Efficient electro-chemical sensor for sensitive Cd2+detection based on novel in-situ synthesized hydrazonoyl bromide (HB)

Article abstract of DOI:10.1016/j.molstruc.2020.129690

In this approach, an efficient methodology for synthesis of a novel hydrazonoyl bromide (HB) containing trifluoromethyl moiety by using fluorine-containing building blocks was achieved. The synthesized HB was fully characterized with various methods such as Infra-red spectroscopy (IR), Thin layer chromatography (TLC), ¹H NMR, ¹⁹F-NMR, ¹³C NMR, and elemental analyses. In-situ potential examination as reliable technique, an electrochemical sensor based on prepared HB was used for the selective detection of environmental hazardous heavy metal ion, Cd²⁺. The fabricated sensor was found to perform linearly over the concentration range (linear dynamic range) of 0.1 nM~0.01 mM of Cd²⁺ ion and the sensitivity (51.12 μAμM^?1cm^?2) and detection limit (53.85±2.69 pM) of the proposed sensor were estimated from the slope of calibration curve (plot of current versus concentration). Furthermore, the proposed Cd²⁺ ion sensor was exhibited good analytical performances such reproducibility, stability in phosphate buffer medium and efficiency to detect Cd²⁺ ion in real environmental samples. This progress in the field of metal ion sensor development might be a cost effective and efficient method in the detection of unsafe and hazardous ions for the safety of environmental and ecological fields in broad scales.

Full text of DOI:10.1016/j.molstruc.2020.129690

ARTICLE IN PRESS
JID: MOLSTR
[m5G;December 8, 2020;15:13]
Journal of Molecular Structure xxx (xxxx) xxx
Contents lists available at ScienceDirect
Journal of Molecular Structure
journal homepage: www.elsevier.com/locate/molstr
2
+
Efficient electro-chemical sensor for sensitive Cd detection based on
novel in-situ synthesized hydrazonoyl bromide (HB)
Faisal M. Aqlana,b, M.M. Alam , Abdullah S. Al-Bogami , Tamer S. Saleha,d,
c
a
a
e
f,g
f,g
Mohmmad Y. Wani , Ammar Al-Farga , Abdullah M. Asiri , Mohammad Razaul Karim ,
h
i
f,g,∗
Jahir Ahmed , M.A. Fazal , Mohammed M. Rahman
a
Department of Chemistry, College of Sciences, University of Jeddah, 21589 Jeddah, P.O. Box 80327, Saudi Arabia
Department of Chemistry, Faculty of Science, University of IBB, IBB, Yemen
b
c
d
e
f
Department of Chemical Engineering and Polymer Science, Shahjalal University of Science and Technology, Sylhet 3100, Bangladesh
Green Chemistry Department, National Research Centre, Dokki, Cairo 12622, Egypt
Department of Biochemistry, College of Sciences, University of Jeddah, 21589 Jeddah, P.O. Box 80327, Saudi Arabia
Center of Excellence for Advanced Materials Research, Faculty of Science, King Abdulaziz University, Jeddah 21589, Saudi Arabia
Department of Chemistry, Faculty of Science, King Abdulaziz University, Jeddah 21589, P.O. Box 80203, Saudi Arabia
Promising Centre for Sensors and Electronic Devices (PCSED), Advanced Materials and Nano-Research Centre, Najran University, P.O. Box: 1988, Najran
g
h
11001, Saudi Arabia
i
Department of Mechanical and Materials Engineering, University of Jeddah, Saudi Arabia
a r t i c l e i n f o
a b s t r a c t
Article history:
In this approach, an efficient methodology for synthesis of a novel hydrazonoyl bromide (HB) contain-
ing trifluoromethyl moiety by using fluorine-containing building blocks was achieved. The synthesized
HB was fully characterized with various methods such as Infra-red spectroscopy (IR), Thin layer chro-
matography (TLC), 1H NMR, 19 F-NMR, 13 C NMR, and elemental analyses. In-situ potential examination as
reliable technique, an electrochemical sensor based on prepared HB was used for the selective detection
Received 2 October 2020
Revised 20 November 2020
Accepted 26 November 2020
Available online xxx
of environmental hazardous heavy metal ion, Cd2 . The fabricated sensor was found to perform linearly
+
Keywords:
Hydrazonoyl bromide
Cd2 ion detection
Electrochemical method
In-situ visual inspection
Environmental safety
over the concentration range (linear dynamic range) of 0.1 nM~0.01 mM of Cd2 ion and the sensitivity
+
+
−1
−2
(51.12 μAμM cm ) and detection limit (53.85± 2.69 pM) of the proposed sensor were estimated from
2+
the slope of calibration curve (plot of current versus concentration). Furthermore, the proposed Cd
ion sensor was exhibited good analytical performances such reproducibility, stability in phosphate buffer
medium and efficiency to detect Cd2 ion in real environmental samples. This progress in the field of
metal ion sensor development might be a cost effective and efficient method in the detection of unsafe
and hazardous ions for the safety of environmental and ecological fields in broad scales.
+
©
2020 Elsevier B.V. All rights reserved.
1
. Introduction
ceuticals [11–13]. The fact that fluorinated organic compounds and
materials often show unusual physical, chemical, and/or biological
properties and behavior (in comparison with their nonfluorinated
counterparts) is often called ‘‘fluorine effects’’ or ‘‘fluorine magic’’
[13,14]. Therefore we intend here to synthesize novel hydrazonyl
bromide containing trifluromethyl moiety identified as 2-oxo-
2-phenyl-N-(4-(trifluoromethyl)phenyl)acetohydrazonoyl bromide.
Meanwhile, design and development of sensor molecules for recog-
nition and sensing of cationic analytes are of major interest since
cations may be hazard and need to be detected easily [15,16]. Cad-
mium (Cd) is one of these elements, which element is existing in
group IIB of periodic table and the toxicity of it is well known
A plethora of heterocyclic biologically active molecules has been
much reported in literature synthesized via utilization of Hydra-
zonoyl halides [1–6]. Our previous research work has described
the utility of Hydrazonoyl halides as quite reactive polyfunctional
reagents in the synthesis of a variety of novel heterocyclic sys-
tems as pyrazoles and isoxazoles [7–10]. An introduction of tri-
fluromethyl group into Hydrazonoyl bromide will help to find
novel synthons of wide applications and utilization in chemistry
field. Especially The highest impact of fluorine in life sciences is
associated with the development of agrochemicals and pharma-
[
17–19]. Due to chloric exposure of Cd2 in human and animals,
+
it is accumulated in the liver, lungs and kidney and results re-
nal tubular dystunction, emphysema, osteoporosis and osteomala-
∗
Corresponding author.
E-mail address: mmrahman@kau.edu.sa (M.M. Rahman).
https://doi.org/10.1016/j.molstruc.2020.129690
0
022-2860/© 2020 Elsevier B.V. All rights reserved.
Please cite this article as: F.M. Aqlan, M.M. Alam, A.S. Al-Bogami et al., Efficient electro-chemical sensor for sensitive Cd2+detection based
on novel in-situ synthesized hydrazonoyl bromide (HB), Journal of Molecular Structure, https://doi.org/10.1016/j.molstruc.2020.129690

ARTICLE IN PRESS
JID: MOLSTR
[m5G;December 8, 2020;15:13]
F.M. Aqlan, M.M. Alam, A.S. Al-Bogami et al.
