Arabian Journal of Chemistry (2023) 16, 104866

King Saud University

Arabian Journal of Chemistry

www.ksu.edu.sa
www.sciencedirect.com

ORIGINAL ARTICLE

A resorcinarene based chelating agent for selective

cloud point extraction of Pb2+ ions in water:
Synthesis, structural characterization and
analytical applications
Jing-Long Liu a,b, Xin-Min Zhou a, Meng Sun a, Ai-Quan Jia a,*, Hua-Tian Shi a,
Qian-Feng Zhang a,*

a
Institute of Molecular Engineering and Applied Chemistry, Anhui University of Technology, Ma’anshan, Anhui 243002, PR China
b
Jiangsu Nanjing Environmental Monitoring Center, Nanjing, Jiangsu 210013, PR China

Received 8 February 2023; accepted 23 March 2023

Available online 29 March 2023

KEYWORDS Abstract A sulfonate-functionalized C-iso-butyl-calix[4]resorcinarene was synthesized by the sul-

Sulfonatomethylated calix[4] fomethylation reaction from calix[4]resorcinarene with formaldehyde solution and sodium sulfite.
resorcinarene; Sulfonatomethylated calix[4]resorcinarene (C4RS) adopts a symmetrical bowl-shaped conforma-
Chelating agent; tion in solution and has four methylene sulfonate groups with flexible structure, which provide
Lead; the possibility of trapping specific metal ions. C4RS is an excellent metal chelating agent and rec-
Selectivity; ognizer with good water solubility in the surfactant solution. It is worth noting that C4RS shows
Cloud point extraction; selectivity of the Pb2+ ion over a variety of other competing metal ions such as Cr3+, Ag+,
Inductively coupled plasma Cu2+, Co2+, Ni2+, Mn2+, Mg2+, Sb3+ and Cd2+. Using C4RS and Trtion X-114 as chelating
atomic emission and extractant agent, respectively, the procedure of cloud point extraction (CPE) could extract
spectrometry
Pb2+ ion with high efficiency and selectivity. The method of CPE combined with inductively cou-
pled plasma atomic emission spectrometry (ICP-OES) showed low detection limit of 0.0006 mg L-1,
high recovery rate and acceptable precision, and could apply to the determination of lead in the tap
water and lake water.
Ó 2023 The Author(s). Published by Elsevier B.V. on behalf of King Saud University. This is an open
access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

* Corresponding authors.
E-mail addresses: [email protected] (A.-Q. Jia), [email protected] (Q.-F. Zhang).
Peer review under responsibility of King Saud University.

Production and hosting by Elsevier

https://doi.org/10.1016/j.arabjc.2023.104866
1878-5352 Ó 2023 The Author(s). Published by Elsevier B.V. on behalf of King Saud University.
This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
2 J.-L. Liu et al.

1. Introduction 2. Materials and methods

Calix[4]resorcinarene, as a special subset of calix[4]arene, has been rec- 2.1. Reagents

