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Functionalized Nanomaterial Based Electrochemical Sensors Principles Fabrication Methods and Applications Chaudhery Mustansar Hussain Full Chapter
Functionalized Nanomaterial Based Electrochemical Sensors Principles Fabrication Methods and Applications Chaudhery Mustansar Hussain Full Chapter
Functionalized
Nanomaterial-Based
Electrochemical Sensors
Principles, Fabrication Methods, and
Applications
Edited by
Jamballi G. Manjunatha
Department of Chemistry, FMKMC College,
Constituent College of Mangalore University,
Madikeri, Karnataka, India
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ISBN: 978-0-12-823788-5
ISBN: 978-0-12-824185-1
Contributorsxiii
Preface xix
Index 579
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Contributors
R. Acevedo Faculty of Engineering and Technology, San Sebastian University,
Santiago, Chile
S. Boobas Department of Physics, Sri Vasavi College, Bhavani, Tamil Nadu, India
Since the last decade, utility of nanomaterials and functionalized nanostructures has
become significant in multidisciplinary fields including biomedical, environmental,
food and beverages, textiles, pharmaceutical, cosmetics, agricultural, sensors, energy
storage management, electronic materials, etc. Specifically, new methods in the syn-
thesis of functionalized nanomaterials (FNMs) and their applications in different areas
of science have been developed. Functionalization of nanomaterials is a method of
inserting a particular material onto the surface of the nanomaterial to boost its proper-
ties and reduce its toxicity. Functionalized nanomaterials can be synthesized through
covalent, noncovalent, grafting, physical methods, etc. They have a great impact on
the fabrication of electrochemical sensors and biosensors for the determination of
a wide spectrum of molecules, toxic ions, and even disease diagnosis applications.
Their real-time applications are extensive due to their unique characteristics like high
electrical, thermal, mechanical, and electronic properties and biocompatibility, large
surface, etc. Electrochemical sensors and devices are well known for their versatile
applications and advantages like simple handling procedure, quick results, high sensi-
tivity and selectivity, low consumption of sample, etc.
This book gives the readers a holistic insight into functionalized nanomaterial-based
electrochemical sensors from design to application. This book is categorized into sev-
eral sections: Section A explains “Modern Perspectives in Electrochemical-Based
Sensors: Functionalized Nanomaterials (FNMs)”; Section B deals with “Fabrication
of Functionalized Nanomaterial-Based Electrochemical Sensor Platforms”; Section C
describes “Functionalized Carbon Nanomaterial-Based Electrochemical Sensors”;
Section D provides “Noble Metals, Non-Noble Metal Oxides, and Noncarbon-Based
Electrochemical Sensors”; Section E conveys “Functionalized Nanomaterial-Based
Electrochemical Sensors for Environmental Applications”; Section F emphasizes on
“Functionalized Nanomaterial-Based Electrochemical Sensor Technology for Food
and Beverage Applications”; Section G focuses on “Functionalized Nanomaterial-
Based Electrochemical Sensors for Point-of-Care Applications”; Section H deals with
“Health, Safety, and Regulation Issues for Functionalized Nanomaterials”; Section I
describes “Economics and Commercialization of Functionalized Nanomaterial-
Based Electrochemical Sensors”; and Section J explains “Future of Functionalized
Nanomaterial-Based Electrochemical Sensors.”
The goal of this book is to provide a comprehensive insight from the basic level
to the application of FNMs for the fabrication of electrochemical sensors and bi-
osensors. I hope this book will be a great asset to electrochemists, material scien-
tists, college and university graduates, chemists, biologists, pharmacists, engineers,
xxPreface
p hysicists, industrial researchers, and analytical scientists. The editor and contrib-
utors are eminent researchers and experts from universities and various industries.
On behalf of Elsevier, we thank all the authors of this book for their valuable con-
tributions. We are extremely thankful to John Leonard (editorial project manager) at
Elsevier for his tremendous support and assistance throughout this assignment.
Modern perspective in
electrochemical-based sensors:
Functionalized nanomaterials
(FNMs)
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Functionalized nanomaterial-based
electrochemical sensors: 1
A sensitive sensor platform
Shashanka Rajendracharia and Dileep Ramakrishnab
a
Department of Metallurgical and Materials Engineering, Bartin University, Bartin, Turkey,
b
Department of Chemistry, School of Engineering, Presidency University, Bangalore, India
1.1 Introduction
A great advancement in science and technology as an indispensable technology growth
is the use of Nanomaterials and nanotechnology. Nanomaterials are materials that have
one of their dimensions less than or equal to 100-nm scale [1–4]. With the advance-
ment in synthetic methodologies, the preparation of a variety of these nanomaterials is
permitted with the desired size, surface properties, shape, and other physicochemical
properties [5–7]. Moreover, the materials that can be functionalized thus present a great
panorama for uniting biological credit and signal transduction mechanisms which lead
to the development of novel bioelectronic devices with outstanding sensor properties
[8–13]. Nanomaterials usually have a larger surface area and this compliments the
improvement in electron-transfer rate [14–17]. Thus, these properties are quite utilized
in catalysis, polymer technology, drug delivery, food production, painting, and elec-
trochemical sensing [18]. Electrochemical sensors form a vital subdivision of chem-
ical sensors in which the transduction element is designed from an electrode source
[19,20]. It works on the principle of electrochemistry, which is a very influential elec-
troanalytical technique that shows the advantages in terms of high sensitivity, instru-
ment simplicity, portability, easy miniaturization, and is relatively cost-effective [21].
