous determination of DA and UA in human blood serum and urine samples.

ip
cr
Babaei and Taheri [532] investigated the electrochemical oxidation of DA and serotonin (ST)

by application of Nafion/Ni(OH)2-multiwalled carbon nanotubes modified glassy carbon

us
electrode (Nafion/Ni(OH)2-MWNTs/GCE), using CV, differential DPV and CA methods.

an
The modified electrode worked as an efficient electron-mediator for DA and ST in the

presence of AA. Voltammetric techniques separated the anodic peaks of DA and ST, and the
M
interference from AA was effectively excluded from DA and ST determination. The DPV

data showed that the obtained anodic peak currents were linearly proportional to
d

concentration in the range of 0.05–25 µmol L−1 with a detection limit (S/N = 3.0) of 0.015
te

µmol L−1 for DA and in the range of 0.008–10 µmol L−1 and with a detection limit of 0.003

µmol L−1 for ST. The proposed sensor was used for the determination of ST and DA in
p

human blood serum with satisfactory results.

ce

Chih and Yang [513] used a 2, 2’-azino-bis(3-ethylbenzthiazoline-6-sulfonic acid) (ABTS)-

Ac

immobilised CNT electrode to simultaneously detect DA and UA in the presence of AA with

DPV. When ABTS was immobilised onto the CNT electrode in the presence of DA, UA and

100. µM AA, the sensitivity to DA increased from 0.600 (±0.013) to 1.334 (±0.010). µA/µM

in the concentration ranges of 0.90-10 µM and 1.87-20. µM, respectively, and the sensitivity

to UA increased from 0.030 (±0.005) to 0.078 (±0.006). µA/µM in the concentration ranges

of 2.16-240 µM and 3.07-400 µM respectively. These findings demonstrated that the ABTS-

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Page 97 of 165
immobilised CNT electrode attained a higher sensitivity to UA and also a wider linear range

of concentrations. Canbay and Alkymas [533] synthesised (MWCNT)–Nafion–cysteamine

(CA) modified tyrosinase biosensor, which brought a new and original perspective to

biosensor technology intended for the development of DA determination. DA measurements

t
were done at 0.2 V with the amperometric method by the developed biosensor system. In

ip
addition, in this study dopamine determination was carried out by using the differential pulse

cr
voltammetry method between potentials of 0.4 and −0.15 V. In the optimisation studies of the

biosensor, some parameters, such as optimal pH, optimal temperature, optimal enzyme

us
amount and effect of MWCNT concentration, were investigated. Afterward, in the

an
characterisation studies, some parameters such as linearity and reproducibility were

determined. In the reproducibility experiment, an average value of 1.026 µM, a standard

M
deviation of ±0.03975 and a coefficient of variation of 3.8%, were determined for a 1-µM DA

concentration (n = 15). Determination of DA was carried out in drug samples by the

d

developed biosensor.
te

Bujduveanu et al. [534] reported the fabrication of a highly sensitive dopamine biosensor
p

based on the entrapment of tyrosinase into CaCO3 nanoparticles at MWCNT electrodes.

ce

CaCO3 acts as host matrix for tyrosinase. MWCNT provides a highly porous conductive

network enhancing the enzyme immobilisation and the electrochemical transduction of the
Ac

enzyme reaction by boosting the amplification phenomenon involved in the biosensing of

catechol and DA. The comparison of the performance of CaCO3-tyrosinase electrodes with

and without MWCNT film clearly indicates the improvement in sensitivity and maximum

current brought by the combination of MWCNTs and inorganic nanomaterials. These

nanostructured hybrid bioelectrodes exhibit a high sensitivity for the detection of catechol

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Page 98 of 165
and DA, namely 35.7Amol-1Lcm-2, the detection limit for DA being 15nmolL-1 with no

influence of the presence of interferents, i.e. UA and AA

Ensafi et al. [33] studied the voltammetric behaviour of DA on a glassy carbon electrode

(GCE) modified-NiFe2O4 magnetic nanoparticles decorated with MWCNT. Impedance

t
spectroscopy and CV were used to characterize the behavior of DA at the surface of

ip
modified-GCE. The modified electrode showed a synergic effect toward the oxidation of DA.

cr
The oxidation peak current is increased linearly with the DA concentration (at pH 7.0) in

wide dynamic ranges of 0.05-6.0 and 6.0-100 µmol L- 1 with a detection limit of 0.02 µmol L

us
- 1
, using DPV. The selectivity of the method was studied and the results showed that the

an
modified electrode is free from interference of organic compounds, especially AA, UA,

cysteine and urea. Its applicability in the determination of DA in pharmaceutical, urine

M
samples and human blood serum was also evaluated. The proposed electrochemical sensor

has appropriate properties such as high selectivity, low detection limit and wide linear
d

dynamic range when compared with that of the previous reported papers for DA detection.
te

Figueiredo-Filho [535] developed a simple and highly selective electrochemical method for

the single or simultaneous determination of DA and epinephrine (EP) in human body fluids,
p

using a glassy carbon electrode modified with nickel oxide nanoparticles and CNTs within a
ce

dihexadecylphosphate film, using square-wave voltammetry (SWV) or differential-pulse

voltammetry (DPV). Using DPV with the proposed electrode, a separation of ca. 360 mV
Ac

between the peak reduction potentials of DA and EP present in binary mixtures was obtained.

The analytical curves for the simultaneous determination of dopamine and epinephrine

showed an excellent linear response, ranging from 7.0 10-8 to 4.8 10-6 and 3.0 10-7 to 9.5 10-6

mol L-1 for DA and EP respectively. The detection limits for the simultaneous determination

of DA and EP were 5.0 ×10-8 mol L-1 and 8.2 ×10-8 mol L-1 respectively. The proposed

99
Page 99 of 165
method was successfully applied in the simultaneous determination of these analytes in

human body fluid samples of cerebrospinal fluid, human serum and lung fluid.

