Molecularly imprinted sensor based on 1T/2H MoS2 and MWCNTs for voltammetric detection of acetaminophen

https://doi.org/10.1016/j.sna.2022.113772Get rights and content

Highlights

  • The proposed MIP sensor had great sensitivity with the LOD of 3.0 nM.

  • Stabilized hybrid 1 T/2 H MoS2 was prepared by the induction of MWCNTs.

  • The formation of hybrid 1 T/2 H MoS2 was ascribed with the functional groups of MWCNTs.

  • The improved conductivity, active sites and area enhanced the sensing property.

Abstract

1T phase molybdenum disulfide (MoS2) possesses excellent electrical conductivity, 107 times higher than that of 2H phase MoS2. Thus, metallic 1T MoS2 is highly desirable for electrochemical analysis and catalysis. In this study, hybrid 1T/2H MoS2/multi-walled carbon nanotubes (MoS2/MWCNTs) composite was prepared by a facile and simple hydrothermal approach. Powder X-ray diffraction, field emission scanning and transmission electron microscopes, Fourier transform infrared spectroscopy, Raman spectroscopy, cyclic voltammetry (CV), and electrochemical impedance spectroscopy were used to characterize the composites. The results show that metallic 1T phase MoS2 was formed by the inductive effect of MWCNTs. The high conductivity and large specific surface area of hybrid 1T/2H MoS2/MWCNTs composite endow great catalysis activity in electrochemical analysis. Polypyrrole molecularly imprinted polymer (MIP) film imprinted with acetaminophen (AP) template was electrochemically deposited on glassy carbon electrode (GCE) modified by 1T/2H MoS2/MWCNTs (MoS2/CNTs/GCE) to construct MIP based sensor. The prepared MIP/MoS2/CNTs/GCE sensor shows a sensitive current response towards AP. Through the optimization of the ratio of monomer and template, CV electropolymerization cycles, CV elution cycles, incubation time, and pH, the accessible linear range of 0.01–300 μM was obtained with the limit of detection of 0.003 μM (S/N = 3) by differential pulse voltammetry. In addition, the prepared sensor shows great detecting robustness with excellent selectivity, anti-interference property, reproducibility, and stability. In the urine sample tests, the sensor shows desirable reliability with the recovery rate of 88.1–95.9%.

Introduction

Acetaminophen (AP, N-acetyl-p-aminophenol) is known as Paracetamol or Tylenol and is one of the most widely antipyretic and analgesic drugs [1]. It is commonly used as over-the-counter (OTC) analgesic to relieve pain, such as backache, arthritis pain, migraine and neuralgia headaches, as well as postoperative pain. It is also used for the reduction of fever and cough symptoms [1], [2], [3]. Single dose of AP shows analgesic activity in a variety of acute pain syndromes without any side effects. However, the overdose of AP (4.0 g/daily) may cause serious acute liver injury and irreversible liver necrosis and kidney failure that can be life-threatening [1], [4]. According to the Rumack-Matthew nomogram [1], [5], [6], serum levels at and above 200 μg/mL (1.323 mM) for 4 h or 6.25 μg/mL (43.1 μM) for 24 h can cause hepatotoxicity. The sustainable growth and severity of acute liver failure caused by overdose of AP in the United States and Europe have drawn the attention of the medical profession and the authorities [1], [2], [3]. The quantitative detection of AP is of great significance not only for clinical applications but also for the quantity control of its pharmaceutical formulations.

Electrochemical method is one of the preferable quantitative detection methods because of its great sensitivity and selectivity, fast response, low cost, portability, easy operation, and free of or with simple sample pretreatment. In the domain of AP detection, electrochemical detection has been extensively investigated by many researchers [1], [2], [3], [7], [8]. The research interests mainly focused on exploring new (nano)materials and strategies of modifying electrodes that can endow great sensitivity and selectivity for the detection of AP. For example, bismuth oxide (Bi2O2.33) nanostructure (nanorods) [1], arginine/graphene [2], magnetic surface molecularly imprinted membrane [3], three-dimensional mesoporous polymeric g-C3N4/PANI/CdO nanocomposite [9], etc. were explored as modifying materials for the detection of AP.

There are three key indicators that strongly control the performance of electrochemical sensor, namely selectivity, sensitivity, and stability (3 S). In terms of the selectivity, molecular imprinting technology (MIT) is capable to provide excellent selectivity for sensors [10], [11]. Molecular imprinting polymer (MIP) is a kind of artificially prepared biomimetic receptor with specific identification sites complementary to template molecules in size, shape, and functional groups by simulating the mechanism of antibody antigen identification in organisms [12], [13]. MIP has the advantages with respect to the (bio)analytical techniques in the detection of trace analytes. The MIP sensors by integrating MIT and electroanalysis technique show the merits of speediness, accuracy, simple preparation, high stability, and low cost. Thus, MIP sensors have attracted increasing attentions in the fields of biomedicine, food, drug, environment analysis, and biosensors etc., and extensive research works have been reported each year [14]. To further sensitize the detecting response for MIP-based sensors, the general practice is to functionally hybridize or integrate nanomaterials with high conductivity and/or great catalytic activity into MIP systems [15], [16]. Because of the significant improvements of MIP sensors in sensitivity, research and development for real-life applications and point-of-care (PoC) testing on real human samples has been realized [17].

