Advances in Nanosensors for

Biological and Environmental Analysis

Aakash Deep
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Advances in
Nanosensors for
Biological and
Environmental
Analysis
This page intentionally left blank
 Advances in
Nanosensors for
Biological and
Environmental
Analysis
EDITED BY

AKASH DEEP, MSC, MPHIL, PHD

Nanotechnology Lab
CSIR-Central Scientific Instrument Organisation (CSIR-CSIO)
Chandigarh, India
Academy of Scientific and Innovative Research (AcSIR-CSIO)
Chandigarh, India

SANDEEP KUMAR, PHD

Department of Bio and Nano Technology
Guru Jambheshwar University of Science and Technology
Hisar, India
Department of Civil Engineering
University of Nebraska Lincoln
Lincoln, United States

]
ADVANCES IN NANOSENSORS FOR BIOLOGICAL AND ISBN: 978-0-12-817456-2
ENVIRONMENTAL ANALYSIS
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List of Contributors

Valerio F. Annese Girish Chandra Mohanta

Electronics and Nanoscale Engineering CSIR-Central Scientific Instrument Organisation
School of Engineering (CSIR-CSIO)
University of Glasgow Chandigarh, India
Glasgow, United Kingdom Academy of Scientific and Innovative Research
(AcSIR-CSIO)
Gaurav Bhanjana Chandigarh, India
Department of Chemistry and Center of Advanced
Studies in Chemistry Ganga Ram Chaudhary
Punjab University Department of Chemistry and Center of Advanced
Chandigarh, India Studies in Chemistry
Panjab University
Neha Bhardwaj Chandigarh, India
Nanotechnology Lab
CSIR-Central Scientific Instrument Organisation Moondeep Chauhan
(CSIR-CSIO) Department of Environment Studies
Chandigarh, India Punjab University
Academy of Scientific and Innovative Research Chandigarh, India
(AcSIR-CSIO) Department of Chemistry and Center of Advanced
Chandigarh, India Studies in Chemistry
Panjab University
Sanjeev Kumar Bhardwaj Chandigarh, India
Nanotechnology Lab
Department of Bio and Nano Technology
CSIR-Central Scientific Instrument Organisation
Guru Jambheshwar University of Science and
(CSIR-CSIO)
Technology
Chandigarh, India
Hisar, India
Academy of Scientific and Innovative Research
(AcSIR-CSIO) David R.S. Cumming
Chandigarh, India Electronics and Nanoscale Engineering
School of Engineering
Deepanshu Bhatt University of Glasgow
Nanotechnology Lab Glasgow, United Kingdom
CSIR-Central Scientific Instrument Organisation
(CSIR-CSIO) Akash Deep
Chandigarh, India Nanotechnology Lab
Academy of Scientific and Innovative Research CSIR-Central Scientific Instrument Organisation
(AcSIR-CSIO) (CSIR-CSIO)
Chandigarh, India Chandigarh, India
Academy of Scientific and Innovative Research
(AcSIR-CSIO)
Chandigarh, India

v
vi LIST OF CONTRIBUTORS

Neeraj Dilbaghi Sandeep Kumar

Department of Bio and Nano Technology Department of Bio and Nano Technology
Guru Jambheshwar University of Science and Guru Jambheshwar University of Science and
Technology Technology
Hisar, India Hisar, India
Department of Civil Engineering
Ashraf Aly Hassan University of Nebraska Lincoln
Department of Civil & Environmental Engineering Lincoln, NE, United States
United Arab Emirates University
Al Ain, United Arab Emirates Poonma Malik
CSIR-Central Scientific Instrument Organisation
Sven Ingebrandt (CSIR-CSIO), Colony
IWE1eInstitut für Werkstoffe der Elektrotechnik1 Chandigarh, India
RWTH Aachen University
Germany Ruchi Mutreja
Chemical Biology Lab
Manpreet Kaur Biotechnology Department
Graduate Student IIT Roorkee
Indian Institute of Science Education and Research Roorkee, India
Mohali (IISER Mohali)
Mohali, India Suresh Neethirajan
BioNanoLab
Rajnish Kaur University of Guelph
Department of Physics Canada
Panjab University
Chandigarh, India Monika Nehra
Ubiquitous Analytical Techniques Department of Electronics and Communication
CSIR-Central Scientific Instruments Organisation Engineering
(CSIR-CSIO) Guru Jambheshwar University of Science and
Chandigarh, India Technology
Hisar, India
Madhu Khatri Department of Bio and Nano Technology
Faculty Guru Jambheshwar University of Science and
University Institute of Engineering and Technology Technology
(UIET) Hisar, India
Punjab University (PU)
Chandigarh, India Satish Kumar Pandey
CSIR-Central Scientific Instrument Organisation
Parveen Kumar (CSIR-CSIO)
CSIR-Central Scientific Instrument Organisation Chandigarh, India
(CSIR-CSIO)
Chandigarh, India Samadhan B. Patil
Electronics and Nanoscale Engineering
Rajeev Kumar School of Engineering
Department of Environment Studies University of Glasgow
Panjab University Glasgow, United Kingdom
Chandigarh, India
 LIST OF CONTRIBUTORS vii

Sandeep Kumar Sharma S.K. Tripathy

Department of Applied Science Department of Physics
Desh Bhagat University Panjab University
Mandi Gobindgarh, India Chandigarh, India

