A sandwich-type photoelectrochemical immunosensor based on ReS2 nanosheets for high-performance determination of carcinoembryonic antigen
Graphical abstract
Introduction
Photoelectrochemical (PEC) sensing system combines the characteristics of spectroscopic and electrochemical techniques. It can provide some superior properties, especially excellent sensitivity, due to the totally different in-put and output signals, avoiding from the background signals [[1], [2], [3]]. Thus, PEC sensing system will be suitable for assaying trace substances, especially for bioactive molecules in a complex biological system [4,5]. Semiconductors such as CdS quantum dots and TiO2 nanoparticles are commonly used as photosensitive materials for photoelectric conversion, thus producing photocurrent for PEC sensing system [6]. Unfortunately, these photoactive materials often need high-energy light to excite to generate photocurrent due to their wide bandgaps. However, high-energy light often weakens the biological activities of the immobilized antibodies, further leading to low sensitivity and poor stability. Hence, photosensitive materials with narrow bandgaps and excellent photoelectric conversion efficiencies will be very important for the fabrication of PEC immunosensing systems.
Two-dimension transition metal dichalcogenides including MoS2 and WS2 possess excellent electrochemical and photoelectrochemical properties, and thus have been widely used as active elements for improving the sensing performances [7,8]. Rhenium disulfide (ReS2) also belongs to transition metal dichalcogenides, and can provide excellent electronic, vibrational and optical characteristics. Either ReS2 bulk crystal or monolayer ReS2 sheets possess direct bandgap which can be tunable in the range from 1.5 eV to 1.89 eV [9,10]. Compared to MoS2, the interlayer Van der Waals interaction (18 meV) is weaker than that of MoS2 (460 meV). Besides, the bandgap of ReS2 nanosheet is narrower than that of MoS2 nanosheet, enabling ReS2 nanosheets to be illuminated by visible light to generate photocurrent. ReS2 possesses a distorted 1 T phase structure, thus exhibiting some anisotropic electron conductivity characteristics [[10], [11], [12], [13]]. Because ReS2 possesses these unique properties, it has been broadly applied in the preparation of electronic devices [11,[14], [15], [16], [17]], photodetector [[18], [19], [20], [21], [22], [23], [24]] and lithium-ion battery [25,26]. However, to best of our knowledge, photoelectrochemical immunosensor based on ReS2 nanosheets has never been reported for determining tumor biomarkers so far.
Carcinoembryonic antigen (CEA) is an important biomarker that can be used for diagnosing pancreatic cancer, lung cancer, breast cancer and other gynecological tumors [27]. A variation on CEA concentration is a valuable indicator for tumor progression, the differentiation of benign and malignant tumors, monitoring the therapeutic effect and so on [28,29]. Thus, various strategies have been developed for measuring CEA concentration, such as enzyme immunoassay [30], chemiluminescence immunoassays [31,32], radioimmunoassays [33], fluorescent assay [34] and electrochemical immunoassay [35,36]. Unfortunately, the developed assay strategies often encounter many faultinesses such as time-consuming, complex sample pretreatment or expensive equipment. Compared with the aforementioned methods, sandwich-type PEC immunosensors show some unique analytical characteristics such as excellent sensitivity and selectivity, fast analysis speed, good reproducibility and high accuracy [[37], [38], [39]]. Thus, this type of PEC immunosensors will be very efficient in CEA determination.
Herein, a sandwich-type PEC immunosensing platform based on ReS2 nanosheets was constructed for rapid, efficient, and sensitive detection of CEA. Two-dimension rhenium disulfite nanosheets (2D-ReS2) were exfoliated from bulk crystals with ultrasonication in a mixture of 1,3-di-(3-mercaptopropyl)-imidazolium bromide (DMimBr) ionic liquid and alcohol. Compared to ReS2 bulk crystals, ReS2 nanosheets can be facilely dispersed in water or phosphate buffer homogeneously, and no detectable agglomeration and absorbance change can be observed for ReS2 nanosheets dispersions even after being stored for one week. ReS2 nanosheet can be used as an excellent photoactive element to fabricate a photoelectrochemical sensing platform, and can also provides large specific surface area for effective immobilizing anti-CEA antibody (anti-CEA Ab), binding CEA and capturing the alkaline phosphatase labeled CEA antibody to form a sandwich-type PEC immunosensing system (Scheme 1). In comparison to common PEC immunosensor, the sandwich-type PEC immunosensing system exhibits an enhanced effect on the photocurrent response and can effectively amplify the detection signal, thus providing high sensitivity for CEA determination, indicating great potential in clinical diagnosis.