ognized to be a greatly versatile class of supramolecular compound
with a bowl-shaped aromatic cavity (Aoyama et al., 1989;
Timmerman et al., 1996). Various calix[4]resorcinarene derivatives All solvents used in the experiment were commercial products
can be obtained by controlling the type and number of functional of high purity and used as received. Sodium sulfite, hydrochlo-
groups, among which sulfonatomethylated calix[4]resorcinarene is a ric acid, sodium hydroxide and formaldehyde solution (35%)
typical anionic water-soluble derivative (Kazakova et al., 2000). It is were purchased from Sinopharm Chemical Reagent Co.,
well-known that calix[4]resorcinarenes have attracted extensive atten- Ltd. Triton X-114 was purchased from Shanghai Macklin Bio-
tion in various fields such as in supramolecular chemistry chemical Technology Co., Ltd. The stock solution of metals
(Yamanaka et al., 2011; Ma et al., 2003; Kenji et al., 2003), ions recog- (1000 mg L-1) was purchased from Institute of Standard Sam-
nition (Lu et al., 2017; Han et al., 2019; Memon et al., 2016; Rustem
ples of the State Environmental Protection Administration,
et al., 2005; Zhang et al., 2020; Larbi et al., 2020), material science
China. The mixed working solution (1.0 mg L-1) was obtained
(Alina et al., 2017; Shalaeva et al., 2017; Gissawong et al., 2022),
and biological science (Ruslan et al., 2018; Ruslan et al., 2020; by mixing ten single stock solution of metals and diluting by
Janget al., 2018), as versatile host molecules. In recent decades, serial dilution with 1% (v/v) HNO3. C-iso-butyl-calix[4]
water-soluble derivative has been widely applied in the recognition resorcinarene and sulfonatomethylated calix[4]resorcinarene
of amino acids (Pang et al., 2014; Roberta et al.,2016), alkaloids were prepared according to procedures described in the litera-
(Ruslan et al., 2020; Astrid et al., 2019) and anions (Su et al., 2018). ture (Kazakova et al., 2000; Cram et al., 1988; Liu et al., 2022).
If there is a green, environmentally friendly and convenient process All laboratory glassware for trace analysis were treated with
for concentrating and separating to extract metal ions, it must be cloud 5% (v/v) HNO3 for at least 48 h and triplicate rinsed with
point extraction (CPE) (Thongsaw et al., 2019; Ulusoy et al., 2012; ultrapure water before use. Metal ions in ultrapure water
Sayed et al., 2016). However, an effective chelating agent is necessary
and all of reagents were not detected.
to achieve metal recognition with highly selectivity and sensitivity. It
is worthy to mention that p-sulfonatocalix[4]arene has been success-
fully synthesized, and used as a metal chelating agent in CPE proce- 2.2. Materials characterization
dure to achieve selective separation and determination of trace
copper(II) from the stock lanthanoid solutions (Asiya et al., 2006; 1
H NMR spectra were recorded on a NMR spectrometer (Bru-
Zairov et al., 2009; Wei et al., 2010). Therefore, sulfonatomethylated ker, DPX-400, Switzerland) using tetramethylsilane as internal
calix[4]resorcinarene may also be a potential metal chelating agent with standard. FT-IR spectra were measured on an FT-IR spec-
high sensitivity and selectivity to be investigated. Herein, we present
trophotometer (Nicolet, FT 1703X, USA) from 4000 to
synthesis of a iso-butyl-substituted sulfonatomethylated calix[4]resor-
400 cm 1 region using KBr pellets. Elemental analyses were
cinarene(C4RS) which is characterized by 1H NMR spectra, Fourier
Infrared (FT-IR), powder X-ray diffraction (XRD), and scanning elec- carried out using a elemental analyzer (Perkin-Elmer, 2400,
tron microscope with energy dispersive X-ray analyzer (SEM-EDS). Shelton, USA). Powder X-ray diffraction (XRD) experiments
It is well known that lead is one of the most toxic elements in nat- were recorded on a Bruker D8 Advance (operating at 40 kV
ure, and lead pollution is also very harmful to human health. The US and 20 mA) with Ni-filtered Cu-Ka radiation at 1.5406 (Å)
Environmental Protection Agency (EPA) has classified lead as a group with a speed of 0.2 min per step of 0.02° in the range 5° 
B2 (probable) human carcinogen. Based on the chelation of C4RS with 2h  50°. The surface microstructures were investigated under
metal ions, this work propose an application of C4RS as a complexing a scanning electron microscope (SEM, JEOL JSM-6490LV,
agent for selective separation of Pb2+ ions based procedure prior to Japan) with an energy dispersive X-ray analyzer. UV–visible
ICP-OES analysis. The goal of the present work is to study the recog-
spectra were recorded on a TU1900 spectrophotometer (Bei-
nition behaviors of Pb2+ from mixed metal solutions and the separa-
jing Purkinje General, China) equipped with UVWin 6.0.0
tion and determination of Pb2+ with a CPE procedure. The extraction
of Pb2+ in CPE procedure with C4RS and Triton X-114 (TX114) was software, using a 0.1 cm path-length cell.
examined in detail and the effect of the factors such as pH, the concen-
trations of TX-114 and C4RS was evaluated. In the present work, a 2.3. CPE procedure and ICP-OES analysis
CPE pre-concentration methodology combined with ICP-OES has
been developed and optimized for the determination of lead in tap In 50 mL graduated plastic centrifuge tubes, a certain volume
water and lake water based on C4RS.
of metal standard solution, 1.0 g L-1 C4RS solution, 5% (v/v)

Scheme 1 Synthetic procedures of C4RS-Na.