Sharvan Sehrawat Satish K. Tuteja

Faculty IWE1eInstitut für Werkstoffe der Elektrotechnik1
Indian Institute of Science Education and Research RWTH Aachen University
Mohali (IISER Mohali) Germany
Mohali, India
This page intentionally left blank
Preface
An ever-increasing demand of routine tests of various
biological and environmental parameters is driving the
development of portable and user-friendly diagnostic
tools. Many of such tools are nowadays available in
different forms including papers, electrodes, chips, kits,
etc. A growing significance of portable detection tools
has placed them as useful alternatives to conventional
analytical techniques like spectroscopy and biochemical
tests. In order to attain sufficient competitiveness, the
modern-day portable detection tools and diagnostic
devices are being integrated with nanotechnology. The
application of nanomaterials and nanosurfaces has
enabled the researchers to design highly sensitive nano-
sensors that can match the performance of laboratory-
based instruments. Owing to the large surface areas
and various other material properties, the nanosensors
offer many significant advantages, such as high sensi-
tivity, robust attachment of analyte specific receptors,
label-free sensing, signal reproducibility, etc. Recent
decades have witnessed the emergence of carbon nano-
tubes, graphene, metal nanoparticles, quantum dots,
and transition metal dichalcogenides as transducer sur-
faces of choice in the development of nanosensors for
both environmentally and clinically important parame-
ters. This book provides a comprehensive overview on
the most important types of nanosensor platforms
explored and developed in the recent years for efficient
detection of environmental/clinical analytes. It covers
the information in such a way that the readers could
grasp knowledge on important aspects of nanosensor
development, e.g., material synthesis, their functionali-
zation with different receptors, and techniques to record
signals. A commercial perspective of the nanosensor
market is also discussed.
Chapter 1 of the book elaborates the applications of
carbon-based nanomaterials in the development of
various nanosensors. Carbon nanomaterials have
become immensely popular among the researchers
worldwide for designing sensitive sensors on account of
their different useful properties. Carbon nanomaterials
can be synthesized in different forms such as nanosheets,
nanotubes, fullerene, and quantum dots. Consequently,
these nanomaterials have opened up numerous oppor-
tunities in order to seek the realization of nanosensors
for diverse environmental and clinical parameters. As
Chapter 2 discusses, 2-dimensional transition metal
dichalcogenide (2D TMD) nanomaterials have been
touted as promising alternatives to carbon nano-
materials in recent years. Molybdenum- and tungsten-
based disulfides are two important examples in this
category. Atomically thin 2D TMDs possessing direct
band gap property provide the development of plat-
forms for the sensing of pH, gases, heavy metals, pro-
teins, etc. Along with carbon nanomaterials, 2D TMDs
are suitable to be integrated as lab-on-chip type of
devices.
The utility of conducting polymers in the develop-
ment of sensing systems is widely recognized. Chapter 3
elaborates information on the synthesis and sensing
applications of various conducting polymers. In addi-
tion to this, the characteristics and applications of con-
ducting polymer composites with other nanomaterials
have also been outlined. Metaleorganic frameworks
(MOFs) are a class of coordination polymers which are
attracting significante attention of researchers world-
wide. Chapter 3 also focuses on this trending topic of
developing MOF-based sensors. Some extraordinary
material characteristics of MOFs (e.g., their high surface
area, tunable porosity, formation in different forms) are
the factors inspiring scientists and researchers to explore
them in the sensing of gases, proteins, explosives, anions,
cations, antigens, etc. Chapter 4 is dedicated to discuss
different biorecognition molecules and methods of their
isolation and production. Biomolecules are an impor-
tant component of many sensors wherein they help to
attain the desired selectivity during analysis. Nucleic
acids, enzymes, aptamers, and antibodies are the main
categories of biomolecules used in the development of
selective sensors. Nowadays, specific biomolecules are
available in the market to target the selective recognition
of analytes such as antigens, pesticides, heavy metals, etc.
Chapter 5 provides information about the techniques
to modify the nanosurfaces with biomolecules. The
contents of this chapter would help the readers to
ix
x PREFACE
understand different covalent and physical
attachmentebased chemistries in order to immobilize
biomolecules over surfaces of nanomaterials. A robust
immobilization of biomolecules is immensely critical to
define the stability, accuracy, and shelf life of nano-
biosensors. The utilization of nanomaterials in the
fabrication of easy-to-use paper and lateral flow sensors
is described in Chapter 6. These simple sensing devices
find important application in soil, air and, water quality
monitoring due to their low cost and convenient
handling. The advantages and existing limitations/chal-
lenges of nanosensors have been discussed in Chapter 7.
Finally, commercial aspects and an overview of currently
available sensors for various analytes are mentioned in
Chapter 8.
The nanosensor market is growing at an exponential
pace. Important features like fast response, portable
instrumentation, and cost-effectiveness are major factors
behind the escalating demand of these point-of-care
devices. They not only match the detection limits of
laboratory-based instruments but also serve the purpose
utilizing much smaller sample volumes. Nanosensors
are being accepted as preferred tools by clinical labora-
tories, regulatory agencies, and common users. Their
integration with or into smartphones and wearable de-
vices is one of trending technologies of the 21st century.
This book provides information on the most useful
nanosurfaces that are being employed for the develop-
ment of nanosensor. Critical aspects, such as the type of
nanomaterials, their conjugation with biomolecules,
methods of signal collections, applications, challenges,
advantages and limitations, and commercial aspects
have been covered. The book is written for readers from
different related backgrounds including nanotech-
nology, biochemistry, environmental science, chemistry,
material science, and biomedical engineering.
Contents
1 Carbon-Based Nanomaterials for the
Development of Sensitive Nanosensor
Platforms, 1
Monika Nehra, Neeraj Dilbaghi,
Ashraf Aly Hassan and Sandeep Kumar
2 Advances in the Synthesis and
Development of Two-Dimensional
Transition-Metal Dichalcogenide-Based
Nanosensor Platforms, 27
Sanjeev Kumar Bhardwaj, Neha Bhardwaj,
Deepanshu Bhatt, Poonma Malik and
Akash Deep
3 Conducting Polymers and
Metal-Organic Frameworks as
Advanced Materials for Development
of Nanosensors, 43
Moondeep Chauhan, Sanjeev Kumar Bhardwaj,
Gaurav Bhanjana, Rajeev Kumar,
Neeraj Dilbaghi, Sandeep Kumar and
Ganga Ram Chaudhary
4 Synthesis and Production of Different
Biomolecules for Application in the
Sensing of Environmental Pollutants, 63
Manpreet Kaur, Madhu Khatri and
Sharvan Sehrawat
5 Bioconjugation of Different
Nanosurfaces With Biorecognition
Molecules for the Development
of Selective Nanosensor Platforms, 79
Satish K. Tuteja, Ruchi Mutreja,
Suresh Neethirajan and
Sven Ingebrandt
6 Development of Disposable Sensor
Strips for Point-of-Care Testing of
Environmental Pollutants, 95
Satish Kumar Pandey, Girish Chandra Mohanta
and Parveen Kumar
7 Advantages and Limitations
of Environmental Nanosensors, 119
Rajnish Kaur, Sandeep Kumar Sharma and
S.K. Tripathy
8 Commercial Aspects of Biosensors
for Diagnostics and Environmental
Monitoring, 133
Samadhan B. Patil, Valerio F. Annese
and David R.S. Cumming
Index, 143
xi
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CHAPTER 1
Carbon-Based Nanomaterials for the
Development of Sensitive Nanosensor
Platforms
MONIKA NEHRA • NEERAJ DILBAGHI • ASHRAF ALY HASSAN •
SANDEEP KUMAR
INTRODUCTION
Carbon is one of the most commonly found ele-
ments in nature and its understanding has reached
new levels, from macroscopic to nanoscale, with
continuous advancement in nanotechnology.
The nanostructures of carbon in their different
forms have been applied in diverse fields such as
field emission displays, nanoelectronics, energy
conversion and storage, biological and chemical
sensors, and theranostics. In the 21st century,
owing to their extraordinary properties in terms
of structural perfection, carbon nanomaterials
have in fact led general science to many advanced
avenues. The structural properties of carbon mate-
rials have inspired the synthesis of novel nanoma-
terials with similar symmetries and structures, e.g.,
fullerenes, nanotubes, nanodots, and graphene.
Carbon atoms have the ability to form robust
mutual covalent bonds in different hybridization
states such as sp, sp2, and sp3. Carbon atoms also
interact with nonmetallic elements leading to
the formation of a wide range of structures from
small molecules to long chains. The major classi-
fication of carbon materials (such as carbon, dia-
mond, and graphite) is based on the way of
interconnection between carbon atoms, e.g., tetra-
hedral sp3 atom configuration in case of diamond
and hexagonal sp2 carbon atom configuration in
case of graphene monolayers. However, mixed
states also exist and lay the basis for nanocrystal-
line diamond, diamond-like carbon, and
Advances in Nanosensors for Biological and Environmental Analysis. https://doi.org/10.1016/B978-0-12-817456-2.00001-2
Copyright © 2019 Elsevier Inc. All rights reserved.
amorphous carbon. The carbon nanoallotropes
belonging to same group or same arrangement
of carbon atoms have common properties; how-
ever, there are significant differences because of
their different sizes and shapes.
A summary of carbon nanomaterials with
different morphologies but unique chemical
properties is shown in Fig. 1.1 (Yan et al., 2016).
They can be classified according to their structural
dimensionality as, e.g., (1) 0D nanostructures
(fullerenes, carbon dots, nanodiamonds, etc.),
(2) 1D nanostructures (carbon nanotubes
[CNTs]/carbon nanofibers [CNFs], etc.), and (3)
2D nanostructures (graphene, graphene nanorib-
bons, etc.). Diamond, a metastable state of car-
bon, consists of a 3D cubic lattice with 3.57 Å
lattice constant along a CeC bond length of
1.54 Å (Sque et al., 2006). In contrast, graphite
possesses a 2D layered structure having a CeC
bond length of 1.42 Å (Baughman et al., 1987).
In graphene, the layers are single atom thick and
interact through van der Waals forces having
3.35 Å interlayer spacing. Graphite corresponds
to the most thermodynamically stable form of car-
bon at room temperature. Graphene is commonly
referred as a 2D building block of sp2 hybridized
carbonaceous nanomaterials; it can be rolled
and/or distorted in order to form CNTs and fuller-
enes. The first successfully synthesized carbon
nanomaterial was C60 (also known as buckmin-
sterfullerene), through laser ablation of graphite
1
2 Advances in Nanosensors for Biological and Environmental Analysis
FIG. 1.1 Broad family of carbon nanomaterials. (Adapted from Yan, Q.L., Gozin, M., Zhao, F.Q.,
Cohen, A., Pang, S.P., 2016. Nanoscale 8, 4799e4851. Reprinted with permission from RSC.)
under helium flow (Kroto et al., 1985). However,
some reports also exist on the development of
even-numbered carbonaceous clusters before the
development of C60, but these clusters were un-
suitable for characterization because of their large
size distributions (Rohlfing et al., 1984). Fuller-
enes are viewed as the 0D form of graphitic carbon
and also referred as irregular sheets of graphene
that are curled in the form of a sphere via penta-
gons incorporation in the structure. Furthermore,
CNTs were isolated as an offshoot during the syn-
thesis of fullerene. The elongation of fullerene in
one dimension assumes the structure of CNTs
with high aspect ratios (e.g., from 102 to 107).
Different synthesis methods have been devel-
oped for the production of both single-walled
CNTs (SWCNTs) and multiwalled CNTs
(MWCNTs). These include arc discharge (Arora
and Sharma, 2014), chemical vapor deposition
(CVD) (Kumar et al., 2017a), and high-pressure
carbon monoxide method (Liu et al., 2011a).
The initial development of graphene was done
by its growth on insulating substrates by Geim
and coworkers (Novoselov et al., 2004). In the
current perspective, graphene can be referred as
the mother of all graphitic carbon. Graphene has
further been investigated as monolayer to a few-
layered nanomaterial depending on the thickness
requirement in a particular application (Liu et al.,
2018).
Carbon nanomaterials can possibly cover the
characteristics of different substances on the earth,
such as hardest to softest materials, insulators to
semiconductors and further to superconductors,
and fully light-absorbing to completely trans-
parent materials. The superiority of carbon nano-
materials is basically due to their hardness,
radiation characteristics, optical properties, elec-
tric conductivity, chemical resistance, heat resis-
tance, electric insulation, and surface/interface
properties in comparison to many other materials.
CARBON-BASED NANOMATERIALS FOR
NANOSENSOR DEVELOPMENT
Nanosensors are becoming a crucial part of mod-
ern lifestyle, particularly in healthcare due to the
demand of point-of-care devices, personalized
medicine, and cheaper and reliable diagnostic
tools. Carbon nanomaterials have motivated re-
searchers to implement them as ideal transduc-
tion materials mainly because of their geometry,
fast electron transfer kinetics, wide potential win-
dow, low residual current, fluorescent properties,
and readily renewable surfaces (Jariwala et al.,
2013). Voluminous research efforts have been
dedicated to employ carbon nanomaterials in
the development of highly sensitive and selective
nanosensors.
Fabrication of Sensing Platforms
The device architecture of electrochemical nano-
sensors can be broadly classified into two main
categories: (1) the conventional three-electrode
 CHAPTER 1 Carbon-Based Nanomaterials for Nanosensor Development 3

FIG. 1.2 (A and B) A schematic representation of functionalized carbon nanomaterialebased

electrochemical biosensors. (Adapted from Yang, Y., Yang, X., Yang, Y., Yuan, Q., 2018a.
Carbon 129, 380e395. Reprinted with permission from Elsevier.)

setup and (2) the chemiresistive/field-effect tran-
sistor (FET) setup. The three-electrode setup is
commonly used for potentiometric, ampero-
metric, and impedimetric nanosensors that
comprise working, counter, and reference elec-
trodes for detection of different analytes
(Fig. 1.2) (Yang et al., 2018a). Carbon nanomate-
rials have been popularly used to modify the sur-
face of glassy carbon electrode to develop them as
a working electrode. As such, the electrochemical
sensing techniques are particularly helpful in un-
derstanding the behavior of analytes and their
associated electrochemical reaction mechanisms.
The analyte species that can undergo redox transi-
tions on glassy carbon electrodes can be detected
via different categories of electrochemical tech-
niques, e.g., amperometry and potentiometry.
The transfer of ions takes place through a conduc-
tive electrolyte medium. Carbon nanomateriale
based electrodes offer several benefits in terms of
wide potential window, good electrocatalytic ac-
tivities, and chemical inertness during redox reac-
tions. In electrochemical biosensors, carbon
nanomaterials also serve as a platform for biomol-
ecule immobilization, thereby improving electro-
chemical transduction (Hu et al., 2016).
Chemiresistive/FET sensors have attracted
considerable attention because of their enormous
benefits in terms of their fast response time, seam-
less integration with electronic manufacturing
processes, potential for miniaturization, and
parallel sensing (Bandodkar et al., 2016; Barbaro
et al., 2012). Carbon nanostructures, such as
CNTs, have been reported as excellent electrode
material for gas sensors in order to detect the gas
molecules, with high sensitivity, low device cost,
and fast response time even at room temperature
(Dube et al., 2015). In a similar manner, the
detection of gas molecules through graphene is
based on the change in their electric conductivity
as a result of the formation of surface adsorbates.
These surface adsorbates can work as either do-
nors or acceptors depending on their chemical na-
ture, preferential adsorption sites, and the
surrounding environment (Varghese et al., 2015).
The different formats of FET sensors may be
listed as ion-sensitive FET, unmodified comple-
mentary metal-oxide semiconductor, extended-
gate FET, floating-gate FET, and dual-gate FET
(Ramnani et al., 2016). Carbon nanomaterials
have been found very useful to function as the
functional channel in chemiresistor/FET nanosen-
sor configuration; for example, both the tubular
geometry of CNTs and the planar geometry of gra-
phene ensure maximum exposure of surface
atoms for the binding of target analyte molecules
to the electrode material. The Debye length (lD) is
a measure of field penetration into bulk materials
and also causes significant modulation in the elec-
tronic properties of electrode materials upon
exposure to the analytes. The lD is comparable
to the dimensions of the carbon nanostructures,
4 Advances in Nanosensors for Biological and Environmental Analysis
which ensures label-free sensing of analytes with
relatively low limits of detection and high sensi-
tivities. Carbon nanomaterials in an FET configu-
ration can detect multiple analytes concurrently
(Cullen et al., 1990). The fabrication of
graphene-FET devices requires the bulk produc-
tion of graphene films via different synthesis tech-
niques such as the CVD method, which offers
control over crystallinity, grain size, and number
of layers over the desired substrate (Srivastava
et al., 2010). CNTs can be synthesized as cylindri-
cal tubes by rolling up single and/or multiple gra-
phene sheets. The nature of CNTs, either metallic
or semiconducting, depends on their chirality
(armchair, zigzag, or chiral) and the diameter of
the tubes (Dresselhaus et al., 2004). For instance,
armchair SWCNTs are metallic in nature and,
therefore, these cannot be used for fabrication of
FET nanosensors.
Surface Functionalization of
Nanocarbon Electrodes
The surface chemistry of electrode materials has
significant importance with respect to their inter-
action with analytes present in complex solu-
tions/matrices. The surface functionalization of
carbon nanomaterials has been reported through
covalent/noncovalent interactions and/or decora-
tion with some inorganic nanomaterials (Liu
et al., 2015; Karimi et al., 2015; Balasubramanian
and Burghard, 2005). Carbon nanomaterials with
multiple functional groups at their surface/edges
can satisfy the specific requirements of different
kinds of sensors with specific intermolecular inter-
actions. For instance, graphene plays a significant
role in electrochemical sensing application
because of its high carrier mobility, exceptional
electrochemical properties (electron transfer
rates), optical properties, and structural character-
istics. Furthermore, its properties can be
controlled/modulated through adoption of suit-
able preparation methods and or functionaliza-
tion to generate specific target-sensing properties
(Kybert et al., 2014). Likewise, the presence of
functional groups such as carboxyl and amine
makes CNTs compatible in their conjugation
with biomolecules as well as other materials
such as metallic nanoparticles (Kong et al., 2001;
Gao et al., 2012). For covalent functionalization,
carboxylic (eCOOH) groups can be introduced
on the edge planes and sidewalls of the carbon
nanomaterials through oxidation. Some forms of
carbon such as reduced graphene oxide have
readily available eCOOH groups. As a matter of
concern, the covalent functionalization can deteri-
orate the sp2 structure of the honeycomb lattice of
carbon while also inducing some defects on their
surface (such as disruption in p-electronic
network), ultimately resulting in deflation of elec-
tronic properties of the materials. Noncovalent
functionalization can be a solution to this limita-
tion, which does not influence the intrinsic struc-
ture of carbon nanomaterials and also maintains
their electronic and mechanical properties
(Georgakilas et al., 2012).
The functionalization of carbon nanomaterials
helps in improving their dispersibility, biocom-
patibility, and sensing properties. In literature,
carbon nanomaterials have been used in two ma-
jor ways to modify the biosensing electrodes: (1)
modification of the bulk material, for example,
mixing the electrode material with carbon paste
and (2) modification of the electrode surface, for
example, preparation of films on premade elec-
trode through CVD or any other method. The
incorporation of carbon paste in electrode mate-
rials (e.g., other nanomaterials) enhances the
overall electrocatalytic properties and supports
improved signal transduction (Fig. 1.3) (Huang
et al., 2006). Furthermore, the application of car-
bon paste in immobilizing the enzymes can offer
protection of these protein molecules from the
external environment, while also rendering better
stability and durability in comparison to the sys-
tem having enzyme immobilized over the bare
electrode surface (Akyilmaz et al., 2017).
APPLICATIONS OF NANOCARBON
ELECTRODES FOR SENSING OF
DIFFERENT ANALYTES
In the recent years, the nanosensor platforms have
gained significant research interest for sensitive
detection of a wide variety of analytes including
both chemical (such as dopamine, ascorbic acid,
uric acid, and norepinephrine) and biological
 CHAPTER 1 Carbon-Based Nanomaterials for Nanosensor Development 5

