Fabrication of selective and sensitive Pb2+ detection by 2,2′-(?(1,2-phenylenebis(azaneylylidene))bis(methaneylylidene))diphenol by electrochemical approach for environmental remediation

Article abstract of DOI:10.1016/j.molliq.2019.02.109

The Tetradentate Schiff base was easily prepared from o-phenylenediamine and salicylaldehyde and used as a ligand for the detection of heavy metal ions in phosphate buffer medium by electrochemical approach. To fabricate the selective lead (Pb²⁺

Full text of DOI:10.1016/j.molliq.2019.02.109

Accepted Manuscript
Fabrication of selective and sensitive Pb2+ detection by 2,2′-
(−(1,2-phenylenebis(azaneylylidene))bis(methaneylylidene))diphenol
by electrochemical approach for environmental remediation
Faisal M. Aqlan, M.M. Alam, Abdullah M. Asiri, Mohie E.M. Zayed,
Dyab A. Al-Eryani, Fatimah A.M. Al-Zahrani, Reda M. El-
Shishtawy, Jamal Uddin, Mohammed M. Rahman
PII:
S0167-7322(18)36709-6
DOI:
https://doi.org/10.1016/j.molliq.2019.02.109
MOLLIQ 10510
Reference:
To appear in:
Journal of Molecular Liquids
Received date:
Revised date:
Accepted date:
21 December 2018
14 February 2019
22 February 2019
Please cite this article as: F.M. Aqlan, M.M. Alam, A.M. Asiri, et al., Fabrication of
selective and sensitive Pb2+ detection by 2,2′-
−(1,2-phenylenebis(azaneylylidene))bis(methaneylylidene))diphenol by electrochemical
approach for environmental remediation, Journal of Molecular Liquids, https://doi.org/
0.1016/j.molliq.2019.02.109
(
1
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ACCEPTED MANUSCRIPT
2+
Fabrication of selective and sensitive Pb detection by 2,2'-(-(1,2-
phenylenebis(azaneylylidene))bis(methaneylylidene))diphenol by
electrochemical approach for environmental remediation
a,b
c
d,e
e
Faisal M. Aqlan *, M.M. Alam , Abdullah M. Asiri , Mohie E. M. Zayed , Dyab A. Al-
e
e
e,g
h
Eryani , Fatimah A. M. Al-Zahrani , Reda M. El-Shishtawy *, Jamal Uddin ,
Mohammed M. Rahmand,e*
aDepartment of Chemistry, Faculty of Science, University of Jeddah, Jeddah, Saudi Arabia
bDepartment of Chemistry, Faculty of Science, University of IBB, IBB, Yemen
cDepartment of Chemical Engineering and Polymer Science, Shahjalal University of Science and
Technology, Sylhet 3100, Bangladesh
dCenter of Excellence for Advanced Materials Research, Faculty of Science, King Abdulaziz
University, Jeddah 21589, Saudi Arabia.
eChemistry Department, Faculty of Science, King Abdulaziz University, Jeddah 21589, P.O. Box
8
0203, Saudi Arabia.
fChemistry Department, Faculty of Science, King Khalid University, Abha, Saudi Arabia
gDepartment, Textile Research Division, National Research Center, Dokki, Cairo 12622, Egypt
hCenter for Nanotechnology, Department of Natural Sciences, Coppin State University, 2500 W.
North Ave., Baltimore, MD 21216, USA
Corresponding author:
Dr. Faisal M, Aqlan (aqlanfaisal@gmail.com )
Dr. Mohammed M. Rahman (mmrahman@kau.edu.sa )
Dr. Reda M. El-Shishtawy (relshishtawy@kau.edu.sa )
1