A resorcinarene based chelating agent for selective cloud point extraction 3

TX114 solution and 2 mL Britton-Robinson buffer solution solution of water and in a high yield (90%98%). C4RS is
were added, and then the total volume was made up to insoluble in common organic solvents such as chloroform,
50 mL with ultrapure water. The solution was heated with methylene chloride, acetone, 1,4-dioxane, toluene, ethyl acet-
ultrasonic treatment in 50 °C for 10 min, then centrifuged ate, N,N-dimethylformamide (DMF), but it has a good solu-
for 10 min at 3000 rpm and finally kept in an ice-bath for sev- bility in water and form C4RS-Na in basic medium aqueous.
eral minutes. The heavier surfactant-rich phase became viscous C4RS-Na was prepared by adding NaOH solution to C4RS
and settled to the bottom. The supernatant aqueous phase was solution and deprotonating it (Scheme 1). Then, the pure sam-
carefully removed with a pipette. The process of CPE was ple of C4RS-Na was obtained by adding ethanol to re-
shown in Fig. 1. And the lower surfactant-rich phase was crystallization, and the formation of the C4RS-Na sample
diluted to 5 mL with 5% (v/v) HNO3 after the addition of was determined by elemental analysis (Anal. Calc. for C4RS-
0.4 mL tributyl phosphate solution, followed by an inductively Na: C 48.97, H 5.14, O 27.18, S 10.90; found: C 46.22, H
coupled plasma optical emission spectrometer (ICP-OES) 5.31, O 28.66, S 9.88).
analysis (Sounderajan et al., 2010; Souz et al., 2020; The chemical structure of C4RS was confirmed by 1H
Guillaume et al., 2018). NMR (Fig. 2). The peaks at 7.33 ppm (s, 4H) is related to
The inductively coupled plasma atomic emission spectrom- the four equivalent benzene protons, indicating that C4RS
etry (ICP-OES) (PerkinElmer, Optima 8300, Shelton, USA) adopts a symmetrical (C4v) bowl-shaped conformation. The
was used for all determinations of lead (Pb I 220.353 nm), bridging methine protons in C4RS appeared at around 4.36–
chromium (Cr I 267.716 nm), silver (Ag I 328.068 nm), copper 4.41 ppm as a triplet, while the protons of the Ar-CH2-S
(Cu I 327.393 nm), cobalt (Co I 228.616 nm), nickel (Ni I groups are easily identified as a singlet at about 3.88 ppm
231.604 nm), manganese (Mn I 285.213 nm), magnesium (Kazakova et al., 2000; Edilma et al., 2015; Twum et al.,
(Mg I 220.353 nm), antimony (As I 220.353 nm) and cadmium 2020). Especially, C4RS maintains the peaks of partial protons
(Cd I 340.4 nm). The ICP-OES configuration and operation on the hydroxyl groups in solution at 9.74 ppm.
conditions include 40 MHz of generating frequency and In order to further verify the complexation of C4RS with
1300 W of radiofrequency power. The argon gas flow rate Pb2+ ion, the structure of C4RS and C4RS-Pb were also char-
was 15.0 L min 1 for plasma formation, 0.30 L min 1 for aux- acterized by Fourier-transform infrared (FT-IR) spectroscopy
iliary gas, and 0.55 L min 1 for nebulising gas. The measure- (Fig. 3). The FT-IR spectra of C4RS and C4RS-Pb show the
ments were made in triplicate, with 10 s of read time and absorption band of hydroxyl groups (Ar-OH) at about
while viewing axially. The sample introduction system con- 3421 cm 1 and intense absorption bands of stretching vibra-
sisted of a concentric nebuliser and a cyclonic spray chamber. tions of the aromatic ring at 1603 cm 1 and 1461 cm 1. The
peaks at around 1050 cm 1 and 770 cm 1 ascribed to the
S = O and S–O bonds. The FT-IR spectrum of C4RS shows
3. Results and discussion the stretching vibrational absorption band of sulfonate groups
–SO2OH at about 1347 cm 1. However, the FT-IR spectrum
3.1. Synthesis and characterization of C4RS-Pb shows a weak absorption at 1347 cm 1 and an
absorption band of –SO2OH-M+ at about 1133 cm 1
Sulfonatomethylated calix[4]resorcinarene was synthesized by (Edilma et al., 2015; Twum et al., 2020). According to reports
sulfonation of C-iso-butylcalix[4]resorcinarene with in the literature (Milena et al., 2014; Liu et al., 2022), we can
sodium sulfite in the presence of excess formaldehyde in the speculate that lead ions can have strong coordination with sul-