A portable biochemical detection was made possible, very recently, through the use of
smartphones assimilated with sensors, such as test trips, sensor chips, and hand-held
detectors [22]. The assimilation of these miniaturized devices as sensitive arrays was
possible through the application of micro-electro-mechanical systems and of course
nanotechnology [23–25]. Meanwhile, some of the properties of sensors are very high
sensitivity, selectivity, and stability, researchers have been pushing a lot of effort on
refining these properties. In this case, the incorporation of nanomaterials is playing its
role as sensors. Generally, nanomaterials exhibit unique properties and functionalities
which can create a promising evolution of the new analytical schemes that are easily
triggered to detect various biological molecules [26]. These analytical schemes have
been used with numerous sensor programs covering a wide range of nanomaterials
and fabrication convolution [27]. A nano-level fabrication of the electrode surface is
a gifted platform to develop high-performance electrochemical to detect the target
analytes [28]. The design of these types of nano-level electrode materials focuses on
the signal amplification through the catalytic activity and conductivity, facile interac-
tions with chemical and biological reagents, and the immobilization of the functional
moieties with precisely designed as signal tags which are prominent in highly selec-
tive sensing [29]. Therefore, the fabrication of a functionalized nanomaterial-based
electrode is recently progressing with high acceleration. This chapter aims to expose
researchers to the success recorded in this area while hoping that the article will stim-
ulate further discoveries in the area of electrochemical sensors using nanomaterials.
1.2 Quantum-Dot nanomaterial
Quantum dots are semiconductor nanocrystals in which excitons are confined in all
three spatial dimensions. The confinement can be realized by fabricating the semi-
conductor in a very small size, typically several hundred to thousands of atoms per
particle [30,31]. Due to quantum confinement effects, QDs act like artificial atoms,
showing controllable discrete energy levels. QDs were first fabricated in the 1980s
by Louis E. Brus and the unique properties of these special nano-structures attracted
interest from many fields. Quantum-Dot (QD) semiconductor nanocrystals have been
reported to be used for the design of multianalyte electrochemical aptamers biosensors
with sub picomolar (attomole) detection limit [32].
QDs can be optically excited. When absorbing photons, electrons in QDs gain en-
ergy leading to the creation of excitons. An exciton is a bound state of an electron and
a quasiparticle called a hole. After relaxation from the excitonic excited state to its
lower energy state, the electron and hole recombine (exciton recombination), emit-
ting a photon. The overall process of optical excitation, relaxation of the excited state,
recombination of electron and hole, and fluorescent emission is called photolumines-
cence (PL). The number of photons emitted can be measured as a function of energy,
which gives the PL spectrum. Different from many organic dyes, QDs can be excited
by many light sources within a large wavelength range, since QDs have continuous
and broad absorption spectra. Furthermore, many kinds of QDs can be excited by the
same light source and their emission can be easily separated. The emission light spec-
tra of QDs are narrower and more symmetric than conventional organic dyes, making
the sensitivity of detection higher than for organic dyes. Due to this property, QDs are
attractive fluorophores for biological imaging (biological tagging).
The energy gap of excitons in QDs is strongly size dependent. This size-dependent
phenomenon is due to the effect of confinement: The smaller QDs have stronger con-
finement making the energy gap larger. Similarly, a larger size gives a smaller energy
gap. Hence, QDs with different emission colors can be made from the same material
by changing their size. Hence for larger (small) sizes, the emission is more toward
the red (blue). Colloidal QDs, which are synthesized by relatively inexpensive wet
chemistry methods, make it possible to have the desired particle size which makes it
easy to find QDs with the energy spectrum we need and high quantum yield (number
of photons absorbed over the number of photons emitted), even at room temperature.
Currently, CdSe or CdTe QDs with a ZnS shell is commonly used and studied. The
Functionalized nanomaterial-based electrochemical sensors 5
Fig. 1.1 (A) Square-wave stripping voltammograms for different concentrations of thrombin:
(a) 0, (b) 100, and (c) 500 ng L− 1. (B) The resulting calibration plot. (C) Assessment of the
selectivity using nontarget proteins: (a) control (no analyte or interference), (b) 25 μg L− 1
BSA, and (c) 25 μg L− 1 IgG.
Courtesy: J.A. Hansen, J. Wang, A.-N. Kawde, Y. Xiang, K.V. Gothelf, G. Collins, Quantum-
dot/aptamer-based ultrasensitive multi-analyte electrochemical biosensor, J. Am. Chem. Soc.
128 (2006) 2228–2229.
COOH COOH
CdS
OH OH OH OH OH OH OH OH OH
i/µA
S S S S S NHS/EDAC S SSSS S SSSS
Au Au Au Au
(a) (b) (c) (d) -0.8 -0.6
E/V
Scheme 1.2 Operation of the nanoparticle-based bioelectronic sensor for glycans involving
competition of the tagged sugar with the target analytes for the binding sites of the
immobilized lectin. (a) Mixed self-assembled monolayer on the gold substrate; (b) covalent
immobilization of the lectin; (c) addition of the tagged and untagged sugars; (d) dissolution
of the captured nanocrystals, followed by their stripping-voltammetry detection at a mercury-
coated glassy carbon electrode.
Courtesy: Z. Dai, A.-N. Kawde, Y. Xiang, J.T. La Belle, J. Gerlach, V.P. Bhavanandan, L.
Joshi, J. Wang, Nanoparticle-based sensing of glycan–lectin interactions, J. Am. Chem. Soc.
128 (2006) 10018–10019.
II.
III.
PRAYERS. [7]