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Microchemical Journal 182 (2022) 107858

Contents lists available at ScienceDirect

Microchemical Journal
journal homepage: www.elsevier.com/locate/microc

Enzyme free electrochemical determination of bisphenol A using


screen-printed electrode modified by graphdiyne and carbon nanotubes
Shuai He , Hui Xia , Fengxia Chang *
Key Laboratory of Pollution Control Chemistry and Environmental Functional Materials for Qinghai-Tibet Plateau of the National Ethnic Affairs Commission, School of
Chemistry and Environment, Southwest Minzu University, PR China

A R T I C L E I N F O A B S T R A C T

Keywords: Graphdiyne (GDY) was synthesized and for the first time blended with carboxylated multi-walled carbon
Nonenzymatic electrochemical sensor nanotubes (cMWCNTs) to modify screen-printed electrode (SPE). Electrochemical response of bisphenol A (BPA)
Graphdiyne at the as-proposed electrode was studied. And the significant reduction of oxidation peak potential and
Carbon nanotubes
enhancement of peak current were recorded, showing excellent performance for the determination of BPA. The
Bisphenol A
Screen-printed electrode
pH of supporting electrolyte, proportion of GDY and cMWCNTs, and modification amount were optimized. At the
optimal conditions, BPA was determined by linear sweep voltammetry with the linear concentration ranging
from 0.2 μM to 500 μM and the estimated detection limit being 0.013 μM (S/N = 3). This sensor also showed
good performance in BPA measurement of the lake water and tissue samples.

1. Introduction fluorescent labels. By comparison, the electrochemical biosensors with


the inherent advantages like low-cost equipment, uncomplicated pro­
Endocrine-disruptors are substances which mimic, block, or interfere cess, high selectivity and sensitivity are ideal alternatives. To obtain the
with body’s hormones and have been related to many adverse health effective electrochemical responses of BPA, various kinds of materials
issues. Bisphenol A (BPA, 2,2-bis (4-hydroxyphenyl) propane) as an including carbon nanotubes, graphene, quantum-dots, metal composites
endocrine-disruptor, has been reported to cause heart diseases, diabetes, and nanocomposites have been used to prepare the working electrodes
developmental and behavioral problems and other metabolism prob­ [15]. For example, a carbon nanotubes modified glassy carbon electrode
lems [1,2]. Unfortunately, people are easily exposed to BPA, since it has was used for the amperometric monitoring of BPA with a detection limit
been extensively used to produce polymer materials that are widely of 98 nM and linear range of 0.3–100 μM [16]. The copper(II)
applied in plastic food containers, medical equipment and nursing bot­ phthalocyanine-modified multi-walled carbon nanotube-based electro­
tles [3–5]. BPA has once also been detected in seafood and water-source chemical BPA sensor showed a detection limit of 18.9 nM and the linear
[6]. Due to the serious threat to human health and high exposure range was 0.1–27.5 μM [17]. The liner range of Pt/graphene-carbon
probability, it is really significant to establish simple, efficient and nanotubes nanocomposite based sensor for BPA detection was
reliable detection means for BPA. 0.06–80 μM with the detection limit being 42 nM [18]. However, the
So far, various conventional analytical techniques, including HPLC- sensing performance like sensitivity and linear range needs to be pro­
FLD [7], LC-MS/MS [8], GC–MS [9], CE [10], and ELISAs [11] have moted further for application in increasing kinds of real samples. For this
been reported for BPA detection. But the time-consuming procedure, purpose, tyrosinase has been combined with a variety of superior ma­
large and expensive equipment and skilled analyzer are usually required terials like carbon nanomaterials [19–21], metal–organic frameworks
in the application of these techniques. In addition, many emerging op­ [22], MXenes [23], and metal dichalcogenides [24] for the detection of
tical methods which have the virtues of fast-response and simpleness BPA in recent years. But the use of enzyme can easily lead to problems
have also been tried in BPA detection, like colorimetric [12], chem­ such as limited lifetime, stability problem and complex procedures. In
iluminescence [13], and SPR [14]. However, these sensors usually suffer this regard, it is significant to establish enzyme free electrochemical
from low sensitivity, susceptible to interference, and requirement of sensor with high sensitivity and practicability for BPA determination.

* Corresponding author at: Key Laboratory of Pollution Control Chemistry and Environmental Functional Materials for Qinghai-Tibet Plateau of the National Ethnic
Affairs Commission, School of Chemistry and Environment, Southwest Minzu University, Chengdu 610041, PR China.
E-mail address: changfengxia@swun.edu.cn (F. Chang).

https://doi.org/10.1016/j.microc.2022.107858
Received 5 May 2022; Received in revised form 31 July 2022; Accepted 3 August 2022
Available online 6 August 2022
0026-265X/© 2022 The Author(s). Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-
nc-nd/4.0/).
S. He et al. Microchemical Journal 182 (2022) 107858

Scheme 1. Illustration of fabricating the BPA sensor.