Fig. 1 The procedure of cloud point extraction.

4 J.-L. Liu et al.

1
Fig. 2 H NMR spectrum of C4RS (The assignments of the signals were indicated).

C4RS
Expermental
C4RS-Pb Simulated

C=CAr

S-O
SO2OH

S=O
10 20 30 40 50
2 theta

Fig. 4 The simulated and experimental PXRD of C4RS-Na.

SO2OH-M+

4000 3600 3200 2800 2400 2000 1600 1200 800 400
Wavenumber (cm-1)

Fig. 3 FT-IR spectra of C4RS and C4RS-Pb.

fonic acid groups in C4RS. In the aqueous solution, Pb2+ may

bond with the oxygen atoms from several water ligands and
sulfonate groups from C4RS units.
The phase purity of the as-synthesized products of C4RS-
Na were verified by the simulated and experimental powder
X-ray diffractometry patterns, as shown in Fig. 4. The simu-
lated XRD patterns were calculated from single-crystal data
in our previous paper (Liu et al., 2022), which compared with
the patterns obtained from the the bulk power solid samples of
C4RS-Na. Nearly all reflections of the measured pattern corre-
spond to the simulation, indicating the phase purity of the
C4RS-Na samples. To understand the surface morphologies
of C4RS-Na, the microstructures were investigated by scan- Fig. 5 SEM image of C4RS-Na.
A resorcinarene based chelating agent for selective cloud point extraction 5

ning electron microscopy (SEM) as shown in Fig. 5. The SEM absorption gradually increases and the maximum absorption
image of C4RS-Na reveals the amorphous morphology com- wavelength exhibited a bathochromic shift from 287 nm to
posed of the large assembly of particles. The corresponding 296 nm, as shown in Fig. 6(a). It is clearer that C4RS-Pb com-
EDS results of site 1–4 are summarized in Table 1, which were plex has maximum characteristic absorption at 302 nm when
principally correspond to the theoretical calculation. C4RS solution was used as reference solution, shown in
Fig. 6(b). In addition, the relative absorbance of C4RS-Pb at
3.2. UV–vis spectroscopy and quantitative analysis 302 nm shows a good linear relationship with the concentration
of Pb2+ ions in the range of 0.02–0.64 mg L-1, with r = 0.9996,
To verify the quantitative binding ability of C4RS and Pb2+, shown in Fig. 6(c). The linear regression equation was
the UV–vis absorption spectra of C4RS and a series of lead A302nm – A(C4RS, 302 nm) = 1.426[Pb2+] + 0.0007, where
standard solutions were analyzed. Using water and C4RS as [Pb2+] was the mass concentration (mg L-1) of Pb2+, A302nm
reference solutions respectively, a series of UV–vis spectra were was the absorbance of C4RS-Pb at 302 nm, and
obtained (Kashapov et al., 2015; Liu et al., 2020). With the A(C4RS,302 nm) was the absorbance of C4RS without of Pb2+
addition of Pb2+ ion, the absorption intensity of UV–vis at 302 nm.

