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Chapter 1
A New Method for Determination

of Molecular Weight of
Compounds Soluble in Protic
Solvents by Electrochemical
Impedance Spectroscopy
Subramaniam Rameshkumar, Panjaiyan Karthikeyan,
Iman Danaee and Manogaran Obulichetty
Abstract
This chapter deals with a new method for determining the molecular weight of
chemical substances soluble in protic solvents. One of the well-known methods for the
determination of molecular weight of a substance, based on one of the colligative
properties, is Ostwald and Walker’s method, which depends on relative lowering of
vapor pressure of solvent. In this paper we proposed a new method for determining
the molecular mass of the substances that are soluble in protic solvents such as water,
methanol and ethanol employing electrochemical impedance spectroscopy (EIS)
technique and Raoult’s law. The moisture and vapor pressure dependent proton con-
ductivity of some organic compounds and metal-organic frame works (MOFs) can be
utilized to find the molecular mass of solutes soluble in protic solvents. This property
is considered as key for determination of molecular weight of chemical substances
using EIS and is simpler than Ostwald and Walker’s method. This method is a
non-destructive and also useful to determine the molecular weight of polymers and
proteins soluble in protic solvents.
Keywords: impedance, molecular weight, vapor pressure, Raoult’s law
1. Introduction
Electrochemical impedance spectroscopy (EIS) finds a special place among the

various electrochemical techniques. It is a powerful tool for analyzing the interfaces
formed in the heterogeneous systems. EIS supplies a large amount of informations,
though it may not provide all the answers. EIS uses tools developed in electrical
engineering and describes the behavior of the systems under study in terms of an
equivalent circuit consisting of the circuit elements resistors, capacitors, Warburg
impedance etc. The mathematical foundations of EIS were dealt by Heariside [1],
through which it is possible to solve the integrodifferential equations appearing in the
1
Frontiers in Voltammetry
solutions of electrical circuits by converting them into a system of algebraic equations.

The main advantage of EIS is the fact that it is based on the linear time invariant (LTI)
theory and validity of the data may be verified using Kramers-Kronig integral trans-
forms. Nernst was the first person who described the chemical applications of imped-
ance spectroscopy through his work [2], followed by many others including those
applications to the distribution of relaxation time constants by Cole and Cole [3] and
Davidson and Cole [4]. The impedance of mass transfer was explained by Warburg
using so called Warburg impedance, which extended EIS to apply for redox reactions
[5]. With further development in the understanding of EIS, the structure of double
layer in the absence and presence of adsorbed species was studied initially at dropping
mercury electrode and then at solid electrodes using AC bridge. The analysis of
electrochemical reactions using the electro analog circuit was introduced by Dolin and
Ershler [6] and Randles [7, 8], where the age of electrical analog began [9] and
continues up till now. The fundamental aspects of EIS give the idea to validate the data
and to model the processes limited by diffusion, electrode kinetics and adsorption on
different types of electrode geometries. The availability of modern instrumentation to
obtain impedance data as well as computer programs to interpret the results have
made this technique popular. Now a days, EIS finds applications in corrosion, bio-
sensors, battery development, fuel cell development, drug cell membrane interaction
[10], paint characterization, sensor development, polymers etc.
The development of organic proton conducting materials to substitute the per
fluorinated polymers such as nafion is an important area of research in the field of fuel
cell technologies [11–15]. Recent research in this field emerged some coordination
polymers and metal-organic frame works (MOFs) for their proton transport capabil-
ities, though the literature on these materials in other domains such as magnetism,
catalysis, inclusion phenomenon and in supramolecular chemistry are quite extensive
[16–23]. Under high humidity conditions or with water channels, MOFs show high
degree of proton conductivities, comparable to nafion [24–28]. The proton conducting
ability of these materials primarily depend on the existence of charge carrying
molecular or ionic species such as H3O+, OH, or NHþ 4 Lewis acidic moieties. These
molecular or ionic species with the complex network of hydrogen bonds or their
arrangements with the water molecules play a vital role for proton conductivity. These
characteristics are considered to be the important structural requirements of the
proton conducting polymers and MOFs [29–33]. With the above-mentioned features,
several new MOFs that exhibit Nafion-like proton conducting characters, under
humidified and ambient temperature conditions have been reported [34]. The proton
conducting ability of these materials was evaluated using EIS [34–36] which depends
on humidity levels of the surroundings.
In this chapter, through an innovative approach we would like to propose a new
method for the determination of molecular weight of compounds which are soluble
in water and other protic solvents, using proton conducting ability of organic
compounds or MOFs by EIS technique.
2. Electrochemical impedance spectroscopy—a tool to evaluate the proton

conductivity of solid materials theory and discussion
Now a days proton conducting solid state electrolytes gained a considerable atten-
tion owing to their application in fuel cells1, electrochromic devices [37], humidity
2
2
A New Method for Determination of Molecular Weight of Compounds Soluble in Protic…
DOI: http://dx.doi.org/10.5772/106558
sensors [38] and gas separators [39]. Nafion, a perfluorinated polymer with sulphonic
acid is used as solid-state proton conductor under hydrated conditions [40]. This
polymer has many disadvantages, under high temperature (>80°C) the water clusters
are lost in the pores of Nafion. At low humidity levels water clusters in the Nafion
pores are low. Both factors reduce the conductivity of Nafion [40]. In addition to
these drawbacks, high cost, high fuel cross over, non eco-friendly synthesis and
variation of conductivity with degree of sulphonation limit its applications. These
limitations made the researchers to look for alternate solid state proton conducting
materials. Many coordination compounds and MOFs having proton conducting ability
were not explored for their proton conductivities. Recent reports on proton
conducting nature of MOFs promise their enhanced proton conductivity at high
temperature and low fuel cross over.
It was reported that the organic compounds with heteroatoms incorporated within
the pores of MOFs as guests with controlled loading. The amphoteric heterocyclic
moiety has shown electrolytic conductance through proton. This system has shown an
improved proton conductance even at higher temperatures and precisely the theoret-
ical open circuit potential of hydrogen-oxygen fuel cell. Only few compounds have
been studied for their proton conductivities. Their proton conducting properties can
further be extended to calculate the molecular weight of solutes dissolved in the protic
solvents and the vapor pressure of the protic solvents at any temperature knowing the
normal boiling point. Conversely, this property can also be used for the calculation of
molar enthalpy of vaporization of protic solvents. These applications have not been
verified for these compounds. This method could be an alternate for Ostwald and
Walker Method for determining molecular weight of substances and a useful tech-
nique for knowing the molecular weight of polymers soluble and an unknown sub-
stance in protic solvent. The proposed method is based on EIS technique.
EIS is a routine method for characterization of various electrical properties of
different types of materials and the interfaces formed by the materials with electron-
ically conducting materials. EIS is a simple non-destroying technique, where a system
study is perturbed by an AC sinusoidal voltage of small amplitude at different applied
frequencies and the resulting current varying with the applied frequency is used to
extract the required kinetic informations.
2.1 Fundamentals of electrochemical impedance spectroscopy
The resistance of a system under study comes from the hindrance offered for the
flow of electrical current through its circuit elements. The resistance, R, of the mate-
rial is defined by Ohm’s law, in terms of voltage, E and current I ratio:
E
R¼ (1)
I
Similar to resistance, the term impedance measures the ability of a material to

resist the flow of charges in definite direction. However, impedance differs from
resistance in two main aspects. First, it is associated with alternating current (AC);
second, it is usually mentioned at a particular frequency.
Measurement of impedance is done by applying a sinusoidally varying an AC
potential to the system under study and measuring the current through the system.
The response to the applied sinusoidally varying potential at a frequency is a
sinusoidally varying current at the same frequency with shift in phase. The ratio of
3
3
applied sinusoidally varying potential to the resulting sinusoidally varying current at

the same frequency is called impedance, using which the information on conductivity
of the system can be obtained.
The input or excitation signal, i.e. sinusoidally varying potential at a frequency can
be expressed as a function of time as follows:
EðtÞ ¼ E0 sin ðωtÞ (2)
Where,
E(t) refers to the potential at time t, E0 is the amplitude of the applied AC potential
and ω is the angular frequency given by the expression ω ¼ 2πf (f = applied frequency
in Hz)
In a linear system the excitation of voltage at a frequency ‘ω’ provides a current ‘I’
at the same frequency. This generated current is different in amplitude and phase
from voltage as given below:
IðtÞ ¼ I0 sin ðωt þ φÞ (3)
In a non-linear system I-V relation gives a distorted response which is not purely
sinusoidal, but it is still periodic [41].
An analogous expression to Ohm’s law allows us to calculate the impedance of the
system as:
EðtÞ E0 sin ðωtÞ sin ðωtÞ

Z¼ ¼ ¼ Z0 (4)
IðtÞ I0 sin ðωt þ φÞ sin ðωt þ φÞ
The impedance is therefore expressed in terms of a magnitude, Z0, and a phase

shift (φ). Using Euler’s relationship, the impedance is then represented as a complex
number
EðtÞ E0 sin ðωtÞ

Z¼ ¼ ¼ Z 0 ð cos φ þ j sin φÞ (5)
IðtÞ I0 sin ðωt þ φÞ
Accordingly, the impedance is a vector quantity since it has a magnitude, Z0, and
direction given by phase shift, φ:
When we apply the above concepts to a pure resistor, for which the phase angle (φ)
is zero,
EðtÞ ¼ E0 sin ðωtÞ (6)

IðtÞ ¼ I0 sin ðωtÞ (7)
EðtÞ E0 sin ðωtÞ E0

R¼ ¼ ¼ (8)
I ð tÞ I0 sin ðωtÞ I0
When the concept is applied for a capacitor, where, φ ¼ π2

Charge in the capacitor,
q ¼ CE (9)
4
4
Current,
dq dE
I¼ ¼C¼ (10)
dt dt
I ¼ CE0 ω cos ðωtÞ (11)
E0 π
I¼ sin ωt þ (12)
XC 2
Where XC is capacitive reactance, i.e. the resistance offered by a pure capacitor for
the alternate current flows across it. Its value depends on frequency of AC excitation
voltage and is given as:
1
XC ¼ (13)
ωC
Where, ‘C’ is capacitance of the pure capacitor (in F).