Kutluay et al. [511] obtained MWCNTs functionalised by cobalt nanoparticles using a single

t
step chemical deposition method in an ultrasonic bath. The composite material was

ip
characterised using SEM and EDX. The electroactivity of the cobalt-functionalized

cr
MWCNTs was assessed in respect to the electrooxidation of paracetamol (PAR) and DA. It

was found that the CNT supported cobalt nanoparticles have significantly higher catalytic

us
properties. The proposed electrode has been applied for the simultaneous determination of

an
PAR and DA. The modified electrode could resolve the overlapped voltammetric waves of

PAR and DA into two well-defined voltammetric peaks with peak to peak separation of about
M
203 mV. On the other hand, the presence of potential drug interfering compounds, AA and

UA, did not affect the voltammetric responses of PAR and DA. The current of oxidation
d

peaks showed a linear relationship which is dependent on the concentrations of PAR and DA
te

in the range of 5.2 × 10-9-4.5 × 10-7 M (R2 = 0.9987) and 5.0 × 10-8-3.0 × 10-6 M (R2 =

0.9999) respectively. The detection limits of 1.0 × 10-9 M and 1.5 × 10-8 M were obtained for
p

PAR and DA respectively. The proposed electrode showed good stability (peak current
ce

change: 4.9% with RSD of 2.6% for PAR; 5.5% with and RSD of 3.0% for DA over 3

weeks), reproducibility (RSD 2.3% for PAR and RSD 1.5% for DA), repeatability (RSD
Ac

2.25% for PAR and RSD 2.50% for DA) and high recovery (99.7% with an RSD of 1.3% for

PAR 100.8% with an RSD of 1.8% for DA). The proposed method was successfully applied

to the determination of PAR and DA in pharmaceuticals. Various groups have earlier shown

that CNTs-based- dopamine biosensors exhibit good sensitivity, selectivity and

reproducibility and recent studies have shown that CNTs-based dopamine biosensors exhibit

good sensitivity, selectivity and reproducibility [113, 527, 530, 533, 535-539].

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Page 100 of 165
7.10. Metal ions electrochemical sensors

Nanomaterials, particularly carbon nanomaterials, have shown great promise in

environmental applications. They show a better performance in environmental remediation

t
than other conventional techniques because of their high surface area (surface-to-volume

ip
ratio) and their associated high reactivity. Recent advances have emerged in the fabrication of

cr
novel nanoscale materials and processes for the treatment of drinking water and industrial

waste water contaminated by toxic metal ions, radionuclides, organic and inorganic solutes,

us
bacteria and viruses. The treatments of air and polluted water are major steps taken by

an
various environmentalists and researchers for cleaner and safer environment. Metal ions are

major pollutants of the environment, thus, there is the need for their accurate quantitative and
M
qualitative determinations. Metal ion sensors require specific functionalities on the surface of

CNTs substrates which showed potential affinity towards particular metal ions. This can be
d

achieved by modifying the electrode surface with suitable indicator species.

te

Recently, Zhang et al. [540] developed a simple, signal-on electrochemical biosensor for

sensitive detection of Ag+ based on the three components of alkanethiol, SWNT and silver
p

ion-specific oligonucleotide (SSO) layer-by-layer modified electrode, where square wave

ce

voltammetry (SWV) response of K3[Fe(CN)6] at the modified electrode was used for signal

transduction. A gold electrode was first assembled with 1-dodecanethiol (C12H25SH)

Ac

monolayer to which SWNTs were attached. The SWNT surfaces were further noncovalently

bound with SSO probes to obtain the sensor interface. The negatively charged SSO probe

acts as a physical obstacle and electrostatic repulsion barrier to block the SWNT-mediated

long-distance electron transfer of K3[Fe(CN)6] across the -SC12H25 monolayer. Upon Ag+

binding, the SWNT surface-bound SSO probe forms a unimolecular duplex through C-Ag+-

C interaction-mediated intramolecular hybridization and departs from the SWNT surface,

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Page 101 of 165
resulting in decreased electron transfer resistance and increased SWV current of K3[Fe(CN)6]

at the modified electrode. This current enhancement effect provides a signal-on mechanism

for sensitive transduction of Ag+ recognition and the resulted current increase is linear with

the logarithmic concentration of Ag+ from 2.0 nM to 100 nM. The developed biosensor was

t
highly selective and its practical applicability in tap water was also tested with a satisfactory

ip
result.

cr
Moyo et al. [541] described a biosensor for trace metal ions based on HRP immobilised on

maize tassel-MT-MWCNT through electrostatic interactions. The biosensor was

us
characterised using FTIR, UV spectrometry, voltammetric and amperometric methods. The

an
FTIR and UV results inferred that HRP was not denatured during its immobilisation on MT-

MWCNT composite. The biosensing principle was based on the determination of the
M
cathodic responses of the immobilised HRP to H2O2, before and after incubation in trace

metal standard solutions. Under optimum conditions, the inhibition rates of trace metals were
d

proportional to their concentrations in the range of 0.092–0.55 mg L−1, 0.068–2 mg L−1 for
te

Pb2+ and Cu2+, respectively. The limits of detection were 2.5 µg L−1 for Pb2+ and 4.2 µg L−1

for Cu2+. Representative Dixon and Cornish-Bowden plots were used to deduce the mode of
p

inhibition induced by the trace metal ions. The inhibition was reversible and mixed for both
ce

metal ions. The biosensor showed good stability, selectivity, repeatability and reproducibility.