FIG. 1.3 A schematic representation of the different strategies used to design functionalized
carbon nanotube electrodes. SWCNTs, single-walled carbon nanotubes. (Adapted from Huang,
X.J., Im, H.S., Yarimaga, O., Kim, J.H., Jang, D.Y., Lee, D.H., Kim, H.S., Choi, Y.K., 2006. Journal of
Electroanalytical Chemistry 594, 27e34. Reprinted with permission from Elsevier.)

(such as airborne bacteria, folic and pantothenic
acid, protein, and mycotoxins). The use of carbon
nanomaterials as the functional electrode surface
of nanosensor platform offers several advantages
in terms of good electrocatalytic activity, enhanced
interfacial adsorption properties, fast electron
transfer kinetics, and high biocompatibility in
comparison to traditional materials. There are
different strategies for incorporation of these
nanomaterials into electrochemical sensors, e.g.,
drop casting (Kaniyoor et al., 2009), direct growth
on a substrate (Wang et al., 2009), polymer-based
coatings (Barsan et al., 2015), use of binders such
as Nafion or dihexadecyl hydrogen phosphate
(Liao et al., 2015), and screen printing (Chen
et al., 2016). In comparison to drop casting or
dip coating, the direct growth of the carbon nano-
materials over electrode surface provides more ho-
mogeneous coating as well as supports the batch
fabrication of nanosensors (Gooding, 2005).
Furthermore, polymer-based coatings can aid in
the physical and chemical properties of the carbon
nanomaterials as well as their dispersion for depo-
sition. Additional incorporation of metallic nano-
particles in polymer matrix is sometimes desired
to maintain the requisite level of electrode conduc-
tivity (Chun et al., 2010).
Detection of Heavy Metal Ions
The quantification/detection of heavy metal ions
(including Hg2þ, Cd2þ, Cu2þ, Pb2þ, As3þ, etc.) is
a major concern among chemists, environmental-
ists, and biologists due to their toxic nature as well
as prolonged persistence in the biosphere. The
heavy metal ion contamination has mainly been
caused by the fast industrial development and
related activities such as electroplating, battery
manufacturing, mining, and smelting. The metal-
lurgical industries release various harmful toxins
into our environment, which include nonbiode-
gradable chemicals and heavy metals. The exis-
tence of these contaminants, especially heavy
metal ions in water bodies, has direct influence
over the health of living systems (Bhanjana
et al., 2015, 2017). The conventional methods
for the analysis of heavy metal contamination
are based on different techniques such as atomic
absorption spectroscopy (AAS) (Luo et al.,
2015), atomic emission spectroscopy (Zhang
et al., 2014), inductively coupled plasma mass
spectrometry (ICP-MS) (Li et al., 2015), and
X-ray fluorescence spectrometry (Sitko et al.,
2015). These techniques are very costly and not
appropriate for on-site analysis. Moreover, these
approaches can only quantify the total amount
of heavy metals and it is not possible to analyze
the bioavailable concentrations that are accessible
to the living bodies. Electrochemical detection us-
ing nanosensors is among the simple, accurate,
and sensitive methods for the detection of metal
contamination in food and environment. The
electrochemical sensing techniques offer several
6 Advances in Nanosensors for Biological and Environmental Analysis
benefits in terms of low cost, portability, high
sensitivity, short analytical time, and easy adapt-
ability for in situ detections (Bhanjana et al.,
2016). The working electrode of the three-
electrode electrochemical system can be modified
with nanomaterials for improving the sensitivity
of the nanosensors (Cheng et al., 2018). Such
nanosensors are then operated by recording
changes in their potential, current, electrochemi-
cal impedance, and electroluminescence upon
the recognition of an analyte (Simpson et al.,
2018).
Among nanomaterials, carbon nanomaterials
are most interesting materials as adsorbents/
preconcentrator agents or transducer materials
used in the development of nanosensors. The car-
bon nanomaterials can respond to both organic
and inorganic analytes. The functionalization of
carbon nanomaterials with biological recognition
elements (e.g., enzymes, antibodies, DNA, or mi-
croorganisms) enables highly specific and sensi-
tive sensing of metal ions (Wanekaya et al.,
2008). In particular, DNA-based nanosensors
have gained much research interest in the recent
years for the detection of heavy metal ions owing
to their stability in biological pH environments
(Primo et al., 2015). Wen et al. (2018) have re-
ported the application of DNA-modified gra-
phene oxide/Prussian blue nanoparticles for
arsenite detection. The interaction of graphene ox-
ide with 50 -thiolate-labeled (GT)21-ssDNA facili-
tated the generation of Prussian blue
nanoparticles on gold electrode surface. The
(GT)21-ssDNAecontaining arsenite recognition
sequence offered excellent specificity for arsenite
detection (detection limit down to 0.058 ppb)
in real water samples. DNAzyme-functionalized
carbon nanostructureebased biosensors have
also been developed for some other metal ions
including Pb2þ, Hg2þ, and Cu2þ (Zhou et al.,
2016).
The utility of carbon nanomaterials has also
been demonstrated in the development of sensi-
tive chemosensors. For example, Lu et al. (2018)
proposed a novel 3D honeycomb structure of
N-doped carbon nanosheet framework decorated
with bismuth nanoparticles (Bi-NCNF) for selec-
tive and sensitive electrochemical sensing of
Pb2þ and Cd2þ (Fig. 1.4). The proposed system
offered a detection limit of 0.04 and 0.02 mg L1
for Pb2þ and Cd2þ, respectively.
In many reported cases, the performance of car-
bon nanomaterialebased nanosensors for detect-
ing heavy metal ions has been successfully
validated with standard techniques such as AAS
and ICP-MS. A summary of the recently developed
glassy carbonebased nanosensors (electrode sur-
face modified with different carbon nanostruc-
tures) for heavy metal detection is provided in
Table 1.1, which is intended to acquaint the
readers about the main design and performance
parameters of these related technologies. The
coupling of nanosensitive platform with carbon
nanomaterials has resulted in high sensitivity,
fast response, multianalyte detection, and low
detection limits. In spite of numerous benefits,
there are a few challenges associated in this area:
(1) accurate detection of metal ions in biological
samples (involving blood, saliva, urine, etc.), (2)
issue of false-positive signal interference and
chemical fouling, (3) detection of heavy metal
ions in their complex form, and (4) continuous
monitoring of water resources for detection of
metal ions (Gumpu et al., 2015). As per the
commercialization perspective, the research ef-
forts should be directed toward reusability, mass
production, and system integration.
Detection of Food Additives and
Pesticide Residues
The innovation in food industry is increasing at an
immense speed in terms of development and
application of pesticides, food additives, and ma-
terials for food protection/processing/coating/
packaging. Pesticides are excessively used in agri-
cultural activities to enhance the production yield
by controlling pests, insects, weeds, etc. Food ad-
ditives are introduced to deliver functional attri-
butes in order to improve food life/safety.
Undesirably high concentrations of food additives
and accidental contamination of veterinary drug
residues and pesticides in foodstuff and water re-
sources have become issues of major health
concern. The pesticide residues are very toxic sub-
stances and can lead to several health issues (such
as cholinergic dysfunction) in both humans and
 CHAPTER 1 Carbon-Based Nanomaterials for Nanosensor Development 7

FIG. 1.4 A schematic layout for fabrication of 3D N-doped carbon nanosheet framework
decorated with bismuth nanoparticles (Bi-NCNF) followed by their application for electrochemical
detection of Pb2þ and Cd2þ. EG, ethylene glycol; GCE, glassy carbon electrode; NPs, nanoparticles;
PVP, polyvinylpyrrolidone. (Adapted from Lu, Z., Dai, W., Lin, X., Liu, B., Zhang, J., Ye, J., Ye, J.,
2018. Electrochimica Acta 266, 94e102. Reprinted with permission from Elsevier.)

animals. The analysis of various types of contam-
inations (i.e., toxic food additives, veterinary drug
residues, and pesticides) that can affect our food
samples is usually carried out using methods
such as high-performance liquid chromatography
(HPLC) (Wahed et al., 2016), HPLC-mass spec-
trometry (Hoffmann et al., 2017), gas
chromatography-mass spectrometry (Jiménez-
Salcedo and Tena, 2017), and capillary electro-
phoresis (Omar et al., 2017). The development
of nanosensors has been reported based on elec-
trochemical biosensing of contaminants in food-
stuff and water. The electrochemical biosensors
offer fast operation and high selectivity, sensi-
tivity, and reproducibility (Rotariu et al., 2016;
Herzog et al., 2008).
The incorporation of carbon nanostructures en-
hances the loading of bioreceptors on the elec-
trode surface, apart from providing high
stability. Carbon nanoparticles also serve as a
relay for transfer of electrons between biomole-
cules and the electrode. Elyasi et al. (2013) re-
ported a Pt/CNT nanocompositeemodified
ionic liquid carbon electrode for specific determi-
nation of Sudan I (a coloring agent) with an excel-
lent limit of detection (0.003 mM). The
immobilization of an enzyme (from Inga edulis)
onto a carbon paste electrode containing
MWCNTs and Nafion has been reported to pro-
vide a highly selective and sensitive detection of
tert-butylhydroquinone (TBHQ, an antioxidant),
with quantification and detection limits of 1.25
and 0.41 mg L1, respectively (de Oliveira et al.,
2014). This sensing method can offer determina-
tion of TBHQ in commercial salad dressing sam-
ples with an acceptable level of accuracy (e.g.,
the relative error limiting to 5.4%). Likewise, a
gold-modified carbon paste electrode has been
demonstrated for electrochemical sensing of syn-
thetic dyes (e.g., Sunset Yellow and tartrazine) in
 8
TABLE 1.1
List of Different Carbon Nanomaterials Used in Glassy Carbon ElectrodeeBased Nanosensors of Heavy Metal Ions.
Metal Ion Details of the Electrode Interface Limit of