Since the current leads the voltage by a phase angle of π2, the capacitive reactance is
taken along the ordinate (Y-axis) and is given as imaginary component.
i EðtÞ
i:e: iX C ¼ ¼ (14)
ωC IðtÞ
pffiffiffiffiffiffi
Where, i ¼ 1, an imaginary number.
When a capacitor and a resistor are in series connection, the excitation voltage is
given as,
E ¼ ER þ EC (15)
E ¼ IR iX C I (16)
E
¼ R iX c (17)
I
Since the value of XC depends on frequency, the total resistance in this series
depends on the frequency of excitation voltage and is called impedance (Z).
Z ¼ R iX C (18)
In general, the impedance can be represented as,
Z ðωÞ ¼ Z Re iZ Im (19)
Where, Z Re = real part of impedance,

Z Im = imaginary part of impedance.
The magnitude of impedance is given as,
qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
jZ j ¼ ðZ Re Þ2 þ ðZ Im Þ2 (20)
rffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
1
jZ j ¼ R2 þ 2 2 (21)
ωC
5
5
The phase angle φ is given as,
φ ¼ tan 1 ðZ Im =Z Re Þ (22)
1
φ ¼ tan ðX C =RÞ (23)
φ ¼ tan 1 ð1=ωCRÞ (24)
It is well known that impedance is a specific form of the transfer function of the
system [41]. If Ī(s) and Ē(s) are the Laplace transforms of the sinusoidal current and
voltage respectively, the transfer function [41] is given as,
EðsÞ E0 s
TFðsÞ ffi ≃ cos φ þ sin φ (25)
IðsÞ I0 ω
Were, s is the Laplace complex variable or frequency,
s ¼ iω (26)
Now solutions to the Eq. (26) are confined to the frequency domain.
E0
Z ffi TFðiωÞ ¼ ð cos φ þ i sin φÞ (27)
I0
2.2 Variation of frequency
When we consider a homogeneous system, it is represented by a conductance (G)

or resistor (R) in parallel connection with a capacitor (C) as shown in Figure 1.
The corresponding Nyquist and Bode (phase and impedance) plots for the above
equivalent circuit are presented in the Figures 2 and 3 respectively.
By rule the net impedance of this homogeneous system, from the above equivalent
circuit, is given as,
1 1 1
¼ (28)
Z R iX C
1 1 i
¼ þ (29)
Z R XC
1
¼ G þ iωC (30)
Z
Figure 1.
An equivalent circuit for a homogeneous system.
6
6
Figure 2.
Nyquist plot for the equivalent circuit proposed for homogeneous system (arbitrarily assumed value for R is 100 Ω
and C is 5 106 F).
Figure 3.
Bode impedance and phase angle plots for the equivalent circuit proposed for homogeneous system (arbitrarily
assumed value for R is 100 Ω and C is 5 106 F).
1
Z¼ (31)
G þ iωC
Conductance (G) and capacitance (C) of the homogeneous material describe its
ability to conduct and store electric charge respectively. If the homogeneous material
is considered as a slab of cross-sectional area ‘A’ and thickness ‘l’, these properties are
given by the following expressions,
A
G¼σ (32)
l
A
C¼ε (33)
l
Where σ and ε are conductivity and permittivity of the homogeneous system

respectively.
From Eqs. (27) and (31),
7
7
1 E0
¼ ð cos φ þ i sin φÞ (34)
G þ iωC I0
1
¼ jZ jð cos φ þ i sin φÞ (35)
G þ iωC
1
G þ iωC ¼ ð cos φ i sin φÞ (36)
jZ j
Therefore,
1
G¼ cos φ (37)
jZ j
1
C¼ sin φ (38)
jZ jω
Using the above equations, we can measure the thickness of the homogeneous
material.
Inspection of the above equation reveals that the impedance of the homogeneous
material is dispersed with frequency and the dispersion is more pronounced for the
frequencies greater than G/C,
G
ω¼ (39)
C
Giving the condition at which, the impedance measurement provides the most
accurate estimates of both properties. This characteristic frequency of the homoge-
neous system is called ‘natural frequency’ of the system.
A heterogeneous system can be considered to consist of a number of different
materials or slabs sandwiched together. The total impedance of such a system is
given as,
X
N
1
Z N ð ωÞ ¼ (40)
G þ iωCn
n¼1 n
Each slab in the heterogeneous system has its own natural frequency defined by
the expression ω ¼ G C. If the magnitudes of impedance of corresponding N slabs are
sufficiently different, then these slabs can be easily identified within the combined
dispersions immediately.
For example, using the last expression, the total impedance of a heterogeneous
system consisting of two different materials or slabs (P and M), the impedance
dispersion can be written as,
1 1
Z N ðωÞ ¼ þ (41)
GP þ iωCP GM þ iωCM
Dispersion of conductance (G) and capacitance (C) with frequency are obtained
by simplifying this equation as,
8
8

GM GP ðGM þ GP Þ þ ω2 C2M GP þ C2P GM
G¼ (42)
ðGP þ CM Þ2 þ ω2 ðCP þ CM Þ2
CM G2P þ CP G2M þ ðω2 CM CP ÞðCP þ CM Þ

C¼ (43)
ðGP þ CM Þ2 þ ω2 ðCP þ CM Þ2
The solid-state proton conducting electrolytes can be synthesized by simple

solution crystallization method. The Nyquist plots recorded will not be straight
forward to give the electrical properties of solid-state proton conductors. Equivalent
circuits are used to derive the electrical properties of solid-state electrolytes. The
equivalent circuit that fits well with the Nyquist plots will also provide the nature
of arrangement of different dielectric slabs inside the soild-state protonic conductor.
The mechanism for proton conduction could be derived from the temperature
studies.
3. Determination of molecular mass using the electrochemical impedance

spectra of solid-state proton conductors
Vapor pressure is a characteristic property of a substance in the condensed phase at

constant temperature. It is the pressure exerted by the vapor molecules of a substance
on the surface of the condensed phase of the same substance, when the vapor mole-
cules are in equilibrium with its condensed phase at constant temperature. The vapor
pressure of a liquid at constant temperature is constant and increases with tempera-
ture. At one temperature the vapor pressure of the liquid becomes equal to atmo-
spheric pressure at which the liquid boils and temperature is called boiling point of the
liquid. At the same temperature the vapor pressure of a liquid decreases when a non-
volatile solute is dissolved in it which is called lowering of vapor pressure of the
solvent. The proton conducting ability of coordination polymers and MOFs depends
on the humidity levels or water vapor level in an environment. Greater the humidity
level greater will be the proton conductivity. The proton conductivity of a coordina-
tion polymer or MOF is measured from the charge transfer resistance (Rct) value
obtained from EIS [34–36]. The charge transfer resistance measured using EIS is
inversely proportional to proton conducting of the CPs or MOFs, which in turn
directly proportional to humidity level or moisture level in the atmosphere.
Therefore, the charge transfer resistance (Rct) of CPs or MOFs in the presence of
known volume of pure water or protic solvents, measured in a closed container,
1
Rct α (44)
P0
Where P0 is vapor pressure of pure protic solvent.

The charge transfer resistance measured after dissolving a known weight of solute
in the same volume of water or protic solvents in the closed container at same
temperature,
1
R0ct α (45)
P
9
9
Where P is vapor pressure of solvent in solution

From Raoult’s law
P ¼ P0 X 1 (46)
or
P
X1 ¼ (47)
P0
Where X 1 is mole fraction of protic solvent.

Therefore
Rct
X1 ¼ (48)
R0ct
n1 Rct
¼ (49)
n1 þ n2 R0ct
Where n1 and n2 are number of moles of solvent and solute respectively.
W 2 M1 Rct
M2 ¼ (50)
W 1 R0ct Rct
Using Eq. (50) the molecular weight of the solute can be calculated.
This method is also applicable for determining molecular weight of the substances
which are insoluble in water but soluble in methanol or ethanol, since some CPs or
MOFs showing reversible proton conductivity in CH3CH2OH are also reported
[35, 36].
4. Conclusion
The measurement of vapor pressure of solvents in pure form and in solutions is a

tedious one in Ostwald and Walker’s method of determining molecular mass from
relative lowering of vapor pressure, the proposed method is easy with simple experi-
mental setup and can be used to determine the molecular weight of substances and
polymers soluble in protic solvents.
Abbreviations
EIS electrochemical impedance spectroscopy

MOF metal organic framework
R resistance
C capacitance
E voltage
I current
10
10
11
References
[1] Ardavan H. A speed-of-light barrier [10] Mallaiya K, Subramaniam R,

in classical electrodynamics. Physical Srikandan SS, Gowri S, Rajasekaran N,
Review D. 1984;29(2):207 Selvaraj A. Electrochemical
characterization of the protective film
[2] Lai W, Haile SM. Impedance formed by the unsymmetrical Schiff’s
spectroscopy as a tool for chemical and base on the mild steel surface in acid
electrochemical analysis of mixed media. Electrochimica Acta. 2011;56(11):
conductors: A case study of ceria. Journal 3857-3863
of the American Ceramic Society. 2005;
88(11):2979-2997 [11] Wycisk R, Pintauro PN, Park JW.
New developments in proton conducting
[3] Cole KS, Cole RH. Dispersion and membranes for fuel cells. Current
absorption in dielectrics I. Alternating Opinion in Chemical Engineering. 2014;
current characteristics. The Journal of 4:71-78
Chemical Physics. 1941;9(4):341-351
[12] Peighambardoust SJ,
[4] Davidson DW, Cole RH. Dielectric Rowshanzamir S, Amjadi M. Review of
relaxation in glycerol, propylene the proton exchange membranes for fuel
glycol, and n-propanol. The Journal of cell applications. International Journal of
Chemical Physics. 1951;19(12):1484-1490 Hydrogen Energy. 2010;35(17):
9349-9384
[5] Warburg E. Ueber das Verhalten
sogenannter unpolarisirbarer Elektroden [13] Li Q , Jensen JO, Savinell RF,
gegen Wechselstrom. Annalen der Bjerrum NJ. High temperature proton
Physik. 1899;303(3):493-499 exchange membranes based on
polybenzimidazoles for fuel cells.
[6] Dolin P, Ershler B. The kinetics of Progress in Polymer Science. 2009;
discharge and ionization of hydrogen 34(5):449-477
adsorbed at Pt-electrode. Acta
Physicochimica URSS. 1940;13:747 [14] Le HH, Abhijeet S, Ilisch S, Klehm J,
Henning S, Beiner M, et al. The role of
[7] Randles JEB. Kinetics of rapid linked phospholipids in the rubber-filler
electrode reactions. Transactions of the interaction in carbon nanotube (CNT)
Faraday Society. 1947;1:11 filled natural rubber (NR) composites.
Polymer. 2014;55(18):4738-4747
[8] Yeager E, Breiter MW. Transactions
of the symposium on electrode processes. [15] Phair JW, Badwal SP. Review of
Journal of The Electrochemical Society. proton conductors for hydrogen
1962;109(1):25C separation. Ionics. 2006;12(2):103-115
[9] Macdonald DD. Reflections on the [16] Kepert CJ. Advanced functional
history of electrochemical impedance properties in nanoporous coordination
spectroscopy. In: Paper Presented at 6th framework materials. Chemical
International Symposium on Communications. 2006;7:695-700
Electrochemical Impedance
Spectroscopy; 17–21 May 2004; Cocoa [17] Rowsell JL, Yaghi OM. Metal–
Beach, Florida organic frameworks: A new class of
12
12
porous materials. Microporous and one-dimensional ferrous oxalate

Mesoporous Materials. 2004;73(1-2): dihydrate. Journal of the American
3-14 Chemical Society. 2009;131(9):3144-3145
[18] Maspoch D, Ruiz-Molina D, [27] Sahoo SC, Kundu T, Banerjee R.