Du et al. [542] focused their research on the use of two carbon nanomaterials, CNTs and
Ac

graphene-based sensors for water monitoring and detection of hazardous chemicals. The

excellent electrochemical behaviours of CNTs and graphene indicate that they are promising

electrode materials in electroanalysis. Sensors based on CNTs and graphene have shown

excellent performance in electrochemical detection of metal ions, pesticides, and other

pollutants. Ali and Mohameed [543] recently reported a novel derivatised MWCNTs based

on Mn(II) carbon paste electrodes. At optimum values of variable conditions, the proposed

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Page 102 of 165
electrodes responded toward Mn(II) ion linearly in the range of 7.8 × 10-7-1.0 × 10-1 and 2.7

× 10-8-1.0 × 10-1 mol L-1 with slope of 27.72±0.8 and 30.04±0.5 mV decade-1 of Mn(II) ion

concentration and detection limit of 7.8 × 10-7 and 2.7 × 10-8 mol L-1 for KTpClPB-CPE

(electrode (IV) and KTpClPB/MWCNTs-CPE (electrode (VIII), respectively. The electrodes

t
response is independent of pH in the range of 4-8 and 3-9, with a fast response time (8 and 5

ip
s) at 25 °C for electrode (IV) and electrode (VIII), respectively. Moreover, the electrodes also

cr
showed high selectivity and long life time (more than 3 and 4 months) for electrode (IV) and

electrode (VIII), respectively. The electrodes showed good selectivity for Mn(II) ion toward

us
wide variety of metal ions. The proposed sensors were successfully applied for the

an
determination of Mn(II) ion in different real and environmental samples and as indicator

electrodes. The results obtained compared well with those obtained using atomic absorption
M
spectrometry (AAS).

Mambo et al. [544] used the change in electrochemical behaviour of HRP activity induced by
d

trace metals as a basis for developing an amperometric biosensor. The HRP was immobilised
te

on maize tassel-multiwalled carbon nanotube (MT-MWCNT) through electrostatic

interactions. The FTIR and UV-Vis results inferred that HRP was not denatured during its
p

immobilisation on MT-MWCNT composite. Using Cd2+ as a model divalent metal ion, the
ce

inhibition rate was proportional to the concentration in the range from 0.002-0.030 mg L-1

with a limit of detection of 0.51 µg L -1. Cui et al. [545] developed a highly sensitive and
Ac

selective electrochemical sensor for the detection of Cu2+ by the assembly of Ag

nanoparticles (AgNPs) at dithiobis [succinimidylpropionate] encapsulated Au nanoparticles

(DSP-AuNPs), which was regulated by copper-catalysed oxidation of cysteamine (Cys). The

electrochemical sensor was constructed using layer-by-layer modification of glassy carbon

electrode with CNTs, poly(amidoamine) dendrimers and DSP-AuNPs. In the absence of

Cu2+, Cys could bind to the surface of citrate-stabilized AgNPs via Ag-S bond, thus, AgNPs

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Page 103 of 165
could be assembled on the sensor surface through the reaction between DSP and Cys. In

contrast, the copper-catalyzed oxidation of Cys by dissolved oxygen in the presence of Cu2+

inhibited the Cys-induced aggregation of AgNPs, leading to the decrease of the

electrochemical stripping signal of AgNPs. Under the optimised conditions, this method

t
could detect Cu2+ in the range of 1.0-1000nM with a detection limit of 0.48nM. The

ip
proposed Cu2+ sensor showed good reproducibility, stability and selectivity. It has been

cr
satisfactorily applied to determine Cu2+ in water samples. Modified MWCNTs/Nafion films

on GCE provided suitable stripping responses for Cd (II) and Pb (II) ions [546]. A similar

us
approach was followed to determine Europium (III) [547]. A SWCNT modified GCE was

an
also employed to determine Cd (II) in water samples [548]. A thiol-tethered-MWCNTs

chemically modified gold electrode has been prepared for As (III) speciation and Bi (III)
M
determination at trace levels in natural and high salinity waters [549]. Gold NPs modified-

nanotubes were used to determine As (III) via anodic stripping voltammetry [550]. Other
d

metal ions detected electrochemically by the use of CNT-modified electrodes include Pb2+
te

[551-553], Fe3+, [554], Hg+1[554], Ag+ [540, 555] and Eu3+[556].

p
ce

7.11. Pesticides (organophosphorous and non organophosphorous)

Ac

There has been urgent demand for rapid, sensitive and cost-effective pesticide assay

technologies due to the global attention of environmental and food-safety problems.

Organophosphorus (OP) compounds are used as pesticides and chemical warfare agents.

Hence, the detection of OP neurotoxins is essential for the protection of water resources and

food supplies, as well as monitoring detoxification processes. Organophosphate compounds

are heavily used in agriculture and military activities, while non-organophosphate pesticides

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Page 104 of 165
are mostly used in agriculture and home defense. Discriminative detection of such toxic

compounds is very challenging and requires sophisticated and bulky instrumentation.

Biosensors offer an effective solution to the problem and may become a versatile analytical

tool for discriminative detection of different pesticides. AChE-based electrochemical sensors

t
have attracted significant interest in pesticides detection and analysis [557-560].

ip
cr
Recently, Grawe et al. [561] constructed a biosensor by physical adsorption of the isolated

endophytic fungus Eupenicillium shearii FREI-39 esterase on halloysite, using graphite

us
powder, MWCNTs and mineral oil for the determination of carbofuran pesticide by inhibition

an
of the esterase, using square-wave voltammetry (SWV). Specific esterase activities were

determined every 2 days over a period of 15 days of growth in four different inoculation
M
media. The highest specific activity was found on the 6th day, with 33.08 U on PDA broth.