Journal of Molecular Structure xxx (xxxx) xxx
cia [20,21]. It is also responsible to pathological change of central
nervous system and finally the damage [22]. The various reports
have been claimed that the toxicity of cadmium is destroy the soil
ecosystem due to killing of microorganisms which are necessary
for fertility of soil [23]. Globally, the significant amount of cad-
mium is accumulated in environment due to number of anthro-
pogenic and man making activities. Industrially, Cd is widely used
as anticorrosive agent, to stabilize PVC goods, pigment in cooler, in
batteries and fertilizers [24–26]. There is a great possibility to af-
2.2. Synthesis of
2-oxo-2-phenyl-N-(4-(trifluoromethyl)phenyl)acetohydrazonoyl
bromide (5)(HB)
Method A: To stir the solution of dimethylphenacylsulfonium
bromide (2) (50.0 mmol) in ethanol (250.0 ml), it was added the
sodium acetate trihydrate (12.0 g) into the reactor. After stirring for
10 min, the mixture was cooled to −5 °C as well as treated with
4-(trifluoromethyl)benzen diazonium salt solution [prepared by di-
azotizing 4-(trifluoromethyl)aniline (50 mmol) in hydrochloric acid
(6.0 M, 6.0 ml) with sodium nitrite solution (3.5 g, 50.0 mmol),
fect human and animals with toxicity of Cd2 ion through food
+
chain. Thus, it is very important to check Cd2 ion contamina-
+
tion of environment with a reliable method. The existing methods
in H O (15.0 ml)]. The addition of the diazonium salt was car-
2
to detection of Cd2 ions are atomic absorption [27], ICP-ES (in-
ductively coupled plasma-optical emission spectrometry) [28] and
ICP-MS (inductively coupled plasma-mass spectroscopy) [29]. But
these methods are uncomforted with expensive, large and heavy
instruments, time consuming and unfavorable for in-situ detection.
Recently, a number of researches based on electrochemical ap-
proach are efficiently executed to overcome these drawbacks [30–
+
ried out with rapid stirring over the period of 60 min. Later the
reaction mixture was stirred for further 2 h at 0 °C and then
left for 6 h at 4 °C into the refrigerator. The resulting solid pre-
cipitate was collected by filtration, washed thoroughly with wa-
ter, then finally dried. The crude solid product was crystallized
from ethanol to afforded 9.5 g (70% yield) of 2-oxo-2-phenyl-N-
(4-(trifluoromethyl)phenyl)acetohydrazonoyl bromide.
3
3]. Thus, this study will be reported the synthesis of new com-
Method B: To a solution of dimethylphenacylsulfonium bromide
(2) (10 mmol) in ethanol (50.0 ml), it was added with the N-
nitroso-N-(4-(trifluoromethyl)phenyl)acetamide (4) (10 mmol). The
reaction mixture was warmed slightly and shaken till complete
dissolution of the reactants, then finally continuously stirred for
4 h. The precipitated crystalline product was collected, washed
with methanol and re-crystallized from ethanol to afford com-
pound with identical in all respects to those synthesized by
method A. Finally the product is fully characterized and analyzed
pound based on the hydrazonyl bromide backbone scaffold bear-
ing trifluromethyl moiety (HB). Furthermore, In this study, the de-
sired Cd2 metal ion sensor was fabricated using a GCE coated
+
with prepare HB as thin uniform layer and applied to detect Cd2
+
ion in phosphate buffer medium. The analytical performances of
sensor prove were inspected in detail in-term of sensitivity, repro-
ducibility, stability, efficiency, linear dynamic range and detection
limit. Besides this, it was effectively to measure Cd2 ion real en-
vironmental samples successively. Thus, this effectual process to
development of heavy metal ion sensor might be a most reliable
methodology in approaching future.
+
for melting point, mixed melting points, IR spectroscopy, and 1
H
NMR spectrum.
The physical data of the synthesized compound are listed be-
low:
2
. Experimental
orange solid; mp 157–159 °C; IR (KBr) v/cm 1: 3320 (NH),
−
1
1
702(CO), 1601 (C = N); H NMR (DMSO–d ): δ7.41–7.43 (m,
2
.1. Reagents and methodology
6
3
H, ArH), 7.65–7.69 (m, 4H, ArH), 7.92–7.94 (m, 2H, ArH),
1
1.18 (br s, 1H, NH, D O exchangeable);13C NMR (DMSO–d ):
All organic solvents were purchased from commercial sources
2
6
δ 117.0,120.1(q, 2JCF = 32.93 Hz), 124.2 (q, 1JCF= 270.10 Hz),
and used as received unless otherwise stated. From Sigma-Aldrich
USA), the analytical grade cobalt (II) nitrate, barium (II) nitrate,
1
26.14 (q, 3JCF = 6.55 Hz), 128.65,129, 134.32, 137.85, 146,
(
1
64, 185;19F NMR (DMSO–d ): δ −61.21; MS (m/z): 369
magnesium (II) chloride, silver nitrate, arsenic (III) chloride, zinc
sulfate, cadmium sulfate, mercury (II) chloride, chromium (III)
chloride and aluminum sulfate were procured and used with-
out farther any treatment. The other sub-ordinary chemical such
6
+
M ); C15H BrF N O: Anal. Calcd: C, 48.54; H, 2.72; N, 7.55.
10 3 2
(
Found C, 48.79; H, 2.64; N, 7.39%.
as NH , nafion (5% nafion suspension in ethanol), monosodium
2.3. Modification of glassy carbon electrode (GCE) using HB
3
and disodium phosphate buffer were implemented to fulfill this
study. All other chemicals were purchased from Merck, Aldrich or
Acros and used without further purification. Thin-layer chromatog-
raphy (TLC) was performed on pre-coated Merck 60 GF254 silica
gel plates with a fluorescent indicator, and detection by means
of UV light at 254 and 360 nm. The melting points were mea-
sured on a Stuart melting point apparatus and are uncorrected.
IR spectra were recorded on a Smart iTR, which is an ultra-high-
performance, versatile Attenuated Total Reflectance (ATR) sampling
accessory on the Nicolet iS10 FT-IR spectrometer. The NMR spec-
tra were recorded on a Bruker Avance III 400 (9.4 T, 400.13 MHz
for 1H, 100.62 MHz for 13C and 376.25 MHz for 19 F) spectrom-
eter with a 5-mm BBFO probe, at 298 K. Chemical shifts (δ in
2
The modification of GCE (Surface area: 0.0316 cm ) is the most
important task of this study before development of sensor HB/GCE
probe. Using ethanol, the prepared HB was subjected to make
thicker slurry and was to deposit onto the flat part of GCE as thin
uniform layer. Then, it was kept at laboratory conditions to dry
and smooth the fabricated film completely. To bringing the stabil-
ity of modified GCE during the electrochemical analysis in phos-
phate buffer medium, a drop of 5% nafion (1.0 μL) was added on
GCE and put inside a low temperature oven at 35 °C temperature
to dry. After complete the modification of GCE, an electrochemi-
cal cell was arranged with Keithley electrometer, the modified GCE
was used as working and a simple Pt-wire as counter electrode
ppm) are given relative to internal solvent, DMSO–d6 2.50 for 1
H
respectively. A series of Cd
2+
ion solution ranging the concentra-
and 39.50 for 13C. Mass spectra were recorded on a Thermo ISQ
Single Quadrupole GC–MS. Elemental analyses were carried out
on a EuroVector instrument C, H, N, S analyzer EA3000 Series.
dimethylphenacylsulfonium bromide (2) [34] and N-nitroso-N-(4-
tion as 0.1 nM ~ 0.01 mM were prepared in deionized water and
used as desired analyte. A curve known as calibration was plot-
ted as current versus concentration of Cd2 ion relation. The slope
+
of resulted calibration curve was used to estimate the sensitivity
and detection limit (DL) of desired Cd2 ion electrochemical sen-
sor. Considering the maximum linear segment in calibration curve,
the linear dynamic range (LDR) was identified and related all ana-
lytical parameters were also calculated from this range.