Veciana J. Old materials with new tricks: Helical water chain mediated proton
Multifunctional open-framework conductivity in homochiral metal–
materials. Chemical Society Reviews. organic frameworks with unprecedented
2007;36(5):770-818 zeolitic unh-topology. Journal of the
American Chemical Society. 2011;
[19] James SL. Metal-organic 133(44):17950-17958
frameworks. Chemical Society Reviews.
2003;32(5):276-288 [28] Wong NE, Ramaswamy P, Lee AS,
Gelfand BS, Bladek KJ, Taylor JM, et al.
[20] Maji TK, Kitagawa S. Chemistry of Tuning intrinsic and extrinsic proton
porous coordination polymers. Pure and conduction in metal–organic
Applied Chemistry. 2007;79(12): frameworks by the lanthanide
2155-2177 contraction. Journal of the American
Chemical Society. 2017;139(41):
[21] Brammer L. Developments in 14676-14683
inorganic crystal engineering. Chemical
Society Reviews. 2004;33(8):476-489 [29] Ramaswamy P, Wong NE,
Shimizu GK. MOFs as proton
[22] Janiak C. Engineering coordination conductors–challenges and
polymers towards applications. Dalton opportunities. Chemical Society
Transactions. 2003;14:2781-2804 Reviews. 2014;43(16):5913-5932
[23] Zhao D, Timmons DJ, Yuan D, [30] Horike S, Umeyama D, Kitagawa S.

Zhou HC. Tuning the topology and Ion conductivity and transport by porous
functionality of metal-organic coordination polymers and metal–
frameworks by ligand design. Accounts of organic frameworks. Accounts of
Chemical Research. 2011;44(2):123-133 Chemical Research. 2013;46(11):
2376-2384
[24] Nagao Y, Kubo T, Nakasuji K,
Ikeda R, Kojima T, Kitagawa H. [31] Shimizu GK, Taylor JM, Kim S.
Preparation and proton Proton conduction with metal-organic
transport property of N, N0 - frameworks. Science. 2013;341(6144):
diethyldithiooxamidatocopper 354-355
coordination polymer. Synthetic Metals.
2005;154(1-3):89-92 [32] Yoon M, Suh K, Natarajan S, Kim K.
Proton conduction in metal–organic
[25] Sadakiyo M, Yamada T, Kitagawa H. frameworks and related modularly built
Rational designs for highly proton- porous solids. Angewandte Chemie
conductive metalorganic frameworks. International Edition. 2013;52(10):
Journal of the American Chemical 2688-2700
Society. 2009;131(29):9906-9907
[33] Kitagawa H. Transported into fuel
[26] Yamada T, Sadakiyo M, Kitagawa H. cells. Nature Chemistry. 2009;1(9):
High proton conductivity of 689-690
13
13
[34] Saravanabharathi D, Obulichetty M,

Rameshkumar S, Kumaravel M.
Humidity based proton conductivity of
calcium-L-tartrate tetrahydrate: An
environmentally benign coordination
polymer as a solid electrolyte. Synthetic
Metals. 2014;196:76-82

Rameshkumar S, Kumaravel M. Rapid
crystallization and proton conductivity
of copper (II)-L-tartrate. Synthetic
Metals. 2012;162(17-18):1519-1523

Rameshkumar S, Kumaravel M. New 2-
methyl benzimidazole based zinc
carboxylates: Supramolecular structures,
biomimetic proton conductivities and
luminescent properties. Inorganica
Chimica Acta. 2015;437:167-176
[37] Singh K, Tiwari RU. Solid state

battery of proton conducting sodium
thiosulphate pentahydrate. In:
Proceedings of the 4th Asian Conference
on Solid State lonics. 1994. pp. 403
[38] Chikh L, Delhorbe V, Fichet O.

(Semi-)interpenetrating polymer
networks as fuel cell membranes. Journal
of Membrane Science. 2011;368(1-2):1-7
[39] Nasar A, Perveen R. Applications of

enzymatic biofuel cells in bioelectronic
devices–a review. International Journal
of Hydrogen Energy. 2019;44(29):
15287-15312
[40] Ye G, Janzen N, Goward GR. Solid-

state NMR study of two classic proton
conducting polymers: Nafion and
sulfonated poly (ether ether ketone)s.
Macromolecules. 2006;39(9):3283-3290
[41] Coster HG, Chilcott TC, Coster AC.

Impedance spectroscopy of interfaces,
membranes and ultra structures.
Bioelectrochemistry and Bioenergetics.
1996;40(2):79-98
14
Chapter 2
Development of An Impedimetric
Nanoplatform for Cu(II) Detection
Based on Carbon Dots and Chitosan
Nanocomposite
Mosaab Echabaane and Chérif Dridi
Abstract
In this chapter, an impedemitric sensor based on carbon dots (CDs) and chitosan
(CS) nanocomposite for Cu (II) detection has been studied. The synthesized carbon
dots were characterized by TEM, FTIR, XRD, UV-visible, and PL. The obtained
carbon dot/chitosan/GCE structure was characterized by scanning electron micros-
copy (SEM) and electrochemical impedance spectroscopy (EIS). The behavior, inter-
face processes of GCE/electrolyte, and sensor properties of the studied structures were
investigated. In particular, the performance of the proposed impedimetric sensor to
Cu ions, such as sensitivity, dynamic range, detection limit, and selectivity, was
studied. Subsequently, the proposed sensor was applied for the determination of
copper ions in real water samples.
Keywords: carbon dots, chitosan, nanocomposite, copper(II), Impedimetric sensors,

introduction
1. Introduction
Essential transition metals such as copper, zinc, iron, and manganese play vital
roles in several biological processes [1]. One of the essential transition metal ions,
copper is the most abundant metal ion in the human body. It contributes to blood
formation, connective tissue development, transcriptional events, and the functioning
of several enzymes [2, 3]. However, exposure to an excess level of copper ion can
cause gastrointestinal disturbance, neurodegenerative diseases, and liver and kidney
damage [4]. The maximum content of Cu2+ ions in drinking water is limited to 30 nM
by the World Health Organization (WHO) [5].
Hence, it is very important to develop a simple, fast, economically advantageous,
selective, and sensitive analytical technique for the determination of copper in aquatic
environments to avoid side effects. Notably, numerous techniques have been used to
determine the copper ion, including atomic absorption spectroscopy, chromatography
spectrofluorimetry, and spectrophotometry [6–9]. These techniques can provide good
accuracy and sensitivity, but they have various disadvantages, such as expensive
15
equipment, time-consuming operation, and an inability to do onsite analysis. Thus,

their use is restricted. Therefore, to circumvent these limitations, electrochemical
sensors have attracted great attention for detecting trace levels of copper ions due to
their inherent advantages, such as simple operation, low-cost, rapidity, excellent
sensitivity, and selectivity [10]. Notably, the presence of numerous advanced elec-
trode modified nanomaterials improved sensing performance significantly [11–15].
Amongst such nanomaterials, nanocomposites have been employed in electrochemical
sensors for environmental analysis [16–21]. Nowadays, analytical measurements are
altered by nanocomposites of various sizes, shapes, and compositions. Chitosan as
well as carbonaceous nanoparticles have an interest in the construction of electro-
chemical sensors [22–28]. Chitosan exhibits interesting properties due to its
nontoxicity, film-forming ability, high permeability, adsorption ability, and biocom-
patibility. It has been extensively used as a good biomaterial in designing sensors
[29, 30]. As compared to other carbonaceous nanoparticles, carbon dots have consid-
erable importance because of their simple synthetic routes, high surface area, high
biocompatibility, and high conductivity [31, 32]. The aim of this chapter is to develop
an impedimetric sensor for copper ion detection based on carbon dots and chitosan
nanocomposite. The synthesized carbon dots were characterized by transmission
electron microscope (TEM), X-ray diffraction (XRD), FTIR spectroscopy, UV–Vis
absorption, and photoluminescence spectroscopy. The morphological and electro-
chemical properties of carbon dot/chitosan/GCE structure were investigated by
scanning electronic microscopy (SEM) and electrochemical impedance spectroscopy
(EIS). The weather sensors’ performance was discussed. The proposed sensor can be
used to determine copper ions in real water samples.
2. Experimental details
2.1 Reagents
Copper sulfate (CuSO4, ≥ 99.9%), mercury nitrate monohydrate (Hg(NO3)2.H2O,

≥ 99.9%), cadmium nitrate tetrahydrate (Cd(NO3)2,4H2O, ≥ 99%), lead nitrate (Pb
(NO3)2, ≥ 99%), nickel nitrate hexahydrate (Ni(NO3)26H2O, ≥ 98.5%), zinc nitrate
hexahydrate (Zn(NO3)26H2O, ≥ 98%), sodium chloride (NaCl, ≥ 99%), calcium
chloride (CaCl2, ≥ 96%), potassium chloride (KCl, ≥ 99%), glucose (≥ 99.5%), sulfu-
ric acid (H2SO4, ≥ 99.9%), Deionized (DI) water, sodium hydroxide (NaOH, ≥ 97%),
ammonium acetate (CH3COONH4, ≥ 98%), and chitosan (CS, ≥ 85%). All chemicals
used in this work were purchased from of Sigma- Aldrich.
2.2 Instrumentations
For further investigation of the synthesized carbon dots (CDs), an X-ray diffrac-
tometer (Bruker AXS D8 Advance), Fourier Transform Infrared Spectroscopy (FTIR)
(Perkin Elmer, Spectrum Two), UV–vis spectrophotometry (Specord 210 Plus), and a
spectrophotometer (Perkin Elmer) were employed.
Scanning Electron Microscopy (SEM) (Jeol JSM-5400 emission) was used to char-
acterize the CS-CDs film.
The electrochemical impedance measurements were carried out using an imped-
ance analyzer (EC-LAB BIOLOGIC) with a sinusoidal excitation signal amplitude of
10 mV and a 0.01 Hz-100 kHz frequency range. The polarization potential used for
2
16
Development of An Impedimetric Nanoplatform for Cu(II) Detection Based on Carbon Dots…
Figure 1.
Schematic representation of CDs formation from glucose.
these measurements was optimized at 600 mv. An aqueous ammonium acetate