The best performance of the proposed biosensor was obtained using 0.5 U esterase activity.
d

The carbofuran concentration response was linear in the range from 5.0 to 100.0 µg L−1
te

(r=0.9986) with detection and quantification limits of 1.69 µg L−1 and 5.13 µg L−1

respectively. A recovery study of carbofuran in spiked water samples showed values ranging
p

from 103.8±6.7% to 106.7±9.7%. The biosensor showed good repeatability and

ce

reproducibility and remained stable for a period of 20 weeks. The determination of

carbofuran in spiked water samples using the proposed biosensor was satisfactory when
Ac

compared to the chromatographic reference method. The results showed no significant

difference at the 95% confidence level with t-test statistics. The application of enzymes from

endophytic fungi in constructing biosensors broadens the biotechnological importance of

these microorganisms.

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Page 105 of 165
Zhang et al. [562] reported a novel bi-enzyme biosensing system incorporating

electrostatically interacted enzyme-armored MWCNT-OPH and MWCNT-AChE along with

a set of cushioning bilayers consisting of MWCNT-polyethyleneimine and MWCNT-DNA

on glassy carbon electrode for discriminative detection of organophosphorus (OP) and non-

t
organophosphorus (non-OP) pesticides. LbL interfaces were characterised by surface

ip
plasmon resonance and EIS, demonstrating stepwise assembly and electron conductivity

cr
studies. The detection limit was found to be ~0.5 for OP pesticide paraoxon and 1 µM for

non-OP pesticide carbaryl, in a wide linear range. The biosensor performance was also

us
validated using apple samples. Remarkable discriminative and straightforward detection

an
between OP and non-OP neurotoxins was successfully achieved with CV and UV methods on

the MWCNT-(PEI/DNA)2/OPH/AChE biosensor, showing great potential in large screening

M
of OP and non-OP pesticides in practical applications.
d

Keshik et al. [563] developed a novel amperometric biosensor based on a conducting polymer
te

using MWCNTs modified electrode for detection of organophosphorus pesticides. AChE was

successfully immobilised by covalent linkage on the modified graphite electrode. CNTs were
p

functionalised by electrochemical treatment. A conducting polymer; poly(4-(2,5-di(thiophen-

ce

2-yl)-1H-pyrrol-1-yl)benzenamine)(poly(SNS-NH2)), was synthesised via

electropolymerisation to examine its matrix properties for biomolecule immobilisation. This

Ac

strategy enhanced electron transfer rate at a lower potential (+100 mV vs. Ag reference) and

catalysed electrochemical oxidation of acetylthiocholine effectively. SEM, X-ray

photoelectron spectroscopy (XPS), contact angle measurements and EIS, CV techniques were

used to monitor changes in surface morphologies and electrochemical characterisations. The

proposed biosensor design offered a fast response time (6 s), a wide linear range (0.05 mM

and 8.00 mM) and a low detection limit (0.09 mM) with a high sensitivity (24.16 µA mM−1

106
Page 106 of 165
cm−2) for acetylthiocholine. The inhibition responses of paraoxon, parathion and

chlorfenvinphos on the enzymatic activity of AChE were detected. The fabricated biosensor

was tested for the detection of pesticides in fortified tap water samples. The results were

found to be in good agreement with the ones determined by HPLC/DAD technique.

t
ip
Sun et al. [564] developed an amperometric CNTS-(AChE) biosensor for quantitative

cr
determination of carbaryl. Zhai et al. [565] attached abricatedchitosan-prussian blue-

multiwall CNTs-hollow gold nanospheres (Chit-PB-MWNTs-HGNs) film onto the gold

us
electrode surface by one-step electrodeposition method; and then AChE and Nafion were

an
modified onto the film to prepare an AChE biosensor. Incorporating MWNTs and HGNs into

Chit-PB hybrid film promoted electron transfer reaction, enhanced the electrochemical
M
response and improved the microarchitecture of the electrode surface. The morphologies and

electrochemistry properties of the composite were investigated by using SEM, TEM, CV and
d

EIS, respectively. Parameters affecting the biosensor response such as pH, enzyme loading
te

and inhibition time were optimised. Based on the inhibition of pesticides on the AChE

activity, using Malathion, chlorpyrifos, monocrotophos and carbofuran as model compounds,

p

this biosensor showed a wide range, low detection limit, good reproducibility and high
ce

stability. Moreover, AChE/Chit-PB-MWNTs-HGNs/Au biosensor can also be used for direct

analysis of practical samples, which would be a new promising tool for pesticide analysis.
Ac

Du et al. [566] described a highly sensitive amperometric biosensor for organophosphates

(OPs) pesticides based on immobilisation of AChE on MWCNTs-β-cyclodextrin (β-CD)

composite modified glassy carbon electrode. The synthesised composite through polymer

wrapping strategy has been characterised by attenuated total reflection Fourier-transform

infrared spectra (ATR-FTIR) measurement and SEM images. Due to the good dispersibility

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and porous structures of MWCNTs-β-CD composite, the resulting surface provided a

favourable microenvironment for AChE biosensor fabrication and maintained the bioactivity

of AChE for screening of OPs exposure. MWCNTs promoted electron-transfer reactions at a

lower potential and catalysed the electro-oxidation of thiocholine, thus increasing detection

t
sensitivity. Based on the inhibition of OPs on the AChE activity, using dimethoate as a model

ip
compound, the inhibition of dimethoate was proportional to its concentration, ranging from

cr
0.01 to 2.44 and 2.44 to 10.00 µM, with a detection limit of 2 nM (S/N = 3). The developed

biosensor exhibited good reproducibility and acceptable stability, thus providing a new

us
promising tool for analysis of enzyme inhibitors.

an
Deo et al. [567] described an amperometric biosensor for OP pesticides based on a CNT-
M
modified transducer and an organophosphorus hydrolase (OPH) biocatalyst. A bilayer

approach with the OPH layer atop of the CNT film was used for preparing the CNT/OPH
d

biosensor. The CNT layer leads to a greatly improved anodic detection of the enzymatically
te

generated p-nitrophenol product, including higher sensitivity and stability. The sensor

performance was optimised with respect to the surface modification and operating conditions.
p

Under the optimal conditions, the biosensor was used to measure as low as 0.15 M paraoxon
ce

and 0.8 M methyl parathion, with sensitivities of 25 and 6 nA/M respectively.