3.3. Optimum extraction conditions

Table 1 Semi-quantitative EDS results for site 1  4 in Fig. 5. Take metal ions mixed standard solution (Pb2+, Cr3+, Ag+,
Element (wt. %) C O Na S Other Cu2+, Co2+, Ni2+, Mn2+, Mg2+, Sb3+, Cd2+) with a concen-
site 1 49.33 31.22 7.20 5.67 6.58 tration (1.0 mg L-1) into a 50 mL centrifuge tube and then the
site 2 49.10 31.10 6.68 4.64 8.48 total volume was made up to 50 mL with ultrapure water.
site 3 51.61 27.98 6.92 5.68 7.81 After adding C4RS solution and surfactant TX114 solution,
site 4 49.37 30.03 6.19 6.37 8.04 the pH was adjusted, and the cloud point extraction (CPE)
theoretical calculation 48.97 27.18 7.81 10.89 5.15 procedure was carried out for the mixed metal solution. In
order to explore the optimum extraction conditions for

1.0
1.4 (a) C4RS
C4RS+ 0.02 mgL-1 Pb2+
(b) max=302nm
C4RS+ 0.02 mgL-1 Pb2+
C4RS+ 0.04 mgL-1 Pb2+
max= 296 nm C4RS+ 0.04 mgL-1 Pb2+ C4RS+ 0.08 mgL-1 Pb2+
C4RS+ 0.08 mgL-1 Pb2+ C4RS+ 0.16 mgL-1 Pb2+
1.2 C4RS+ 0.16 mgL-1 Pb2+ 0.8 C4RS+ 0.32 mgL-1 Pb2+
C4RS+ 0.32 mgL-1 Pb2+ C4RS+ 0.64 mgL-1 Pb2+
Relative absorbance (a.u.)

C4RS+ 0.64 mgL-1 Pb2+

1.0 0.64 mg L-1 0.64 mg L-1
Absorbance (a.u.)

0.6
0.8

0.6 0.4

0.4
0.2
0.2 0.00 mg L-1 0.02 mg L-1

0.0 0.0
250 275 300 325 350 375 400 250 275 300 325 350 375 400
Wavelength(nm) Wavelength(nm)

1.0
2+
] + 0.007, r=0.9998 (c)

0.8 max=302nm
Relative absorbance (a.u.)

0.6

0.4

0.2

0.0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7
[Pb2+] (mg L-1)

Fig. 6 UV–vis spectra of CSRS in aqueous solutions of Pb2+ with different concentrations.
6 J.-L. Liu et al.