Advances in Nanosensors for Biological and Environmental Analysis

Detected Detection Mechanism Material/s Detection Sensitivity References
1 3
Cadmium Anodic stripping Cysteine functionalized SWCNTs 0.3 mg L (9.7  2.5)  10 Gutierrez et al.
voltammetry mA mg L1 (2017)
Differential pulse Reduced graphene oxide-chitosan/ 0.01 mg L1 d Guo et al. (2016)
anodic stripping ply-L-lysine nanocomposites
voltammetry
Square wave anodic Phenylsulfonic groupegrafted 0.08 mM d Chen et al. (2018)
stripping voltammetry MWCNTs with dye molecules
Square wave Calixarene-functionalized reduced 2  1011 M d Göde et al. (2017)
voltammetry graphene oxide
Cyclic voltammetry Ruthenium(II)-textured graphene 2.8 nM 3.43 mA mM1 Gumpu et al. (2017)
oxide nanocomposite
Arsenic Differential pulse Gold-coated, boron-doped diamond 0.005 mg L1 9.7  2.5 mA mg L1 Song and Swain
anodic stripping thin film (2007)
voltammetry
Anodic stripping Gold nanoparticleemodified carbon 0.9 mg L1 0.0176 nA mg L1 Carrera et al. (2017)
voltammetry fiber ultramicroelectrodes
Cyclic voltammetry Clay-modified carbon paste 5e40 mg L1 d Tiwari and Lee
(2017)
Flow injection analysis Gold nanoparticleedecorated 11.4 mg L1 218.1 nA mg L1 Nellaiappan et al.
carbon nanofiber-chitosane (2018)
modified carbon
Cyclic voltammetry DNA-modified graphene oxide/ 0.058 mg L1 d Wen et al. (2018)
Prussian blue nanoparticles
Fluorescence Carbon quantum dots 0.086 mg L1 d Pooja et al. (2017)
spectrophotometry
Square wave anodic Amine-functionalized graphene 0.162 mg L1 130.631 mA Yang et al. (2017)
stripping voltammetry oxideedecorated gold nanoparticles mg L1 cm2
Cyclic voltammetry Ruthenium(II)-textured graphene 2.3 nM 2.11 mA mM1 Gumpu et al. (2017)
oxide nanocomposite
 Mercury Anodic stripping CNT/asymmetric 0.36 nM d Selvan and
voltammetry N4 tetradentate Schiff base ligand Narayanan (2018)
N,N0 -bis(pyrrole-2-ylmethylene)-2-
aminobenzylamineecoated graphite
Cyclic voltammetry Polypyrrole/carbon nanofiber 0.05 mg L1 d Oularbi et al. (2017)
nanocomposite

CHAPTER 1 Carbon-Based Nanomaterials for Nanosensor Development

Cyclic voltammetry Ruthenium(II)-textured graphene 1.6 nM d Gumpu et al. (2017)
oxide nanocomposite
Lead Square wave anodic Nitrogen-doped and thiol groupe 0.3 mg L1 d Li et al. (2016)
stripping voltammetry grafted MWCNTs
Anodic stripping CNT/asymmetric 1.1 nM d Selvan and
voltammetry N4 tetradentate Schiff base Narayanan (2018)
ligand N,N0 -bis(pyrrole-2-
ylmethylene)-2-aminobenzylaminee
coated graphite
Square wave Carbon paste electrode 3.8 pM 20683 A L mol1 Alizadeh et al. (2017)
voltammetry impregnated with ion-imprinted
polymer and MWCNTs
Square wave Calixarene functionalized reduced 2  1011 M d Göde et al. (2017)
voltammetry graphene oxide
Cyclic voltammetry Ruthenium(II)-textured graphene 1.41 nM d Gumpu et al. (2017)
oxide nanocomposite
Differential pulse Reduced graphene oxide-chitosan/ 0.02 mg L1 d Guo et al. (2016)
anodic stripping ply-L-lysine nanocomposites
voltammetry
Copper Square wave anodic Graphene quantum dots/gold 0.05 nM 3.69 mgA/nM Ting et al. (2015)
stripping voltammetry nanoparticles
Differential pulse Biochar-modified carbon paste 4.0  107 M d Oliveira et al. (2015)
anodic stripping
voltammetry
Chromium Cyclic voltammetry Manganese oxide nanoflakes/ 0.3 mM 18.7 nA mM Salimi et al. (2015)
MWCNTs/chitosan nanocomposites
Linear sweep Gold nanoparticleedecorated 5.4 mg L1 1.1 nA mg L1 Tu et al. (2018)
voltammetry screen-printed carbon electrode

CNT, carbon nanotube; MWCNTs, multiwalled CNTs; SWCNTs, single-walled CNTs.

9
10 Advances in Nanosensors for Biological and Environmental Analysis

commercially available soft drinks (Ghoreishi
et al., 2012).
The detection of pesticide residues (organo-
phosphate, organochlorine, carbamates, pyre-
thrum, etc.) is generally carried out using gas or
liquid chromatography. This technique is highly
sensitive and selective, but requires expensive
instrumentation and skilled personnel. Electro-
chemical biosensors are regarded as the potential
choice for pesticide detection with desired selec-
tivity, sensibility, and reproducibility. For
example, a screen-printed electrode has been
modified with carbon nanoparticles. After subse-
quent immobilization with butyrylcholinesterase,
the electrode could detect the presence of para-
oxon in spiked wastewater samples. This biosensor
electrode was stable up to 78 days at room temper-
ature under dry conditions. The inhibition of the
enzyme activity was directly correlated with the
concentration of paraoxon (up to 30 mg L1).
Many other label-free nanosensor platforms have
also been designed for the detection of pesticides.
For instance, Li et al. (2018a) have reported the
application of acetylcholinesterase (AChE)-immo-
bilized fluorescence carbon dots for dual-mode
(fluorometric as well as colorimetric) detection
of organophosphate pesticides (Fig. 1.5). This
sensor functioned on the principle of generation
of fluorometric and colorimetric responses as a
result of the formation of a yellow reaction prod-
uct (5-thio-2-nitrobenzoic acid [TNBA]) after the
decomposition of 5,5-dithiobis(2-nitrobenzoic
acid), which was triggered by the reaction of
AChE with acetylthiocholine. TNBA functioned
as a powerful absorber for quenching the fluores-
cence of carbon dots. Hence, this method could
be used for the detection of pesticides, as the inhi-
bition in enzyme activity of AChE led to the resto-
ration of fluorescence signal alongside a reduction
in the absorbance intensity.
Research efforts have also been directed toward
the development of nonenzymatic nanosensors
for pesticides. Hsu et al. (2017) reported the
peroxidase-like activity of Ag nanoparticlee
decorated oxidized MWCNTs, which could be
exploited in the fluorometric assay of dimethoate.
This method offered good selectivity for
sensing dimethoate in a linear range of
0.01e0.35 mg mL1 from lake water and fruit
samples. Facure et al. (2017) reported a novel
enzyme-free impedimetric electronic tongue
(e-tongue) comprising graphene hybrid nano-
composites for sensing the trace levels of organo-
phosphate pesticide mixture (i.e., malathion and
cadusafos). This e-tongue system detected the
presence of organophosphate at nanomolar con-
centrations (as low as 0.1 nM) in real samples.
The use of reduced graphene oxide, containing

FIG. 1.5 Dual signalebased (fluorescence and colorimetry) detection of organophosphate

pesticides using acetylcholinesterase (AChE)-immobilized fluorescence carbon dots (CDs).
DTNB, 5,50 -dithiobis-(2-nitrobenzoic acid); OPs, organophosphates; TNBA, 5-thio-2-nitrobenzoic
acid. (Adapted from Li, H., Yan, X., Lu, G., Su, X., 2018a. Sensors and Actuators B: Chemical 260,
563e570. Reprinted with permission from Elsevier.)
 CHAPTER 1 Carbon-Based Nanomaterials for Nanosensor Development
the residual oxygenecontaining functional
groups, offered the realization of a sensing plat-
form with high conductivity. The functional
groups behaved as active sites for the sensing of
pesticide residues and increased the sensitivity of
the system. Table 1.2 lists some important carbon
nanomaterialebased electrochemical nanosen-
sors used for the detection of food additives and
pesticide residues.
Detection of Bacterial Pathogens or
Viruses
Bacterial pathogens and viruses are potential
threats to human health. Therefore the develop-
ment of tools for simple and fast detection or
diagnosis of bacterial pathogens is crucial to con-
trol their outbreak and to ensure appropriate ther-
apeutic treatments. The existing methods of
detection (including polymerase chain reaction
and enzyme-linked immunosorbent assay) are
sensitive enough and selective, but they involve
complex steps of sample preparation and take
long assay times (Berg et al., 2015; Nguyen
et al., 2017). Several evidences have been pro-
jected in the literature about the potential useful-
ness of biosensors for the analysis of bacterial
pathogens. Carbon nanomaterialemodified
glassy carbon (Dekanski et al., 2001) and pyro-
lytic graphite electrode (Banks and Compton,
2005) have been usefully exploited in this context.
In one of the important reports, Gheith et al.
(2006) suggested that lateral currents in highly
conductive SWCNT multilayers can cause the
stimulation of neural cells. Therefore CNTs have
a future in biomedical devices in which electrically
responsive cells, such as the muscle cells, endo-
crine cells, can be examined at even single-cell
level. CNTs can be used in systematic biosensors
in order to monitor the immune response in
case of immunodeficient patients (Fadel et al.,
2008). These studies led to the development of
cancer antibodyefunctionalized SWCNTs for the
thermal ablation of tumor cells (Kostarelos
et al., 2009). The selective nature of the treatment
makes SWCNTs promising for biosensing applica-
tions as antibody-functionalized SWCNTs track
only cancer cells upon irradiating them with
infrared energy. The high sensitivity and selectivity
11
of carbon-based electrochemical biosensors facili-
tate the sensing of the pathogens even in the com-
plex sample matrices (Kumar et al., 2015;
Mokhtarzadeh et al., 2017). Bhaisare et al.
(2016) reported the fluorescent detection of path-
ogenic bacteria, i.e., Staphylococcus aureus and
Escherichia coli (E. coli), in urine sample through
their strong adhesion over amine-functionalized
magnetic nanoparticles decorated with carbon
dots. Carbon nanomaterials can also be function-
alized to support the immobilization of various
selective ligands, single-stranded DNA, and even
other types of nanoparticles. For instance, CNTs
immobilized with an antimicrobial peptide
(clavanin A) have been reported to offer effective
and sensitive detection of Klebsiella pneumoniae,
Enterococcus faecalis, E. coli, and Bacillus subtilis in
concentration of 102e106 colony-forming unit
(CFU) mL1 (Fig. 1.6) (Andrade et al., 2015).
The antibody-conjugated SWCNTs have also
been proposed for highly specific and sensitive
electrochemical immunosensing of S. aureus
with a low detection limit of 13 CFU mL1
(Bhardwaj et al., 2017). The biosensors were
able to quantify S. aureus in spiked milk samples
even in the presence of other bacteria, e.g., E. coli
B, Staphylococcus epidermidis, and B. subtilis.
The recognition and quantification of cyano-
bacterial bloom are of great importance, as it
may cause many structural and functional distur-
bances to the liver because of the inhibition of
protein phosphatase (type 1 and 2A) (Zamyadi
et al., 2016). Besides complex and expensive chro-
matography and protein phosphatase inhibition
assays (Catanante et al., 2015), the electrochemi-
cal immunosensors have emerged as viable op-
tions due to their high sensitivity, simplicity, low
cost, and easy miniaturization (Zhang et al.,
2010b).
Carbon nanomaterials have also been inte-
grated in FET designebased electrochemical
immunosensors for real-time identification of
pathogens (Yamada et al., 2016). Thiha et al.
(2018) developed a lab-on-chip device for label-
free chemiresistive biosensing of Salmonella typhi-
murium using carbon nanowires functionalized
with aptamers. The device offered highly sensitive
and specific detection of Salmonella, with a
 12
TABLE 1.2
List of Different Carbon NanomaterialeModified Glassy Carbon ElectrodeeBased Voltammetric Nanosensors of Food
Additives and Pesticides.