Chen et al. [568] introduced MWNTs into their sensor design, where they played dual
Ac

enhancement roles. First is that MWNTs loaded on glassy carbon (GC) electrodes

significantly increase surface areas, facilitating the electrochemical polymerisation of PB, a

redox mediator for the electrochemical oxidation of the enzymatic product, thiocholine

(TCh). Second, MWNTs enhance the enzymatic activity of AChE, as manifested by the

decreased Michaelis-Menten constant (Km). As a result of these two important enhancement

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Page 108 of 165
factors offered by MWNTs, the electrochemical pesticide sensor produced exhibited rapid

response and high sensitivity toward the detection of a series of pesticides.

Chauhan and Pundir [569] immobilised AChE purified from maize seedlings covalently onto

iron oxide nanoparticles (Fe3O4NP) and carboxylated multi-walled carbon nanotubes (c-

t
MWCNT) modified Au electrode. An OP biosensor was fabricated using this

ip
AChE/Fe3O4/c-MWCNT/Au electrode as a working electrode, Ag/AgCl as standard and Pt

cr
wire as an auxiliary electrode connected through a potentiostat. The biosensor was based on

inhibition of AChE by OP compounds/insecticides. The properties of nanoparticles modified

us
electrodes were studied SEM, FTIR, CVs and electrochemical EIS. The synergistic action of

an
Fe3O4NP and c-MWCNT showed excellent electrocatalytic activity at low potential (+0.4 V).

The optimum working conditions for the sensor were pH 7.5, 35 °C, 600 µM substrate
M
concentration and 10 min for inhibition by pesticide. Under optimum conditions, the

inhibition rates of OP pesticides were proportional to their concentrations in the range of 0.1–
d

40 nM, 0.1–50 nM, 1–50 nM and 10–100 nM for Malathion, chlorpyrifos, monocrotophos
te

and endosulfan, respectively. The detection limits were 0.1 nM for Malathion and

chlorpyrifos, 1 nM for monocrotophos and 10 nM for endosulfan. The biosensor exhibited

p

good sensitivity (0.475 mA µM−1), reusability (more than 50 times) and stability (2 months).
ce

The sensor was suitable for trace detection of OP pesticide residues in milk and water.

Cesareno et al. [570] developed a sensitive electrochemical AChE biosensor on polyaniline

Ac

(PANI) and MWCNTs core–shell modified GC, and used it to detect carbamate pesticides in

fruit and vegetables (apple, broccoli and cabbage). The pesticide biosensors were applied in

the detection of carbaryl and methomyl pesticides in food samples, using chronoamperometry

(CA). The GC/MWCNT/PANI/AChE biosensor exhibited detection limits of 1.4 and 0.95

µmol L−1 respectively for carbaryl and methomyl. These detection limits were below the

allowable concentrations set by Brazilian regulation standards for the samples in which these

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Page 109 of 165
pesticides were analysed. Reproducibility and repeatability values of 2.6% and 3.2%

respectively were obtained in the conventional procedure. The proposed biosensor was

successfully applied in the determination of carbamate pesticides in cabbage, broccoli and

apple samples without any spiking procedure. The obtained results were in full agreement

t
with those from the HPLC procedure.

ip
cr
Cesareno et al. [571] electrodeposited a core-shell structure based on polyaniline (PANI) and

MWCNT films on glassy carbon (GC) for the immobilisation of AChE as enzyme in

us
developing a biosensor for pesticides. The characterisation and advantages of using the

an
hybrid materials were examined by FTIR, field-emission gun scanning electron microscopy

(FEG-SEM), CV and EIS. The immobilisation of AChE on the surface of the electrode was
M
largely improved due to the unique synergistic effect of PANI and MWCNT. The developed

GC/MWCNT/PANI/AChE biosensor was evaluated for the determination of carbamate by

d

SWV and chronoamperometry. SWV allowed carbaryl to be determined in a linear range

te

between 9.9 and 49.6 nmol L-1, with a detection limit of 4.6 nmol L-1 and using

chronoamperometry, the analytical curve was linear in the concentration ranges of 9.9 to 49.6
p

mol L-1, with a detection limit of 1.4 mol L-1. Du et al. [572] developed a simple method for
ce

the immobilisation of AChE on MWNTs–chitosan (MC) composite to construct a sensitive,

fast and stable amperometric sensor for quantitative determination of organophosphorous

Ac

insecticide. Atomic force microscopy showed that this matrix possessed homogeneously

netlike structure, which prevented enzyme from leaving out of the electrode. MWNTs

promoted electron transfer reactions at a lower potential and catalysed the electro-oxidation

of thiocholine, thus increasing detection sensitivity. Based on the inhibition of

organophosphorous insecticide to the enzymatic activity of AChE, using triazophos as a

model compound, the conditions for detection of the insecticide were explored. Under

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Page 110 of 165
optimal conditions, the inhibition of triazophos was proportional to its concentration in two

ranges, from 0.03 to 7.8 µM and 7.8 to 32 µM, with a detection limit of 0.01 µM. A 95%

reactivation of the inhibited AChE could be regenerated for using pralidoxime iodide within

8 min. The amperometric sensor has potential application in the characterisation of enzyme

t
inhibitors and detection of toxic compounds.