extracting metal ions by C4RS, the most suitable conditions of other ions. However, with the increase of alkalinity of the solu-
pH, C4RS and TX114 concentration, extraction temperature tion, the selectivity of C4RS to metal ions decreases, and the
and time were investigated. The content of mixed metal ions extraction efficiency of all ions except Sb3+ tended to be uni-
in the surfactant phase after extraction was simultaneously form. It can be concluded that C4RS/TX114 extraction system
determined by ICP-OES. The extraction efficiency was calcu- can selectively extract Pb2+ and Cr3+ ions under neutral con-
lated by spiked recovery rate in the following discussion of ditions, and has a especially high extraction efficiency for
results. Pb2+. Therefore, all the following experiments were carried
out at pH 7.
3.3.1. Effect of pH on CPE.
In the process of CPE, pH plays an important role in the for- 3.3.2. Effect of TX114 dosage on CPE
mation and chemical stability of metal-chelate (Mortada et al., TX114 and C4RS were used as extractant and chelating agent
2020). It is well known that the deprotonation of C4RS to complete the identification and extraction of metal ions,
depends on the acidity of the solution, which heavy metal ions respectively. C4RS and TX114 have good mutual solubility
to different coordination ability of C4RS toward the metals. in H2O, which is a double-edged sword. In other words,
However, metal ions will precipitate or oxide in alkaline solu- TX114 can improve the solubility of C4RS in solution, but
tions, which cannot be extracted, while hydrophobic com- good intersolubility will increase the temperature of cloud
plexes cannot be formed in strongly acidic solutions. In point and even cause the disappearance of cloud point phe-
addition, it has been reported in literature that the neutral nomenon. Therefore, it is necessary to study the optimal
form of chelate could interact with the micellar aggregate dosage of chelating agent and extractant and improve their
strongly than its ionic form (Frankewich et al., 1994). synergistic effect. The extraction of the metals with TX114
As shown in Fig. 7, it can be seen that the extraction effi- being in the range of 0.2–2.5 mL was investigated, as shown
ciency of all metal ions is low in the range of pH 1–5, and in Fig. 8. It can be seen from the results that the concentration
the selectivity of Ag+ ion is significantly higher than other ions of TX114 is too low to completely extract metal chelates, but
in pH the range of 3–5. The extraction system showed high not the more the better. Because the high concentration of sur-
extraction efficiency and selectivity for Pb2+ and Cr3+ ions factant will make the viscosity of the extraction liquid increase
higher at pH 7. It indicates that C4RS has stronger coordina- and reduce the atomization efficiency of ICP-OES to affect the
tion ability with Pb2+ and Cr3+ ions than other ions under determination results. When the dosage of TX114 solution is
neutral conditions, and the hydrophobic association could be 1.2–1.5 mL, the extraction efficiency of Pb2+ and Cr3+ ions
effectively extracted into micellar phase than ionic association could reach 88.0%–99.9% and 62.5%–80.3%, which is signif-
(Asiya et al., 2006). The extraction efficiencies of Pb2+ and icantly higher than that of other ions, showing good selectivity
Cr3+ ions were 99.9% and 80.3%, respectively. C4RS was for Pb2+. Further investigations were carried out in the pres-
basically deprotonated at pH＞7 and more metal ions bind ence of 1.5 mL of TX114 solution.
to C4RS and extracted into the surfactant phase, such as
Pb2+, Cr3+, Cu2+, Mn2+, Ni2+, Co2+ and Cd2+. When 3.3.3. Effect of C4RS dosage on CPE
the pH = 8, more kinds of metal ions can be combined by The effect of C4RS concentration on the extraction of metal
C4RS, and mutual interference is enhanced, resulting in false ions was studied in the range of 0.2–2.0 mL and the results
positives. Therefore, under neutral conditions, the selectivity were illustrated in Fig. 9. Generally speaking, the larger the
of lead ions can be improved to reduce the interference of amount of chelating agents, the more complete the binding

Fig. 7 Effect of pH on the extraction of metal ions represented as bar graphs; Pb2+ and Cr3+ were also specially shown as dot plots. pH
1, 2, 3, 4, 5, 6, 7, 8, 9; C4RS: 0.03 mmol L 1, 1.5 mL; Triton X-114: 0.15 % (v/v). The error bars standard for‘‘± one standard deviation of
three trials”.
A resorcinarene based chelating agent for selective cloud point extraction 7

Fig. 8 Effect of TX114 on the extraction of metal ions represented as bar graphs; Pb2+ and Cr3+ were also specially shown as dot plots
(The inset photograph in the figure shows the separation at different dosage of TX114). pH 7; C4RS, 0.03 mmol/L; Triton X-114 solution
concentration (%, v/v), 0.02,0.05, 0.08, 0.12, 0.15, 0.20, 0.25.

of metal ions. However, in the process of CPE, the chelating 3.3.4. Equilibrium temperature and time
agents and extractants synergistically interact and influence In order to obtain the lowest equilibrium temperature and the
each other. As the concentration of C4RS increases, on the shortest equilibrium time in the extraction process, the effects
one hand, the cloud point of the surfactant is not obvious or of equilibrium temperature and time on extraction efficiency of
not generated in the extraction process; on the other hand, Pb2+ ion were studied in the range of 20–80 °C and 5–30 min,
when C4RS reaching a concentration value, it forms hydrophi- as shown in Fig. 10. In this experiment, ultrasonic water bath
lic complex with the metal ions, which cannot be extracted by was used for extraction balance, and the extraction was com-
the surfactant. When the dosage of C4RS solution is 0.8– pleted in the shortest time and at a lower equilibrium temper-
1.5 mL, the extraction efficiency of Pb2+ and Cr3+ ions can ature. The results show that the extraction efficiency is higher
reach 85.6%–102% and 68.0%–80.3%. when the equilibrium temperature is above 50 °C, but it does