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Abstract:
The Tetradentate Schiff base was easily prepared from o-phenylenediamine and
salicylaldehyde and used as a ligand for the detection of heavy metal ions in phosphate buffer
2
+
medium by electrochemical approach. To fabricate the lead (Pb ) ion sensor, a slurry of the
synthesized 2,2'-(-(1,2-phenylenebis(azaneylylidene))bis(methaneylylidene))diphenol (TDL)
ligand was deposited on glassy carbon electrode (GCE) as uniform thin layer. The calibration
2
+
curve of the proposed Pb ion sensor in form of a current vs. concentration plot is found to be
2
+
linear over a Pb ion concentration range of 0.1nM0.01mM. The sensitivity of the sensor is very
-1
-2
high (8.84 µAµM cm ) and detection limit is as low as 98.02±0.50 pM (Limit of detection is
2
+
3
16.73 pM). The projected Pb sensor with active TDL shows reliability, precise reproducibility
and short response time (16.0 sec.) during sensing performances. Above all, it was showed
successive applicability to detect real environmental samples. In the field sensor development, this
methodology using TDL onto GCE might be ae efficient and reliable innovative technique for the
detection of heavy metal ions by electrochemical methods.
2
+
Keywords: 2,2'-(-(1,2-phenylenebis(azaneylylidene))bis(methaneylylidene))diphenol; Pb cation
sensor; Glassy carbon electrode; Electrochemical method; Environmental safety
1
. Introduction
The Schiff bases are nitrogenous organic compounds, and known as imines or azomethines.
They are utilized in optical and electrochemical sensors, and additionally in different
chromatographic strategies, to empower recognition of upgraded selectivity and affectability [1-
3
]. These can be shaped as bi-tri-and tetradentate ligands containing nitrogen and other electron
donor (molecules). This class of compound is effortlessly orchestrated and proved effective as
2

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sensors to detect metal ion and as well as a ligand to the synthesis of numerous organometallic
complexes [4-14]. The liquid crystals with anisotropic properties and the semiconducting polymers
have been synthesized from Schiff bases [15,16].
Nowadays, the overwhelming metal particles are pulled with exceptional consideration on
account of the perilous poisonous impacts towards the earth and the human being [17,18].
Specially, Pb2+ is substantially more lethal than other metals and known as neurotoxin. The
exposure of Pb2+ ion is responsible for a number of syndromes in human including,
neurobehavioral disorders, neurological damage, cognitive dysfunction, hypertension, renal
impairment and the diseases of liver and kidney. In case of infants and children, it can be delayed
2
+
the mental and physical growth [19-22]. The environmental lead (Pb ) ion contamination is
effective due to effluent of the household, paints, pharmaceuticals, hair colorants, colors,
mechanical poisons, composts, and others [23-27].
According to the prescription of the World Health Organization (WHO), the acceptable
2
+
level of Pb ion in drinking water should be 10µg/L as maximum [28]. The most extreme worthy
2
+
level of Pb in blood is 10.0 mg/L, as per the Center for Disease Control and Prevention [29]. To
2
+
ensure the healthy life, the sensitive and high selective method to detect Pb ion in food chain
including drinking water and bio-system is necessary. The existing methods such as plasma atomic
emission spectroscopy [30], electrochemical techniques [31], colorimetric [32], anodic stripping
voltammetry [33], atomic absorption spectroscopy (AAS) [34], biochemical [35] and surface
2
+
enhanced Raman spectroscopy [36] are potentially applied to detect Pb ion. Considering some
significant issues such as cost, heavy and complicated instrumentation, time of detection and non-
portability, the most of above mentioned methods except electrochemical technique are not
suitable. To overcome these disadvantages of traditional methods, the researches based on
3