+
(trifluoromethyl)phenyl)acetamide (4) [35] were prepared accord-
ing to reported literature. For electrochemical analysis, the Keith-
ley electrometer (Model: 6517B, USA) was used to find the sensor
parameters.
2

ARTICLE IN PRESS
JID: MOLSTR
[m5G;December 8, 2020;15:13]
F.M. Aqlan, M.M. Alam, A.S. Al-Bogami et al.
Journal of Molecular Structure xxx (xxxx) xxx
Scheme 1. Synthesis of HB by using fluorine-containing building blocks methodology.
3
. Results and discussion
related to the CF3 group was found at approximately δ 124.13 ppm
with 1JCF 273.70 Hz, and a quartet signal related to C-4 was
observed at approximately δ133.46 ppm with 2JCF 31.78 Hz and
at δ126.38 ppm with 3JCF 3.75 Hz. Fluorinated carbons are of-
ten difficult to find in 13C spectra with low signal-to-noise ra-
tios because the signal is spread over multiple lines and can be
buried in the noise. The presence of C-F coupling added sharp
evidence for the proposed structure of the formed compound
5 (HB).
ꢀ
The new hydrazonoyl bromide 5 were prepared by coupling
of dimethylphenacylsulfonium bromide (2) with diazotized 4-
trifluoromethyl)aniline 3 in ethanol solution buffered with sodium
acetate or with N-nitroso-N-(4-(trifluoromethyl)phenyl)acetamide
(
(4) in ethanol (Scheme 1).
Noteworthy, several attempts at direct coupling of 2–
bromo–1-phenylethan-1-one (1) with diazonium salt of 4-
trifluoromethyl)aniline and N-nitrosoacetarylamides were
(
3
failed (Scheme 1). This may be due to the extreme acidity of
α-hydrogen that present in β-ketosulfonium salt 2, which make
the sulfonium susceptible for electrophilic substitution reaction.
Structure of compound 5 (HB) was confirmed on bases of el-
emental analysis and spectral data, in which the IR show pres-
2+
3
.1. Detection of Cd by HB
The potential application of synthesized HB onto GCE was to
2+
development of an electrochemical sensor selective to Cd cation.
As it was described, the prepared HB was deposited on the flat part
of GCE with conductive nafion binder. The conductive nafion was
used to improve both the binding strength and electron transfer
rate of working electrode. Thus, the fabricated sensor shows long-
term stability in phosphate buffer medium and enhanced activ-
ity during electrochemical analysis. Firstly, the assembled electro-
chemical sensor with HB/binder/GCE was implemented to measure
the selectivity and to execute this performance, the heavy metal
−
1
ence of one band due to NH group at 3312 cm
in addition to
−
1
two bands at 1702 and 1601 cm due to carbonyl and C = N re-
spectively. The 1H NMR of compound 5 shows a D O exchange-
2
able singlet signal at δ11.18 in addition to multiple signals δ 7.41–
7
.95 due to nine protons of aromatics. In addition, the 19 F NMR
spectrum is the key analysis in research that deals with fluo-
rine chemistry. 19 F NMR of compound 5 shows only the signal
of trifluoromethyl group was observed at δ−61.21 ppm, and al-
ways C-F coupling of compounds that contain fluorine was used
to study it. The 13C NMR of compound 5 shows that the 19 F-
decoupled 13C NMR spectrum of 5. A characteristic quartet signal
2+
2+
2+
+
3+
2+
2+
2+
3+
ions such as Co , Ba , Mg , Ag , As , Zn , Cd , Hg , Cr
3+
and Al were analyzed at 0.1 μM concentration of each metal ion
and applied potential 0 ~ +1.5 V as illustrated in Fig. 1(a). As it
2+
is perceived in Fig. 1(a), the cadmium (Cd ) ion shows the high-
3

ARTICLE IN PRESS
JID: MOLSTR
[m5G;December 8, 2020;15:13]
F.M. Aqlan, M.M. Alam, A.S. Al-Bogami et al.
Journal of Molecular Structure xxx (xxxx) xxx
Fig. 1. The electrochemical analysis of propped sensor to fix its properties and performances. (a) Evaluation of selectivity, (b) electrochemical response based on concentra-
tion variation of Cd2 ion from lower to higher, (c) calibration of Cd ion sensor based on HB/binder/GCE, and (d) computation of the LDR.
+
2+
cuted with 0.1 μM concentration of Cd2 ion in phosphate buffer
+
est electrochemical response among all the metal ions. Then, the
electrochemical responses of Cd2 ion were investigated lower to
higher concentration as represented in Fig. 1(b). From Fig. 1(b), it
is clearly stated that I-V responses can be distinguished from lower
+
medium illustrated in Fig. 2(a).
As it is recorded, the Cd2
+
cation sensor based on
HB/binder/GCE shows an appreciable response time around 18.0 s.
Thus, this 18.0 s. is required by proposed electrochemical sensor to
complete an electrochemical response. The capability to reproduce
the similar electrochemical responses in identical conditions is a
reliability measuring analytical performance. As it is demonstrated
in Fig. 2(b), the seven runs are completely identical and undis-
tinguished and the intensity of electrochemical responses are not
altered even the washing of electrode after each trail. This test was
experimented with 0.1 μM concentration of Cd2 ion and potential
ranging as 0 ~ +1.5 V. The precession of current data at potential
+1.5 V was measured and in-term of relative standard deviation,
it is equal to 1.10%, a result provides information about high preci-
sion. From the outcome of reproducibility performance, it is clear
to higher concentration of Cd2 ion. Thus, it can be predicted that
+
I-V responses are varied with the corresponding concentration of
Cd2 ion. To estimate the sensor analytical performances such as
sensitivity, linear dynamic range and detection limit, it is necessary
to make calibration. Thus, a relation of current vs. concentration of
+
Cd2 ion was established as demonstrated in Fig. 1(c). To establish
this calibration, the current data are isolated from Fig. 1(b) at ap-
plied potential +1.5 V and plotted against the corresponding con-
centration of Cd2 ion. As it is perceived in Fig. 1(c), the current
data are contentiously distributed from 0.1 nM to 0.01 mM in lin-
ear manner and this range of concentration is identified as linear
dynamic range (LDR). Obviously, the resulted LDR is a wider range
of concentration. To, verify the linearity of LDR, the current vs. log
+
+
+
that the projected Cd2 ion sensor is capable to measure Cd
+
2+
(
conc.) are plotted as in Fig. 1(d) and the current data are fitted
ion preciously in an identical conditions. Since, this sensor probe
will perform in phosphate buffer medium, the stability is very
2
with the regression co-efficient value r =0.99, provides the infor-
important. Thus, the stability of this Cd2 ion was inspected by
reproducibility performance for elongated period of time around
seven days as represent in Fig. 2(c). The similar observation as in
Fig. 2(b) is found. The comparison with similar study is presented
in the Table 1 [36,37] to check the validity of this newly fabricated
HB/Nafion/GCE sensor probe. As it is apparent from Table 1, the
comparison is executed based on the analytical performance of
electrochemical sensor [36–41] such as sensitivity, LDR and DL and
+
mation about the linearity of LDR.
The sensitivity of projected Cd2 cation sensor based on
+
HB/binder/GCE is calculated using the slope of calibration curve
and resulted sensitivity is equal to 51.12 μAμM 1cm , is a satis-
factory sensitivity. The detection limit (53.85 ± 2.69 pM) is esti-
mated at signal to noise ratio of 3, a result might be appreciably
lower limit of detection. The response time of an electrochemical
sensor is an efficiency measuring performance. This test was exe-
−
−2
4

ARTICLE IN PRESS
JID: MOLSTR
[m5G;December 8, 2020;15:13]
F.M. Aqlan, M.M. Alam, A.S. Al-Bogami et al.