(solution of 0.1 M, with pH = 7, was used as an electrolyte in the electrochemical cell
formed by three electrodes: a working electrode (GCE), a platinum counter electrode,
and an Ag/AgCl electrode (SCE).
2.3 Synthesis of CDs
Glucose (3 g) and H₂SO₄ (1 ml) were dissolved in DI water (10 ml). Then, the
mixed solution was heated for 30 min at a temperature of 100°C (Figure 1). The
solution changed from colorless to yellow-brownish, signaling the formation of CDs.
Then, this latter was neutralized using NaOH. In order to remove impurities, the
prepared solution was centrifuged (14,000 rpm), filtered, and dried for 6 hours at a
temperature of 80°C [33].
2.4 Preparation of modified glassy carbon electrode (GCE)
The surface of the GCE electrode was polished with 0.05 μm and 0.3 μm alumina
powder. Then, the electrode was washed successively with distilled water, ethanol,
and distilled water in an ultrasonic bath, and dried at room temperature. For the
preparation of the CDs-CS nanocomposite solution: 0.5 mL of 1.0% CS solution was
added to 1.5 mL of CDs solution by ultrasonication. Then, 2 μL of nanocomposite was
dropped onto the surface of GCE and dried in the oven at 60°C for 30 min.
3. Characterization of CDs and CS-CDs/GCE
The TEM image of the synthesized CDs is shown in Figure 2(a). It is noticed that
the CDs are spherical in shape and their mean size is approximately 3.2 nm. The X-ray
diffraction pattern of CDs is shown in Figure 2(b). It exhibited a broad peak at 2θ ¼
22:35°, corresponding to the (002) hkl plane of the graphitic structure (JCPDS card no.
26–1076). The FTIR transmittance spectrum of the CDs is presented in Figure 2(c).
The peaks at 3319 cm1, 1727 cm1, 1642 cm1, and 1092 cm1 were assigned to O-H,
C = O, C = C, and C-O. These indicate that carboxyl and hydroxyl groups may be
found on the surface of CDs. The UV–Vis absorption spectrum of CDs exhibited two
absorption bands located at 280 nm and 375 nm (Figure 2(d)), which are ascribed to
3
17
Figure 2.
Characterization of CDs: (a) TEM images, (b) XRD pattern, (c) FTIR spectra, (d) UV–visible spectra, (e) PL
spectra.
π-π* and n-π* respectively. Figure 2(e) presents the PL spectra of the CDs. The
fluorescence emission peak of CDs located at 470 nm is a blue light luminescent
spectral region.
4
18
Figure 3.
Images SEM of (a) bare GCE electrode, (b) CS-CDs nanocomposite/GCE electrode.
SEM images of the bare GCE and the CS-CDs/GCE film are shown in Figure 3. It
exhibits that the bare GCE electrode has a flat and smooth surface (Figure 3(a)),
whereas the surface of the CS-CDs nanocomposite is rough with a few apparent pores
(Figure 3(b)). This result shows that the CS-CDs film was deposited on the GCE
surface.
4. EIS characterization of the CS-CDs/GCE electrode
Electrochemical impedance spectroscopy is a sensitive tool for investigating the

characteristics of the electrode-solution interface. The Nyquist diagrams of the bare
GCE electrodes and functionalized CS-CDs film are shown in Figure 4. The Nyquist
of CS-CDs/GCE electrodes is higher than that of bare CGE electrodes. This is due to
the immobilization of the film. Besides, Figure 4 shows that the Nyquist plot of the
CS-CDs/GCE structure is a single semicircle with a large diameter. This might be
explained by the fact that it is an overlapping of two semicircles.
Figure 4.
Impedance spectra of bare GCE, and CS-CDs/GCE structures.
5
19
Figure 5.
Equivalent circuit used to fit the impedance spectra.
The EIS spectrum of the CS-CDs/GCE electrode was simulated with the equivalent
electrical circuit presented in Figure 5. This circuit is an association of three compo-
nents.
This circuit is an association of three components.
• The first one, in the low-frequency range, is used to represent the GCE/
electrolyte interface, including in a parallel combination the constant phase
element CPEdl that substitutes the electrical double layer capacitance (Cdl) with
the charge transfer resistance Rct.
• The second component at higher frequencies is attributed to the film/electrolyte

interface formed by a parallel combination of the resistance Rm and the
capacitance CPEm. Where Rm refers to the resistance of the film and CPEm
donates the constant phase element capacitance, is assigned to the electric
capacitor consisting of the metal and the electrolyte, with the film as the
dielectric.
• The last component is the series resistance of the electrolyte solution.
The two constant phase elements (CPE) are non-ideal capacitances and can be
expressed by (Eq. (1)):
Z CPE ¼ 1=Q ðjωÞn (1)
where Q is a constant, j is the imaginary number, ω is the angular frequency, and 0

< n < 1. CPE becomes more capacitive, when the value n tends to be 1.
Finally, the experimental EIS measurements were fitted using the ZView software.
The different fits were made with a total error value of χ2 ≈ 104.
5. Impedance characterization for the detection of Cu ion
The electrochemical impedance response of copper at the CS-CDs/GCE is charac-

terized using EIS. The Nyquist spectra of the CS-CDs film obtained after the addition
of different concentrations of copper ions is shown in Figure 6.
It is noted that the Nyquist plot of the CS-CDs film clearly decreases as a function
of Cu2+ concentration from 109 M to 105 M. The response of the CS-CDs modified
electrode to copper ions is due to a complexation process. This is induced by coordi-
nation between the donor groups of nanocomposites and the copper ions. In fact, the
6
20
Figure 6.
Impedance spectra for different copper concentrations of CS-CDs/GCE.
[Cu2+] (M) Rs (kΩ) CPEm (μF) n1 Rm (kΩ) CPEdl (μF) n2 Rct (kΩ) χ2 (104)
109 0.11 1.70 0.90 17.40 9.20 0.59 67.24 2.7

8
10 0.10 1.73 0.89 16.24 10.01 0.60 56.56 6.8
7
10 0.11 1.60 0.88 15.01 9.22 0.60 45.05 7.3
6
10 0.12 1.56 0.90 13.40 9.52 0.61 36.16 2.1
5
10 0.13 1.66 0.88 12.50 10.10 0.62 27.72 4.2
Table 1.
Fitting parameters of CS-CDs/GCE versus copper concentrations.
interaction of the copper ions (Lewis acid, acceptor electrons) with the amide and
hydroxyl groups of CS (Lewis base, donor electrons) is possible by the acid–base
reaction. Furthermore, the negatively charged carboxyl and hydroxyl groups existing
on the surface of CDs enable interactions with the positively charged copper ions.
Thus, the interaction mechanism is evolved by an electrostatic interaction that occurs
between the copper ions and the nanocomposite film.
Table 1 summarizes the circuit parameters of the CS-CDs film as determined by
the fit to the previous equivalent circuit.
6. Physical meaning of parameters obtained from the Nyquist plots
Figure 7 shows the plot of the film resistance versus p[Cu2+]. The value of film
resistance (Rm) decreases when increasing the concentration of copper. This is may be
explained by the increase in the ionic conductivity of the CS-CDs film.
Figure 8 represents the variation of the charge transfer resistance (Rct) parameters
upon the addition of Cu2+. It was observed that Rct decreased with increasing Cu2+
concentration. This can be due to improvement in the charge transfer at the GCE/CS-
CDs electrode electrolyte interface.
7
21
Figure 7.
Variation of the Rm of CS-CDs/GCE.
Figure 8.
Variation of the Rct of CS-CDs/GCE.
Electrode/p [Cu2+] Rm (KΩ) Rct (KΩ)
CS-CDs/GCE 1.3 9.9
Table 2.
Rm and Rct slope values of CS-CDs/GCE.
Table 2 presents the Rm and Rct slope values. It is noted that the Rct slope value is
higher than the Rm slope value. This can indicate that the recognition process was at
the electrolyte/GCE interface. Therefore, the Rct is provided as the primary factor
determining the sensors’ response.
8
22
7. Analytical performance of impedimetric sensors
Figure 9 shows the variation of -log(Rtc/Rtc0) as a function of copper concentra-

tion, where Rtc0 is the charge transfer resistance value without copper ions in the
solution. Here, a linear behavior with a large detection range between 109 and
105 M was observed. The equation of linear regression is -log (Rtc/Rtc0) = 0.1 log
[copper] + 0.9, where the slope is 0.1 of the sensor sensitivity. The detection limit of
our copper sensor was ≈ 5 1010 M, according to the formula LOD = (3 standard
deviation)/slope.
8. Specificity
The specificity of the GCE/CS-CDs sensor has been studied towards some interfer-
2+
ing cations: Hgh , Cd2+i
, Pb2+, Ni2+, Zn2+, Na+, Ca+, and K+. Figure 10 shows the relative
RtcRtc0
signal change Rtc0 as a function of the interfering cations. The results noted that
GCE/CS-CDs displayed good selectivity for Cu2+ in the presence of other ions.
9. Determination of copper ion in water samples
To evaluate the practical feasibility of the GCE/CS-CDs sensor, it is applied for the
detection of copper in water samples (tap water). 1 mL of sample solution (tap water)
is added to 1 mL of electrolyte (acetate ammonium at pH 7). The impaled copper
amounts are of 106 M and 108 M. The recovery percentage is calculated as
Found ðMÞ
Added ðMÞ 100. It can be seen in Table 3 that the recoveries are less than 5%. There-
fore, the proposed GCE/CS-CDs impedimetric sensor is efficient for the detection of
Cu2+ ions in real water samples.
Figure 9.
Calibration curve of -log (Rtc/Rtc0) versus log ([copper]).
9
23
Figure 10.
Influence of interferences (104 M) on the response copper (106 M).
Sample Added (M) Found (M) Recovery (%) RSD (%)

8 9
Tap water 10 9.70 10 97.0 4.12
106 1.02 106 102. 0 1.47
Table 3.
Determination of copper ion in tap water samples (n = 3).
10. Conclusion
In this chapter, we fabricate a highly sensitive, selective, impedimetric sensor for

the determination of copper-based on carbon dots/chitosan nanocomposite modified
glassy carbon electrode. A simple, fast, low-cost method to prepare carbon dots using
glucose by heating has been demonstrated. The electrochemical performance of the
copper sensor was examined by electrochemical impedance spectroscopy. Based on
the excellent properties of CS-CDs/GCE, the impedimetric sensors had high sensitiv-
ity, a low limit of detection, and good selectivity. The newly developed impedimetric
sensor for the determination of copper ions was applied in water for real samples with
satisfactory results. Thus, this indicates that these sensors offer promising potential
for water monitoring.
10
24
25
References
[1] Cowan JA. Handbook of Inorganic [7] Ali A, Shen H, Yin X. Simultaneous
Biochemistry: An Introduction. 2nd ed. determination of trace amounts of
New York: Wiley; 1997. 456 p. DOI: nickel, copper and mercury by liquid
978-0-471-18895-7 chromatography coupled with flow-
injection on-line derivatization and
[2] Nasiri MM, Taher MA, Fazelirad H. preconcentration. Analytica Chimica
Preparation and application of a simple Acta. 1998;369:215-223. DOI: 10.1016/
electrochemical sensor for the S0003-2670(98)00252-9
determination of copper in some real and
standard samples. Ionics. 2016;22: [8] Amjadi M, Fakhri ZA. Gold nanostar-
289-296. DOI: 10.1007/s11581-015- enhanced chemiluminescence probe for
1533-9 highly sensitive detection of Cu (II) ions.
Sensors and Actuators B: Chemical.
[3] Rouis A, Echabaane M, Sakly N, 2018;257:629-634. DOI: 10.1016/j.
Bonnamour I, Ouada HB. snb.2017.11.013
Characterization of a sensitive and
selective copper optode based on β- [9] Agnihotri NK, Singh VK, Singh HB.
ketoimine modified calix[4]arene Derivative spectrophotometric
derivative. Materials Science and determination of copper (II) in non-
Engineering: C. 2015;46:125-131. DOI: ionic micellar medium. Talanta. 1997;45:
10.1016/j.msec.2014.10.026 331-341. DOI: 10.1016/S0039-9140(97)
00137-9
[4] Ansari R, Delavar AF, Aliakbar A,
Mohammad-khah A. Solid-state Cu (II) [10] Kaur I, Sharma M, Kaur S, Kaur A.
ion-selective electrode based on Chemical sensors based on self-
polyaniline-conducting polymer film assembled chelating dithiol on
doped with copper carmoisine gold electrode for trace level detection
dye complex. Journal of Solid of copper (II) ions. Sensors and
State Electrochemistry. 2012;16: Actuators B: Chemical. 2020;312:
869-875. DOI: 10.1007/s10008-011- 127935-127946. DOI: 10.1016/j.snb.2020.
1436-2 127935
[5] Wu T, Xu T, Ma Z. Sensitive [11] Mahmoud A, Echabaane M, Omri K,