Recently, various novel two-dimensional (2D) materials are gaining (TBAF), tetrahydrofuran (THF), pyridine and carboxylated multi-walled
great attention for electronic, energy, sensing and cancer immuno­ carbon nanotubes (cMWCNTs) were obtained from Aladdin (China).
therapy [25,26]. For example, MXenes was applied to fabricate an THF and pyridine were dried via distillation prior to use. Copper foil was
electrochemical sensor for detection of acetaminophen and isoniazid provided by Sinopharm Chemical Reagent (China). Bisphenol A (BPA)
[27]. 2D MoS2 combined with polydiacetylene was used to construct a and other reagents were of analytical grade and purchased from Kelong
flexible transparent colorimetric wrist strap sensor for selectively (China).
monitoring N,N-dimethylformamide vapor [28]. Bismuthene, a mono­
elemental 2D material has been used to establish a fluorescence
quenching biosensor for microRNA-specific detection [29]. 2D black 2.2. Instruments
phosphorus in combination with aCD47 has the ability for inhibition of
distal tumours [30]. 2D lateral heterojunction, selenium-coated tellu­ Electrochemical tests as well as impedance spectrum (EIS) were
rium nanoheterojunction showed tumor-targeting and antitumor effects implemented using a CHI760E workstation (China). Screen-printed
[31]. Among the emerging 2D materials, graphdiyne (2D) has received electrodes (SPE) were from Zensor R&D (China). Transmission elec­
much attention since synthesized via an in-situ Glaser coupling reaction tron microscopy (TEM) images were obtained via a FEI Tecnai G2 F20
in 2010 [32] due to its impressive properties such as high third-order instrument (USA). The Mapada 1800PC UV–vis spectroscope (China)
nonlinear optical susceptibility, high charge carrier mobility, extreme was used for the optical characterization and N, N-dimethyl formamide
hardness, evenly distributed pores, and good stability [33]. GDY has (DMF) was used as reference. Raman spectrogram was gained on a
been explored in many fields like membrane separation [34], catalysis Renishaw-inVia spectrometer (UK). A JEOL-JSM-7500 scanning elec­
[35,36], environmental remediation [37], energy [38,39], electronics tron microscopy (SEM) (Japan) was used to obtain SEM images.
[40] and sensor [41]. For sensor construction, its large π conjugation,
rich surface chemistry and uniformly distributed pores are benefit to the 2.3. Synthesis of GDY
adsorption of analytes, which can improve the response of sensors [42].
Also, the sp carbon atoms that have chemical activity offer a variety of GDY was synthesized using the cross-coupling reaction according to
possibilities for modification, which could present selective binding the reported method [21,43]. Firstly, TBAF was mixed into the THF
features [42]. solution containing HEB-TMS, and stirred at 0 ◦ C for 10 min to obtain
Herein, we firstly established an enzyme free BPA sensor using GDY HEB monomer. After that, under nitrogen atmosphere, GDY generated
and excellent nano-material carboxylated multi-walled carbon nano­ on copper foils at 60 ◦ C for 72 h with pyridine in presence. Afterwards,
tubes (cMWCNTs). See (Scheme 1). The combination of these two ma­ the produced GDY was collected by ultrasound and rotary evaporation,
terials was coated onto a screen-printed electrode (SPE). With this and washed using heated acetone and DMF sequentially. The obtained
electrode, excellent electrochemical sensing of BPA namely significantly product was refluxed in diluted hydrochloric acid and sodium hydroxide
amplified peak current and reduced oxidation peak potential was ob­ at 80 ℃ for 3 h in turn, and then washed and centrifuged for several
tained. Besides the features of enzyme free, simple preparation, wide times. Finally, centrifugation and drying in vacuum were carried out to
linear range, good sensitivity and desirable selectivity, this fabricated obtain GDY powder.
sensor also performed quite well in the application of water samples and
tissue samples.
2.4. Preparation of modified SPE
2. Experimental section
The SPEs were rinsed with ultrapure water and dried naturally before
2.1. Chemicals use. The GDY and cMWCNTs nanocomposite was prepared by adding 20
mg GDY and 20 mg cMWCNTs powder into 10 mL DMF followed by
Hexakis [(trimethylsilyl) ethynyl] benzene (HEB-TMS) was pur­ ultrasonic for 30 min. The modified SPE was prepared by casting the
chased from Jiangsu XFNANO (China). Tetrabutylammonium fluoride suspension of GDY-cMWCNT nanocomposite (6 μL) onto the working
electrode area and dried with an infrared lamp.

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S. He et al. Microchemical Journal 182 (2022) 107858

Fig. 1. The TEM image (A), HRTEM image (B), UV–vis absorption spectra (C) and Raman spectra (D) of GDY. The inset in C is the photograph of GDY dispersed
in DMF.

2.5. Electrochemical measurements 0.1 M KCl) as supporting electrolyte, and the scan potential region was
0.2 V-1.2 V with scan rate being 50 mV⋅s− 1 apart from the scan rate
All the solution was saturated with N2 during electrochemical mea­ study section. The parameters for linear sweep voltammetry (LSV) scans
surements. EIS tests with potential set as 0.0 V and frequency 0.1 Hz- were the same with CV.
100 kHz were carried out in potassium ferrocyanide (5 mM) solution
containing 0.1 M KCl in it. Cyclic voltammetry (CV) scans were con­
ducted with 0.1 M phosphate buffer solution (PBS, pH 7.0, containing

Fig. 2. SEM images of GDY (A) and GDY-cMWCNT (B). (C) Nyquist plots (0.1 Hz − 100 kHz) in potassium ferrocyanide solution.