Section snippets
Materials and instruments
All reagents and apparatus were detailed in the Supporting Information.
DMimBr ionic liquid preparation
Under an ice-bath condition, sodium hydride (0.705 g, 0.0300 mol) was slowly introduced into imidazole (1.02 g, 0.0150 mol) acetonitrile solution and kept stirring gently. When the reaction was accomplished, no bubble releasing, the obtained imidazole sodium derivative was added dropwise into a mixture of 1,3-dibromopropane (40.2 g, 0.200 mol) and anhydrous acetonitrile (50.0 mL). Then, the system kept reacting at 55 °C for
Characterizations of ReS2 nanosheets
We developed a simple strategy to prepare two-dimension ReS2 nanosheets exfoliated from bulk crystals. For the first time, DMimBr ionic liquid was employed as an assistant reagent to obtain ReS2 nanosheets by one-step ultrasonication in alcohol. With ultrasonication, alcohol and DMimBr ionic liquid will insert into the interspace in-between ReS2 atom layer, and help to exfoliating ReS2 bulk crystal to produce monolayer or a-few-layer ReS2 nanosheets. DMimBr ionic liquid can attached on the
Conclusions
In conclusion, a versatile, facile, and robust strategy has been proposed for highly efficient detection of CEA from clinical serum samples by a ReS2 nanosheets based PEC immunosensing platform. Two-dimension rhenium disulfite nanosheets were facilely exfoliated from ReS2 bulk crystals via ultrasonication with the assistance of DMimBr ionic liquid and alcohol. ReS2 nanosheets possess excellent photoelectrochemical activity and have large specific surface area for immobilizing CEA antibody, thus
Credit author statement
Miss Kou Liu does the experiments and prepares the manuscript.
Dr. Hongping Deng collects and treats the clinical serum samples, and helps to assay them.
Dr. Yanying Wang helps to draw some schematics and analysis the data.
Dr. Shibo Cheng helps to revise the manuscript.
Dr. Xiaoxing Xiong helps to assay the clinical serum samples.
Dr. Chunya Li helps to design the experiments and to revise the manuscript thoroughly.
Declaration of Competing Interest
The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.
Acknowledgements
The authors gratefully acknowledge the financial supports from The National Natural Science Foundation of China, China (No. 21675175, 21874157 and 21275166), Major Projects of Technical Innovation of Hubei Province, China (No. 2017ACA172) and The Natural Science Foundation of Hubei Province, China (No. 2018CFB617 and 2015CFA092), and the Fundamental Research Funds for the Central Universities, South-Central University for Nationalities, China (CZY18031).
Kou Liu is a graduate student who is studying Analytical Chemistry in the College of Chemistry and Materials Science of South-Central University for Nationalities, Wuhan, China. Her research mainly focuses on nanomaterials and their applications in photoelectrochemical sensing.
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Kou Liu is a graduate student who is studying Analytical Chemistry in the College of Chemistry and Materials Science of South-Central University for Nationalities, Wuhan, China. Her research mainly focuses on nanomaterials and their applications in photoelectrochemical sensing.
Hongping Deng is an associate professor in Department of Vascular Surgery, Renmin Hospital of Wuhan University. His current research work is mainly concentrated in biomedicine and biosensors.
Yanying Wang is a lecturer in South-Central University for Nationalities. In 2017, she got her PhD degree from Huazhong University of Science and Technology, Wuhan, China. And she also received her Master degree in 2012 from this university. Her researches mainly focus on the preparation of nanomaterials and their applications as biosensors.
Shibo Cheng is a lecturer in South-Central University for Nationalities. In 2019, he got her PhD degree from Wuhan University, Wuhan, China. His researches mainly focus on the preparation of nanomaterials and their applications in biomolecules separation.
Xiaoxing Xiong is a professor in the Central Laboratory, Renmin Hospital of Wuhan University. His current research work is mainly concentrated in biomedicine and bioimaging and biosensors.
Chunya Li is a professor in the College of Chemistry and Materials Science, South-Central University for Nationalities. His current research interests are nanomaterials, ionic liquid and biosensors.
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The first two authors contribute equally to this work.