Fig. 9 Effect of C4RS on the extraction of metal ions represented as bar graphs; Pb2+ and Cr3+ were also specially shown as dot plots.
pH 7; C4RS, 0.004, 0.010, 0.016, 0020, 0.024, 0.030, 0.040 mmol/L; Triton X-114, 0.15 % (v/v).
 8 J.-L. Liu et al.

Equilibrium time (min) metal ions. The reasonable explanation might be that the
0 5 10 15 20 25 hydrophobic compounds formed by C4RS and Pb2+, which
120
Equilibrium temperature extracted into micellar pseudo-phase much more efficiently
Equilibrium time than ionic associates formed by other ions.
100
3.4. Method evaluation
Extraction Efficiency (%)

80
Under the optimized experimental conditions, the limits of
detection, precision and accuracy of the method were taken
60
as the characteristic indexes to investigate the analytical per-
formance of this method for 50 mL samples. Under the oper-
ating parameters of ICP-OES, the concentrations of Pb2+
40 were linearly related to the emission intensity values in the
range of 0.1–2.0 mg/L, with correlation coefficients better than
0.999.
20
20 30 40 50 60 70 80
Equilibrium temperature (°C) 3.4.1. Limit of detection and quantification (LOD and LOQ)
As no lead was detected in the blank sample experiment, the
Fig. 10 Effect of equilibrium temperature and time on the LOD was determined by the spiked sample. 1.0 mL of the lead
extraction of Pb2+ ions. standard solution of 1.0 mg L-1 was added in a 50 mL cen-
not increase with the temperature increasing. At a tiny ultra- trifuge tube, and the pH was adjusted to 7 buffer solution
sonic frequency, the micelles can more quickly and fully cap- before making the total volume up to 50 mL with ultrapure
ture hydrophobic chelates compared with non-ultrasound- water. Eleven samples with a concentration of 0.02 mg L-1
assisted extraction. However, ultrasound assisted extraction Pb2+ were prepared by this method. According CPE proce-
can not reduce the cloud point temperature. Ultrasonic assis- dure, C4RS solution and TX-114 solution were successively
tance can shorten the balancing time and complete the extrac- added. The samples were tested by ICP-OES after CPE. The
tion balancing process within 10 min. But the longer ultrasonic results of the eleven samples were shown in Table 2. The
time will damage the micelles and reduce the extraction method detection limit for determination of Pb2+ was studied
efficiency. under the optimal experimental conditions of CPE. The LOD
and LOQ were obtained from LOD = 3r and LOD = 10r, r
3.3.5. Antifoam agent stands for standard deviation (SD). The LOD and LOQ could
reach 0.0006 mg L-1 and 0.002 mg L-1. The LOD could below
The surfactant will produces heavy foams during atomization,
actual maximum acceptable concentration for Pb in the drink-
which affect the stability of the signal and damage the equip-
ing water by WHO and China (0.010 mg L-1).
ment. Therefore, the addition of antifoam agent to the surfac-
tantrich phase before determination for eliminating the
3.4.2. Precision and accuracy of method
influence of surfactants. So, the tributyl phosphate used as
antifoam agent in this case. The tributyl phosphate needed According to the CPE procedure, the spiked samples with con-
to be diluted by ethanol before use due to its large viscosity. centrations of 0.05, 0.10 and 0.12 mg L-1 were preprocessed
Further study showed that 0.4 mL of 50% (v/v) tributyl phos- and then tested by ICP-OES. The relative standard deviations
phate ethanol solution could significantly suppress surfactant (RSD) of the three spiked samples were 5.3%, 4.4% and 2.6%
foaming. (n = 6), with excellent spiked recoveries of 98.1%, 101% and
Based on the above experimental results, the extraction effi- 101% respectively, indicating that the method has good
ciency of Pb2+ is the highest, and far higher than that of other accuracy, as shown in Table 3.