Journal of Molecular Structure xxx (xxxx) xxx
Fig. 2. Optimization of HB/Nafion/GCE sensor probe by electrochemical mehtod. (a) Response time, (b) reproducibility, and (c) stability.
Table 1
Comparison of analytical performances of Cd2+cationic sensor by electrochemical method with HB/Nafion/GCE sensor
probe.
∗
#LDR
Modified GCE
DL
Sensitivity
Ref.
−
−2
−2
MPEBSH/GCE
140.0 pM
32.4 pM
17.39 pM
0.11 nM
0.33 μg/L
—
0.35 nM – 0.35 mM
0.1 nM – 0.1 mM
0.1 nM – 0.1 mM
1.0 nM – 1.0 mM
—
2.22 μAμM 1cm
[36]
−
BZNA/GCE
2.93 μAμM 1cm
[37]
5.459 μAμM 1cm
−
−2
[38]
ZnYCdO/NafionlGCE
Poly(N-Methylaniline) Ce2(WO4)3@CNT
Mesoporous silica
ZnO nanosheets
5.138 μAμM 1cm
−
−2
[39]
—
—
[40]
−
1
0 to 150.0 mg L
0.1 nM - 0.01 mM
[41]
−
−2
HB/Nafion/GCE
53.85 pM
51.12 μAμM 1cm
This work
∗
DL (detection limit)
..#LDR (linear dynamic range), pM (picomole), mM (millimole).
the Cd2 cation sensor with HB/binder/GCE shows the appreciable
performances. The sensitivity of this HB/Nafion/GCE sensor probe
shows the highest value compared to reported sensor in similar
electrochemical methods.
+
there is a smaller surface coverage of Cd ions on HB/nafion/GCE
film (Fig. 3a) and hence the surface reaction proceeds steadily. By
2+
increasing the Cd2 ions concentration, the surface reaction is in-
+
creased significantly (gradually increased the response as well) due
In this approach, current-voltage behaviors of the HB are ac-
to surface area (assembly of HB/Nafion/GCE) contacted with Cd2
+
tivated as a function of Cd2 ions concentration at room condi-
tions, where improved current response is observed. The possible
complexation bonding mechanism between Cd(II) and HB is ex-
plained here in Fig. 3. As obtained, the current response of the HB-
+
ions molecules (Fig. 3b). Further increase of Cd
2+
ions concentra-
tion on HB/Nafion/GCE surface, it is exhibited a more rapid in-
creased the current responses, due to larger area covered by Cd2
+
ions and the π-π interaction of the functional groups in HB. The
π-π interaction could be approaches as inter-molecular and intra-
molecular interactions of the HB [48]. Usually, the surface coverage
∗
film is increased (π-π interaction) with the increasing concentra-
tion of Cd2 ions in the bulk solution, however similar phenom-
+
of Cd2 ions on HB/Nafion/GCE surface is reached to saturation,
+
ena for toxic chemical detection have also been reported earlier
[
42–47]. For a low concentration of Cd2 ions in buffer medium,
+
based on the regular enhancement of current responses (Fig. 3c).
5

ARTICLE IN PRESS
JID: MOLSTR
[m5G;December 8, 2020;15:13]
F.M. Aqlan, M.M. Alam, A.S. Al-Bogami et al.
Journal of Molecular Structure xxx (xxxx) xxx
Fig. 3. Schematic representation of Cd2 interaction onto HB/Nafion/GCE electrode. Sensing mechanism of the probable interaction of Cd2+with HB with conducting 5%
+
nafion binders embedded onto flat-GCE. (a) Fabricated GCE electrode, (b) ꢀ-ꢀ inter-molecular bonding interactions between lone-pair of nitrogen (HB) and Cd2 , and (c)
+
Electrochemical responses of fabricated HB/Nafion/GCE electrode.
cess in the detection of 0.1 μM Cd2 . From this observation, it is
concluded that HB/Nafion/GCE sensor probe has no interfering ef-
fect during detection unsafe cadmium ion by electrochemical ap-
proach at room conditions. Finally, the analytical performances of
+
Here, the significant result was achieved by HB/Nafion/GCE,
which can be employed as efficient electron mediators for the
development of efficient cationic sensors. Actually the response
time was around 18.0 s for the fabricated HB/Nafion.GCE to reach
the saturated steady-state level. The higher sensitivity of the fab-
Cd2 ions using HB/Nafion/GCE sensor probe are investigated by
reliable electrochemical method in terms of sensitivity and detec-
tion limit in short response time as well as reproducibility. This
extensive research is performed in terms of preparation and char-
acterization of HB and applied for the Cd2 ions sensor using elec-
trochemical method. From this novel sensor probe development, it
informs the highest selectivity and fast detection for environmental
carcinogenic heavy metal cadmium ion to the HB-fabricated-GCE-
probe. Potentially, the same concept might be applied to the fabri-
cation of new sensor probes with various composites or polymers
for monitoring other environmentally unsafe cationic heavy metal
ions [88–96]. Hence, this approach is introduced a new route for
an efficient heavy cationic sensor probe development for the safety
of environmental and healthcare fields in a broad scales.
+
ricated HB/Nafion/GCE toward selective Cd2 could be attributed
to the excellent absorption (porous surfaces in HB/Nafion/GCE),
adsorption ability and high electro-catalytic activity of HB com-
pared to other cations. The estimated sensitivity of the fabricated
sensor is relatively higher and detection limit is comparatively
lower than previously reported chemical sensors based on other
nano-composites or nano-materials modified electrodes measured
by electrochemical sensors [49–57]. Due to high specific surface
+
+
area, HB provides a favorable nano-environment for the Cd2
+
detection with good quantity. The modified HB/Nafion/GCE sen-
sor has also better reliability and stability. The high sensitivity
of HB/Nafion/GCE provides high electron communication features
which enhanced the direct electron transfer between the active
sites of HB and coated-GCE [58–76]. The HB/Nafion/GCE system
is demonstrated a simple and reliable approach for the detection
of toxic cations. It is also revealed that the significant access to a
large group of cations for wide-range of ecological and biomed-
ical applications in environmental and health-care fields respec-
3
.2. Real environmental samples analyses by HB/Nafion/GCE sensor
probe
The electrochemical sensor based on HB/Nafion/GCE was in-
tively [77–87]. In presence and absence of target analyte (Cd2 ),
the HB/Nafion/GCE sensor is measured and included in the Fig. 4a.
The potential interference effect from the typical inorganic ions
+
2+
vestigated to detect the Cd
ion in real environmental samples
in recovery method by using electrochemical technique. The sam-
ples are collected from the underground mineral water, municipal
water and read sea water. The analyzed data by electrochemical
method are calculated and represented in Table 2. As it is obtained
and organic compounds during this Cd2 detection was studied
+
and presented in Fig. 4b. Obtained results indicate that 10-folds of
+
2+
2+
+
−
2−, NO3−, CO32−
Na , Fe , Ba , K , Cl , SO , ethanol, methanoic
4
from Table 2, the outcomes are acceptable and satisfactory. There-
acid, and ethanoic acid have negligible interfering effect with cad-
mium ion by HB/Nafion/GCE sensor probe in electrochemical pro-
2+
fore, it can be concluded that the proposed Cd
ion sensor with
HB/Nafion/GCE sensor probe by electrochemical technique is able
6

ARTICLE IN PRESS
JID: MOLSTR
[m5G;December 8, 2020;15:13]
F.M. Aqlan, M.M. Alam, A.S. Al-Bogami et al.
Journal of Molecular Structure xxx (xxxx) xxx
Fig. 4. Sensing performance of HB/Nafion/GCE sensor in the absence and presence of other ions by electrochemical approach. (a) Control experiment (in presence and
absence of Cd2 ion) and (b) Interfering effect of various inorganic and organic components.
+
Table 2
Analyses of real environmental samples with HB/Nafion/GCE sensor by electrochemical method.