Molybdenum disulfide (MoS2) is one of the most widely studied transitional metal dichalcogenides that are two-dimension (2D) materials composed of thin and semiconducting nanolayers of transition metals and chalcogen atoms [18]. There are three types of atomic configurations in light of the arrangement of S atoms in the structure of MoS2, 1T, 2H, and 3R with distinct electronic properties ranging from highly conductive metal to semiconductor. 2H MoS2 is the most stable structure that is easy to be prepared and stored [19], [20]. Up to date, in the application domain of electrochemical sensors, 2H MoS2 exhibits analogous performance, such as large specific surface area, which can increase the electrode/electrolyte interface area and greatly expose active sites on the plane edges to enhance electrochemical reactivity. However, due to the semiconductive property of 2H MoS2, the obstacle comes when the conductivity of electrode needs to be taken care [21], [22]. Furthermore, the electrocatalytic performance of 2H MoS2 is relatively modest when compared with other two-dimensional carbon materials, e.g., carbon nanotubes or graphene [23], [24]. Whereas, the metallic 1T MoS2 is 107 times more conductive than 2H MoS2 due to the appreciable decrease in electrical resistance [24]. Additionally, it was reported that only the edges are active for 2H MoS2, while 1T MoS2 has been reported to be highly active at both edges and basal planes [25], [26]. Though 1T MoS2 possesses great conductivity and high electrochemical activity, 1T MoS2 suffers from the rigorous synthesis process and poor stability. Up to now, there are two approaches for the fabrication of 1T MoS2, the one is based on the conversion reaction of 2H MoS2, where the atoms of Mo and S rearrange to form 1T configuration depending on the trigger of high-temperature or microwave annealing, light irradiation, electron beam bombardment, and metal or other elements doping [27], [28], [29]. The other preparation strategy refers to the intercalation inducing phase change from 2H to 1T phase using water molecules [30], ammonium ions (NH3/NH4+) [20], scandium [31], Li [32], and solvent [33], etc.

Given the few reports of 1T MoS2 utilized in the domain of electrochemical analysis, here we present a simple and facile hydrothermal approach to fabricate 1T/2H hybrid MoS2 under the induction of multi-walled carbon nanotubes (MWCNTs) (the preparation process is shown in Scheme 1). Compared with the strategies of induced phase change by various high energy, the present protocol is much facile and easy to achieve just in virtue of the induction of MWCNTs, especially due to the induction of the functional groups on MWCNTs, resulting in the formation of hybrid 1T/2H phase MoS2 with wrinkle nanostructure. As well, the combination of MoS2 with MWCNTs leads to the improvement of electrocatalytic effect and more stability [34]. At the same time, the agglomeration problem suffered by MWCNTs in actual applications is alleviated to a large extent by constructing hybrid structure with MoS2 [35]. Then, this paper is devoted to manufacture a promising electrochemical sensing platform based on 1T/2H MoS2/MWCNTs (labeled as MoS2/CNTs for short) and polypyrrole MIP film for the sensitive determination of AP. The hybrid 1T/2H MoS2/CNTs composite exhibits greater electrochemical activity towards the detection of AP compared with the MoS2 or MWCNTs alone. Under optimized conditions, the sensor shows a wide detection range and a much low limit of detection (LOD) with great selectivity, anti-interference, reproducibility, and stability.

Section snippets

Reagents and apparatus

MWCNTs (98 wt%, the length 0.5–2 µm) were obtained from XFNANO, INC, China. Hydrofluoric acid (HF, 40 wt%), N,N-dimethylformamide (DMF), and Nafion (5 wt%) were obtained from Alfa Aesar. Potassium ferricyanide (K3Fe(CN)6), potassium chloride (KCl), sodium phosphate monobasic anhydrous (NaH2PO4), and disodium hydrogen phosphate (Na2HPO4.12 H2O) were obtained from Sinopharm Chemical Reagent Co., Ltd., China. Sodium molybdate (Na2MoO4), L-cysteine, AP, pyrrole (Py), lithium perchlorate (LiClO4),

Characterization of prepared materials

The structure of MoS2 and 1T/2H MoS2/CNTs composite was determined by the XRD patterns. As depicted in Fig. 1a, with respect to absolute MoS2, diffraction peaks at 13.4, 32.8, 35.5, 42.7, and 57.2° are assigned to (002), (100), (102), (103), and (110) planes, respectively, of 2H MoS2 with the space group of P63/mmc, which is consistent with the Joint Committee on Powder Diffraction Standards (JCPDS) card No. 65–1951 [20]. The broad diffraction peaks demonstrate the declined crystallinity and

Optimization studies of the sensor

Given the eminent response towards AP, the MIP/MoS2/CNTs modified electrode is respectable to be used to sensitively detect trace AP. In order to obtain the optimal selectivity and sensitivity for the sensor, the parameters and conditions, i. e. the ratio of MoS2 to MWCNTs in mass, the ratio of monomer to template molecule, the number of scanning cycles of electropolymerizing MIP film, the incubation time before detection, and electrolyte pH were optimized by CV and DPV tests.