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S. He et al. Microchemical Journal 182 (2022) 107858

aromatic rings [44]. The intensity ratio of the two bands is 0.63,
demonstrating relatively high structure regularity of GDY [44].
The morphologies of the prepared GDY and GDY-cMWCNT com­
posite were investigated by SEM. The SEM image in Fig. 2A shows
aggregated nanoparticles that form a porous structure, which is
consistent with report [45] and can confirm the successful preparation
of GDY. The homogeneous mixture of the two nanomaterials was dis­
played in the SEM image of GDY-cMWCNT (Fig. 2B), showing that these
two substances had good dispersion in DMF.
EIS was applied to characterize the electron transfer resistance Rct
that is represented by the semicircle diameter in Nyquist plot. As shown
in Fig. 2C, the unmodified SPE shows a certain semicircle at high fre­
quencies, and the Rct value is about 193 Ω. The plot of GDY/SPE shows a
smaller diameter with the Rct being 129 Ω, indicating a lower electron
transfer resistance with the unmodified SPE as comparison. The smallest
semicircle was recorded with cMWCNT/SPE, implying lowest resistance
(95 Ω). And the Rct value of GDY-cMWCNT/SPE is 115 Ω and between
the Rct value of GDY/SPE and cMWCNT/SPE. The results proved the
Fig. 3. CV curves at unmodified and modified SPE with 50.0 μM BPA in 0.1 M good conductivity of the GDY-cMWCNT nanocomposite.
PBS (pH 7.0). Scan rate: 50 mV⋅s− 1.
3.2. Electrochemical behaviors towards BPA
2.6. Sample preparation and analysis
To investigate the response of BPA at the GDY-cMWCNT /SPE, CV
The water samples were collected from the Yinyuetan lake was carried out and the result was displayed along with that at bare SPE,
(Chengdu, China) and PBS (pH 7.0) was prepared with it before elec­ GDY/SPE and cMWCNT/SPE in Fig. 3 and Fig. S1. Comparing the CV
trochemical scans. The tissue was purchased from local market curves in the blank PBS and PBS containing BPA (Fig. S1A-D), it is clear
(Chengdu, China), and was then crushed and soaked in PBS (pH 7.0, that the peaks at around 0.6 V generated from the oxidation of BPA.
prepared with ultrapure water) for a week. Finally, it was filtered and Although BPA could be recognized at all the listed electrodes, the
the LSV measurements were experimented. The recovery tests were oxidation peak potentials and currents were significantly different
performed by the standard addition method. BPA was spiked in the (Fig. 3). Compared with the unmodified SPE, the oxidation peak
water samples immediately after collected from the lake. And for tissue appeared at lower potential and the peak current increased at the GDY
samples, BPA was spiked immediately when the crushed tissue was modified SPE, stating that GDY has certain electrocatalytic effect for the
soaked in PBS. For each sample, three parallel experiments were oxidation of BPA. Similar response of BPA was observed at the
conducted. cMWCNTs modified SPE: besides the obvious oxidation peak at 0.653 V,
higher oxidation current was recorded. However, by simply blending
3. Results and discussions GDY and cMWCNTs, the peak potential at GDY-cMWCNT/SPE shifted
negatively to 0.532 V and the peak current was further enhanced to
3.1. Characterization of GDY and GDY-cMWCNT composite about 4 times of that at SPE modified by only GDY or cMWCNTs
respectively. The significant reduction of oxidation peak potential and
The as-synthesized GDY was characterized using the TEM, UV–vis improvement of peak current can be ascribed to the synergistic inter­
spectrometer and Raman spectroscopy. As shown in Fig. 1A, the stacked action of GDY and cMWCNTs. Overall, the GDY-cMWCNT based elec­
layers with uniform and continuous microstructure were observed in the trochemical senor presented remarkable sensitivity for the measurement
TEM image. According to the high resolution TEM (HRTEM) image of BPA.
(Fig. 1B), the layer distance is about 0.327 nm. The UV–vis spectra of
GDY (Fig. 1C) shows a strong absorption peak at 273 nm because of its 3.3. Scan rate investigation
large conjugated structure. In the Raman spectrogram of GDY (Fig. 1D),
two apparent peaks at 1368.7 and 1585.6 cm− 1 were recorded. The D- CV diagrams of BPA at a serious of scan rates were collected with the
band at 1368.7 cm− 1 can be attributed to the vibration of sp2 carbon GDY-cMWCNT/SPE (Fig. 4A). As shown by the results, the oxidation
domains, while the G-band at 1585.6 cm− 1 is corresponding to the first- peak currents (Ipa) of BPA increased with the scan rate (ν) in linear
order scattering of the E2g mode for in-phase stretching vibration in correlation (Fig. 4B). The regression formula is as following: Ipa (μA) =
0.1726ν (mV/s) + 31.99 (R = 0.999). Thus, it can be stated that the

Fig. 4. (A) CV results of 25.0 μM BPA with GDY-cMWCNT/SPE at various scan rates (40–200 mV⋅s− 1) in 0.1 M PBS (pH 7.0). (B) Linear correlation of peak current
with scan rate. (C) Linear curve of peak potential with natural logarithm of scan rate.

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Fig. 5. (A) CV results of 25.0 μM BPA in PBS with different pH at GDY-cMWCNT/SPE. Scan rate: 50 mV⋅s− 1. (B) Peak currents and potentials at different pH and
linear relationships between peak potentials and pH.