ip
cr
Sgoobi et al. [573] reported amperometric biosensors for pesticide detection based on AChE

which employs the enzymatically generated thiocholine as the electrochemical probe. The

us
mechanism is generally assumed to be: 2 thiocholine → 2 H+ + 2e- + dithio-bis-choline

an
(dimer). The anodic oxidation of synthetic thiocholine at a pyrolytic carbon electrode,

modified with MWCNTs, was studied using electrochemical, spectrophotometric and

M
spectroelectrochemical techniques. CV was used to determine the linear relationship between

Ip and thiocholine concentration. A detection limit of 5.96 (± 0.22) µM (S/N = 3) and a

d

detection sensitivity of 3.16 × 10-2 (± 2.65 × 10 -3) µA µM-1 were observed with a linear range
te

from 5.0 to 100.0 µM and correlation coefficient of 0.9954. Using controlled potential

electrolysis coupled to a spectrophotometric probe in situ, the number of electrons involved

p

in the electrochemical oxidation was confirmed to be 2. By the reaction with dithiothreitol

ce

through Cleland's method in which the disulfide compound generated presents an absorption

peak at 283 nm, the dimeric product of the assumed oxidation reaction was also confirmed.
Ac

Ebrahim et al. [269] investigated the detection of Malathion (organophosphorous pesticide)

based on composite of polyaniline nanofiber and SWCNT deposited onto graphite electrode.

Fourier transforms infrared and UV-vis absorption spectra, XRD, SEM and CV were used to

characterise the prepared composite. Malathion concentration was detected using differential

pulse voltammetry technique at polyaniline-SWCNT modified graphite electrode. The

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Page 111 of 165
fabricated polyaniline-single wall carbon nanotubes modified graphite electrodes exhibited

higher accuracy toward the reduction of Malathion. Malathion was found to exhibit one well-

defined reduction peak at pH 7. A linear response to Malathion in the concentration range

from 2.0 × 10-7 M to 14.0 × 10-7 M was observed. The minimum detection limit in the linear

t
range for the modified electrodes was 2.0 × 10-7 M Malathion.

ip
Anirudhan and Alexsandra [270] prepared a novel potentiometric sensor based on ion

cr
imprinted polymer inclusion membrane (IPIM) from the modification of MWCNT-based

molecularly imprinted polymer for the trace determination of the pesticide 2,4-D (2,4-

us
dichlorophenoxyacetic acid in natural water samples. MWCNTs were initially functionalised

an
with vinyl groups through nitric acid oxidation along with reacting allylamine. MWCNT -

based imprinted polymer (MWCNT-MIP) was synthesised by means of methacrylic acid

M
(MAA) as the monomer, trimethylol propane trimethacrylate (TRIM) as the cross linker, α,

α′-azobisisobutyronitrile (AIBN) as the initiator and 2, 4-D an organochlorine pesticide

d

molecule as the template. Organised material was characterised by means of FTIR, XRD and
te

SEM analyses. The sensing membrane was developed by the inclusion of 2,4-D imprinted

polymer materials in the polyvinyl chloride (PVC) matrix. The optimisation of operational
p

parameters such as amount and nature of plasticisers sensing material, pH and response time
ce

was conducted. From the non-imprinted (NIPIM) and imprinted polymer inclusion membrane

(IPIM) sensors, the response behavior of 2, 4-D was compared under optimum conditions.
Ac

The IPIM sensor responds in the range of 1 × 10-9-1 × 10-5 M and the detection limit was

found to be 1.2 × 10-9 M. The stability of MWCNT-IPIM sensor was checked by various

methods and it was found to be 3 months and it can be reused many times without losing its

sensitivity. Various groups have previously shown that CNTs-based-pesticides biosensors

exhibit good sensitivity, selectivity and reproducibility [569, 574-577] and recent studies

have shown that CNTs-based pesticides biosensors exhibit good sensitivity, selectivity and

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Page 112 of 165
reproducibility towards detection of organophosphorus, non-organophosphorus pesticides and

nerve agents [433, 542, 560, 561, 563, 565, 566, 570, 576-591] .

8. Conclusion and future perspective

t
ip
This review presents recent synthesis and applications of CNTs for electrochemical

cr
biosensing. A rapid growth in the use of CNT-based electrodes for electrochemical

biosensing has been witnessed. These biosensors have exhibited excellent sensitivity and

us
selectivity towards the detection of glucose, cholesterol, Hb, H2O2, UA, AA, DA, DNA,

metals ions and organophosphorus and non-organophosphorus pestisides. Studies of CNT-

an
based materials will enhance research in the field of biosensor because CNT are excellent
M
materials for the development of electrochemical sensors. Biosensor based on functionlised

CNts for detecting biomolecules is a virgin research area and environmental electrochemical
d
sensor based on fuctionalised CNTs is emerging research area in detecting pollutant in water
te

such as heavy metal ions and persistent organic pollutants. It is thus critical in future to

develop effective functionalised method for heterogeneous CNTS composites. Future

p

applications of CNTs and it composites in sensor and biosensor are very bright because CNTs
ce

and its composites have wide potential window, they are chemically inactive and they show

electrocatalytic activity for several reactions. They display exceptional electric conductivity
Ac

for signal transduction, high sensitivity and selectivity. In future, the development of more

versatile fabrication strategies, higher number of sensing device can be prepared and the

number of analytes that can be determined will increase considerably. Mass production of

disposable CNTcomposite sensors in future will emerge and the cost of CNTs-composite will

be minimal.