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electrochemical technique have conducted applying various organometallic nanocomposites as
sensing elements for reliable, sensitive and selective detection of various heady metal ions [37-
4
1].
Up to date, a number of researches have reported to the detection of toxic Pb2+ with various
sensing elements such as nanocomposites of metal oxides, organometallic nanocomposites,
organic composites with NCT and polymer. It has reported that the nanocomposites of Ni-ZnO
2
+
and SnO
2
-Sb
2
O have been applied to the selective detection of Pb by adsorption method [42,43].
3
The graphene oxide (GO)/carbon nanotube (CNT)/poly(O-toluidine) NCs and glutathione-
functionalized gold nanoparticles/multi-walled carbon nanotubes (MWCNT) NCs have been
2
+
found as highly active materials on GCE to detect Pb ion in phosphate buffer medium as reported
2
+
previously [44,45]. Besides this, the detection and quantification of Pb ion have executed by
applying the polymer and biomolecules [46-49]. Moreover, the ligands have found to be applied
2+
2+
for selective detection of heavy metal ions such as Cu and Hg reported by previous authors
[
50,51]. Since, it has been evidently proved that the ligands are active sensing element to detect
heavy metal ions. Therefore, the aim of this study is to the development of an electrochemical
sensor selective to metal ion by applying synthesized organic ligand (TDL) on GCE.
2
+
In this novel research, TDL were implemented to the development of Pb ion sensor. The
synthesized organic ligand was deposited on a GCE with electrically conductive nafion binder (5%
nafion suspension in ethanol). Then, the assembled electrochemical sensor was potentially applied
2
+
2+
to detect Pb ion in phosphate buffer medium. The analytical performances of Pb ion such as
sensitivity, detection limit, linear dynamic range, response time, reproducibility and stability were
investigated in details. Finally, it was tested in real environmental samples to conform its
applicability.
4

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2
2
. Experimental section
.1 Materials and methods
All the solvents and the reagents in the form of analytical grade were purchased from
Sigma-Aldrich Company (USA) and used as received. As part of this study, the analytical grade
inorganic salts including Ga(NO , MnSO , SnCl , CrCl , HgCl , AsCl , Ce(NO , Co(NO and
PbCl were used to the preparation of the heavy metal ions solutions and received from the similar
Sigma-Andrich. Besides this, monosodium, disodium phosphate buffer and conductive binding
3
)
3
4
2
3
2
3
3
)
2
)
3 2
2
1
13
agent nafion (5% nafion suspension in ethanol) were purchased as axillary reagents. H and C
NMR spectra was recorded in CDCl solution on a Bruker Avance 600 MHz spectrometer. Infrared
3
spectra was performed on PerkinElmer spectra 100 FTIR spectrometer. Elemental analyses were
performed at the Microanalytical Unit, Cairo University, Cairo, Egypt, and the found values were
within ±0.4% of the theoretical values. Melting point was determined in open capillary tube in a
Stuart Scientific melting point apparatus and was uncorrected. To assemble the desire
electrochemical cell, the Keithly electrometer from USA was used as the dominating equipment
and the main source of constant supply of current.
2
.2 Synthesis of 2,2'-(-(1,2-phenylenebis(azaneylylidene))bis(methaneylylidene))diphenol
The title compound was prepared as shown in Scheme 1 following a reported method [4].
Typically, a mixture of salicylaldehyde (2.44, 20 mmol) and o-phenylenediamine (1.08 g, 10
mmol) in absolute ethanol (30.0 ml) was refluxed for 2 h. The obtained orange solid product was
o
filtered off and recrystallized from dioxane. Yield 85% (2.67 g) ; mp 162-164 C; Anal. Calcd. For
-1
C
20
H
16
N
2
O
2
(316.36) C, 75.93; H, 5.10; N, 8.85. Found C, 76.56; H, 4.78; N, 8.96. IR (Cm ):
5

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1
2
710 (OH), 1611 (C=N), 1585, 1561, 1480 (C=C), 1276 (C-O). HNMR (δ, ppm): 12.97
(s,2H,=Ar-OH), 8.95 (s,2H, CH=N), 6.96-7.68 (m,12H, Ar-H).
Scheme 1. Synthesis of TDL by condensation process.
2
.3 Fabrication of desire working electrode using TDL on GCE
The fabrication of GCE is very sensitive work and the efficiency of the electrochemical
responses are depended on the fabricated GCE. Thus, a thick slurry of synthesized TDL in ethanol
was formed and in the form of very thin uniform layer, it was deposited on the flat part of GCE.
Then, the modified GCE was dried by keeping at room conditions. To enhance the legibility of
modified GCE, a drop of nafion was added on it and placed inside a low temperature oven at 35˚C
for adequate time to dry it entirely. The desire electrochemical sensor was assembled using the
6