Calibration curve and limit of detection

Under the optimal experimental conditions, DPV tests were carried out on AP solutions with different concentrations. As shown in Fig. 6a, oxidation current increases with the increase of AP concentration, and shows a linear relationship with AP concentration in the range of 0.01–300 μM (Fig. 6b). The linear equation is Ip (μA) = 0.1435 C (μM) + 4.2504 (R2 = 0.993). The limit of detection of the obtained sensor is 0.003 μM (S/N = 3). Table 1 is a comparison of AP detection by multifarious

Selectivity, anti-interference, reproducibility, and stability

In order to prove the feasibility of the proposed sensor in practical application, its selectivity, anti-interference, reproducibility, and stability were studied. Selectivity is an important index for the evaluation of MIP sensor. As shown in Fig. 7a, DPV tests were carried out to compare the current response of MIP and NIP electrodes towards AP, DA, GL, and UA with a concentration of 0.03 mM, respectively. Towards AP, the MIP and NIP exhibit the biggest disparity of approximately 7 μA, while

Real sample detection

In order to verify the feasibility of the proposed sensor in practical application, we performed the detection of AP in biological real sample, i. e. urine, by spiking AP into biological sample, whose pH was adjusted by PBS. On the one hand, the detected concentration of AP was compared with the theoretically calculated value. On the other hand, the effect of the substances of urine on the detection of AP by the proposed sensor in the investigated potential window can also be assessed by

Conclusions

In this paper, a MIP-based electrochemical voltammetric sensor based on the conductive carriers of 1T/2H MoS2 and MWCNTs followed by electropolymerization of Py was constructed. The presence of MWCNTs could induce the formation of metallic 1T phase of MoS2 to form hybrid 1T/2H phase with the wrinkle structure with smaller size. The high conductive hybrid 1T/2H MoS2 combined with MWCNTs shows sensitive response towards AP when modified GCE. The MIP film endows great selectivity to the proposed

CRediT authorship contribution statement

Shufang Ren: Validation, Conceptualization, Visualization, Writing – review & editing, Funding acquisition. Wangyong Cui: Investigation, Material preparation, Data curation, Formal analysis, Writing – original draft. Ying Liu: Validation, Supervision. Shounian Cheng: Data curation, Formal analysis. Qingtao Wang: Validation, Supervision, Writing – review & editing. Runyan Feng: Investigation, Formal analysis, Software. Zhixiang Zheng: Validation, Funding acquisition.

Declaration of Competing Interest

We declare that we do not have any commercial or associative interest that represents a conflict of interest in connection with the work submitted.

Acknowledgements

Financial supports from the National Natural Science Foundation of China (22164003 and 21865032), the Natural Science Foundation of Gansu Province (20JR5RA173), the Double First-class Scientific Research Major Projects of Gansu Province (GSSYLXM-07), and the Higher Education Innovation Fund Project of Gansu Province (2020A–088) are gratefully acknowledged.

Shufang Ren, female, doctor, associate researcher of Key Laboratory of Evidence Science Research and Application of Gansu Province, Gansu University of Political Science and Law. She received her bachelor degree from Hebei Agricultural University (2005) and a Ph.D. degree (2010) in Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences. In 2010, she was a research assistant in Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences. In 2017, She engaged in scientific

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    Shufang Ren, female, doctor, associate researcher of Key Laboratory of Evidence Science Research and Application of Gansu Province, Gansu University of Political Science and Law. She received her bachelor degree from Hebei Agricultural University (2005) and a Ph.D. degree (2010) in Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences. In 2010, she was a research assistant in Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences. In 2017, She engaged in scientific research in the Key Laboratory of Evidence Science and Technology Research and Application of Gansu Province, Gansu University of Political Science and Law. Her current research interests include molecularly imprinted electrochemical sensors, drug and toxicant evidence detection and traceability.

    Qingtao Wang, male, doctor, associate professor of School of Chemistry and Chemical Engineering, Northwest Normal University. He received his bachelor degree from Shandong University (2005) and a Ph.D. degree (2010) in Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences. In 2010, he worked in College of Chemistry and Chemical Engineering, Northwest Normal University. His research interests focus on the materials of energy storage and conversion.

    Zhixiang Zheng, male, doctor, professor, laboratory chief of Ley Laboratory of Evidence Science Techniques Research and Application, Gansu Province. He received his bachelor degree from Ningxia University (1997) and a Ph. D. Degree (2013) in Lanzhou University. He engaged in scientific research in the Key Laboratory of Evidence Science Techniques Research and Application, Gansu Province, Gansu University of Political Science and Law. His current research interests include: source apportionment, pollution warning and risk assessment of environmental hormone organics and heavy metals in water, preparation of electrochemical sensor based on novel nanomaterials and study on drug toxicity analysis in biological fluids.

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