electrochemical detection of copper ions ElMir L, Chaabane RB. Development of
based on the copper (II) ion assisted an impedimetric non enzymatic sensor
etching of Au@ Ag nanoparticles. based on ZnO and Cu doped ZnO
Analyst. 2015;140:8041-8047. nanoparticles for the detection of
DOI: 10.1039/C5AN01888A glucose. Journal of Alloys and
Compounds. 2019;786:960-968.
[6] Soylak M, Narin I, Dogan M. Trace DOI: 10.1016/j.jallcom.2019.02.060
enrichment and atomic absorption
spectrometric determination of lead, [12] Somashekharappa KK,
copper, cadmium and nickel in drinking Rajendrachari S. Handbook of
water samples by use of an activated Carbon Nanomaterial-Based Sensors.
carbon column. Analytical Letters. 1997; 1st ed. Elsevier. 2022. p. 3. DOI: 10.
30:2801-2810. DOI: 10.1080/ 1016/B978-0-323-91174-0.
00032719708001823 00001-9
12
26
[13] Rajendrachari S, Ramakrishna D. 2012;16:499-504. DOI: 10.1007/

Handbook of Functionalized s10008-011-1358-z
Nanomaterial-Based Electrochemical
Sensors. 1st ed. Elsevier; 2022. p. 3. [19] Lisak G, Bobacka J, Lewenstam A.
DOI: 10.1016/B978-0-12-823788- Recovery of nanomolar detection limit of
5.00010-7 solid-contact lead (II)-selective
electrodes by electrode conditioning.
[14] Shashanka R, Jayaprakash GK, Journal of Solid State Electrochemistry.
Prakashaiah BG, Kumar M, Swamy BEK. 2012;16:2983-2299. DOI: 10.1007/
Electrocatalytic determination of s10008-012-1725-4
ascorbic acid using a green synthesised
magnetite nano-flake modified carbon [20] Intarakamhang S, Schuhmann W,
paste electrode by cyclic voltammetric Schulte A. Robotic heavy metal anodic
method. Materials Research Innovations. stripping voltammetry: Ease and efficacy
2022;26:229-239. DOI: 10.1080/ for trace lead and cadmium
14328917.2021.1945795 electroanalysis. Journal of Solid State
Electrochemistry. 2013;17:1535-1542.
[15] Shashanka R, Swamy BEK. DOI: 10.1007/s10008-013-2018-2
Simultaneous electro-generation and
electro-deposition of copper oxide [21] Özcan A, Hamid F, Özcan AA.
nanoparticles on glassy carbon electrode Synthesizing of a nanocomposite based
and its sensor application. SN Applied on the formation of silver nanoparticles
Sciences. 2020;2:956. DOI: 10.1007/ on fumed silica to develop an
s42452-020-2785-1 electrochemical sensor for carbendazim
detection. Talanta. 2021;222:
[16] Jebril S, Aguilera LC, Santander JMP, 121591-112160. DOI: 10.1016/j.
Dridi C. A novel electrochemical sensor talanta.2020.121591
modified with green gold
sononanoparticles and carbon black [22] Rizwan M, Elma S, Lim SA,
nanocomposite for bisphenol a Ahmed MU. AuNPs/CNOs/
detection. Materials Science and SWCNTs/chitosan-nanocomposite
Engineering B. 2021;264:114951-114961. modified electrochemical sensor for the
DOI: 10.1016/j.mseb.2020.114951 label-free detection of carcinoembryonic
antigen. Biosensors & Bioelectronics.
[17] Raghu GK, Sampath S, 2018;107:211217. DOI: 10.1016/j.
Pandurangappa M. Chemically bios.2018.02.037
functionalized glassy carbon spheres: A
new covalent bulk modified composite [23] Jiang H, Du C, Zou Z, Li X,
electrode for the simultaneous Akins DL, Yang H. A biosensing
determination of lead and cadmium. platform based on horseradish
Journal of Solid State Electrochemistry. peroxidase immobilized onto chitosan-
2012;16:1953-1963. DOI: 10.1007/ wrapped single-walled carbon
s10008-011-1595-1 nanotubes. Journal of Solid State
Electrochemistry. 2009;13:791-798.
[18] Yin T, Pan D, Qin W. A solid-contact DOI: 10.1007/s10008-008-0612-5
Pb2+ selective polymeric membrane
electrode with nafion-doped poly [24] Li Y, Li Y, Yang Y. A new
(pyrrole) as ionto-electron transducer. amperometric H2O2 biosensor based on
Journal of Solid State Electrochemistry. nanocomposite films of
13
27
chitosan6MWNTs, hemoglobin, and Macromolecules. 2020;160:456-469.

silver nanoparticles. Journal of Solid DOI: 10.1016/j.ijbiomac.2020.05.205
State Electrochemistry. 2012;16:
1133-1140. DOI: 10.1007/s10008-011- [30] Sheng Q , Liu R, Zheng J, Lin W,
1503-8 Li Y. Direct electrochemistry of glucose
oxidase immobilized on porous carbon
[25] Wang L, Zhu H, Hou H, Zhang Z, nanofiber/room temperature ionic
Xiao X, Song Y. A novel hydrogen liquid/chitosan composite film and its
peroxide sensor based on Ag biosensing application. Journal of Solid
nanoparticles electrodeposited on State Electrochemistry. 2012;6:739-745.
chitosan-graphene oxide/cysteamine- DOI: 10.1007/s10008-011-1420-x
modified gold electrode. Journal of Solid
State Electrochemistry. 2012;16: [31] Wang X, Feng Y, Dong P. Huang J a
693-1700. DOI: 10.1007/s10008-011- mini review on carbon quantum dots:
1503-8 Preparation, properties and
electrocatalytic application. Frontiers in
[26] Huang J, Xie Z, Huang Y, Xie L, Chemistry. 2019;7:671-680.
Luo S, Fan Q , et al. Electrochemical DOI: 10.3389/fchem.2019.00671
immunosensor with Cu (I)/Cu
(II)-chitosan-graphene nanocomposite- [32] Campuzano S, Sedeño PY,
based signal amplification for the Pingarrón JM. Carbon dots and graphene
detection of Newcastle disease virus. quantum dots in electrochemical
Scientific Reports. 2020;10:1-12. biosensing. Nanomaterials. 2019;9:
DOI: 10.1038/s41598-020-70877-3 634-652. DOI: 10.3390/nano9040634
[27] Comino CS, Rassas I, Minot S, [33] Echabaane M, Hfaiedh S, Smiri B,

Bessueille F, Arab M, Chevallier V, et al. Saidi F, Dridi C. Development of an
Voltammetric sensor based on impedimetric sensor based on carbon
molecularly imprinted chitosan-carbon dots and chitosan nanocomposite
nanotubes decorated with gold modified electrode for Cu(II) detection
nanoparticles nanocomposite deposited in water. Journal of Solid State
on boron-doped diamond electrodes for Electrochemistry. 2021;25:1797-1806.
catechol detection. Materials. 2020;13: DOI: 10.1007/s10008-021-04949-3
688-699. DOI: 10.3390/ma13030688
[28] Jalali F, Hassanvand Z, Barati A.

Electrochemical sensor based on a
nanocomposite of carbon dots,
Hexadecyltrimethylammonium bromide
and chitosan for Mesalazine
determination. Journal of Analytical
Chemistry. 2020;75:544-552.
DOI: 10.1134/S1061934820040061
[29] Nazari F, Ghoreishi SM, Khoobi A.

Bio-based Fe3O4/chitosan
nanocomposite sensor for response
surface methodology and sensitive
determination of gallic acid.
International Journal of Biological
28
Chapter 3
An Overview of the Synergy

of Electrochemistry and
Nanotechnology for Advancements
in Sensing Applications
Rajni Bais
Abstract
Electrochemical sensors have been widely employed in diverse domains of