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Kiethly electrometer as a source for the constant supply of current and the modified GCE with
TDL and a simple Pt-wire were connected with kiethly electrometer where, fabricated GCE and
Pt-wire were performed as working and counter electrode respectively. The lead chloride salt was
diluted in deionized water to prepare a series of solutions based on concentration ranging as 0.1mM

0.1nM. During the analysis of the obtained I-V data from assembled electrochemical sensor, a
2
+
calibration curve was plotted as current vs. concentration of Pb ion. Considering the maximum
linear segment in the resulted calibration curve, the linear dynamic range (LDR) was defined. The
2
+
sensitivity of the proposed Pb cationic sensor was estimated from the slope of calibration curve
2
and the surface area of GCE (0.0316 cm ). Applying signal-to-noise ratio of 3, the detection limit
(
DL) of Pb2+ ion sensor was calculated. The electrochemical (I-V) analysis of Pb2+ ion was
performed in phosphate buffer medium and 10.0 mL phosphate buffer solution was taken in
measuring beaker as constant throughout the experiment. The projected sensor is simple two
electrodes system.
3
3
. Results and discussion
2
+
.1 The detection of Pb ion by TDL
To the development of the cationic electrochemical sensor with active TDL and GCE, the
fabrication of working electrode is the major concern. For the fabrication of the desire cationic
sensor, a slurry of TDL in ethanol was subjected to deposit on GCE in the form of thin uniform
layer and the stability of TDL on CGE was enhanced by the addition of a drop of nafion. Since,
the nafion is a conductive copolymer commercially available as 5% suspension in ethanol, the
resulted working electrode shows suitable stability and enhances electrochemical (I-V) activities
with high electron transfer facilities as mentioned in our previous report to detect toxic chemicals
[
52-57]. The numerous toxic heavy metal ions were analyzed by assembled sensor and these
7

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experiments were executed at 0.1µM of metal ions and potential of 0  +1.5 V in phosphate buffer
3
+
medium with pH value of 7.0. The Fig. 1 (a) presents the electrochemical (I-V) responses of Ga ,
2
+
2+
3+
2+
3+
2+
2+
2+
2+
Mn , Sn , Cr , Hg , As , Ce , Co and Pb . From Fig. 1(a), it is evidently shown that Pb
2
+
ion exhibits the highest I-V response among all metal ions and based on this, the Pb ion is
identified as selective to the assembled electrochemical sensor. The assembled electrochemical
Pb2+ ion sensor based on TDL/binder/GCE is not equally active in all the phosphate buffer
2
+
medium. Therefore, the sensor was subjected to analyze of Pb ion with 0.1µM concentration in
a range of buffer medium with pH 5.7 to 8.0 illustrated in Fig. 1(b). Obviously, our assembled
Pb2+ ion sensor is found maximum responsive at pH 7.0. Subsequently, the lead ion with
concentration ranging 0.1 mM to 0.1 nM was applied to I-V analysis as demonstrated in Fig. 1(c).
As it is apparent from Fig. 1(c), the electrochemical responses are distinct from lower to higher
2
+
2+
concentration of Pb ion. Thus, a direct relation of I-V responses with concentration of Pb ion
2
+
are experimented as described in previous articles [58-61]. To calibrate the Pb cationic sensor ,
the current data are isolated from Fig. 1(c) at potential +1.5V and a new graph known as calibration
2
+
curve is plotted using current vs. concentration of Pb ion relation as presented in Fig. 1(d). As
it is perceived from Fig. 1(d), the current data are continuously distributed in a linear manner from
concentration of 0.1 nM to 0.01mM and it is defined as linear dynamic range (LDR). Evidently,
2
+
the resulted LDR is a wider range of concentration. The sensitivity of Pb ion sensor is measured
2
from the slop of calibration curve and surface area (0.0316 cm ) of GCE and an noticeable value
-1
-2
of sensitivity (8.8386 µAµM cm ) is obtained. Counting the signal to noise ratio of 3, the
detection limit is perceived around 98.02±0.50 pM (Limit of detection is 316.73 pM), the result
might be high satisfactory. To identify the linearity of LDR, a plot current vs. log (conc. of Pb2+
8