Scheme 2. Mechanism of oxidation of BPA at GDY-cMWCNT/SPE.

Fig. 6. CVs of 50.0 μM BPA at SPE modified with GDY-cMWCNT composite of different ratios (A) and different volumes (C). (B) Oxidation peak currents at different
ratios of GDY and cMWCNTs. (D) Oxidation peak currents at different volumes of GDY-cMWCNT.

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Fig. 7. (A) LSV results using GDY-cMWCNT/SPE in 0.1 M PBS (pH 7.0) including BPA of (a) 0 μM, (b) 0.200 μM, (c) 2. 50 μM, (d) 7.50 μM, (e) 10.0 μM, (f) 25.0 μM,
(g) 50.0 μM, (h) 75.0 μM, (i) 100 μM, (j) 200 μM, (k) 500 μM). Scan rate: 50 mV⋅s− 1. (B) Linear correlation of peak current and BPA concentration.

reaction process of BPA at the GDY-cMWCNT/SPE is adsorption- 3.5. Optimization of detection conditions
controlled. Moreover, the peak potential enlarged as the scan rate
increased, varying proportionally to the natural logarithm of scan rate Fig. 5B shows that the maximum of BPA peak current appeared at pH
(lnν) (Fig. 4C). The fitted result is Epa (V) = 0.03184 lnν (mV/s) + 7.0, and the peak potential showed at proper value at this condition
0.4688 (R = 0.999). Based on the Laviron theory [46], the slope for compared with that at low pH values. Therefore, pH 7.0 was used in the
irreversible and adsorption-controlled process is: following study.
GDY-cMWCNT suspensions with different mass ratio of GDY:
RT
cMWCNTs (2:1, 1:1, 2:3, and 1:2) were modified onto SPE separately, at
αnF
which the CV curves of BPA were recorded (Fig. 6A). The oxidation peak
where n is the electron transfer number, and α is the electron transfer current (Ipa) approached highest at the ratio 1:1 (Fig. 6B). Additionally,
coefficient of which the value is usually 0.5 for irreversible process. Thus the oxidation peak potential Epa exhibited an upward trend with higher
n was calculated to be 1.61. The above analysis demonstrates that the ratio of cMWCNTs. Considering the highest peak current and lower peak
electron number involved in the electrode reaction is 2. potential, 1:1 was chosen as the optimal mass ratio.
The amount of GDY- cMWCNT composite modified onto the SPE was
optimized by comparing the CV results of BPA obtained with SPE
3.4. pH study modified with different volumes of GDY- cMWCNT suspension. As
shown in Fig. 6C-D, the maximum peak current appeared as the volume
CV scans were experimented to investigate how supporting electro­ being 6 μL, while larger volume would result in decreased peak current.
lyte pH affected the response of BPA at GDY-cMWCNT/SPE (Fig. 5). As Thicker modification film might hinder the charge transfer from the BPA
Fig. 5A shows, the oxidation peak potentials (Epa) of BPA shifted nega­ molecule to the working electrode. Thus, 6 μL was applied for the
tively as pH increased. Furthermore, the Epa of BPA showed linear following study.
relationship with pH value (Fig. 5B) and the fitted result was listed as:
Epa (V) = – 0.0656 pH + 1.041 (R = 0.998). The analysis states that the 3.6. Quantitative measurement of BPA
electrode reaction of BPA includes protons. Furthermore, according to
the Nernst equation [47]: For more rapid measurement of BPA with GDY-cMWCNT/SPE, LSV
dEpa 2.303mRT was used for the quantitative measurement of BPA. The sweep diagrams
dpH
=
nF at a series of concentrations were recorded using the optimal conditions
(Fig. 7). Two regression equations were obtained and expressed as Ipa
where m and n are respectively the proton number and electron number, (μA) = 2.770C (μM) + 0.615 (R = 0.999, from 0.2 μM to 25 μM) and Ipa
m/n was calculated to be 1.11, illustrating that equal numbers of protons (μA) = 1.235C (μM) + 41.39 (R = 0.999, from 25 μM to 500 μM). And
and electrons participated in the reaction. Along with the conclusion in the detection limit was assessed as 0.013 μM (S/N = 3). It can be seen
the scan rate study that n equals to 2, the probable reaction mechanism from the two regression equations that the sensitivity of the two con­
of BPA can be described as Scheme 2. centration ranges is different. In the first linear region (0.2 μM to 25 μM),

Table 1
Performance of electrodes for BPA measurement.
Electrode Epa (V) Linear range (μM) LOD (nM) Samples Interferencesa Ref
b
Tyr-SF-MWNTs-CoPc/GCE 0.625 0.05–3 30 plastic package NP [48]
MWCNT-Tyr/GCE NP 2–100 500 moat water NP [49]
CuMOF-Tyr-Chit/GCE NP 0.05–3 13 plastic package NP [22]
MWCNT-AuNPS/GCE 0.56 0.02–20 7.5 plastic package NP [50]
rGO-Ag/PLL/GCE 0.49 1–80 540 drinking water NP [51]
MoS2/AuNRs/GCE 0.55 0.01–50 3.4 tap water, milk NP [52]
Cu2O-rGO/GCE 0.55 0.1–80 53 water samples NP [53]
CNT/TiO2/CPE 0.7 0.1–60 560 NP NP [54]
GDY-cMWCNT/SPE 0.532 0.2–500 13 lake water, tissue NP This work

a. Interferences that have influence on the signals of BPA with deviations higher than 5%.
b. NP: not provided in the references.