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

between electrode and analyte) is converted into an applicable quantitative or qualita-
tive signal by electrochemical sensors. The sensors can generate electronic outputs
in the form of digital signals that can be analysed further [1]. Depending on the
mechanism involved in recognition, the sensors can be chemical or biological (biosen-
sor). Electrochemistry is found to play a crucial role in medical technology, forensics,
food, environmental sciences, defence settings, agriculture, among others [2, 3].
29
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estates bring me in nothing. As Minister at Frankfurt I always had a
balance to my credit, and also in St. Petersburg, where I was not
obliged to entertain, and did not.”
In the afternoon Friedlander called upon me with an invitation,
which I was obliged to decline. Our fat friend knew exactly why the
bombardment did not take place. “Blumenthal will not agree to it
because the Crown Prince does not want it,” he said; “and behind
him are the two Victorias.” So an Artillery officer told him a few days
ago.
Addendum.—According to a pencil note which I have now laid
hands on, Bohlen remarked yesterday at dinner that he understood
many valuable pictures and manuscripts removed by the French
from Germany had not been returned. Some one else observed that
it would be difficult to put this right now. “Well,” said the Chief, “we
could take others of equal value in their stead. We could, for
instance, pack up the best of the pictures out of the Gallery here.”
“Yes, and sell them to the Americans,” added Bohlen; “they would
give us a good price for them.”
According to another note the Chancellor related (doubtless on
the occasion when Holnstein dined with us): “In Crehanges the
Augustenburger again tricked me into shaking hands with him. A
Bavarian Colonel or General came over to me and held out his hand,
which I took. I could not put a name to the face, and when I had, it
was too late. If I could only come across him again, I would say to
him, ‘You treacherously purloined a hand from me at Crehanges; will
you please restore it?’”
I afterwards wrote an article on the neutrality of Luxemburg, and
the perfidious way in which people there are taking advantage of it to
help the French in every sort of way. It ran as follows:—We declared
at the commencement of the war that we would respect the neutrality
of the Grand Duchy, the neutrality of its government and people
being thereby assumed. That condition, however, has not been
fulfilled, the Luxemburgers having been guilty of flagrant breaches of
neutrality, although we on our part have kept our promise in spite of
the inconvenience to which we have often been put, especially in
connection with the transport of our wounded. We have already had
occasion to complain of the fortress of Thionville having been
provisioned by trains despatched at night with the assistance of the
railway officials and police authorities of the Grand Duchy. After the
capitulation of Metz numbers of French soldiers passed through
Luxemburg with the object of returning to France and rejoining the
French army. The French Vice-Consul opened a regular office at the
Luxemburg railway station, where soldiers were provided with money
and passports for their journey. The Grand Ducal Government
permitted all this to go on without making any attempt to prevent it.
They cannot, therefore, complain if in future military operations we
pay no regard to the neutrality of the country, or if we demand
compensation for the injury done by breaches of neutrality due to
such culpable negligence.
Sunday, December 4th.—We were joined at dinner by
Roggenbach, a former Baden Minister, and von Niethammer, a
member of the Bavarian Ambulance Corps, whose acquaintance the
Chief made recently in the hospital.
The Chief spoke at first of having again visited the wounded, and
afterwards added:—“Leaving Frankfurt and St. Petersburg out of
account, I have now been longer here than in any other foreign town
during my whole life. We shall spend Christmas here, which we had
not expected to do, and we may remain at Versailles till Easter and
see the trees grow green again, whilst we wait for news of the Loire
army. Had we only known we might have planted asparagus in the
garden here.”
The Minister afterwards said, addressing Roggenbach:—“I have
just looked through the newspaper extracts. How they do abuse the
treaties! They simply tear them into shreds. The National Zeitung,
the Kölnische,—the Weser Zeitung is still the most reasonable, as it
always is. Of course one must put up with criticism; but then one is
responsible if the negotiations come to nothing, while the critics have
no responsibility. I am indifferent as to their censure so long as the
thing gets through the Reichstag. History may say that the wretched
Chancellor ought to have done better; but I was responsible. If the
Reichstag introduces amendments every German Diet can do the
same, and then the thing will drag on and we shall not be able to
secure the peace we desire and need. We cannot demand the
cession of Alsace if no political entity is created, if there is no
Germany to cede it to.”
The question of the peace negotiations to follow in the
approaching capitulation of Paris was then discussed, and the
difficulties which might arise. The Chief said:—“Favre and Trochu
may say, ‘We are not the Government. We were part of it at one
time, but now that we have surrendered we are private persons. I am
nothing more than Citizen Trochu.’ But at that point I should try a
little coercion on the Parisians. I should say to them: ‘I hold you, two
million people, responsible in your own persons. I shall let you starve
for twenty-four hours unless you agree to our demands.’ Yes, and yet
another four-and-twenty hours, come what might of it.
“I would stick to my point—but the King, the Crown Prince, the
women who force their sentimental views upon them, and certain
secret European connections—I can deal with those in front of me—
but those who stand behind me, behind my back, or rather who
weigh upon me so that I cannot breathe!—people for whom the
German cause and German victories are not the main question; but,
rather, their anxiety to be praised in English newspapers. Ah, if one
were but the Landgrave!—I could trust myself to be hard enough.
But, unfortunately, one is not the Landgrave.[16] Quite recently, in
their maudlin solicitude for the Parisians, they have again brought
forward a thoroughly foolish scheme. Great stores of provisions from
London and Belgium are to be collected for the Parisians. The
storehouses are to be within our lines, and our soldiers are merely to
look at them, but not to touch them, however much they may
themselves suffer from scarcity and hunger. These supplies are to
prevent the Parisians starving when they shall have capitulated. We,
in this house, it is true, have enough, but the troops are on short
commons; yet they must suffer in order that the Parisians, when they
learn that supplies have been collected for them, may postpone their
capitulation till they have eaten their last loaf and slaughtered their
last horse. I shall not be consulted, otherwise I’d rather be hanged
than consent to it. But I am, nevertheless, responsible. I was
imprudent enough to call attention to the famine that must ensue. It
is true I mentioned it merely to the diplomatists. But they have thus
become aware of the fact. Otherwise it would not have occurred to
them.”
Swiss cheese having been handed round, some one raised the
question whether cheese and wine went well together. “Some
descriptions with certain wines,” was the Minister’s decision. “Not
strong ones like Gorgonzola and Dutch cheese, but others are all
right. I remember that at the time when people drank hard in
Pomerania—two hundred years ago or more—the good folks of
Rammin were the greatest topers in the country. One of them
happened to get a supply of wine from Stettin, which was not quite to
his liking. He complained accordingly to the merchant, who replied:
‘Eet kees to Wien, Herr von Rammin, deen smeckt de Wien wie in
Stettin ook to Rammin.’” (Low German: “Eat cheese to your wine,
good sir, from Rammin, then the wine will taste as good in Rammin
as it does here in Stettin.”)
Abeken, who had been with the King, came in afterwards, and
reported that his Majesty considered it would be well to write again to
the Emperor of Russia, and give him the views held here respecting
the Gortschakoff Note. The Chief said: “I think not. Enough has been
already written and telegraphed on the subject. They know in St.
Petersburg what we think. At least we must not write discourteously,
but rather in a friendly and amiable spirit: It is better however to say
nothing. If it were England! But we shall still want Russia’s good will
in the immediate future. When that is no longer necessary, we can
afford to be rude.”
Bohlen said: “They are quite beside themselves in Berlin. They
will have tremendous rejoicings there to-morrow, about the Emperor.
They are going to illuminate the town, and are making immense
preparations—a regular scene from fairyland!” “I fancy that will have
a good effect on the Reichstag,” observed the Chief. “It was really
very nice of Roggenbach to start off at once for Berlin” (in order to
urge moderation upon the grumblers in the Reichstag). “They” (the
members of Parliament, or the Berliners?) “attach much more
importance to the title of Emperor than the thing really deserves—
although I do not mean to say it is of no value.”
“That was really funny,” said Bohlen, “what Holnstein told us
about his interview with the King of Bavaria while he had a
toothache!”
“And the way I wrote to him in order to bring him round,” added
the Chancellor. “I knew that he could not bear me, and did not trust
me. So I wrote to him at last, that one of our estates had been
granted to our family by Ludwig, the Bavarian, as Lord of
Brandenburg, and that consequently we had had relations with his
house for more than five centuries. That was true, in so far as the
estates which we now hold were given to us in exchange for those
which the Hohenzollerns extorted from us. Holnstein said the letter
must have pleased the King very much, as he asked to read it again.
It was Holnstein who did most in this matter. He played his part very
cleverly. Tell me (to Bohlen), what Order can we give him?”
Bohlen: “He got the first class of the red fowl (the Red Eagle),
when the Crown Prince was in Munich.”
“Well then,” said the Chief, “he has got the highest decoration
that can be given to him.”
Bohlen: “Well, the King might give him the Imperial German
Order, about which Stillfried is already meditating, or he can found a
new Prussian Order, and thus supply a long-felt want.”
The Chief: “The Green Lion.”
Bohlen: “The German Order, with a black, white, and red ribbon.”
The Chief: “Or with the colours of the German Knights, a white
ribbon with small black stripes. It looks very well. The King did not
rightly know what it was all about when Holnstein requested an
audience. He said to me, ‘I observed to Holnstein, that I supposed
he wished to see Versailles.’ Of course, he (King William) could not
have arranged that himself”—(i.e., he could not have arranged to
acquire the Imperial dignity through the good offices of Bavaria.)
Werther, our Minister at Munich, seems to have reported that it
was intended there to commission Prince Luitpold with the
proclamation of the Emperor. The Chancellor observed: “A singular
idea! Another example of the way in which Bray treats matters of
business. How is he to do it? Step on to a balcony, and proclaim it?
—to whom? That might do if all the Princes were here—but with the
three or four now present! I had hoped that we should have made
peace before German unity was secured.”
Bohlen: “How pleased the King will feel at being made Emperor!
and still more so, the Crown Prince!”
The Chief: “Yes, and no doubt he is already thinking about the cut
of the Imperial robes.”
Monday, December 5th.—The Chief sent for me, and gave me
his instructions for a démenti with regard to the Bavarian Treaty, in
which his ideas were to be somewhat differently expressed. It was to
the following effect. The rumour that the Chancellor of the
Confederation only concluded the treaties with the South German
States, in anticipation that they would be rejected, or at least
amended in the Reichstag, is entirely without foundation. The debate
on the treaties must be brought to a close during the month of
December, and they must be adopted in their entirety, in order that
they may come into force on the 1st of January. Otherwise,
everything will remain uncertain. If the representatives of North
Germany alter the treaties, the South German Diets will be entitled to
make further amendments in a contrary sense, and there is no
knowing how far that right might not be exercised. In such
circumstances, the nation might have still to wait a long time for its
political unity. (“Perhaps ten years,” said the Chief, “and interim
aliquid fit.”) In that case, also the Treaty of Peace might not be what
we desire. The treaties may be deficient, but they can always be
gradually improved by the Reichstag, in co-operation with the
Bundesrath, and through the pressure of public opinion and national
sentiment. There is no hurry about that. If public opinion brings no
pressure to bear in that direction, it is obvious that the present
arrangement meets the views of the majority of the nation. Men of
national sentiment at Versailles are very anxious and uneasy at the
prevailing dispositions in Berlin. They are, however, to some extent
reassured by the fact that the Volkszeitung opposes the Bavarian
Treaty, as people have gradually grown accustomed to find that all
persons of political insight as a rule reject whatever that journal
praises and recommends, and are disposed to adopt whatever it
deprecates and censures.
At dinner Bamberger, the member of the Reichstag, was on the
Chief’s left. He is also going to Berlin in order to plead for the
adoption, without alteration, of the treaties with South Germany. The
conversation first turned on doctors and their knowledge, whereupon
the Chief (I cannot now remember on what grounds) delivered the
following weighty judgment: “Ah, yes, if doctors were only sensible
men; but as it is, they are dolts.” The question of the treaties was
then discussed, and the attitude of the Princes in this matter was
admitted to be correct. “Yes, but the Reichstag,” said the Chancellor;
“it reminds me of Kaiser Heinrich and his ‘Gentlemen, you have
spoiled my sport.’[17] In that instance it ultimately turned out all right,
but in this! All the members of the Reichstag might sacrifice
themselves one after another upon the altar of the Fatherland—it
would be all to no purpose.” After reflecting for a moment, the
Minister continued, with a smile: “Members of the Diet and the
Reichstag should be made responsible, like Ministers, no more and
no less, and placed on a footing of absolute equality. A Bill should
provide for the impeachment for treason of members of Parliament
when they reject important State treaties, or, as in Paris, approve of
a war undertaken on frivolous pretexts. They were all in favour of the
war, with the exception of Jules Favre. Perhaps I shall bring in some
such measure one day.”
The conversation then turned upon the approaching capitulation
of Paris, which must take place, at latest, within a month. “Ah!”
sighed the Chancellor, “it is then that my troubles will begin in
earnest.”... Bamberger was of opinion that they should not be
allowed merely to capitulate, but should immediately be called upon
to conclude peace. “Quite so,” said the Chief. “That is exactly my
view, and they should be forced to do so by starvation. But there are
people who want, above all else, to be extolled for their humane
feelings, and they will spoil everything—altogether forgetting the fact
that we must think of our own soldiers, and take care that they shall
not suffer want and be shot down to no purpose. It is just the same
with the bombardment. And then we are told to spare people who
are searching for potatoes; they should be shot too, if we want to