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Page 113 of 165
Future developments of CNTs based biosensors will address future biosensing challenges in

clinical diagnostics; environmental monitoring, energy and security control by technological

and the known advantages of CNTs and the electrochemical techniques. These developments

will depend on the unique properties of CNTs. The ability to rapidly and selectively detect

t
H2O2, glucose, cholesterol, neurotransmitters, proteins and DNA or biomolecules with CNTs

ip
biosensors, could lead to more exciting discoveries in biomedical studies.

cr
us
an
M
d
p te

Abbreviations
ce

PTH Poly(thionine hydrochloride)

AA Ascobic Acid
Ac

AP Aminophenol

AChE Acetylcholinesterase

AFM Atomic force microscopy

ATR-FTIR Attenuated total reflection Fourier-transform infrared spectra

AF-MWCNTEPI Amino-functionalised MWCNT/electroactive polyimide

AFP α-fetoprotein

CAF Caffeic acid

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Page 114 of 165
CPE Carbon paste electrode

CNTs Carbon nanotubes

CV Cyclic Voltammetry

CVD Chemical vapour deposition

t
COx Cytochrome c oxidase

ip
ChOx Cholesterol oxidase

cr
Cyt-c Cytochrome c

Cys Cysteamine

us
DWCNT Double wall carbon nanotube

DA Dopamine

an
DET Direct electron transfer

DPV Differential-pulse voltammetry

M
EDC 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide

EP Epinephrine
d

ESPR Electrochemical surface plasmon resonance (ESPR)

te

FEG-SEM Field-emission gun scanning electron microscopy

p

FIA Flow injection analysis

ce

FTIR FourearTransform Infra Red

GCE Glassy carbon electrode

Ac

GC Glassy Carbon

GOD Glucose oxidase

Hb Haemoglobin

HBV Hepatitis B virus

HIgG Human IgG

hCG Human chorionic gonadotropin

H2O2 Hydrogene Peroxide

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Page 115 of 165
HPLC High performance liquid chromatography

HRP Horseradish peroxidase

ITO Indium tin oxide

EIS Electrochemical impedance spectroscopy

t
IPIM Imprinted polymer inclusion membrane

ip
LOD Limit of detection

cr
MAA Methacrylic acid

MT Maize tassel

us
MWCNT Multiwall carbon nanotube

MWCNT-g-PLA MWCNT grafted Poly(lactic acid)

MC

MB-MWNTs
MWNTs–chitosan

an
Methylene blue-multiwalled carbon nanotubes
M
MC Mesoporous carbon
d

MWCNT –MIP MWCNT-based imprinted polymer

te

MB Molecular beacon

MC-LR Microcystin-LR
p
ce

MDI Methylene diphenyl diisocyanate

NAD Nicotinamide adenine dinucleotide

Ac

NP Nanoparticle

OP Organo phosphorous

OPH Organophosphorus hydrolase

PANI Polyaniline

P(MAA-co-AAM Poly(methacrylic acid-co-acrylamide)

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Page 116 of 165
PBG Poly(brilliant green)

PPy Polypyrrole

PAH Poly(allylamine

PEDOT Poly(3,4-ethylenedioxythiophene)

t
ip
SDBS Sodium dodecylbenzenesulfonate

cr
SPE Screen printed electrode (SPE)

SWV Square-wave voltammetry

us
SEM Scaning Electron Microscopy

an
SCE Saturated calomel electrode

tDNA Target Aeromonas DNA

M
TCh Thiocholine

TRIM Trimethylol propane trimethacrylate

d

TEM Transmissio electron micrscopy

te

UA Uric Acid
p

XPS X-ray photoelectron spectroscopy

ce

XRD X-ray Diffraction

Ac

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cr
[587] T.M.B.F. Oliveira, M. Fátima Barroso, S. Morais, P. De Lima-Neto, A.N. Correia,
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novel green technique, J. Phys. Chem. C 117 (2013) 13202-13209.
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[590] J. Liu, Y. Li, G. Song, K. Zhang, B. Ye, Sensitive determination of pesticide
imidacloprid using a glassy carbon electrode modified with a film composed of multi-walled
carbon nanotubes and poly(aspartic acid), International Journal of Environmental Analytical
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[591] D. Chen, X. Sun, Y. Guo, L. Qiao, X. Wang, Acetylcholinesterase biosensor based on

multi-walled carbon nanotubes-SnO2-chitosan nanocomposite, Bioprocess and Biosystems
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[593] S. Hocevar, J. Wang, R. Deo, M. Musameh, B. Ogorevc, Carbon Nanotube Modified

Microelectrode for Enhanced Voltammetric Detection of Dopamine in the Presence of
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Ascorbate,Electroanalysis 17 (2005) 417-422.

[594] J. Wang, R. Deo, M. Musameh, Stable and Sensitive Electrochemical Detection of
Phenolic Compounds at Carbon Nanotube Modified GlassyCarbon,Electrodes,Electroanalysis
15 (2003) 1830-1834.
Ac

[595] Q. Zhao, L. Guan, Z. Gu, Q. Zhuang, Determination of Phenolic Compounds Based on

the Tyrosinase- Single Walled Carbon Nanotubes Sensor, Electroanalysis 17 (2005) 85-88.
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Chen, Y. Lin, Determination of organophosphate pesticides at a carbon
nanotube/organophosphorus hydrolase electrochemical biosensor,Anal.Chim. Acta 530
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Table 1 CNT-metal composites biosensor used for determination of various biomolecules

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Table 2 CNT-based biosensors for various biomolecules [6]

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Table 3 Summary of the various CNT-based glucose sensors based on nanotubes reported in
the literature, along with their important parameters [6]

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Fig. 1 (a) Roll-up of a graphene sheet leading to three different types of SWCNTs; (b)
Structure of a multi-walled carbon nanotube made up of three

shells of differing chirality.[76]

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Fig. 2 Applications of carbon nanotubes

Fig. 3 Various functionalisation processes

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Fig.4 Schematic of simplified electrostatic adsorption between a negatively charged MWNT

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and positively charged PANI molecules. Reprinted with permission from ref. 142. Copyright
2007. American Chemical Society
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Fig. 5 Wiring ofproteinsbyCNT forelectrochemistry.CNT-supported

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hemeproteinsatthesurfaceofglassy-carbonelectrodes

Fig.6 Assembly of the CNT electrically contacted glucose oxidase electrode. Reprinted
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with permission from [132]. Copyright (2008) American Chemical Society.