Advances in Nanosensors for Biological and Environmental Analysis

Details of Modification of
Electrode by Carbon Food Samples Limit of
Nanomaterials Analyzed Target Analytes Linear Detection Range Detection References
(A) NANOSENSORS FOR FOOD ADDITIVES
Pt/CNT nanocomposites with Chilli sauce, chilli Sudan I 0.008e600 mM 0.003 mM Elyasi et al.
1-methyl-3-butylimidazolium powder, tomato (2013)
bromide as binder sauce, strawberry
sauce
Nanocomposite comprising Chilli powder, ketchup Sudan I 0.05e2 mM 0.03 mM Mo et al.
hydrophobic ionic liquid sample (2010)
([P6,6,6,14][NTf2]), MWCNTs,
and cationic gemini
surfactants
MWCNTs-ionic liquids gel Soft drink samples Sudan I 0.005e15 ppm 0.001 ppm Chailapakul
Sudan II 0.005e20 ppm 0.001 ppm et al. (2008)
Sudan III 0.05e20 ppm 0.005 ppm
Sudan IV 0.10e25 ppm 0.025 ppm
Immobilized peroxidase Commercial salad tert- 1.65e9.82 mg L1 0.41 mg L1 de Oliveira
enzymes (Inga edulis Mart.) in dressing samples Butylhydroquinone et al. (2014)
carbon paste containing
MWCNTs and mineral oil, and
Nafion
Gold nanoparticleemodified Commercially Sunset Yellow 1.0  107 to 3.0  108 M Ghoreishi
carbon paste available soft drinks Tartazine 2.0  106 M 2.0  109 M et al. (2012)
5.0  108 to
1.6  106 M
MWCNTs Commercially Ponceau 4R 25 mg L1 to 15 mg L1 Zhang et al.
available soft drinks Allura Red 1.5 mg L1 25 mg L1 (2010a)
50 mg L1 to
0.6 mg L1
Boron-doped diamond Commercial food Butylated 0.60e10 mM for 0.14 and Medeiros
products hydroxyanisole both 0.25 mM et al. (2010)
and butylated
hydroxytoluene
 (B) NANOSENSORS FOR PESTICIDES
Molecular imprinting polymer Wastewater samples Atrazine 1.0  1012 M to 1.5  1013 M Yola and Atar
and platinum nanoparticles/ 1.0  1010 M (2017)
carbon nitrite nanotubee
based nanocomposite
MWCNT-functionalized Standard solution Dopamine 1e70 mM 0.15 mM Mercante

CHAPTER 1 Carbon-Based Nanomaterials for Nanosensor Development

polyamide 6/poly(allylamine et al. (2015)
hydrochloride)
Butyrylcholinesterase- Wastewater samples Paraoxon Up to 30 mg L1 5 mg L1 Arduini et al.
immobilized carbon black (2015)
nanoparticles
AChE-immobilized reduced Standard solution Malathion 7.98 to 2.0  103 pg mL1 4.14 pg mL1 Zhao et al.
graphene oxide-Au Carbaryl 4.3 to 1.0  103 pg mL1 1.15 pg mL1 (2015)
nanoparticles-b-cyclodextrin
and Prussian blue-chitosan
nanocomposite
AChE controlled fluorescence Standard solution Paraoxon 0e0.5 mg mL1 0.4 ng mL1 Li et al.
carbon dots (2018a)
Ag nanoparticleemodified Lake water and fruit Dimethoate 0.01e0.35 mg mL1 0.003 mg mL1 Hsu et al.
oxidized MWCNTs samples (2017)
Screen-printed carbon Real cucumber and Carbofuran 1e250 mM 0.22 mM Jirasirichote
electrode modified with rice samples et al. (2017)
graphene oxide and Au
nanoparticles
Praseodymium molybdatee Water and vegetable/ Methyl parathion 0.002e1.55 mM and 1.8 nM Karthik et al.
decorated reduced fruit samples 1.55e114 mM (2018)
graphene oxide

AChE, acetylcholinesterase; CNT, carbon nanotube; MWCNTs, multiwalled CNTs.

13
14 Advances in Nanosensors for Biological and Environmental Analysis

FIG. 1.6 Schematic fabrication of a carbon nanotube (CNT)-based biosensor for the detection of
pathogenic bacteria: (1) formation of a cysteine self-assembled monolayer over bare gold surface,
(2) activation of electrode surface for coupling of CNTs, (3) binding of antimicrobial peptide
clavanin A (ClavA) on CNT surface, and (4) interaction of electrode surface with analyte bacteria.
(Adapted from Andrade, C.A., Nascimento, J.M., Oliveira, I.S., de Oliveira, C.V., de Melo, C.P.,
Franco, O.L., Oliveira, M.D., 2015. Colloids and Surface B: Biointerfaces 135, 833-839. Reprinted
with permission from Elsevier.)

FIG. 1.7 Fabrication of a microfluidic chip, with the application of graphene oxide
(GO) nanosheetewrapped multiwalled carbon nanotubes (MWCNTs). This chip was used for the
detection of Salmonella typhimurium bacterial cells. EDC-NHS, 1-ethyl-3-(3-dimethylaminopropyl)-
carbodiimide-N-hydroxysuccinimide; StAb, Salmonella typhimurium antibody. (Adapted from Singh,
C., Ali, M.A., Reddy, V., Singh, D., Kim, C.G., Sumana, G., Malhotra, B.D., 2018. Sensors and
Actuators B: Chemical. 255, 2495e2503. Reprinted with permission from Elsevier.)

detection limit of 10 CFU mL1 with reduced
sample volume requirement (5 mL). Singh et al.
(2018) reported a novel microfluidic chip devel-
oped on a graphene oxide wrapped carboxyl
MWCNT platform for the detection of S. typhimu-
rium, with a detection limit of 0.376 CFU mL1
(Fig. 1.7). This biosensor offered negligible inter-
ference even in the copresence of E. coli O157:
H7. Such microfluidic chipebased biosensing
platforms offer important feature in terms of sam-
ple volume miniaturization, reduced processing
time, and reduced use of expensive chemicals.
These microfluidic immunosensors can also be
applied for the detection or quantification of
other pathogens by immobilizing the electrode
surface with suitable bioreceptors. Future research
efforts are needed to further elaborate intricate
sensor designs and fabrication processes of carbon
nanomaterialebased FET devices and related bio-
sensors. Table 1.3 lists some important examples
of carbon nanomaterialebased biosensors for
pathogens or viruses.
TABLE 1.3
List of Different Carbon NanomaterialeBased Bionanosensors for Detection of Bacterial Pathogens or Viruses.
Details of
Modification of Bacterial Type of
Electrode by Carbon Pathogens Biosensor Limit of
Nanomaterials or Viruses Signal Bioreceptor Used Linear Range Detection References

CHAPTER 1 Carbon-Based Nanomaterials for Nanosensor Development

(A) BACTERIAL PATHOGENS
Quantum dots (green- Vibrio Fluorescence DNA sequence 50e106 25 CFU mL1 and Duan et al.
and red-emitting)- parahaemolyticus CFU mL1 35 CFU mL1 (2015)
amorphous carbon and Salmonella
nanoparticles typhimurium
SWCNTs Staphylococcus Electrochemical Antibody d 13 CFU mL1 Bhardwaj
aureus et al. (2017)
Gold tungsten wires S. aureus and Electro- Streptavidin and 102e105 102 CFU mL1 Yamada
coated with PEI and Escherichia coli chemical bio-tinylated CFU mL1 et al. (2016)
SWCNTs K-12 immune- antibodies
sensors in FET
design
Amine-functionalized S. Fluorescence d d 3  102 and Bhaisare
magnetic iron oxide aureus and E. coli 3.5  102 et al. (2016)
nanoparticles CFU mL1
decorated with carbon
dots
Polypyrrole/Au E. coli O157:H7 Electrochemical Antibody 3  101 to 30 CFU mL1 Güner et al.
nanoparticles/ 3  107 (2017)
MWCNTs/chitosan CFU mL1
nanocomposite
CNTs Klebsiella Electrochemical Antimicrobial 102e106 102 CFU mL1 Andrade
pneumoniae, peptide clavanin A CFU mL1 et al. (2015)
Enterococcus (ClavA)
faecalis, E. coli, and
Bacillus subtilis
Carbon nanowires S. typhimurium Chemiresistive Salmonella-specific 10 CFU mL1 d Thiha et al.
aptamer probes (2018)
Graphene-wrapped E. coli O157:H7 Electrochemical Monoclonal 10e108 3.8 CFU mL1 Pandey
copper(II)-assisted antibodies CFU mL1 et al. (2017)

15
cysteine hierarchical
structure
Continued
 16
TABLE 1.3
List of Different Carbon NanomaterialeBased Bionanosensors for Detection of Bacterial Pathogens or Viruses.dcont'd
Details of

Advances in Nanosensors for Biological and Environmental Analysis

Modification of Bacterial Type of
Electrode by Carbon Pathogens Biosensor Limit of
Nanomaterials or Viruses Signal Bioreceptor Used Linear Range Detection References
Carbon dote S. aureus Fluorescence S. aureus antibody 1  102 to 1  104 30 CFU mL1 Yang et al.
encapsulated CFU mL1 (2018b)
organosilica
nanocapsules
(B) VIRUSES
Graphene oxide HIV Electrochemical 38-Base synthetic 1.0  1012 to 1.1  1013 M Hu et al.
sequence (ssDNA) 1.0  106 M (2012)
Graphene quantum HBV Electrochemical Probe DNA 10 e500 nM 1 nM Xiang et al.
dots (2018)
MWCNTs/polypyrrole AIV Electrochemical DNA aptamer 5.0  1012 M 4.3  1013 M Liu et al.
nanowires/gold to 1.0  109 M (2011b)
nanoparticles
Graphene oxide DNA (H1V1) and Fluorescence ss DNA 0.1 pM to 10 nM 0.1 pM Bi et al.
protein (thrombin) (2012)
MWCNTs Influenza virus Electrochemical DNA sequence d 0.5 nM Tam et al.
(type A) (2009)
Fullerene- MTB Electrochemical DNA sequence 1015 M to 3.3  1016 M Chen et al.
functionalized 109 M (2018)
polyaniline-doped
tufted CNTs
Porous reduced HPV Electrochemical RNA (Sc5-c3) 0.2e2 ng mL1 0.1 ng mL1 Chekin et al.
graphene oxide/ Aptamers (2018)
molybdenum disulfide