reduce the city by starvation.”
After 8 o’clock, I was called to the Chief several times, and wrote
two paragraphs for the Spenersche Zeitung in accordance with his
instructions. The first ran as follows:—“The Vienna newspapers
recently stated that ‘the German Austrians did not wish for war, and
the majority of the Austrian Slavs just as little.’ But there is in Austria,
and in Hungary, a not very numerous but influential party which does
desire war. When inquiry is made as to their real motive for doing so,
it is found to arise from pride and arrogance, from a kind of frivolous
chivalry, from a real hunger for political luxuries, from the
determination to play the Grand Seigneur before the world. The
Austrians of this party, in which very distinguished personages are
the moving spirits, seem to us to resemble the princely family of
Esterhazy. It is an ancient house, of high rank, with great estates and
a large fortune. Its members might well have been content to occupy
so eminent a position. But the evil genius of the family continually
drove them into extravagance, into making too great demands upon
their resources, into squandering enormous sums on horses,
diamonds, &c., with the object of displaying their wealth and
importance; so that they fell into debt, and, finally, came to the verge
of bankruptcy. The Esterhazy Lottery was then resorted to, and
actually did tide them over their difficulties. The family was saved.
But scarcely have they begun to breathe freely, and to regain their
footing, when their evil genius once more inspires them, and the old
game goes on again, until, at length, a time will come when even a
lottery will no longer save them. The Austrian party to which we have
already referred seems to us to present a close resemblance to the
Esterhazys. The State is a fine property, with excellent natural
advantages, a rich soil, and a great variety of valuable resources.
But the policy of the proprietors is exactly the same as that of the
Esterhazys. They must always overreach themselves, and try to be
more than they really are. The evil genius of the State regards as a
necessity what is in reality mere luxury, self-conceit, and the desire
to cut a great figure in the world. In that way, the ancient and wealthy
house has become a comparatively poor one, with a touch of the
Quixotic, and a still stronger flavour of unfair dealing, which is very
badly suited to our matter-of-fact age, when so much importance is
attached to the ability to pay one’s way. Every now and then, the
State, like its prototype the Esterhazys, escapes out of its troubles by
means of a lottery, or of some not particularly respectable financial
manœuvre; but then it suddenly puts forward fresh claims to a
position beyond its means, presumes to play the part of a great
Power, squanders millions on mobilisation, as its prototype does on
stables and diamonds, and thus sinks deeper and deeper into
financial difficulties. Instead of being able to satisfy its creditors by
good management and a modest bearing, it moves steadily forward,
without pause or rest, towards that bankruptcy which for a
considerable space has only been a question of time.”
The foregoing is an almost literal reproduction of the Chief’s own
words. I did not venture, however, to incorporate his concluding
remarks, which were as follows: “The Hapsburgs have really become
great through plundering old families—the Hungarians, for instance.
At bottom they are only a family of police spies (polizeilich-
Spitzelfamilie) who lived upon and made their fortune by
confiscations.”
The second paragraph, which referred to a statement in the
Indépendance Belge, pointed out that the relationship between the
Orleans and the House of Hapsburg-Lorraine through the Duc
d’Alençon, could not induce us Germans to regard them with any
special favour. The paragraph was to the following effect. It is known
that Trochu declined the offer of the Princes of the House of Orleans
to take part in the struggle against us. The Indépendance Belge now
states that the Duc d’Alençon, second son of the Duc de Nemours,
who was at that time incapacitated by illness from joining his uncles
and cousins in their offer of service, has now sought salvation by
adopting a similar course. The Brussels organ adds the significant
remark: “It will be remembered that the Duc d’Alençon is married to a
sister of the Empress of Austria.” We understand that hint, and
believe we shall be speaking in the spirit of German policy in replying
to it as follows:—The Orleans are quite as hostile to us as the other
dynasties that are fishing for the French throne. Their journals are
filled with lies and abuse directed against us. We have not forgotten
the hymn of praise which the Duc de Joinville raised after the battle
of Wörth to the franctireurs who had acted like assassins. The only
French Government we care for is that which can do us the least
harm, because it is most occupied with its own affairs, and with
maintaining its own position against its rivals. Otherwise Orleanists,
Legitimists, Imperialists, and Republicans are all of the same value
or no value to us. And as for those who throw out hints about the
Austrian relationship, they would do well to be on their guard, as we
are on ours. There is in Austria-Hungary one party in favour of
Germany and another hostile to her,—a party that wants to continue
the policy of Kaunitz in the Seven Years’ War, a policy of constant
conspiracy with France against German interests, and particularly
against Prussia. That is the policy which has recently been
connected with Metternich’s name, and which was pursued from
1815 to 1866. Since then more or less vigorous attempts have been
made to continue it. It is the party of which the younger Metternich is
regarded as the leader. He has for years past been looked upon as
the most ardent advocate of a Franco-Austrian alliance against
Germany, and one of the principal instigators of the present war. If
the Orleans believe that their prospects are improved by their
connection with Austria, they ought also to know that for that very
reason they have nothing to hope from us.
After Bucher, Keudell and myself had been for some time at tea,
we were joined by the Chief, and afterwards by Hatzfeldt, who had
been with the King. He said it was intolerably dull there.
“Grimm, the Russian Councillor of State, gave us a variety of
wearisome particulars about Louis Quatorze and Louis Quinze. The
W. worried us, and me in particular, with silly questions.” (He pouted
his lips, assumed a killing smile, and bent his head to one side,
imitating the Grand Duke’s affectations.) “He informed us that the
students at St. Cyr all received a portrait of Madame Maintenon, and
that he himself had one also. The King, who had occasionally rubbed
his eyes, observed somewhat pointedly, ‘I suppose they were
photographs.’ ‘No, oh no, engravings.’ ‘Well, then, what did you do
with yours?’ the King asked. ‘Why, nothing, I kept it.’ The Grand
Duke then asked me—he had obviously prepared the question in
advance, and perhaps learnt it by heart—‘Is the Revue des Deux
Mondes still published? An interesting newspaper.’ I replied, ‘I do not
know, your Royal Highness.’ ‘Who is the editor?’ ‘I do not know that
either.’ ‘So-o-o!’ The aides-de-camp were cruelly bored, and one of
them nudged Lehndorff, begging him in a whisper to give the old fool
a rap on the head with his crutch.”
“Yes, he is a fearful bore,” added the Chief. “What a miserable
position it must be for a man whose father was a Court official to him
or one like him, and who has to assume the same office himself—a
chamberlain or something of that kind, who has to listen day after
day to all that twaddle, and has no prospect of ever becoming
anything else! The Queen is just such another. She was educated in
the same school. I remember she once questioned me on a literary
subject, I believe it was about some French book or other. ‘I do not
know, your Majesty,’ I replied. ‘Ah, I suppose that does not interest
you.’ ‘No, your Majesty.’ Radowitz was very strong on those
subjects. He boldly gave every kind of information, and in that way
secured a great deal of his success at Court. He was able to tell
exactly what Maintenon or Pompadour wore on such and such a
day; such and such a gewgaw on her neck, her head-dress trimmed
with colibris or grapes, her gown pearl-grey or peacock-green with
furbelows or lace of this or that description—exactly as if he had
been there at the time. The ladies were all ear for these toilette
lectures, which he poured forth with the utmost fluency.”
The conversation then turned upon Alexander von Humboldt,
who appears to have been a courtier too, but not of the amusing
variety. The Chief said: “Under the late King I was the sole victim
when Humboldt chose to entertain the company in his own style. He
usually read, often for hours at a time, the biography of some French
savant or architect in whom nobody in the world except himself took
the slightest interest. He stood by the lamp holding the paper close
to the light, and occasionally paused for the purpose of making some
learned observation. Although nobody listened to him he had the ear
of the house. The Queen was all the time at work on a piece of
tapestry, and certainly did not understand a word of what he said.
The King looked through his portfolios of engravings, turning them
over as noisily as possible, evidently with the intention of not hearing
him. The young people on both sides and in the background enjoyed
themselves without the least restraint, so that their cackling and
giggling actually drowned his reading, which however rippled on
without break or stop like a brook. Gerlach, who was usually present,
sat on his small round chair which could barely accommodate his
voluminous person, and slept so soundly that he snored. The King
was once obliged to wake him, and said, ‘Pray, Gerlach, don’t snore
so loud!’ I was Humboldt’s only patient listener, that is to say I sat
silent and pretended to listen, at the same time following my own
thoughts, until at length cold cake and white wine were served. It put
the old gentleman in very bad humour not to be allowed to have the
talk all to himself. I remember once there was somebody there who
managed to monopolise the conversation, quite naturally, it is true,
as he was a clever raconteur and spoke about things that interested
everybody. Humboldt was beside himself. In a peevish surly temper
he piled his plate so high (pointing with his hand) with pâté de foie
gras, fat eels, lobsters’ tails, and other indigestible stuff,—a real
mountain,—it was astounding that an old man could put it all away.
At last his patience was exhausted, and he could not stand it any
longer. So he tried to interrupt the speaker. ‘On the peak of
Popocatapetl,’ he began,—but the other went on with his story. ‘On
the peak of Popocatapetl, seven thousand fathoms above’—but he
again failed to make any impression, and the narrative maintained its
easy flow. ‘On the peak of Popocatapetl, seven thousand fathoms
above the level of the sea,’ he exclaimed in a loud and excited tone,
—but with as little success as before. The talker talked on, and the
company had no ears for anybody else. That was something
unheard of, outrageous! Humboldt threw himself back in morose
meditation over the ingratitude of mankind, and shortly afterwards
left. The Liberals made a great deal of him, and counted him as one
of themselves. He was however a sycophant who aspired to the
favour of Princes and who was only happy when basking in the
sunshine of royalty. That did not prevent him however from criticising
the Court afterwards to Varnhagen, and repeating all sorts of
discreditable stories about it. Varnhagen worked these up into books,
which I also bought. They are fearfully dear when one thinks how
few lines in large type go to the page.” Keudell observed that they
were nevertheless indispensable for historical purposes. “Yes, in a
certain sense,” replied the Chief. “Taken individually the stories are
not worth much, but as a whole they are an expression of the
sourness of Berlin at a period when nothing of importance was
happening. At that time everybody talked in that maliciously impotent
way. It was a society which it would be hardly possible to realise to-
day without the assistance of such books, unless one had personal
experience of it. A great deal of outward show with nothing genuine
behind it. I remember, although I was a very little fellow at the time, it
must have been in 1821 or ’22. Ministers were still like strange
animals, regarded with wonder as something mysterious. There was
once a large party, which was at that time called an assemblée,
given at Schuckmann’s—what a monstrous huge beast he was as a
Minister! My mother also went there. I remember it as if it were to-
day. She wore long gloves that went up to here.” (He pointed to the
upper part of his arm.) “A dress with a short waist, her hair puffed out
on both sides, and a big ostrich feather on her head.” (The Chief left
this anecdote unfinished, if indeed there was any conclusion to it,
and returned to his former subject.) “Humboldt, however,” he
continued, “had a great many interesting things to tell when one was
alone with him, about the times of Frederick William III., and in
particular about his own first sojourn in Paris. As he liked me, owing
to the attention with which I listened to him, he told me a number of
pretty anecdotes. It was the same with old Metternich, with whom I
spent a few days at Johannisberg. Thun afterwards said to me, ‘I do
not know how you have managed to get round the old Prince, but he
has indeed looked into you as if you were a golden goblet, and he
told me if you do not come to an understanding with him then I really
don’t know what to say.’ ‘I can explain that to you,’ I replied. ‘I
listened to all his stories, and often prompted him to continue them.
That pleases the garrulous old people.’”
Hatzfeldt said that Moltke had written to Trochu telling him how
affairs stood at Orleans, and expressing his readiness to allow one
of Trochu’s officers to satisfy himself of the truth of his statement. He
would be furnished with a safe conduct to Orleans. The Chief said: “I
know that. But he should not have done so. They ought to find that
out for themselves. Our lines are now thin at various points, and they
have also a pigeon post. They will only imagine we are in a hurry to
get them to capitulate.”
Tuesday, December 6th.—In the morning I telegraphed to Berlin
and London more detailed particulars of the victory at Orleans. Then
wrote articles for the Moniteur and the German papers on the way in
which French officers interned in Germany are breaking their parole.
So long as this unworthy conduct receives approval and
encouragement from the Government of National Defence, it is
impossible for us to carry on any negotiations with it.
Dr. Lauer and Odo Russell dined with us to-day. The
conversation was not of particular interest. We had, however, a
delicious Palatine wine—Deidesheimer Hofstück and Forster
Kirchenstück, a noble juice, rich in all virtues, fragrant, and fiery. Aus
Feuer ward der Geist erschaffen. Even Bucher, who usually drinks
only red wine, did justice to this heavenly dew from the Haardt Hills.
I afterwards wrote an article in which I politely expressed surprise
at the brazen impudence with which Grammont reminds the world of
his existence in the Brussels Gaulois. He who, through his
unparalleled ineptitude, has brought so much misery upon France,
should, like his colleague Ollivier, have hidden himself in silence and
been glad to be forgotten. Or, inspired by his ancient name, he
should have joined the army and fought for his country, so as in
some degree to expiate the wrong he has done it. Instead of doing
anything of the kind, however, he dares to remind the world that he
still lives, and once conducted the foreign policy of France. “A
blockhead, a coward, an impudent fellow!” said the Chief, when he
instructed me to write this article. “You can use the strongest
expressions in dealing with him.”
CHAPTER XIV
THE PROSPECTS OUTSIDE PARIS IMPROVE
Wednesday, December 7th.—At dinner the Chief related some of his