Fig. 7 CNT-based electrochemical immunosensors with HRP enzyme labels: use

of CNT-based immuno-nanotubes, containing both the secondary antibody and

the enzyme label. [449]

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Carbon nanotubes

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o This review discusses synthesis and applications of carbon nanotubes sensors.
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o The review summarises contributions of carbon nanotube to electrochemical
biosensor
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o Good electrical conductivity makes carbon nanotubes a good material for
biosensors
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o Carbon nanotubes promotes electron transfer that aids biosensing of

biomolecules.
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Table 1.

S/N CNT-Metal nanocomposite Analyte Sensitivity Detection Reference

limit (μM)
mAM-1cm-2

1 CNT-Pt H2O2 49 +/- 1.4 A 203

2 AuNPs/G/MWCNTs Glucose 29.72 4.8 204

3 (POPD)-grafted Au/Pt Aflatoxin 191

bimetallic MWCNT B1

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4 BLG-MWCNTs-GNP Glucose 3.98 1.1 228

5 CNT-Cu Glucose - 0.025 206

6 CNT-Pt H2O2 1.99 60 208

7 CNT-Au–Ti Glucose - 0.077 211

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8 CNT-ZnSe Paeonol - 0.04 213

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9 CNT-ZnO Urea 43 - 216

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10 CNT-Au chrysoidine - 1.7 224

11 CNT-Pd H2O2 307.5 1 226

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12 CNT-CdSe Glucose 31.13 25 238

13 CNT-ZnO IgG - 1.2 255

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14 CNT-Au-Pt Glucose - 28 261

15 CNT-TiO2 Glucose - 30 266

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Table2.

Analyte Occurrence Enzyme Sensor

Blood, body CTS+PTFE/GOx/MWCNTs/PTH[41]

Glucose Glucose oxidase (GOx)
fluids GCE/(SWCNT–PEI, PEG, PPY)[307]

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Analyte Occurrence Enzyme Sensor

PEDOT-CNT/CNx-CCl[301]

poly(2,6-diaminopyridine)/CNTs[150]

MWCNTPE [6]

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Brain tissue, Polyphenol oxidase

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Dopamine PPOx/MWCNTPE [592]
blood (PPOx)

MWCNT-Nafion/CFE[593]

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PPOx/MWCNTPE [592]

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Other phenolic Water, food
Tyrosinase (Ty), PPOx MWCNT-Nafion/GCE [594]
compounds products

Nafion/Ty/SWCNT/GCE [595]

an OPH/CNT-Nafion/GCE [596]

AChE-ChOx-MWCNT[578]
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Water
Organophosphate Organophosphorus poly (diallyldimethy-lammonium
resources,
pesticides hydrolase (OPH) chloride) –MWCNT-G[564]
agriculture
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(MWCNTs)-β-cyclodextrin (β-CD[566]
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MWCNTs-CHIT-SnO2-CHIT[591]

ChOx/MWCNT/CPE [597]
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Cholesterol oxidase ChOx (LBL)/MWCNT/Gold [598]

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Blood
Cholesterol (ChOx)
ChOx/PANI-MWCNT/ITO[423]

ChOx/PANI–MWCNT/ITO[423]
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PSMA-g-3ABA/MWCNTs[205]

PLL/f-MWCNT[364]
H2O2 Tissue Hb, CAT
MWCNT-g-PLA-Pd[365]

CoNP-Pt/CNTs[374]

chitosan-CNT-MB[493]
DNA Blood. Tissue
MWCNT–Chi–Bi[484]

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Analyte Occurrence Enzyme Sensor

CNT-DNA[134]

Water, Food MT-MWCNT[544]

Metal ions
products MWCNT-Chitosan[551]

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CFE carbon fiber electrode, CNTPE CNT paste electrode, CPE Carbon paste electrode, LBL layer-by-
layer technique, CAT catalyase

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Table 3.

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Fabrication Sensitivity Linear range Response
No. Sensors Stability
methodology [(mmol/L)−1] [mmol/L] time [s]

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Nanoparticle
S1 CuNP-SWCNT-Nafion/GCE [31] 256 μA 0–0.5 10
decoration

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Nanoparticle 73.5%
Nafion/GOx/PtNP/CNT/Graphite
S2 decoration, Enzyme 14 μA 0.1–13.5 <5 after 22

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[20]
adsorption days

Nanoparticle
GOx/PtNP-SWCNT-Nafion/GCE
S3 decoration, Enzyme 2.11 μA 0.0005–5 3
M
[30]
adsorption

S4 Electropolymerization POAP-GOx/FePc-MWCNT [42] 735 nA 0.0005–4 <8 120 days

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PPy-GOx-MWCNT array/Gold 70% after 3

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S5 Electropolymerization 350 nA 2.5–20

[24] days

S6 Encapsulation GOx-Nafion-MWCNT/GCE [46] 330 nA 0–0.002 <3

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Encapsulation, Sol-gel
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S7 GOx-SGC/MWCNT/bppg [44] 196 nA 0.2–20 <5 3 weeks

process

S8 Electropolymerization PPy-GOx-MWCNT/GCE [40] 2.33 nA 0.2–50 15

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The blanks in the columns for response time and stability indicate that these values were not
available in the corresponding reported works. bppg basal plane pyrolytic graphite, FePc iron
phthalocyanine, GCE glassy carbon electrode, GOx Glucose oxidase, POAP poly-o-aminophenol, NP
Nanoparticle, PPy polypyrrole, SGC sol-gel composite

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Fig. 1

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Fig. 2.
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Fig.3
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Fig.4
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Fig. 5

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Fig. 6

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Fig.7
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