Determined Cd2 conc.a by HB/Nafion/GCE (μM)
+
Added Cd2 ion conc. (μM)
+
Average recoveryb (%)
RSDc (%) (n = 3)
Sample
R1
R2
R3
Tape water
Sea water
0.01000
0.01000
0.00964
0.00977
0.00970
0.00953
0.01018
0.00940
0.00969
0.01040
0.00924
96.20
101.17
94.47
0.85
3.16
2.47
Mineral water 0.01000
a
Mean of three repeated determination (signal to noise ratio 3) with by HB/Nafion/GCE.
b
c
2+
Concentration of Cd ion determined/Concentration taken. (Unit: μM).
Relative standard deviation value indicates precision among three repeated measurements(R1,R2,R3).
to detect the selective Cd2 reliably in real samples obtained from
+
CRediT authorship contribution statement
various sources.
Faisal M. Aqlan: Data curation, Formal analysis. M.M. Alam:
Formal analysis, Validation. Abdullah S. Al-Bogami: Data curation.
Tamer S. Saleh: Formal analysis. Mohmmad Y. Wani: Formal anal-
ysis. Ammar Al-Farga: Formal analysis. Abdullah M. Asiri: Con-
ceptualization, Supervision. Mohammad Razaul Karim: Investiga-
tion, Formal analysis. Jahir Ahmed: Validation, Investigation. M.A.
Fazal: Writing - review & editing. Mohammed M. Rahman: Writ-
ing - review & editing.
4
. Conclusion
We found that the versatile fluorine-containing building blocks
such diazonium salt of 4-(trifluoromethyl)aniline or N-nitroso-N-
4-(trifluoromethyl)phenyl)acetamide (1) are useful for the synthe-
(
sis of novel hydrazonoyl bromide containing a trifluoromethyl moi-
ety (HB). The structure of the HB was confirmed via elemental and
spectroscopic analyses. The proposed Cd2 cation electrochemical
+
Acknowledgments
sensor was fabricated as HB/binder/GCE and implemented to de-
tect selective Cd2 ion in phosphate buffer medium successfully.
The analytical performances such as sensitivity, LDR, DL, response
time, reproducibility and stability were calculated and found as
satisfactory. In real time application, it showed excellent perfor-
+
Center of Excellence for Advanced Materials Research, King Ab-
dulaziz University, Jeddah, Saudi Arabia is highly acknowledged for
financial supports and research facilities.
mance to detect selective Cd2 ion in real environmental samples
by HB/binder/GCE sensor probe in electrochemical method. It is in-
troduced a noble route to detect the carcinogenic heavy metal ions,
+
References
[1] T.A. Farghaly, M.A. Abdallah, H.K. Mahmoud, The Utility of Hydrazonoyl
Cd2+ by using fabricated HB/binder/GCE sensor probe using elec-
Halides in theSynthesis of Bioactive Heterocyclic Compounds, Curr. Org. Synth.
14 (2017) 430–461.
trochemical method for the safety of environmental and healthcare
fields in large scales.
[2] A.S. Shawali, A review on bis-hydrazonoyl halides: Recent advances in their
synthesis and their diverse synthetic applications leading to bis-heterocycles
of biological interest, J. Adv. Res. 7 (2016) 873–907.
[3] N.A. Kheder, T.A. Farghaly, Bis-Hydrazonoyl chloride as precursors for synthesis
of novel polysubstituted bis-azoles, Arabian J. Chem. 10 (2017) S3007–S3014.
Declaration of Competing Interest
[4] A.R. Sayed, M.M. Saleh, M.A. Al-Omair, H.M.A. Al-Lateef, Efficient route syn-
thesis of new polythiazoles and their inhibition characteristics of mild-steel
corrosion in acidic chloride medium, J. Mol. Struct. 1184 (2019) 452–461.
I declare the following states, The article is original, The article
has been written by the stated authors who are ALL aware of its
content and approve its submission, The article has not been pub-
lished previously, The article is not under consideration for publi-
cation elsewhere, and No conflict of interest exists.
[
5] I. Yavari, M. Nematpour, S. Yavari, F. Sadeghizadeh, Copper-catalyzed one-pot
synthesis of tetrasubstituted pyrazoles from sulfonyl azides, terminal alkynes,
and hydrazonoyl chlorides, Tetrahedron Lett 53 (2012) 1889–1890.
6] R.M. Mohare, E.M. Samir, P.A. Halim, Synthesis, and anti-proliferative, Pim-1
kinase inhibitors and molecular docking of thiophenes derived from estrone,
Bioorg. Chem. 83 (2019) 402–413.
[
7

ARTICLE IN PRESS
JID: MOLSTR
[m5G;December 8, 2020;15:13]
F.M. Aqlan, M.M. Alam, A.S. Al-Bogami et al.
Journal of Molecular Structure xxx (xxxx) xxx
[
7] T.S. Saleh, K. Narasimharao, N.S. Ahmed, S.N. Basahel, S.A. Al-Thabaiti,
M. Mokhtar, Mg–Al hydrotalcite as an efficient catalyst for microwave as-
sisted regioselective 1,3-dipolar cycloaddition of nitrilimines with the enam-
inone derivatives: A green protocol, J. Mol. Catal. A Chem. 367 (2013) 12–
[33] A. Wahid, A.M. Asiri, M.M. Rahman, One-step facile synthesis of Nd2O3/ZnO
nanostructures for an efficient selective 2,4-dinitrophenol sensor probe, Appl.
Surface Sci. 487 (2019) 1253–1261.
[34] A.M. Farag, M.S. Algharib, Organic Preparations and Procedures International:
The New Journal for Organic Synthesis 20 (1988) 521–526.
22.
[
8] A.E.M. Mekky, T.S. Saleh, A.S. Al-Bogami, Synthesis of novel pyrazoles incor-
porating a phenothiazine moiety: unambiguous structural characterization of
the regioselectivity in the 1, 3-dipolar cycloaddition reaction, Tetrahedron 69
[35] W.E. Bachmann, R.A. Hoffman, The Preparation of Unsymmetrical Biaryls by
the Diazo Reaction and the Nitrosoacetylamine Reaction, Chapter 6, Organic
reaction (2011) 224–261.
(
2013) 6787–6798.
[36] M.N. Arshad, T.A. Sheikh, M.M. Rahman, A.M. Asiri, H.M. Mar-
wani, M.R. Awual, Fabrication of cadmium ionic sensor based on
[
9] A.S. Al-Bogami, T.S. Saleh, H.M. Albishri, Ultrasonic irradiation assisted ef-
ficient regioselective synthesis of CF3-containing pyrazoles catalyzed by
Cu(OTf)2/Et3N, Chem. Central J. 7 (2013) 101.
10] T.S. Saleh, N.M. Abd-El-Rahman, Ultrasound promoted synthesis of substituted
pyrazoles and isoxazoles containing sulphone moiety, Ultrason. Sonochem. 16
ꢀ
(E)-4-Methyl-N -(1-(pyridin-2-yl)ethylidene)benzenesulfonohydrazide
(MPEBSH) by electrochemical approach, J. Organomet. Chem. 827 (2017)
49–55.
[
[37] R.M. El-Shishtawy, H.A. Al-Ghamdi, M.M. Alam, Z.M. Al-amshany, A.M. Asiri,
M.M. Rahman, Development of Cd2 sensor based on BZNA/Nafion/Glassy car-
bon electrode by electrochemical approach, Chem. Eng. J. 352 (2018) 225–231.
[38] M.A. Hussein, M.M. Alam, N.A. Alenazi, K.A. Alamry, A.M. Asiri, M.M. Rahman,
Nanocomposite Based Functionalized Polyethersulfone and Conjugated Ternary
+
(
2009) 237–242.