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Table 2 0.2 µM to 500 µM with a detection limit of 13 nM. Moreover, the as-
The performance for sample detection. prepared GDY-cMWCNT/SPE performed well in the spike test of BPA
Sample Measured Added Found Recovery RSD in lake water and tissue samples, showing good prospects in the detec­
(μM) (μM) (μM) (%) (%) tion of BPA from actual samples. If miniaturized electrochemical
Lake Not detected 10.0 9.61 ± 96.1 ± 1.9 2.0 workstation was used with the GDY-cMWCNT/SPE, on-site inspection of
water 0.19 BPA can be easily achieved. In conclusion, the composite of GDY and
25.0 25.2 ± 101 ± 1.7 1.7 cMWCNTs has the properties of high conductivity, good electrocatalytic
0.42 performance and stability, which are advantageous to build sensing and
100 97.8 ± 97.8 ± 0.94 0.96
0.94
electronic device. Although the synthesis of GDY with high quality is
Tissue Not detected 10.0 9.53 ± 95.3 ± 2.2 2.3 time-consuming, the GDY-cMWCNT composite proves to be a promising
0.22 electrochemical sensing platform. By combining with other materials,
25.0 24.3 ± 97.2 ± 1.6 1.6 this composite can be further extended to more electrochemical sensing
0.40
devices, creating application opportunities in sensing and environ­
100 96.9 ± 96.9 ± 0.97 1.0
0.97 mental on-site monitoring.

Data from three parallel determinations.


CRediT authorship contribution statement

the local concentration of BPA at the electrode surface was rapidly Shuai He: Conceptualization, Validation, Investigation, Formal
catalyzed into a product, showing the good catalytic activity of the GDY- analysis, Writing – original draft. Hui Xia: Data curation, Visualization,
cMWCNT composite toward BPA. In the second linear region (25 μM to Resources. Fengxia Chang: Conceptualization, Methodology, Investi­
500 μM), the modified electrode surface might be fouled by the reaction gation, Supervision, Writing – original draft, Writing – review & editing,
products, resulting in a lower sensitivity. Compared with similar elec­ Project administration, Funding acquisition.
trodes, the as-proposed electrochemical sensor can achieve excellent
sensitive measurement with wider linear dynamic range for BPA, and
meanwhile has the advantages of simple preparation and easy opera­ Declaration of Competing Interest
tion. See (Table 1).
The authors declare that they have no known competing financial
3.7. Reproducibility and stability interests or personal relationships that could have appeared to influence
the work reported in this paper.
LSV was applied to investigate the repeatability of the performance
with GDY-cMWCNT/SPE. The oxidation peak currents in BPA solution Data availability
were obtained using 6 electrodes prepared in parallel and the relative
standard deviations (RSD) was 3.36 % (Fig. S2A). The stability of the Data will be made available on request.
prepared electrodes was examined via keeping them at room tempera­
ture for 14 days, and the peak currents retained averagely 96.6 % of the Acknowledgement
initial measurements for BPA (Fig. S2B). The results prove the estab­
lished method with satisfactory reproducibility and stability. The Fundamental Research Funds for the Central Universities
(Southwest Minzu University, 2021PTJS36) supported this work.
3.8. Selectivity study
Appendix A. Supplementary data
A variety of interferences were added in the LSV measurements to
examine the selectivity of the GDY-cMWCNT based BPA sensor (Fig.S3). Supplementary data to this article can be found online at https://doi.
It was found that 20-fold ions like K+, Mg2+, Zn2+, Al3+, Fe3+ and Cl- org/10.1016/j.microc.2022.107858.
showed no influence on the analysis of BPA. Additionally, 10-fold
phenol, 4-nitrophenol, 4-aminophenol, resorcinol showed no notice­ References
able change for the measurement of BPA, neither. These results
demonstrate excellent anti-interference ability and selectivity of GDY- [1] T. Geens, D. Aerts, C. Berthot, J.P. Bourguignon, L. Goeyens, P. Lecomte,
cMWCNT/SPE for BPA. G. Maghuin-Rogister, A.M. Pironnet, L. Pussemier, M.L. Scippo, J. Van Loco,
A. Covaci, A review of dietary and non-dietary exposure to bisphenol-A, Food
Chem. Toxicol. 50 (2012) 3725–3740.
3.9. Sample detection [2] H.S.A. Ezz, Y.A. Khadrawy, I.M. Mourad, The effect of bisphenol A on some
oxidative stress parameters and acetylcholinesterase activity in the heart of male
albino rats, Cytotechnology 67 (2015) 145–155.
To examine the performance of GDY-cMWCNT/SPE for practical [3] C.X. Huang, Y.T. Wu, J.S. Chen, Z.Z. Han, J. Wang, H.B. Pan, M. Du, Synthesis and
application, the lake water and tissue samples were detected and spiked electrocatalytic activity of 3Au?1Pd alloy nanoparticles/graphene composite for
with BPA (Fig. S4). The recoveries are 96.1–101 % (Table 2), exhibiting bisphenol A detection, Electroanalysis 24 (2012) 1416–1423.
[4] W.V. Welshons, S.C. Nagel, F.S.V. Saal, Large effects from small exposures. III.
excellent reliability and feasibility of the proposed method for sample endocrine mechanisms mediating effects of bisphenol A at levels of human
analysis. exposure, Endocrinology 147 (2006) S56–S69.
[5] S.N. Loganathan, K. Kannan, Occurrence of bisphenol A in indoor dust from two
locations in the eastern united states and implications for human exposures, Arch.
4. Conclusions Environ. Contam. Toxicol. 61 (2011) 68–73.
[6] C.A. Richter, L.S. Birnbaum, F. Farabollini, R.R. Newbold, B.S. Rubin, C.E. Talsness,
GDY was successfully synthesized and characterized. Based on the J.G. Vandenbergh, D.R. Walser-Kuntz, F.S.V. Saal, In vivo effects of bisphenol A in
laboratory rodent studies, Reprod. Toxicol. 24 (2007) 199–224.
nanocomposite of GDY and cMWCNTs, an electrochemical sensor for
[7] L. Xiong, P. Yan, M. Chu, Y.Q. Gao, W.H. Li, X.L. Yang, A rapid and simple HPLC-
BPA with features of enzyme free, simple-operation, high sensitivity and FLD screening method with QuEChERS as the sample treatment for the
stability was established. Electrochemical studies verified the superior simultaneous monitoring of nine bisphenols in milk, Food Chem. 244 (2018)
performance of GDY-cMWCNT modified SPE. The supporting electrolyte 371–377.
[8] L.K. Sosvorova, T. Chlupacova, J. Vitku, M. Vlk, J. Heracek, L. Starka, D. Saman,
pH, proportion of GDY and cMWCNTs, and modification amount were M. Simkova, R. Hampl, Determination of selected bisphenols, parabens and
optimized. And the proposed method displayed wide linear region of estrogens in human plasma using LC-MS/MS, Talanta 174 (2017) 21–28.