ACCEPTED MANUSCRIPT
ion) is plotted as demonstrated in Fig. 1(d) [inset Fig. 1(e)] and the current data is found to be
2
analogous with regression co-efficient R =0.9994, provides the evidence of the linearity of LDR.
Fig. 1. Optimization of sensor analytical performances of TDL/binder/GCE sensor. (a) Selectivity
test with analyte concentration 0.1 µM, (b) the activity test based on pH variation with 0.1µM
2+
Pb2+ ion (c) I-V responses to Pb ion concentration, (d) exploration of calibration curve as current
2
+
vs. concentration of Pb ion [ inset log (con.) vs. current].
The sensor reproducibility performance was tested using Pb2+ ion solution with
concentration of 0.1µM and potential (V) was applied in range of 0  +1.5 V in phosphate buffer
9

ACCEPTED MANUSCRIPT
medium of pH 7.0 as illustrated in Fig. 2(a). As it is demonstrated in Fig. 2(a), the seven runs in
an identical conditions are indistinguishable and the precision of current data at potential +1.5 V
is equal to 1.31% RSD (relative standard deviation). The intensity of I-V responses are not altered
for reproducibility performances even the washing of electrode after each trail. Thus, the test
provides the information about the reliability of this Pb2+ ion electrochemical sensor based
TDL/binder/GCE.
Fig. 2. Evaluation of reliability performance of sensor TDL/binder/GCE. (a) Reproducibility test
with Pb2+ ion 0.1µM concentration, (b) long time performances test of Pb2+ ion sensor, (c)
1
0

ACCEPTED MANUSCRIPT
2
+
response time for Pb ion 0.1µM concentration and (d ) interference effect test (Concentration:
2+
3+
2+
2+
0
.1µM Pb ion, 0.1µM As ion, 0.1µM Co ion and 0.1µM Hg ion )
2
+
The long term stability performance of Pb cationic sensor with TDL/binder/GCE was
tested as presented in Fig. 2(b). To investigate the stability, the reproducibility performances were
repeated for elongated time around seven days at applied potential 0+1.5 V and 0.1 µM
2+
concentration of Pb ion. The similar achievement is perceived as in reproducibility test in Fig.
2
+
2
(a). Therefore it can be summarized that the projected Pb cationic electrochemical sensor is able
to perform through long period in phosphate buffer medium. The response time is another
important identification of an electrochemical sensor and it provides the information about the
2
+
efficiency. Thus, this test was performed at 0.1µM concentration of Pb ion as shown in Fig. 2(c).
2
+
It is observed that the projected Pb ion sensor based on TDL/binder/GCE shows a very efficient
response time around 16.0 sec. The interference effect of projected Pb2+ cationic sensor was
2
+
3+
2+
experimented during the analysis of Pb ion with other toxic heavy metal ions such as As , Co
2
+
and Hg ions as illustrated in Fig. 2(d). From Fig. 2(d), it is clearly shown that the electrochemical
2
+
(
I-V) response of Pb ion is not changed in present of other heavy metal ion. Therefore, it is
evidently proved that the proposed Pb2+ ion sensor based no TDL/binder/GCE is free of
interference effect due to other metal ions. To find out the validity of this research, a comparison
in term of sensitivity, linear dynamic range (LDR) and detection limit (DL) is illustrated in Table
1
[55,66] and the projected Pb2+ ion sensor is found as reliable and satisfactory in term of
sensitivity, LDR and DL.
1
1