[
11] J. Wang, M. Sanchez-Rosello, J.L. Acena, C. del Pozo, A.E.Sorochinsky,S. Fustero,
V.A. Soloshonok, H. Liu, Fluorine in pharmaceutical industry: fluorine-contain-
ing drugs introduced to the market in the last decade (2001-2011), Chem. Rev.
ZnYCdO Nanomaterials for the Fabrication of Selective Cd2 Sensor Probe, J.
+
1
14 (2014) 2432–2506.
[
12] W. Wan, Y. Gao, H. Jiang, J. Hao, Fluoroalkyl substituted (Z)-dehydro α-amino
ester as a building block for the fluorine-containing cyclopropyl α-amino es-
ters and dihydrooxazole, J. Fluor. Chem. 129 (2008) 510–514.
Polymer Res 25 (2018) 262.
[39] A. Khan, A.A.P. Khan, M.M. Rahman, A.M. Asiri, S.Y.M. Alfaifi,
L.A. Taib, Towards Facile Preparation and Design of Mulberry Shaped
Poly(N–Methylaniline)Ce2(WO4)3@CNT Nanocomposite and Its Application
[
13] L. Bian, X. Lu, J. Xu, J. Chen, H. Deng, M. Shao, Y. Jin, H. Zhang, W. Cao, Facile
synthesis of 2-perfluoroalkylated benzoxazolines and benzothiazolines, J. Fluor.
Chem. 151 (2013) 20–25.
for Electrochemical Cd2
+
Ions Detection for Environment Remediation,
Polym.-Plast. Technol. Eng. 57 (2018) 335–345.
[
14] S.V. Druzhinin, E.S. Balenkova, V.G. Nenajdenko, Recent advances in the
[40] M.R. Awual, M. Khraisheh, N.H. Alharthi, M. Luqman, A. Islam, M.R. Karim,
M.M. Rahman, M.A. Khaleque, Efficient detection and adsorption of cad-
mium(II) ions using innovative nano-composite materials, Chem. Eng. J. 343
(2018) 118–127.
chemistry of α, β-unsaturated trifluoromethylketones, Tetrahedron 63 (2007)
7753–7808.
[
15] P.C. Li, L. Zhang, M. Yang, K.L Zhang, A novel luminescent 1D→2D polyrotax-
ane Zn(II)-organic framework showing dual responsive fluorescence sensing
for Fe3+ cation and Cr(VI) anions in aqueous medium, J. Luminescence 207
[41] S.B. Khan, M.M. Rahman A.M. Asiri, H.M. Marwani, K.A. Alamry, An assessment
of zinc oxide nanosheets as a selective adsorbent for cadmium, Nanoscale Res.
Lett. 8 (2013) 377–385.
(2019) 351–360.
[
16] G. Xiang, L. Wang, W. Cui, X. An, L. Zhou, L. Li, D. Cao,
-Pyridine-1H-benzo[d]imidazole based conjugated polymers: selective
[42] M.R. Awual, M.M. Hasan, A. Islam, A.M. Asiri, M.M. Rahman, Optimization of an
innovative composited material for effective monitoring and removal of cobalt
(II) from wastewater, J. Mol. Liq. 298 (2020) 112035.
[43] X.L. Cheng, H. Zhao, L.H. Huo, S. Gao, J.G. Zhao, ZnO nanoparticulate thin film:
preparation, characterization and gas-sensing property, Sens. Actuator. B 102
(2004) 248.
[44] M.M. Rahman, H.B. Balkhoyor, A.M. Asiri, Removal of a melamine contami-
nant with Ag-doped ZnO nanocomposite materials, New J. Chem. 43 (2019)
18848–18859.
2
A
2
+
+
fluorescent chemosensor for Ni or Ag depending on the molecular linkage
sites, Sens. Actuators B: Chem. 196 (2014) 495–503.
[
[
17] L. Friberg, T. Kjellstrom, G. Nordberg, M. Piscator, Handbook on the toxicology
of metals, Elsevier/North Holland, Amsterdam, 1966, p. 355.
18] L. Friberg, M. Piscator, G.F. Nordberg, T. Kjellstrom, Cadmium in the Environ-
ment, CRC Press, Inc., Cleveland, 1974.
[
19] G.P. Samarawickrama, The Chemistry, Biochemistry and Biology of Cadmium,
Elsevier/North Holland, Amsterdam, 1979, p. 341.
[45] J.K. Srivastava, P. Pandey, V.N. Mishra, R. Dwivedi, Structural and micro struc-
tural studies of PbO-doped SnO2 sensor for detection of methanol, propanol
and acetone, J. Natur. Gas Chem. 20 (2011) 179.
[
20] C.V. Nolan, Z.A. Shaikh, The vascular endothelium asa target tissue inacute cad-
mium toxicity, Life Sci 39 (1986) 1403–1409.
[
21] B.A. Fower, G.F. Nordberg, The Renal Toxicity of Cadmium Metallothionein:
Morphometric and X-Ray Microanalytical Studies, Toxicol. Appl. Pharmacol. 46
[46] M.R. Awual, M.M. Hasan, A. Islam, M.M. Rahman, A.M. Asiri, M.A. Khaleque,
M.C. Sheikh, Offering an innovative composited material for effective lead (II)
monitoring and removal from polluted water, J. Cleaner Production 231 (2019)
214–223.
(1978) 609–623.
[22] G. Gabbiani, D. Baic, C. Dbziel, Toxicity of Cadmium for the Central Nervous
System, Exp. Neurol. 18 (1967) 154–160.
[47] M.M. Rahman, M.M. Alam, A.M. Asiri, M.R. Awual, Fabrication of 4-aminophe-
nol sensor based on hydrothermally prepared ZnO/Yb 2 O 3 nanosheets, New
J. Chem. 41 (2017) 9159–9169.
[48] A. Masoumi, M.S. Gargari, G. Mahmoudi, B. Miroslaw, B. Therrien, M. Abedi,
P. Hazendonk, Structural diversity in mercury (II) coordination complexes with
asymmetrical hydrazone-based ligands derived from pyridine, J. Molecular
Struct 1088 (2015) 64.
[
23] K. Vig, M. Megharaj, N. Sethunathan, R. Naidu, Bioavailability and toxicity of
cadmium to microorganisms and their activities in soil: a review, Adv. Environ.
Res. 8 (2003) 121–135.
[
24] L. Jarup, Hazards of heavy metal contamination, Br. Med. Bull. 68 (2003)
167–182.
[25] Z. Zhang, Z. Zhang, H. Liu, X. Mao, W. Liu, S. Zhang, Z. Nie, X. Lu, Ultratrace and
robust visual sensor of Cd2 ions based on the size-dependent optical proper-
+
[49] M.M. Rahman, Efficient formaldehyde sensor development based on Cu–
codoped ZnO nanomaterial by an electrochemical approach, Sens. Actuators,
B 305 (2020) 127541.
ties of Au@g-CNQDs nanoparticles in mice models, Biosens. Bioelectron. 103
(2018) 87–93.
[
26] Y. Zhang, Y. Zhao, Y. Yang, J. Shen, H. Yang, Z. Zhou, S. Yang, A bifunctional sen-
[50] M.R. Awual, M.M. Hasan, G.E. Eldesoky, M.A. Khaleque, M.M. Rahman,
M. Naushad, Facile mercury detection and removal from aqueous media in-
volving ligand impregnated conjugate nanomaterials, Chem. Eng. J. 290 (2016)
243–251.
sor based on Au-Fe3O4nanoparticle for the detection of Cd2 , Sens. Actuators,
+
B 220 (2015) 622–626.
[
27] G. Kaya, M. Yaman, Online preconcentration for the determination of lead, cad-
mium and copper by slotted tube atom trap (STAT)-flame atomic absorption
spectrometry, Talanta 75 (2008) 1127–1133.