Frankfurt reminiscences. “It was possible to get on with Thun,” he
said. “He was a respectable man. Taken altogether, Rechberg[18]
was also not bad. He was at least honourable from a personal
standpoint, although violent and irascible—one of those passionate,
fiery blondes! It is true that as an Austrian diplomat of those days he
was not able to pay too strict a regard to truth. I remember his once
receiving a despatch in which he was instructed to maintain the best
relations with us, a second despatch being sent to him at the same
time enjoining him to follow an exactly opposite course. I happened
to call upon him, and he inadvertently gave me the second despatch
to read. I saw immediately how matters stood and read it through.
Then handing it back to him I said: ‘I beg your pardon, but you have
given me the wrong one.’ He was fearfully embarrassed, but I
consoled him, saying I would take no advantage of his mistake,
using it merely for my personal information.” “The third, however,—
Prokesch—was not at all to my liking. In the East he had learnt the
basest forms of intrigue and had no sense of honour or truth. A
thoroughpaced liar. I remember being once in a large company
where some Austrian assertion which was not in accordance with the
truth was being discussed. Prokesch, raising his voice in order that I
might hear him, said: ‘If that be not true, then the Imperial and Royal
Cabinet has commissioned me to commit an act of perfidy, indeed
his Imperial and Apostolic Majesty has lied to me!’ and he
emphasised the word lied. He looked at me whilst he was speaking,
and, when he had finished, I replied, quietly: ‘Quite so, Excellency!’
He was obviously aghast, and as he looked round and found all eyes
cast down and a deep silence which showed approval of what I had
said, he turned away without a word and went into the dining-room
where the table was laid. He had recovered himself, however, after
dinner, and came over to me with a full glass in his hand—but for
that I should have thought he was going to challenge me—and said,
‘Well, let us make peace.’ ‘Certainly,’ I replied, ‘but what I said in the
other room was true, and the protocol must be altered.’ The protocol
was altered, an admission that it had contained an untruth. A rascally
fellow!”
Thursday, December 8th.—Some one asked at dinner how the
question of Emperor and Empire now stood. The Chief replied inter
alia: “We have had a great deal of trouble with it in the way of
telegrams and letters. But after all Holnstein has done the greater
part of the work. He is a clever fellow, and not in the least spoilt by or
prepossessed in favour of Court manners.” Putbus asked what
position he held. “Master of the Horse. He showed himself very
willing and energetic, making the journey to Munich and back in six
days. In the present condition of the railways that requires a great
deal of good will. Of course he has the necessary physique. Indeed,
not merely to Munich, but to Hohenschwangau,—and there saw the
King who had just been operated under chloroform for a tumour in
the gum. But King Lewis also greatly contributed to the speedy
settlement of the matter. He received the letter immediately, and at
once gave a definite answer. He might easily have said that he must
first take some fresh air in the mountains, and would answer in three
or four days. The Count has certainly done us a very good service in
the affair; but I really do not know how we can reward him.” I forget
how the conversation came to deal with the terms “Swell,” “Snob,”
and “Cockney,” which were the subject of much discussion. The
Chief mentioned a certain diplomat as a “swell,” and observed: “It is
really a capital word, but we cannot translate it into German.
‘Stutzer,’ perhaps, but that conveys at the same time pompousness
and self-importance. ‘Snob’ is something quite different, while it is
also very difficult for us to render properly. It denotes a variety of
attributes, but principally one-sidedness, narrowness, slavery to local
or class prejudices, philistinism. A ‘snob’ is something like our
‘Pfalbürger,’ yet not quite. It includes also a petty conception of
family interests, political narrow-mindedness, rigid adherence to
ideas and habits that have become a second nature. There are also
female snobs and very distinguished ones. The feminine half of our
Court are snobs. Our two most exalted ladies are snobs. The male
element is not snobbish. One may also talk of party snobs—those
who in larger political issues cannot emancipate themselves from the
rules that govern private conduct—the ‘Progressist snob.’ The
cockney again is quite another person. That term applies more
particularly to Londoners. There are people there who have never
been outside their own walls and streets, never got away from the
brick and mortar, who have never seen life anywhere else nor
travelled beyond the sound of Bow Bells. We have also Berliners
who have never left their city. But Berlin is a small place compared to
London, or even Paris, which has also its cockneys, although they
are known by another name there. There are hundreds of thousands
in London who have never seen anything but London. In such great
cities conceptions are formed which permeate the whole community,
and harden into the most inveterate prejudices. Such narrow and
silly ideas arise in every great centre of population where the people
have no experience, and often not the faintest notion of how things
look elsewhere. Silliness without conceit is endurable, but to be silly
and unpractical, and at the same time conceited, is intolerable.
Country life brings people into much closer contact with realities.
They may be less educated there, but what they know they know
thoroughly. There are, however, snobs in the country also. (Turning
to Putbus.) Just take a really clever shot. He is convinced that he is
the first man in the world, and that sport is everything, and that those

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Functionalized Nanomaterial-Based

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A New Method for Determination

Keywords: impedance, molecular weight, vapor pressure, Raoult’s law

Electrochemical impedance spectroscopy (EIS) finds a special place among the

solutions of electrical circuits by converting them into a system of algebraic equations.

2. Electrochemical impedance spectroscopy—a tool to evaluate the proton

2.1 Fundamentals of electrochemical impedance spectroscopy

Similar to resistance, the term impedance measures the ability of a material to

applied sinusoidally varying potential to the resulting sinusoidally varying current at

EðtÞ ¼ E0 sin ðωtÞ (2)

IðtÞ ¼ I0 sin ðωt þ φÞ (3)

EðtÞ E0 sin ðωtÞ sin ðωtÞ

The impedance is therefore expressed in terms of a magnitude, Z0, and a phase

EðtÞ E0 sin ðωtÞ

EðtÞ ¼ E0 sin ðωtÞ (6)

EðtÞ E0 sin ðωtÞ E0

When the concept is applied for a capacitor, where, φ ¼ π2

Where, ‘C’ is capacitance of the pure capacitor (in F).

In general, the impedance can be represented as,

Where, Z Re = real part of impedance,

The phase angle φ is given as,

Were, s is the Laplace complex variable or frequency,

2.2 Variation of frequency

When we consider a homogeneous system, it is represented by a conductance (G)

Where σ and ε are conductivity and permittivity of the homogeneous system

CM G2P þ CP G2M þ ðω2 CM CP ÞðCP þ CM Þ

The solid-state proton conducting electrolytes can be synthesized by simple

3. Determination of molecular mass using the electrochemical impedance

Vapor pressure is a characteristic property of a substance in the condensed phase at

Where P0 is vapor pressure of pure protic solvent.

Where P is vapor pressure of solvent in solution

Where X 1 is mole fraction of protic solvent.

Where n1 and n2 are number of moles of solvent and solute respectively.

The measurement of vapor pressure of solvents in pure form and in solutions is a

EIS electrochemical impedance spectroscopy

[1] Ardavan H. A speed-of-light barrier [10] Mallaiya K, Subramaniam R,

porous materials. Microporous and one-dimensional ferrous oxalate

[18] Maspoch D, Ruiz-Molina D, [27] Sahoo SC, Kundu T, Banerjee R.

[23] Zhao D, Timmons DJ, Yuan D, [30] Horike S, Umeyama D, Kitagawa S.

[34] Saravanabharathi D, Obulichetty M,

[35] Saravanabharathi D, Obulichetty M,

[36] Saravanabharathi D, Obulichetty M,

[37] Singh K, Tiwari RU. Solid state

[38] Chikh L, Delhorbe V, Fichet O.

[39] Nasar A, Perveen R. Applications of

[40] Ye G, Janzen N, Goward GR. Solid-

[41] Coster HG, Chilcott TC, Coster AC.

Keywords: carbon dots, chitosan, nanocomposite, copper(II), Impedimetric sensors,

equipment, time-consuming operation, and an inability to do onsite analysis. Thus,

Copper sulfate (CuSO4, ≥ 99.9%), mercury nitrate monohydrate (Hg(NO3)2.H2O,

these measurements was optimized at 600 mv. An aqueous ammonium acetate

2.3 Synthesis of CDs

2.4 Preparation of modified glassy carbon electrode (GCE)

3. Characterization of CDs and CS-CDs/GCE

4. EIS characterization of the CS-CDs/GCE electrode