AIV, avian influenza virus, CNTs, carbon nanotubes; FET, field-effect transistor; HBV, hepatitis B virus; HIV, human immunodeficiency virus; HPV, human papilloma virus;
MTB, Mycobacterium tuberculosis; MWCNTs, multiwalled CNTs; PEI, polyethylenimine; ssDNA, single-stranded DNA; SWCNTs, singe-walled CNTs.
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the 24th they were in Lancaster. On the 28th they entered
Manchester, imposed a heavy requisition on the town, and were
joined by some bold spirits among the younger men. On the 1st of
December, Charles Edward entered Macclesfield. On the 4th that
young prince, with 7,000 men, entered Derby, and losing heart, left it
on the 6th, in retreat northward. On the 9th they were again in
Manchester. On Christmas day, they entered Glasgow;—‘a very
indifferent Christmas-box to the inhabitants,’ according to Ray; and
on the 30th of December, Carlisle, in which a rebel garrison was
stationed, surrendered at discretion to the young Duke of
Cumberland. Therewith ended the rebel invasion of England. This
succession of events greatly influenced the metropolis.
When the storm was threatening, and also when it burst,
clergymen in town, and probably in the country also, opened their
Bibles, questioning them as oracles, and interpreting the answers,
according to their respective temperaments. One good man, whose
eye fell upon the words of Jeremiah,—‘Evil appeareth out of the
North, and great destruction,’ proclaimed to his congregation that the
words had reference to the Pretender and his invasion of England.
This application of the text has been pronounced to be as absurd as
that of the ‘casting down of Mount Seir’ to the overthrow of the
French.
For what London was feeling and saying in this FEELING IN
eventful year, 1745, search must be made in the LONDON.
correspondence of the time. The letters of Walpole,
for instance, begin the year with the expression of a fear, if Marshal
Belleisle, who had been made a prisoner at Hanover, where he was
travelling without a passport, should be allowed to go at large, on his
word, in England, as it was reported he would be, that mischief
would come of it. ‘We could not have a worse inmate!
HOPES AND
So ambitious and intriguing a man, who was the FEARS.
author of this whole war, will be no bad general to
head the Jacobites on any insurrection.’ The marshal was, at first,
kept ‘magnificently close’ at Windsor, but as he cost the country
there 100l. a day, he was sent to Nottingham, to live there as he
pleased, and for the Jacobites to make what they could of him. For
the moment, the Duke of Beaufort was more dangerous than the
marshal. The duke was a declared, determined and an unwavering
Jacobite, and led the party against Court and Ministry. At the end of
April there was ‘nothing new.’ In May came the honourable
catastrophe of Fontenoy, and the dishonourable sarcastic song
made by Frederick, Prince of Wales, on his brother, the Duke of
Cumberland’s glorious failure. Alluding to the duke, Walpole writes,
‘All the letters are full of his humanity and bravery. He will be as
popular with the lower class of men as he has been for three or four
years with the low women. He will be the soldiers’ ‘Great Sir,’ as well
as theirs. I am really glad; it will be of great service to the family if
any one of them come to make a figure.’ Walpole saw the necessity
of having a hero opposed to the young Chevalier. One was sorely
needed. Belleisle must have enchanted the Jacobites by his publicly
asserting that this country was so ill-provided for defence, he would
engage, with five thousand scullions of the French army, to conquer
England. Walpole owned his fears. He was depressed by our
disasters in Flanders, the absence of the king from England, that of
ministers from London, ‘not five thousand men in the island, and not
above fourteen or fifteen ships at home. Allelujah!’
The Ministry released Belleisle, who went incog.
HORACE
about London, and was entertained at dinner by the WALPOLE’S
Duke of Newcastle at Claremont, and by the Duke of IDEAS.
Grafton at Hampton Court. Walpole compares the idle
gossip about the French coming over in the interest of the Pretender,
and the neglect of all defence, with the conduct of the Londoners on
a report that the plague was in the city. ‘Everybody went to the house
where it was, to see it!’ If Count Saxe, with ten thousand men, were
to come within a day’s march of London, ‘people will be hiring
windows at Charing Cross and Cheapside to see them pass by.’
Walpole, in truth, was as indifferent as he accused his
contemporaries of being. If anything happened to the ship, what was
that to him, he was only a passenger. He playfully described himself
as learning scraps from ‘Cato,’ in case of his having to depart in the
old, high, Roman fashion. Recollecting that he is writing on the
anniversary of the accession of the House of Brunswick, he tacks a
joyous P.S. to one of his letters, in the words, ‘Lord! ’tis the first of
August, 1745, a holiday that is going to be turned out of the
almanack!’ When the Government did begin to prepare for serious
contingencies, Walpole expressed his belief of their being about as
able to resist an invasion as to make one.
When the young Chevalier, stealing a march upon DIVISIONS IN
Cope, was approaching Edinburgh, Walpole wrote FAMILIES.
from London, that people there had nothing to
oppose, ‘scarcely fears.’ Lord Panmure, who had got his title through
the attainder of his elder brother, for the ’15 affair, and the Duke of
Athol, who owed his dukedom to the attainder of his elder brother,
the Marquis of Tullibardine (who was then with Prince Charles
Edward), for the same affair, left London, in order to raise forces in
Scotland for the defence of the Hanoverian succession. Panmure,
with other Scotch lords, raised a few men. Athol returned to London
to announce his inability to get together a force for such a purpose;
and when it was proposed to send the Duke of Argyle,
Maccullummore excused himself on the singular ground that there
was a Scotch Act of Parliament against arming without authority.
There was a scene in a London house that might furnish a subject to
a painter. The young Whig Duke of Gordon, at an interview with his
Jacobite uncle, told the latter that he must go down to Scotland and
arm his men. ‘They are in arms,’ was the reply. ‘You must lead them
against the rebels.’ ‘They will wait on the Prince of Wales,’ rejoined
the uncle, who alluded to the young Chevalier. The duke flew in a
passion, but the uncle pulled out a pistol, and said it was in vain to
dispute. As Walpole here drops the curtain over this scene, we may
suppose that the little domestic drama was carried no further.
As news reached town that the rebellion did not COURT AND
grow in the North, and that there was no rising in CITY.
England to help it, Walpole wrote, ‘Spirit seems to rise
in London.’ The king, or as Walpole calls him, ‘the person most
concerned,’ took events with heroic imperturbability, or stupid
indifference. Charles Edward had repealed the union between
England and Scotland. King George believed himself to be, and
likely to remain, King of Great Britain, as before. When ministers
proposed to him any measures with reference to the outbreak, his
Majesty only answered, ‘Pooh! don’t talk to me about that stuff!’ It is
not, therefore, to be wondered at that ministers did not summon
Parliament. They had nothing either to offer or to notify. The London
merchants, on the other hand, were zealous and liberal in opening
subscriptions for raising more troops.
In this time of uncertainty, if not trouble, the VARYING
professional patriot came to the surface in the person OPINIONS.
of Alderman Heathcote. At a City meeting, that sham
Jacobite proposed to supplant a loyal address to the king by a
demand for a redress of grievances; ‘but not one man seconded
him.’ Walpole, with all his affected indifference and pretence of
indifference on the part of the public, betrays the true temper of the
metropolis, when he says, ‘We have great hopes the Highlanders will
not follow him [Charles Edward] so far [into England], very few of
them could be persuaded the last time to go to Preston.’ And
something of the general uneasiness may be traced in Walpole’s
intimation to Montagu, of his dislike of becoming ‘a loyal sufferer in a
thread-bare coat, and shivering in an antechamber at Hanover, or
reduced to teach Latin and English to the young princes at
Copenhagen. Will you ever write to me in my garret at
Herrenhausen?’ With all this simulation of light-heartedness, Walpole
writes seriously enough, from Arlington Street, ‘Accounts from
Scotland vary perpetually, and at best are never very certain.... One
can’t tell what assurances of support they may have from the
Jacobites in England ... but nothing of the sort has yet appeared....
One can hardly believe that the English are more disaffected than
the Scotch, and among the latter no persons of property have joined
them.’ The temper of the Government is also described in a few
words: ‘Lord Granville and his faction persist in persuading the king
that it is an affair of no consequence; and, for the Duke of
Newcastle, he is glad when the rebels make any progress in order to
refute Lord Granville’s assertions.’ London was as delighted as
Walpole with the naval watch kept in the Channel, and with the spirit
of the English nobility adding, or promising to add, regiments to the
regular force, to which, however, they gave little or no additional
strength. He who had been laughing and calling others laughers,
confesses in September that his own apprehensions were not so
strong as they had been. ‘If we get over this I shall believe that we
never can be hurt, for we never can be more exposed to danger.
Whatever disaffection there is to the present family, it plainly does
not proceed from love to the other.’
This sense of security was seriously shaken when
LONDON WIT.
London got the news of the victory gained by Charles
Edward’s army near Preston Pans over General Cope. It was known
to ‘the Papists’ on Sunday, but the Government received no official
news till Tuesday! ‘The defeat,’ says Walpole, ‘frightens everybody
but those it rejoices.’ Then he, who had alternately laughed and
trembled, affected the philosopher, and pretended that he could
endure without emotion the ruin which he had foreseen. ‘I shall suffer
with fools, without having any malice to our enemies, who act
sensibly from principle and interest.’ When London found that no
advantage was taken of the victory by the victors, London and
Walpole resumed their good spirits. The latter referred to the
subjoined advertisement as a proof that there was more wit in
London than in all Scotland. ‘To all jolly Butchers.—My dear Hearts!
The Papists eat no meat on Wednesdays, Fridays, Saturdays, nor
during Lent! Your friend, John Steel.’ Such wit can hardly have
alarmed the Papists, but it may have had something to do with a
report which followed,—that they intended to rise and massacre their
enemies in London. It was taken seriously. All the Guards were
ordered out, and the Tower was closed at seven o’clock. When the
murrain among the cattle broke out, it was absurdly said that the
Papists had poisoned the pools! The Papists however did send
money contributions from London to Charles Edward. It is wonderful
that the highwaymen did not intercept the bearers, and make them
deliver.
When Parliament met in October, the attendance THE
was thin. The Pretender had threatened to confiscate PARLIAMENT.
the property of all Scotch members who should
attend, and to make it treason for English members to do so! Yet
there were Jacobites present, and they opposed the address as well
as the suspension of the Habeas Corpus. A proposal to enquire into
the causes of the progress of the Rebellion was shelved by a
majority of 194 to 112. Most of the former felt, it is said, ‘the
necessity of immediately putting an end to it, and that the fire should
be quenched before we should enquire who kindled or promoted it.’
There were many whose fears had been great because of the
greatness of the stake. These rejoiced when the Guards left London,
roaring as they marched from the parade that they would neither
give nor receive quarter. Walpole affirmed that the army adored the
duke who was to be their commander. On the other hand, ‘the
Calligulisms’ of the Prince of Wales brought on him a general
contempt. The working men were, almost without exception, loyal.
When there was an idea of the king going to the encampment at
Finchley, the weavers offered him a guard of a thousand men. It was
in the caricature of the march to Finchley that Hogarth exhibited the
baser side of his character. The wrath of the king at the painter’s
insult to the defenders of their country was well-founded. The
popular feeling was not with the artist. When the prisoners captured
in the ‘Soleil’ were brought to London, it was difficult to save them
from being cruelly handled. Among them was Mr.
THE
Radcliffe who had been condemned to death with his RADCLIFFES.
brother, Lord Derwentwater, in 1716, and Mr.
Radcliffe’s son, who was at first suspected of being Charles
Edward’s brother, Henry. This suspicion very nearly cost the young
captive his life, more than once, on the road. ‘He said that he had
heard of English mobs, but could not conceive they were so
dreadful; and wished he had been shot at the battle of Dettingen,
where he had been engaged. The father, whom they call Lord
Derwentwater, said, on entering the Tower, that he had never
expected to arrive there alive. For the young man, he must only be
treated as a French captive; for the father it is sufficient to produce
him at the Old Bailey, and prove that he is the individual person
condemned for the last Rebellion; and so to Tyburn.’ Walpole
reflected the general feeling of the metropolis which had been kept
so long in a state of suspense, sometimes concealing it under
indifference, at others not caring to conceal its own fears.
Noblemen’s servants were not rendered particularly cheerful in
October, by a report that they were to be made to serve as soldiers,
receiving their pay both as warriors and flunkeys. The soldiery were
so ill off, that civilians bestirred themselves for their relief. The
Quakers contributed ten thousand woollen waistcoats to keep them
warm. The Corporation of London gave them as many blankets and
watchcoats. King George, when everything else had been provided,
paid for their shoes out of his privy purse!
There was a desire to bring the matter to a THE LONDON
conclusion as cheaply as possible. The ‘Craftsman’ JACOBITES.
recommended that the Pretender should be ‘cut off,’ if
that end could be compassed. A hope was expressed that the nation
would not be taxed for encountering a ‘ragged, hungry rabble of
Yahoos of Scotch Highlanders,’ with the cost of an expedition
against an Alexander. There would be no use, it was said, in
constructing an apparatus fit for hunting a lion,—for the catching of a
rat. The rats were, nevertheless, troublesome, if not formidable. The
London Jacobites were ostentatiously ecstatic when news reached
town of the defeat of Cope. King George’s proclamation had ordered
an observation of silence on public affairs. When the removal of
notorious Papists from the city had been contemplated, ‘What will
you get,’ loudly asked the Jacobites of the Romish Church, ‘by
driving us ten miles out of town? We shall then form a camp, and
you will find us a much more formidable body than we now appear to
be while dispersed among you.’ Remove the Papists! why, the Duke
of Newcastle had shown so little disposition that way, that his French
cook still ruled supreme in the kitchen of his mansion in Lincoln’s Inn
Fields! There were others like the duke; and, what trust could be
placed in a militia formed out of servants of noblemen whose lackeys
went to mass in the private chapels of the Ambassadors? Yet,