7
S. He et al. Microchemical Journal 182 (2022) 107858

[9] L. Correia-Sa, S. Norberto, C. Delerue-Matos, C. Calhau, V.F. Domingues, Micro- tumor growth by delivering novel photothermal selenium-coated tellurium
QuEChERS extraction coupled to GC-MS for a fast determination of Bisphenol A in nanoheterojunctions, Sci. Adv. 6 (2020).
human urine, Journal of Chromatography B-Analytical Technologies in the [32] G.X. Li, Y.L. Li, H.B. Liu, Y.B. Guo, Y.J. Li, D.B. Zhu, Architecture of graphdiyne
Biomedical and Life Sciences 1072 (2018) 9–16. nanoscale films, Chem. Commun. 46 (2010) 3256–3258.
[10] K. Ha, G.S. Joo, S.K. Jha, Y.S. Kim, Monitoring of endocrine disruptors by capillary [33] R. Liu, X. Gao, J.Y. Zhou, H. Xu, Z.Z. Li, S.Q. Zhang, Z.Q. Xie, J. Zhang, Z.F. Liu,
electrophoresis amperometric detector, Microelectron. Eng. 86 (2009) 1407–1410. Chemical Vapor Deposition Growth of Linked Carbon Monolayers with Acetylenic
[11] Y. Lu, J.R. Peterson, J.J. Gooding, N.A. Lee, Development of sensitive direct and Scaffoldings on Silver Foil, Adv. Mater. 29 (2017).
indirect enzyme-linked immunosorbent assays (ELISAs) for monitoring bisphenol- [34] H. Qiu, M.M. Xue, C. Shen, Z.H. Zhang, W.L. Guo, Graphynes for Water
A in canned foods and beverages, Anal. Bioanal. Chem. 403 (2012) 1607–1618. Desalination and Gas Separation, Adv. Mater. 31 (2019).
[12] J.Y. Xu, Y. Li, J.X. Bie, W. Jiang, J.J. Guo, Y.L. Luo, F. Shen, C.Y. Sun, Colorimetric [35] Y.R. Xue, B.L. Huang, Y.P. Yi, Y. Guo, Z.C. Zuo, Y.J. Li, Z.Y. Jia, H.B. Liu, Y.L. Li,
method for determination of bisphenol A based on aptamer-mediated aggregation Anchoring zero valence single atoms of nickel and iron on graphdiyne for hydrogen
of positively charged gold nanoparticles, Microchim. Acta 182 (2015) 2131–2138. evolution, Nat. Commun. 9 (2018).
[13] C. Lu, J.G. Li, Y. Yang, J.M. Lin, Determination of bisphenol A based on [36] Y.S. Zhao, N.L. Yang, H.Y. Yao, D.B. Liu, L. Song, J. Zhu, S.Z. Li, L. Gu, K.F. Lin,
chemiluminescence from gold(III)-peroxymonocarbonate, Talanta 82 (2010) D. Wang, Stereodefined Codoping of sp-N and S Atoms in Few-Layer Graphdiyne
1576–1580. for Oxygen Evolution Reaction, J. Am. Chem. Soc. 141 (2019) 7240–7244.
[14] C.C. Zhu, L.L. Zhang, C.B. Chen, J. Zhou, Determination of bisphenol A using a [37] C.Q. Pan, C.Y. Wang, Y.R. Fang, Y.H. Zhu, H.T. Deng, Y.B. Guo, Graphdiyne: an
molecularly imprinted polymer surface plasmon resonance sensor, Anal. Lett. 48 emerging two-dimensional (2D) carbon material for environmental remediation,
(2015) 1537–1550. Environmental Science-Nano 8 (2021) 1863–1885.
[15] K.V. Ragavan, N.K. Rastogi, M.S. Thakur, Sensors and biosensors for analysis of [38] H. Shang, Z.C. Zuo, L. Li, F. Wang, H.B.A. Liu, Y.J. Li, Y.L. Li, Ultrathin Graphdiyne
bisphenol-A, Trac-Trends in Analytical Chemistry 52 (2013) 248–260. Nanosheets Grown InSitu on Copper Nanowires and Their Performance as Lithium-
[16] D. Vega, L. Agüí, A. González-Cortés, P. Yá?ez-Sede?o, J.M. Pingarrón, Ion Battery Anodes, Angewandte Chemie-International Edition 57 (2018) 774–778.
Electrochemical detection of phenolic estrogenic compounds at carbon nanotube- [39] Y.H. Chen, J.F. Li, F.H. Wang, J. Guo, T.G. Jiu, H.B. Liu, Y.L. Li, Chemical
modified electrodes, Talanta 71 (2007) 1031–1038. modification: Toward solubility and processability of graphdiyne, Nano Energy 64
[17] O. Koyun, S. Gorduk, M. Gencten, Y. Sahin, A novel copper phthalocyanine- (2019).