ACCEPTED MANUSCRIPT
2
+
Table 1. Comparison of analytical performances of Pb cation sensors based on TDL/binder/GCE
sensor prove by electrochemical method.
Modified GCE
GO-CNT-POT/GCE
HNMBSH/GCE
DL
LDR
Sensitivity
Ref.
[45]
−1
−2
89.0 pM
24.0 pM
98.0 pM
0.1 nM 1.0 mM
0.1 nM1.0 mM
0.1 nM0.01 mM
8.53 µAμM cm
-
3
−1
−2
3.9*10 µAμM cm
[63]
−1
−2
TDL/Nafion/GCE
8.84 µAμM cm
This work
*
DL (detection limit), LDR (linear dynamic range), pM(picomole), mM(millimole).
2
+
Scheme 1. The sensing mechanism of Pb ion with TDL/Nafion/GCE by electrochemical
method. (1) Bare-GCE, (2) TDL fabricated GCE by using 5% Nafion, and (3) Electrochemical
2
+
response in presence of Pb ions.
2
+
Finally, it can be mentioned that the proposed heavy metal, Pb cationic electrochemical
sensor is performed efficiently in term of various analytical paramters such as sensitivity, linear
dynamic range, LOQ, linearity, stability, reproducibility, repeatability, and detection limit etc.
Moreover, it was found as good reproducibly, long-term stability in phosphate buffer medium and
able to measure real environmental samples very preciously compared to other existing methods
[
64-80].
1
2

ACCEPTED MANUSCRIPT
3
.2 Detection of real environmental samples
Above all, the proposed Pb2+ cationic sensor was subjected to detect Pb2+ ion in
environmental samples for validation, which is demonstrated and presented in Table 2. These
2
+
analyses of real environmental samples were performed using 0.01µM concentration of Pb ion
in recovery method. There were various real samples were investigated by fabricated sensor probe
in electrochemical method such as industrial waste effluents, collected seawater and mineral water
collected from underground well. As it is represented in Table 2, the evaluated data are seemed to
be satisfactory.
Table 2. Analyses of real environmental samples with TDL/binder/GCE sensor.
a
c
Sample
Added Pb2+ ion
concentration
Determined Pb2+ concentration by TDL /GCE
Average RSD (%)
(µM)
recoveryb (n=3)
(%)
(
µM)
R1
R2
R3
Industrial effluent
Sea water
0.01000
0.01000
0.00969
0.01062
0.00983
0.00998
0.01023
0.01009
99.17
2.83
3.35
102.30
Well water
0.01000
0.00985
0.00984
0.00987
98.53
0.18
a
Mean of three repeated determination (signal to noise ratio 3) with by TDL/GCE.
b
c
2+
Concentration of Pb ion determined/Concentration taken. (Unit: µM)
Relative standard deviation value indicates precision among three repeated measurements(R1,R2,R3).
4
. Conclusion
The tetradental Schiff base TDL (2,2'-(-(1,2-phenylenebis(azaneylylidene))bis
methaneylylidene))diphenol) was prepared facile way and implemented to the fabrication of
(
2
+
2+
electrochemical sensor for successive detection of Pb ion in phosphate buffer The Pb cationic
-1
-2
sensor with TDL/binder/GCE is found as sensitive (8.8386 µAµM cm ), reproducible and very
2
+
efficient to detect Pb ion in real environmental samples. Besides this, it has ability to measure
2
+
Pb ion in between a wider range of concentration (0.1 nM  0.01 mM) and it has very trace lower
1
3

ACCEPTED MANUSCRIPT
limit of detection (98.02±0.50 pM). This study may pave the way for further developments and
real implementation in a large scale with this devices based on Schiff base sensor for the detection
of heavy metal ions in aqueous solutions. It is introduced an efficient route for the removal of
contaminated heavy metallic ions using Schiff bases modified GCE by electrochemical method
for the safety of environmental and healthcare fields.
Acknowledgements
Center of Excellence for Advanced Materials Research (CEAMR) and Chemistry
Department, King Abdulaziz University, Jeddah, Saudi Arabia is highly acknowledged for
financial supports and research facilities.
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Graphical abstract
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Highlights
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Tetradentate TDL Schiff-base was prepared by condensation method
2+
TDL/Nafion/GCE Pb sensor probe was fabricated
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The highest sensitivity (~25.05 µAµM cm ) was achieved
The lowest LOD (~37.88±1.89 pM) was found
Environmental and healthcare safety
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