something must be done. It was in vain that proclamations, signed
‘James III.’ and ‘Charles Edward,’ were burnt at the Royal Exchange,
by the common hangman, in presence of the sheriffs. New
documents were circulated as widely as ever. If they were not cried
in the street, there were other ways of bringing them before the
public. In the dusk of the evening, a baker would rest with his basket,
or a street porter with his burthen, against a wall. Inside the basket,
as inside the porter’s burthen, there was a little boy who had all the
necessary contrivances to enable him to paste a Jacobite paper on
the wall. In the morning, London was found to be covered with
treasonable documents, and for some time, magistrates were driven
almost mad in trying to account for the appearance of papers which
seemed to have got on the walls by inexplicable and undiscoverable
means.
On Sunday, October 6th, half of riotous London THE
followed the Foot Guards to Lincoln’s Inn Fields, and VENETIAN
applauded them as they entered the old abandoned AMBASSADOR
play-house, which was converted by them into a .
barrack. A couple of days later all uproarious London was on the
river, or in the streets, to witness the grand entry of the Venetian
Ambassador. His Excellency and suite came in state barges from
Greenwich to the Tower, and he passed in greater state still of coach
and cavalry, from the Tower to his noble residence in Thrift Street,
Soho, as Frith Street was once called. The greetings which
welcomed him on the part of those who hailed in his person an ally
of King George, were as nothing compared with the unceasing
thunder of hurrah-ing which saluted him as he rode, next day, in
greatest state of all, to have audience of the sovereign. When his
wife, as soon as she was installed in her house, in Soho, gave a
masquerade which made everybody forget the perils of the time,
there may have been people who distrusted her Popish principles,
but no one doubted her taste, or objected to her politics.
Yet was there every now and then a cry of alarm. MONARCH
Messengers had seized a waggon load of cutlasses, AND
and they were slow to believe that the weapons were MINISTERS.
not ordered by Pope and Pretender for the slaughter
of Church-and-King men. They proved to have come to London in
due course of trade. Persons who believed, nevertheless, in the
existence of a conspiracy were gratified by the seizure of some Irish
priests who indulged in the utterance of seditious words in public
places. Zealots, of Jacobite proclivities, even had the assurance to
contradict loyal preachers in their own pulpits, but afterwards found
themselves in durance for their boldness. One day, Sir Robert
Ladbroke astounded the Duke of Newcastle by rushing in to his
office and announcing that he had had anonymous warning to leave
his house, as Jacobite insurgents meant on a certain night to set fire
to the city. Everywhere guards were doubled, and there was much
fear. The king showed none. He stood for a couple of hours on the
terrace at St. James’s, overlooking the park, to witness the
manœuvres and the ‘march past’ of six regiments of trained bands,
and he had an air as if he and danger were strangers. Moreover the
Londoners were in a fever of delight with the other king,—the king of
the city. On Lord Mayor’s day, Sir Richard Hoare was resolved that if
he was to be the last Protestant Lord Mayor of London, people
should remember him. On October 29th (old Lord Mayor’s day), he
went from Guildhall to the Court of Exchequer, in the grandest coach
ever seen, and he was accompanied by ‘a large body of associated
gentlemen out of Fleet Street, completely clothed,’ as one, indeed,
might expect they would be!
From the ‘Letters of the First Earl of Malmesbury, NEWS IN
his Family and Friends,’ it is to be gathered that the PRIVATE
Londoners were kept in ignorance of Sir John Cope’s LETTERS.
defeat, till private letters arrived by which the whole
disgrace was revealed. Lord Shaftesbury writes that Pitt’s respectful
motion to advise the king to recall the troops (chiefly cavalry) from
Flanders, and use them in suppressing the rebellion, was lost, or
‘eluded,’ by putting the previous question—ayes 136, noes 148; in
which division young Horace Walpole was in the minority, and old
Horace Walpole on the other side; ‘not a Tory on either side
speaking. I leave you to reflect on this proceeding, though I think a
very little reflection will suffice.’ People who had letters from the
north ran with them from house to house, some, even, to St.
James’s, to impart their contents, and small regard was had to any of
the newspapers. But individuals could be as untrustworthy as the
papers. Old Lord Aylesbury was conspicuous as a ‘terror-raiser.’ He
says ‘the Papists poisoned his grandfather, and made a fool of his
father, and that he believed all the Jacobites would turn to Popery
very easily, if it was to prevail.’ The old lord was to be seen daily
going to Court, ‘to show his public attachment to the Revolution of
1688.’
 With respect to the king reviewing the Trainbands
THE LONDON
from the garden wall of St. James’s, recorded in a TRAINBANDS.
preceding page, Lord Shaftesbury writes, Oct. 26th,
1745: ‘This morning the Trainbands were reviewed by his Majesty.
By what I saw of them myself, I can venture to affirm that,
notwithstanding their deficiency in smartness, from want of an
uniform, which may possibly expose them to the ridicule of some of
our very fine gentlemen, they would make an honourable and
effective stand, if needful, for their religion and liberties. They are
really, upon the whole, good troops.’ The Rev. William Harris gives a
fuller account of the same incident to his brother: ‘I was to-day
accidentally in St. James’s Park, when the City Militia were reviewed
by the King, who stood on the terrace in his own garden, attended by
the Duke, Lord Stair, Dukes of Dorset, Newcastle, Bolton, and
several others of the nobility. It was a most tedious affair, I make no
doubt, to his Majesty; for the London men made but a shabby
appearance, and there could be no great entertainment in seeing
them. Their officers were well enough, and to these, as they made
their salute, passing by under the terrace, his Majesty returned
everyone the compliment by pulling off his hat. There were no less
than six regiments, and I suppose it might be near two hours before
they all had gone in review before his Majesty.’
Conflicting reports flew about, but the SCENES AT
discouragement was not very profound, and the COURT.
birthday drawing-room, on the 30th of October, was
as gay and brilliant as if there were no rebellion afoot. The reverend
writer of the letter quoted above was present, and he describes to
Mrs. Harris the silks of the princesses, the brocades and damasks of
the ladies, and the blaze of Lady Cardigan, who excelled as to
jewels, having on a magnificent solitaire, and her stomacher all over
diamonds. There, too, fluttered the Prince of Wales in light blue
velvet and silver; the Duke of Cumberland strolled about with a little
more gold lace than usual on his scarlet uniform; and Lord Kildare
outdid all other fine and loyal gentlemen present, ‘in a light blue silk
coat, embroidered all over with gold and silver, in a very curious
manner, turned up with white satin, embroidered as the other; the
waistcoat the same as his sleeves.’ But the grandest and quaintest
figure there was the Venetian ambassadress, who had gone in state
from Frith Street, Soho, to the intense delight of the ‘mob.’ This lady
‘drew most people’s attention by somewhat of singularity both in her
air and dress, which was pink, all flounced from top to bottom, with
fringe of silver interspersed. She looks extremely young, has the
French sort of behaviour, and was much taken notice of and spoke
to by all the Royal Family in the Circle.’ The most soberly-dressed
man there was the king himself. He wore a deep blue cloth coat and
waistcoat trimmed with silver, and was as good humoured and
gracious as if Johnny Cope was carrying all before him in the north.
The regiments which arrived in London, in
THE KING’S
November, from Fontenoy, kept the metropolis in SPEECH TO
some commotion, till they were pushed forward, after THE GUARDS.
brief rest, to the midland counties. While they were
receiving tents and arms at the Tower, the Duke of Cumberland had
his headquarters at St. James’s, whence orders were issued (says
Mr. Maclachlan—‘Order Book of the Duke of Cumberland’) of the
most minute character and detail.
The king has been accused of indifference to passing events, and
of having only reluctantly allowed the Duke of Cumberland, who
served so nobly with him at Dettingen, to command the army against
the young Chevalier. Perhaps, what seemed indifference was
confidence in the result. There is evidence, however, that he was not
without anxiety at this critical juncture. In Hamilton’s ‘History of the
Grenadier Guards,’ there is the following description of a scene at St.
James’s, quoted from Wraxall. The incident described is said to have
occurred at the military levee held by the king, previous to the
Guards marching to the north: ‘When the officers of the Guards were
assembled, the king is said to have addressed them as follows:
“Gentlemen, you cannot be ignorant of the present precarious
situation of our country, and though I have had so many recent
instances of your exertions, the necessities of the times and the
knowledge I have of your hearts, induce me to demand your service
again; so all of you that are willing to meet the rebels hold up your
right hand; all those who may, from particular reasons, find it
inconvenient, hold up your left.” In an instant, all the right hands in
the room were held up, which so affected the king, that in attempting
to thank the company, his feelings overpowered him; he burst into
tears and retired.’
While this scene was being acted at St. James’s, ASPECTS OF
Mrs. Elizabeth Montagu, then residing in Dover SOCIETY.
Street, wrote to Dr. Freind: ‘People of the greatest
rank here have been endeavouring to make the utmost advantage of
the unhappy state of their country, and have sold the assistance it
was their duty to give. Self-interest has taken such firm possession
of every breast, that not any threatening calamity can banish it in the
smallest instance. There is no view of the affair more melancholy
than this.... Everything is turned to a job, and money given for the
general good is converted too much to private uses.... There were
some exceptions. Almost all our nobility,’ she writes, ‘are gone to the
army, so that many of the great families are in tears, and indeed it
makes the town appear melancholy and dismal.’ There were
exceptions in this case. ‘Let it be said, to the honour of our sex, there
are no dramas, no operas, and plays are unfrequented; and there is
not a woman in England, except Lady Brown, that has a song or
tune in her head; but indeed her ladyship is very unhappy at the
suspension of operas.’ On the night this letter was written, Mrs.
Clive’s Portia, at Drury Lane, was unattractive, in spite of her
imitations of eminent lawyers, in the trial scene; and Mrs. Pritchard’s
Lappet was equally unavailing to bring the public to witness ‘The
Miser,’ at Covent Garden. But Rich’s three nights of the ‘Beggars’
Opera,’ for the benefit of the patriotic fund, produced happy results.
From Mrs. Cibber down to the candle-snuffers, all sacrificed their pay
with alacrity.
As correct news of the condition of London in the FRENCH
latter half of the year, it was stated in the French NEWS OF
papers that insurrectionary undertakings prevailed; LONDON.
that the principal shops were closed; that suspected
peers were under arrest; that an attempt had been made to murder
the Archbishop of Canterbury, and that the Tower had been captured
by a Jacobite mob, who had liberated nearly three hundred
prisoners! Every quidnunc in Paris turned to the article ‘London’ in
the ‘Gazette de France,’ to read with avidity of the closing of great
firms, the breaking of the chief banks, and the bewilderment of the
king on his reaching the capital from Hanover. The ‘Gazette’ had no
doubt of the crowning of James Stuart in Westminster Abbey during
the Christmas holidays; and, perhaps, hoped for the appearance of
‘the Elector of Hanover’ on Tower Hill!
On Friday, the 5th December 1745, it is undeniable ANXIETY AND
that London was shaken into terror and consternation CONFIDENCE.
by the news of the arrival of Charles Edward on the
Wednesday at Derby. It was long remembered as ‘Black Friday.’
‘Many of the inhabitants,’ says the Chevalier de Johnstone, in his
‘Memoirs of the Rebellion,’ ‘fled to the country with their most
precious effects, and all the shops were shut. People thronged to the
Bank to get payment of its notes; and it only escaped bankruptcy by
a stratagem. Payment was not indeed refused; but as they who
came first were entitled to priority of payment, the bank took care to
be continually surrounded by agents with notes, who were paid in
sixpences in order to gain time. Those agents went out at one door
with the specie they had received, and brought it back by another; so
that the bonâ fide holders of notes could never get near enough to
present them, and the bank by this artifice preserved its credit, and
literally faced its creditors.’
This, of course, was imaginary. The metropolis recovered its
tranquility. The king, on his side, regained his equanimity. At a levee,
held in December, his Majesty and Lord Derby disputed pretty loudly
as to the numbers of the rebels. ‘Sir,’ said Lord Derby, who had just
arrived from Lancashire, whoever tells you the rebels are fewer than
10,000 deceives you;’ which was, as Mr. Harris writes, thought to be
a pretty strong expression for his Lordship to use to the king. At a
court held a day or two later, Sir Harry Liddel, just from the north,
was asked by his Majesty what Sir Harry held the rebel force to be?
He answered about 7,000, to which estimate the king seemed to
assent; but this did not prevent the whole Court and City from falling
into the utmost panic again before the end of December. The
alternation of hope and fear however passed suddenly into
confidence, when, as the year ended, news reached the London
coffee-houses that young Cumberland was likely to turn the tide of
rebel success. Carlisle was evidently on the point of surrendering,
and this important event took place at the close of the year 1745.
Down to that close, traitors were as closely looked for in London
as rebels were now pursued in their retreat. Whether through
delicacy or ignorance, the style in which a successful ‘take’ of traitors
was made was comically mysterious. For example, in this month of
December, the papers announced that ‘A Musician who resided
some years in London as a foreign Nobleman, and an Irish
Comedian who has acted five years on the English Stage, were
committed to the Marshalsea for High Treason.’
In this eventful year, Jacobite Johnson was quietly JOHNSON
engaged on his Dictionary. Aloof from the fray, he AND LORD
could not forbear flinging a stone on an ex-Jacobite GOWER.
who had ratted. When he came to the word
‘renegade,’ he remembered Lord Gower’s abandonment of the old
Jacobite interest, for place at Court; and his prejudice prompted him
to make Lord Gower infamous for ever, by adding his name to the
vocabulary of slang. ‘When I came to the word renegade,’ he said to
Boswell, ‘after telling that it meant “one who deserts to the enemy; a
revolter,” I added, “sometimes we say a Gower.” Thus it went to the
press; but the printer had more wit than I, and struck it out.’ Another
distinguished man was looking on events with an indifference which
seems affectation. ‘I expect no good news,’ writes
BOLINGBROKE.
Bolingbroke to Marchmont, in September, ‘and am
therefore contented to have none. I wait with much resignation to
know to what Lion’s paw we are to fall.’
 CHAPTER VI.