modified multiwalled carbon nanotube-based electrode for sensitive [40] Z. Xue, H. Yang, J. Gao, J.F. Li, Y.H. Chen, Z.Y. Jia, Y.J. Li, H.B. Liu, W.S. Yang, Y.
electrochemical detection of bisphenol A, New J. Chem. 43 (2019) 85–92. L. Li, D. Li, Controlling the Interface Areas of Organic/Inorganic Semiconductor
[18] Z.X. Zheng, Y.L. Du, Z.H. Wang, Q.L. Feng, C.M. Wang, Pt/graphene-CNTs Heterojunction Nanowires for High-Performance Diodes, ACS Appl. Mater.
nanocomposite based electrochemical sensors for the determination of endocrine Interfaces 8 (2016) 21563–21569.
disruptor bisphenol A in thermal printing papers, Analyst 138 (2013) 693–701. [41] Y. Li, H. Huang, R.L. Cui, D.M. Wang, Z. Yin, D. Wang, L.R. Zheng, J. Zhang, Y.
[19] N. Zehani, P. Fortgang, M.S. Lachgar, A. Baraket, M. Arab, S.V. Dzyadevych, D. Zhao, H. Yuan, J.Q. Dong, X.H. Guo, B.Y. Sun, Electrochemical sensor based on
R. Kherrat, N. Jaffrezic-Renault, Highly sensitive electrochemical biosensor for graphdiyne is effectively used to determine Cd2+ and Pb2+ in water, Sensors and
bisphenol A detection based on a diazonium-functionalized boron-doped diamond Actuators B-Chemical 332 (2021).
electrode modified with a multi-walled carbon nanotube-tyrosinase hybrid film, [42] J.F. Li, C.J. Wan, C. Wang, H. Zhang, X.D. Chen, 2D Material Chemistry:
Biosens. Bioelectron. 74 (2015) 830–835. Graphdiyne-based Biochemical Sensing, Chem. Res. Chin. Univ. 36 (2020)
[20] Y. Wee, S. Park, Y.H. Kwon, Y. Ju, K.M. Yeon, J. Kim, Tyrosinase-immobilized CNT 622–630.
based biosensor for highly-sensitive detection of phenolic compounds, Biosens. [43] L.i. Guoxing, Yuliang, Huibiao, Liu, Yanbing, Guo, Yongjun, Daoben, Zhu,
Bioelectron. 132 (2019) 279–285. Architecture of graphdiyne nanoscale films, Chemical communications, England,
[21] L.X. Wu J. Gao X.B. Lu C.S. Huang J.P.C. Dhanjai Graphdiyne, A new promising Cambridge, 2010.
member of 2D all-carbon nanomaterial as robust electrochemical enzyme biosensor [44] N. Wang, J.J. He, Z.Y. Tu, Z. Yang, F.H. Zhao, X.D. Li, C.S. Huang, K. Wang, T.
platform 156 2020 Carbon 568 575. G. Jiu, Y.P. Yi, Y.L. Li, Synthesis of Chlorine-Substituted Graphdiyne and
[22] X. Wang, X.B. Lu, L.D. Wu, J.P. Chen, 3D metal-organic framework as highly Applications for Lithium-Ion Storage, Angewandte Chemie-International Edition
efficient biosensing platform for ultrasensitive and rapid detection of bisphenol A, 56 (2017) 10740–10745.
Biosens. Bioelectron. 65 (2015) 295–301. [45] C. Lu, Y. Yang, J. Wang, R. Fu, X. Zhao, L. Zhao, Y. Ming, Y. Hu, H. Lin, X. Tao,
[23] L.X. Wu, X.B. Lu, Z.S. Dhanjai, Y.F. Wu, X.H. Dong, S.H. Wang, J.P.C. Zheng, 2D High-performance graphdiyne-based electrochemical actuators, Nat. Commun. 9
transition metal carbide MXene as a robust biosensing platform for enzyme (2018) 752.
immobilization and ultrasensitive detection of phenol, Biosens. Bioelectron. 107 [46] E. Laviron, Adsorption, autoinhibition and autocatalysis in polarography and in
(2018) 69–75. linear potential sweep voltammetry, J. Electroanal. Chem. Interfacial Electrochem.
[24] N. Rohaizad, C.C. Mayorga-Martinez, Z. Sofer, M. Pumera, 1T-Phase Transition 52 (1974) 355–393.
Metal Dichalcogenides (MoS2, MoSe2, WS2, and WSe2) with Fast Heterogeneous [47] M.M. Walczak, D.A. Dryer, D. Jacobson, M.G. Foss, N.T. Flynn, pH Dependent