[51] M.M. Alam, A.M. Asiri, M.M. Rahman, Fabrication of phenylhydrazine sen-
sor with V2O5 doped ZnO nanocomposites, Mater. Chem. Phys. 243 (2020)
122658.
[52] M.M. Rahman, M.M. Alam, A.M. Asiri, Potential application of mixed metal
oxide nanoparticle-embedded glassy carbon electrode as a selective 1,4-diox-
ane chemical sensor probe by an electrochemical approach, RSC Adv. 9 (2019)
42050–42061.
[
28] M.H. Mashhadizadeh, M. Amoli-Diva, M.R. Shapouri, H. Afruzi, Solid phase ex-
traction of trace amounts of silver, cadmium, copper, mercury, and lead in
various food samples based on ethylene glycol bis-mercaptoacetatemodified
3-(trimethoxysilyl)-1-propanethiol coated Fe3O4 nanoparticles, Food Chem 151
(2014) 300–305.
[
29] L. Dostal, W.M. Kohler, J.E. Penner-Hahn, R.A. Miller, C.A. Fierke, J. Gerontol,
Fibroblasts from long-lived rodent species exclude cadmium, A Biol. Sci. Med
Sci. 70 (2015) 10–19.
[53] M.M. Rahman, J. Ahmed, A.M. Asiri, Selective bilirubin sensor fabrication based
on doped IAO nanorods for environmental remediation, New J. Chem. 43
(2019) 19298–19307.
[
30] M.S. Alam, M.F. Shabik, M.M. Rahman, M.D. Valle, M.A. Hasnat, Enhanced elec-
trocatalytic effects of Pd particles immobilized on GC surface on the nitrite
oxidation reactions, J. Electroanal. Chem. 839 (2019) 1–8.
[54] M.M. Rahman, A. Wahid, A.M. Asiri, Development of highly sensitive 1, 4-diox-
ane sensor with semiconductor NiO-doped Nd 2 O 3 nanostructures by elec-
trochemical approach, New J. Chem. 43 (2019) 17395–17402.
[55] M.K. Alam, M.M. Rahman, M.M. Rahman, D. Kim, A.M. Asiri, F.A. Khan, In-situ
synthesis of gold nanocrystals anchored graphene oxide and its application in
biosensor and chemical sensor, J. Electroanal. Chem. 835 (2019) 329–337.
[56] M.R. Awual, N.H. Alharthi, Y. Okamoto, M.R. Karim, M.E. Halim, M.M. Hasan,
M.M. Rahman, M.M. Islam, M.A. Khaleque, M.C. Sheikh, Ligand field effect for
Dysprosium (III) and Lutetium (III) adsorption and EXAFS coordination with
novel composite nanomaterials, Chem. Eng. J. 320 (2017) 427–435.
[
31] M.M. Rahman, M.M. Hussain, A.M. Asiri, D-Glucose sensor based on ZnO•V2O5
NRs by an enzyme-free electrochemical approach, RSC Adv. (2019)
1670–31682.
9
3
[
32] D.F. Katowah, M.M. Rahman, M.A. Hussein, T.R. Sobahi, M.A. Gabal, M.M. Alam,
A.M. Asiri, Ternary nanocomposite based poly (pyrrole-co-O-toluidine), cobalt
ferrite and decorated chitosan as a selective Co2+ cationic sensor, Composites,
Part B 175 (2019) 107175.
[
57] M.M. Rahman, M.M. Alam, A.M. Asiri, Carbon black co-adsorbed ZnO nanocom-
posites for selective benzaldehyde sensor development by electrochemical ap-
proach for environmental safety, J. Indust. Eng. Chem. 65 (2018) 300–308.
8

ARTICLE IN PRESS
JID: MOLSTR
[m5G;December 8, 2020;15:13]
F.M. Aqlan, M.M. Alam, A.S. Al-Bogami et al.
Journal of Molecular Structure xxx (xxxx) xxx
[
58] M.R. Awual, M.M. Hasan, J. Iqbal, A. Islam, M.A. Islam, S. Khandaker, A.M. Asiri,
M.M. Rahman, Ligand based sustainable composite material for sensitive
nickel(II) capturing in aqueous media, J. Environ. Chem. Eng. 8 (2020) 103591.
59] M.M. Rahman, K.A. Alamry, M.R. Awual, A.E.M. Mekky, Efficient Hg(II)
ionic probe development based on one-step synthesized diethyl
thieno[2,3-b]thiophene-2,5-dicarboxylate (DETTDC2) onto glassy carbon
electrode, Microchem. J. 152 (2020) 104291.
[78] M.M. Rahman, M.R. Karim, M.M. Alam, M.B. Zaman, N. Alharthi, H. Alharbi,
A.M. Asiri, Facile and efficient 3-chlorophenol sensor development based on
photolumenescent core-shell CdSe/ZnS quantum dots, Sci. Rep. 10 (2020) 557.
[79] M.M. Rahman, M.M. Alam, A.M. Asiri, Detection of toxic choline based on Mn
2 O 3/NiO nanomaterials by an electrochemical method, RSC Adv. 9 (2019)
35146–35157.
[
[80] D.F. Katowah, M.A. Hussein, M.M. Alam, T.R. Sobahi, M.A. Gabal, A.M. Asiri,
[
60] M.R. Awual, M.M. Hasan, A.M. Asiri, M.M. Rahman, Cleaning the arsenic (V)
contaminated water for safe-guarding the public health using novel composite
material, Composites, Part B 171 (2019) 294–301.
M.M. Rahman, Poly (pyrrole-co-o-toluidine) wrapped CoFe
2
O
4/R
(GO–OXSWCNTs) ternary composite material for Ga 3+ sensing ability,
RSC Adv. 9 (2019) 33052–33070.
[
61] M.R. Awual, M.M. Hasan, A. Islam, M.M. Rahman, A.M. Asiri, M.A. Khaleque,
M.C. Sheikh, Introducing an amine functionalized novel conjugate material for
toxic nitrite detection and adsorption from wastewater, J. Cleaner Prod 228
[81] F.M. Aqlan, M.M. Alam, T.S. Saleh, A.M. Asiri, J. Uddin, M.M. Rahman, Synthe-
sis of novel pyrazole incorporating a coumarin moiety (PC) for selective and
sensitive Co 2+ detection, New J. Chem. 43 (2019) 12331–12339.
[82] Z. Mumtarin, M.M. Rahman, M.A. Hasnat, Electrocatalytic reduction of hydrox-
ylamine on copper immobilized platinum surface: Heterogeneous kinetics and
sensing performance, Electrochim. Acta 318 (2019) 486–495.
(2019) 778–785.
[62] M.R. Awual, A. Islam, M.M. Hasan, M.M. Rahman, A.M. Asiri, M.A. Khaleque,
M.C. Sheikh, Introducing an alternate conjugated material for enhanced lead
(
II) capturing from wastewater, J. Cleaner Prod 224 (2019) 920–929.
63] M.M. Rahman, M.M. Hussain, M.N. Arshad, M.R. Awual, A.M. Asiri,
Arsenic sensor development based on modification with
E)-N’(2-nitrobenzylidine)-benzenesulfonohydrazide: real sample analy-
sis, New J. Chem. 43 (2019) 9066–9075.
[83] M.M. Rahman, M.M. Alam, K.A. Alamry, Sensitive and selective m-tolyl hy-
drazine chemical sensor development based on CdO nanomaterial decorated
multi-walled carbon nanotubes, J. Ind. Eng. Chem. 77 (2019) 309–316.
[84] W. Ghann, V. Sharma, H. Kang, F. Karim, B. Richards, S.M. Mobin, J. Uddin,
M.M. Rahman, M.F. Hossain, M.H. Kabir, M.N. Uddin, The synthesis and char-
acterization of carbon dots and their application in dye sensitized solar cell,
Inter. J. Hydrogen Energy 44 (2019) 14580–14587.