(1746.)
n the first day of the year 1746, the parole given at the
Duke of Cumberland’s headquarters, at Carlisle, was
‘London.’ He well knew the joy the metropolis would
soon receive. Part of the general orders then issued
was thus expressed: ‘The Rebels that have or shall be
taken, either concealed or attempting their escape, or in any ways
evading the Capitulation, to be immediately put in Irons, in order to
be hanged.’ After publishing this order, the duke, leaving Hawley to
cross the border in pursuit of the young Chevalier, returned to
London. There was great fear of a French invasion; and the duke
was to have the command of a southern army to repel it. The
invaders were expected in Suffolk, and the Jacobites hoped that the
expectation would be realised. They often reported it as an
established fact. Fielding’s Jacobite squire in ‘Tom Jones’ is made to
exclaim to the landlord of the inn at Upton: ‘All’s our own, boy! ten
thousand honest Frenchmen are landed in Suffolk. Old England for
ever! Ten thousand French, my brave lad! I am going to tap away
directly!’
Carlisle being recaptured, London breathed again,
WAR
and considered its past perils and future prospects. CRITICISM.
The fire-side critics of the war concluded, as the Earl
of Shaftesbury did with his friends in London, ‘that eminus, we
exceeded the ancients, but cominus we fell below them; and this
was the result of our having, it was said, learnt the art of war from
the Spaniards. We never used bayonets in our service till after the
battle of Steinkirk, in King William’s time. Now the Highlanders by
their way of attacking (new to our troops) make a quick impression
and throw our men into confusion. This I imagine to be the principal
reason of the Highlanders gaining such repeated advantages.’
Walpole wrote from Arlington Street: ‘With many other glories, the
English courage seems gone too.’ Yet the old spirit was not extinct.
When the Ministry tried to prevent Mr. Conway going as aide-de-
camp with the Duke of Cumberland, on the ground of his being in
Parliament, the duke informed the young soldier of the fact. ‘He burst
into tears,’ says Walpole, ‘and protested that nothing should hinder
his going—and he is gone.’
Without being uneasy at the idea of invasion the
BREAKING AN
Government took precautions in case of emergency. OFFICER.
It was announced that at the firing of seven guns at
the Tower, answered by the same number in St. James’s Park,
soldiers and officers should repair to previously named places of
rendez-vous. No crowds were allowed to assemble. A race between
two pairs of chairmen, carrying their chairs, round the Park, having
caused a large mob to gather within hail of the palace, was stopped
in mid career by a file of musqueteers, who drove competitors and
spectators into the neighbouring streets. When the park was pretty
well cleared, Captain Stradwick was brought out and ‘broke,’ for
desertion. Why he was not shot, as the king said he deserved to be,
was owing to some influence which seemed to be stronger than the
king himself. Perhaps, as a consequence, the common rank and file
who had deserted were allowed their lives, but at dear cost. They got
a thousand lashes, administered half at a time, in Hyde Park; and on
the off days the mob were regaled with the sight of soldiers getting
their five hundred stripes for speaking evil of his Majesty in their
drink.
Meanwhile, the river one day suddenly swarmed REBEL
with galleys, which picked up numbers of ‘useful PRISONERS.
fellows to serve the king.’ Even the City taverns were
broken into, and there similar seizure was made, but not without
occasional mortal frays, in which there was much promiscuous
shooting, and a forcible carrying off of other ‘useful fellows,’ who
were hurried on board tenders, and thence sent to sea. There was
hardly time for sympathy. A few women in the streets and by the
river side filled the air with shrieks and clamour, but they were not
much heeded. London became full of expectancy of the renewal of
an old and a rare spectacle. The Carlisle prisoners were on their
road to town. There were nearly four hundred of them, including
about threescore officers. Those who were able to march were tied
in couples, and two dragoons had charge of ten prisoners, one
leading them by a rope from his saddle, the other ‘driving them up.’
The captured officers were mounted, but their arms and legs were
tied. Batches of other captive men were sent by sea; some seem to
have been exceptionally treated. The papers announced the arrival
of ‘six coaches and six,’ filled with rebel prisoners, under an escort of
horse and foot. The London gaols were emptied of felons, who were
transferred to distant prisons, in order to ‘accommodate’ the captives
till they were otherwise disposed of. But the most important arrival
was that of the hero himself. The Duke of Cumberland, fresh from
Carlisle, reached London on a dark January morning, at seven
o’clock. Much was made of his having passed only ‘one night in bed,’
in that now easy day’s journey. The duke came with modesty and
great becomingness. Shortly after reaching St. James’s he went
straight to the little Chapel Royal. At the subsequent usual Sunday
drawing-room, there was brilliancy with the utmost gaiety, such as
had not been witnessed for many a year. After a few days the duke
returned northward, departing with the same modesty that had
marked his arrival. He left at one in the morning, but even at that
ghostly hour, and in that inclement season, he was done honour to
by a crowd which he could scarcely penetrate, whose torches were
flashed to their brightest, and whose voices were pitched to the
loudest, as their last ‘God speed!’ The temper of London may be
seen in one of Walpole’s letters, in which he alludes to the too great
favour which had been always shown towards Scotland since the
last rebellion; and he expresses a hope that the duke will make an
end of it.
In the meantime, old rancour against the Jacobites
LONDON
was embittered by the publication of various MOBS.
‘provocating pamphlets;’ and the month came to a
conclusion with the preachings of the 30th of January, and the
comments made on the sermons next day. Bishop Mawson, of
Chichester, preached before the Lords at St. Peter’s, Westminster;
Dr. Rutherford before the Commons at St. Margaret’s; while a
reverend gentleman, who is variously called ‘Pursack’ and
‘Persover,’ aroused the echoes of St. Paul’s in the ears of the Lord
Mayor and Aldermen. Finally, an anonymous poet swept the lyre in
laudation of the duke. How he made the chords ring may be
gathered from a single line:—
Blast, gracious God, th’ assassins’ hell-bred scheme!
The London mob, on the Whig side of politics, cannot be said to
have been more civilised than the same mob of thirty years earlier.
One of its favourite sights was to see Jacobite prisoners brought into
London. The captives were invariably ill-used; but there was a much
more humane feeling manifested for such of them as might end their
career by the axe or the halter. One day in February upwards of forty
officers (including a French colonel of Engineers and four
Frenchmen of lower grade) were brought into London in four
waggons and a coach. The more dignified vehicle carried the French
colonel. They were guarded by a strongly-armed escort. Some were
taken to the New Prison in Southwark, some to Newgate. The
French colonel in the coach, and his four countrymen in a cart, were
driven to the Marshalsea. ‘They were very rudely treated by the
populace,’ say the newspapers, ‘who pelted them with dirt, and
showed all other marks of abhorrence of their black designs.’
Foreigners were just then looked upon with great suspicion. Two
servants of the Portuguese and Sardinian envoys,
AMBASSADORS
respectively, having let their tongues wag too saucily ’ CHAPELS.
at a tavern, under the shield, as they thought, of
ambassadorial protection, had been seized by the constables and
clapped into irons. The envoys demanded their release; and much
correspondence ensued between the Home Office and the envoys. It
was settled that the legation could not shelter an offender against the
law, even though the offender were a fellow-countryman of the
legate. Some attempt was made to compel the foreign
representatives to abstain from employing Popish priests of English
birth in the chapels annexed to the ambassadors’ private residences.
The answer was reasonable enough. As their Excellencies could
bring no foreign priests of the Romish Church with them, they were
obliged to employ English ecclesiastics who were priests of that
Church, in the chapels of the respective embassies. These were the
only ‘mass houses’ to which English Papists, it was said, could
resort, and the Whigs denounced them as the smithies where red
hot conspiracy was beaten into shape between foreign hammers and
a British anvil.
London Whig temper was irritated in another
THE HAVOC
direction. There was not only a reckless assertion of OF WAR.
Jacobitism on the part of the prisoners from the north,
but there was abundance of sympathy manifested for them.
Moreover, full permission was given to the practical application of
this sympathy. Jacobite visitors poured into the prisons, and the
captives ate, drank, and were merry with them, regardless of what
the morrow might bring. Many of the prisoners had pockets well
furnished with gold; and where this was wanting it was supplied by
Jacobite outsiders. Scarcely a day passed without waggoners or
porters depositing in the first lodge hampers of the richest wines and
of the finest delicacies. The warders rejoiced, for they took toll of all;
and the prison chaplains had some idea that this good time was the
beginning of the Millennium.
On the other hand, there was much more misery in the loyal than
in the Jacobite army. The Londoners saw nothing for the
encouragement of loyalty in such a sight as the landing at the Tower
wharf of some of the troops that had been with Cope at Preston
Pans. ‘The poor men,’ say all the papers, ‘were in a most miserable
shocking condition. Some without arms or legs, others their noses
cut off and their eyes put out; besides being hacked and mauled in
many parts of their bodies, after a most terrible and cruel manner.’
This ‘atrocity’ was forgotten in the news that roused London in April.
The course of war in Scotland, from the beginning FLYING
of the year to the 16th of April, was in this wise. On REPORTS.
the 17th of January Hawley was defeated at Falkirk.
On the 30th, the Duke of Cumberland arrived in Edinburgh. March
14th, news came that the Highland army had taken Fort Augustus
and had blown up Fort George. The Ladies Seaforth and Mackintosh
headed two rebel clans on the hills; but their husbands were with the
duke’s army! About the same time old Lord Lovat stimulated the