Electron Transfer: Application on Second-Generation Enzyme-Based Biosensor, Redox Couple: An Illustration of the Nernst Equation, J. Chem. Educ. 74 (1997)
ACS Appl. Mater. Interfaces 9 (2017) 40697–40706. 1195.
[25] L. Zhang, K. Khan, J.F. Zou, H. Zhang, Y.C. Li, Recent Advances in Emerging 2D [48] H.S. Yin, Y.L. Zhou, J. Xu, S.Y. Ai, L. Cui, L.S. Zhu, Amperometric biosensor based
Material-Based Gas Sensors: Potential in Disease Diagnosis, Adv. Mater. Interfaces on tyrosinase immobilized onto multiwalled carbon nanotubes-cobalt
6 (2019). phthalocyanine-silk fibroin film and its application to determine bisphenol A, Anal.
[26] D. Tyagi, H.D. Wang, W.C. Huang, L.P. Hu, Y.F. Tang, Z.N. Guo, Z.B. Ouyang, Chim. Acta 659 (2010) 144–150.
H. Zhang, Recent advances in two-dimensional-material-based sensing technology [49] J. Ren, T.F. Kang, R. Xue, C.N. Ge, S.Y. Cheng, Biosensor based on a glassy carbon
toward health and environmental monitoring applications, Nanoscale 12 (2020) electrode modified with tyrosinase immmobilized on multiwalled carbon
3535–3559. nanotubes, Microchim. Acta 174 (2011) 303–309.
[27] Y. Zhang, X.T. Jiang, J.J. Zhang, H. Zhang, Y.C. Li, Simultaneous voltammetric [50] X.M. Tu, L.S. Yan, X.B. Luo, S.L. Luo, Q.J. Xie, Electroanalysis of Bisphenol A at a
determination of acetaminophen and isoniazid using MXene modified screen- Multiwalled Carbon Nanotubes-gold Nanoparticles Modified Glassy Carbon
printed electrode, Biosens. Bioelectron. 130 (2019) 315–321. Electrode, Electroanalysis 21 (2009) 2491–2494.
[28] T. Wang, Y.L. Guo, P.B. Wan, X.M. Sun, H. Zhang, Z.Z. Yu, X.D. Chen, A flexible [51] Y.H. Li, H.Q. Wang, B. Yan, H.Y. Zhang, An electrochemical sensor for the
transparent colorimetric wrist strap sensor, Nanoscale 9 (2017) 869–874. determination of bisphenol A using glassy carbon electrode modified with reduced
[29] T.Y. Xue, S.R. Bongu, H. Huang, W.Y. Liang, Y.W. Wang, F. Zhang, Z.Y. Liu, Y. graphene oxide-silver/poly-L-lysine nanocomposites, J. Electroanal. Chem. 805
P. Zhang, H. Zhang, X.Q. Cui, Ultrasensitive detection of microRNA using a (2017) 39–46.
bismuthene-enabled fluorescence quenching biosensor, Chem. Commun. 56 (2020) [52] M.X. Wang, Y.F. Shi, Y.B. Zhang, Y. Wang, H.Y. Huang, J.Y. Zhang, J.X. Song,
7041–7044. Sensitive Electrochemical Detection of Bisphenol A Using Molybdenum Disulfide/
[30] Z. Xie, M. Peng, R. Lu, X. Meng, W. Liang, Z. Li, M. Qiu, B. Zhang, G. Nie, N. Xie, Au Nanorod Composites Modified Glassy Carbon Electrode, Electroanalysis 29
H. Zhang, P.N. Prasad, Black phosphorus-based photothermal therapy with aCD47- (2017) 2620–2627.
mediated immune checkpoint blockade for enhanced cancer immunotherapy, Light [53] R.G. Shi, J. Liang, Z.S. Zhao, A.F. Liu, Y. Tian, An electrochemical bisphenol A
Sci. Appl. 9 (2020) 161. sensor based on one step electrochemical reduction of cuprous oxide wrapped
[31] S.Y. Chen, C.Y. Xing, D.Z. Huang, C.H. Zhou, B. Ding, Z.H. Guo, Z.C. Peng, graphene oxide nanoparticles modified electrode, Talanta 169 (2017) 37–43.
D. Wang, X. Zhu, S.Z. Liu, Z. Cai, J.Y. Wu, J.Q. Zhao, Z.Z. Wu, Y.H. Zhang, C. [54] H. Ezoji, M. Rahimnejad, Electrochemical behavior of the endocrine disruptor
Y. Wei, Q.T. Yan, H.Z. Wang, D.Y. Fan, L.P. Liu, H. Zhang, Y.H. Cao, Eradication of bisphenol A and in situ investigation of its interaction with DNA, Sensors and
Actuators B-Chemical 274 (2018) 370–380.

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