Table 2 Analytical results of the spiked sample (n = 11).

Concentration (mg L-1) Mean (mg L-1) r (mg L-1) MDL (mg L-1)
0.0176 0.0180 0.0176 0.0178 0.0177 0.0175 0.0177 0.0002 0.0006
0.0172 0.0176 0.0180 0.0178 0.0175

Table 3 Analytical results of precision and accuracy (n = 6).

Concentration after CPE (mg L-1) Mean (mg L-1) Spiked (mg L-1) RSD (%) Recovery (%)
Spiked sample 1 0.523 0.477 0.474 0.505 0.50 5.3 101
0.536 0.527 0.494
Spiked sample 2 1.033 0.939 0.998 1.012 1.00 4.4 101
1.030 0.264 0.303
Spiked sample 3 1.135 1.149 1.197 1.179 1.20 2.6 98.1
1.212 1.200 1.179
A resorcinarene based chelating agent for selective cloud point extraction 9

Table 4 Analytical results for detection of lead in water samples.

Concentration (mean, n = 3) (mg L-1)
Pb2+ added Pb2+ found RSD(%) Recovery (%)
a
Tap water 1 0.0 ND 1.1 –
0.020 0.0177 ± 0.0020b 88.5
Tap water 2 0.0 ND 1.4 –
0.020 0.0175 ± 0.0025 87.5
Lake water 1 0.0 ND 1.4 –
0.020 0.0180 ± 0.0025 90.0
Lake water 2 0.0 ND 2.5 –
0.020 0.0189 ± 0.0047 94.5
a
Not detected.
b
Mean ± SD (n = 3).

Table 5 Comparison of the reported methods with the proposed method.

Enrichment method Detection method RSD(%) Detection limit (mg L-1) Ref.
c
CPE FAAS 1.6–3.2 0.0045 Silva and Roldan (2009)
CPE ICP-OES 11 0.04 Jolanta et al. (2010)
CPE ICP-OES 6.0 0.00034 Zhao et al. (2012)
CPE FAASc 4.9 0.0043 Wen et al. (2012)
CPE FAAS 1.6 0.005 Sayed et al. (2016)
CPE ICP-OES / 0.0008 Guillaume et al. (2018)
CPE ICP-OES 1.1–2.5 0.0006 This work
c
FAAS: Flame atomic absorption spectrometry.

3.4.3. Determination of selenium in real samples method gave a low LOD of 0.0006 mg L-1, the relative standard devi-
ations were 2.6% to 5.3%, and the recoveries varied between 98.1%
In order to investigate the applicability of this method to the
and 101% depending on the spiked samples of pure water and
analysis of lead content in real water samples, the lake water 87.5% to 94.5% depending on the spiked samples of real water sam-
and tap water samples were analyzed and evaluated. The lake ples. The method could be applied to the determination of lead in
water and tap water filtered by 0.45 lm membrane and acidi- water samples.
fied were pretreatment according to the optimal CPE condi-
tions, and the enrichment factor was 10. Due to Declaration of Competing Interest
preconcentration treatment by CPE, the sensitivity of lead
determination in water is obviously improved. The lead was The authors declare that they have no known competing
not observed in the two tap water and two lake water samples. financial interests or personal relationships that could have
The recoveries were between 87.5% and 94.5% by spiking the appeared to influence the work reported in this paper.
standard at 0.02 mg L-1 with RSDs (1.1%–2.5%), as shown in
Table 4. Thus, the proposed CPE-ICP-OES method was effec-
Acknowledgements
tive and reliable for determination of lead in real water sam-
ples.(See Table 5). This project was supported by National Natural Science Foun-
dation of China (90922008) and the Natural Science Founda-
4. Conclusions
tion of Universities of Anhui Province (KJ2019A0060).
In conclusion, a sulfonate-functionalized C-iso-butyl-calix[4]
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