[
(
a
[
[
[
64] M.M. Alam, M.T. Uddin, A.M. Asiri, M.R. Awual, M.M. Rahman, Detection of uric
acid based on doped ZnO/Ag 2 O/Co 3 O 4 nanoparticle loaded glassy carbon
electrode, New J. Chem. 43 (2019) 8651–8659.
65] M.R. Awual, M.M. Hasan, A.M. Asiri, M.M. Rahman, J Novel optical composite
material for efficient vanadium (III) capturing from wastewater, Mol. Liq. 283
[85] J. Ahmed, R.H. Rakib, M.M. Rahman, I.A. Siddiquey, S.S.M. Islam, M.A. Hasnat,
Electrocatalytic Oxidation of 4-Aminophenol Molecules at the Surface of an
FeS2/Carbon Nanotube Modified Glassy Carbon Electrode in Aqueous Medium,
ChemPlusChem 84 (2019) 175–182.
(2019) 704–712.
66] M.M. Alam, A.M. Asiri, M.T. Uddin, M.A. Islam, M.R. Awual, M.M. Rahman,
One-step wet-chemical synthesis of ternary ZnO/CuO/Co 3 O 4 nanoparticles
for sensitive and selective melamine sensor development, New J. Chem. 43
[86] M.M. Rahman, M.M. Alam, A.M. Asiri, Development of an efficient phenolic
sensor based on facile Ag 2 O/Sb 2 O 3 nanoparticles for environmental safety,
Nanoscale Adv. 1 (2019) 696–705.
(
2019) 4849–4858.
67] M.M. Rahman, T.A. Sheikh, A.M. Asiri, M.R. Awual, Development of
-methoxyaniline sensor probe based on thin Ag 2 O@ La 2 O 3 nanosheets
for environmental safety, New J. Chem. 43 (2019) 4620–4632.
[87] M.R. Karim, M.M. Alam, M.O. Aijaz, A.M. Asiri, M.A. Dar, M.M. Rahman, Fabrica-
tion of 1, 4-dioxane sensor based on microwave assisted PAni-SiO2 nanocom-
posites, Talanta 193 (2019) 64–69.
[88] E.S. Lopes, E. Domingos, R.S. Neves, W. Romao, K.R. de Souza, R. Valaski,
B.S. Archanjo, F.G. Souza, A.M. Silva, A. Kuznetsov, J.R. Araujo, The role of inter-
molecular interactions in polyaniline/polyamide-6, 6 pressure-sensitive blends
studied by DFT and 1H NMR, Eropean Polymer J 85 (2016) 588–604.
[89] F.G.Souza Siddaramaiah, B.G. Soares, P. Prameswara, R. Somashekar, Mi-
crostructural Behaviors of Polyaniline/CB Composites by SAXS, J. Appl. Polym.
Sci. 116 (2010) 673–679.
[
3
[
68] M.R. Awual, M.M. Hasan, M.M. Rahman, A.M. Asiri, Novel composite material
for selective copper (II) detection and removal from aqueous media, J. Mol. Liq.
2
83 (2019) 772–780.
[
69] M.R. Awual, A.M. Asiri, M.M. Rahman, N.H. Alharthi, Assessment of enhanced
nitrite removal and monitoring using ligand modified stable conjugate materi-
als, Chem. Eng. J. 363 (2019) 64–72.
[
70] T.A. Sheikh, M.M. Rahman, A.M. Asiri, H.M. Marwani, M.R. Awual, 4-Hexyl-
resorcinol sensor development based on wet-chemically prepared Co3O4@
Er2O3 nanorods: a practical approach, J. Ind. Eng. Chem. 66 (2018) 446–455.
[90] F.G. Souza, B.G. Soares, G.M.O.Barra Siddaramaiah, M.H. Herbst, Influence
of plasticizers (DOP and CNSL) on mechanical and electrical properties of
SBS/polyaniline blends, Polymer 47 (2006) 7548–7553.
[
71] M.R. Awual, M.M. Hasan, J. Iqbal, A. Islam, M.A. Islam, A.M. Asiri, M.M. Rah-
man, Naked-eye lead (II) capturing from contaminated water using innovative
large-pore facial composite materials, Microchem. J. 154 (2020) 104585.
72] T.A. Sheikh, M.N. Arshad, M.M. Rahman, A.M. Asiri, H.M. Marwani, M.R. Awual,
W.A. Bawazir, Trace electrochemical detection of Ni2+ ions with bidentate
[91] F.G. de Souza, M. Almeida, B.G. Soares, J.C. Pinto, Preparation of a semi-conduc-
tive thermoplastic elastomer vulcanizate based on EVA and NBR blends with
polyaniline, Polym. Test. 26 (2007) 692–697.
[
[92] F.G. de Souza, T.K. Anzai, P.A. Melo, B.G. Soares, M. Nele, J.C. Pinto, Influence
of reaction media on pressure sensitivity of polyanilines doped with DBSA, J.
Appl. Polymer Sci. 107 (2008) 2404–2413.
ꢀ
N,N -(ethane-1,2-diyl)bis(3,4-dimethoxybenzenesulfonamide) [EDBDMBS] as a
chelating agent, Inorg. Chim. Acta 464 (2017) 157–166.
[93] F.G. Souza, G.E. Oliveira, T. Anzai, P. Richa, T. Cosme, M. Nele, C.H.M. Rodrigues,
B.G. Soares, J.C. Pinto, A sensor for acid concentration based on cellulose pa-
per sheets modified with polyaniline nanoparticles, Macromol. Mater. Eng. 294
(2009) 739–748.
[
73] M.R. Awual, N.H. Alharthi, M.M. Hasan, M.R. Karim, A. Islam, H. Znad,
M.A. Hossain, M.E. Halim, M.M. Rahman, M.A. Khaleque, Inorganic-organic
based novel nano-conjugate material for effective cobalt (II) ions capturing
from wastewater, Chem. Eng. J. 324 (2017) 130–139.
74] M.M. Hussain, M.M. Rahman, A.M. Asiri, M.R. Awual, Non-enzymatic simul-
taneous detection of L-glutamic acid and uric acid using mesoporous Co3O4
nanosheets, RSC Adv. 6 (2016) 80511–80521.
[94] F.G. Souza, L. Sirelli, R.C. Michel, B.G. Soares, M.H. Herbst, In situ polymeriza-
tion of aniline in the presence of carbon black, J. Appl. Polymer Sci. 102 (2006)
535–541.
[95] F.G. Souza, B.G. Soares, K. Dahmouche, Effect of Preparation Method on
Nanoscopic Structure of Conductive SBS/PANI Blends: Study Using Small-An-
gle X-ray Scattering, J. Polym. Sci. 45 (2007) 3069–3077.
[
[
75] M.M. Rahman, Selective capturing of phenolic derivative by a binary metal ox-
ide microcubes for its detection, Sci. Rep. 9 (2019) 19234.
[
76] M.M. Rahman, J. Ahmed, Cd-doped Sb2O4 nanostructures modified glassy car-
bon electrode for efficient detection of melamine by electrochemical approach,
Biosens. Bioelectron. 102 (2018) 631–636.
[96] F.G. Souza, B.G. Soares, A.Manjunath Siddaramaiah, R. Somashekar, Blends
of styrene–butadiene–styrene tri-block copolymer/polyaniline-Characterization
by SAXS, J. Mater. Sci. Eng. A 476 (2008) 240–247.
[
77] M.M. Rahman, Label-free Kanamycin sensor development based on CuONiO
hollow-spheres: Food samples analyses, Sens. Actuators, B 264 (2018) 84–91.
9