Stable and reproducible MIP-ECL sensors for ultra-sensitive and accurate quantitative detection of Estrone

Jie Cao; Xiao-Ying Chen

doi:10.3389/fbioe.2024.1329129

Stable and reproducible MIP-ECL sensors for ultra-sensitive and accurate quantitative detection of Estrone

Front Bioeng Biotechnol. 2024 Feb 9:12:1329129. doi: 10.3389/fbioe.2024.1329129. eCollection 2024.

Authors

Jie Cao^{1

2

3

4}, Xiao-Ying Chen⁵

Affiliations

¹ Scientific Research and Experiment Center, Fujian Police College, Fuzhou, China.
² Fuzhou University Postdoctoral Research Station of Chemistry, Fuzhou University, Fuzhou, China.
³ Fujian ShiMing Judicial Expertise Center, Fujian Police College, Fuzhou, China.
⁴ Regional Counter-Terrorism Research Centre, Fujian Police College, Fuzhou, China.
⁵ College of Environment and Safety Engineering, Fuzhou University, Fuzhou, China.

Abstract

Estrone (E1), as an endogenous estrogen, has a variety of physiological functions in human body and is of great significance to human health. On the other hand, it is a widely distributed and highly disturbing environmental endocrine disruptor in water. Therefore, there is an urgent need to develop a sensitive, rapid, and inexpensive method for the on-site determination of E1, which is not only for clinical diagnosis and treatment, but also for the investigation and monitoring of endogenous estrogen pollution in environmental water. In this study, Ru(bpy)₃ ²⁺/MWCNTs/Nafion/gold electrodes were prepared by surface electrostatic adsorption and ion exchange. A molecularly imprinted membrane (MIP) with the capability to recognize E1 molecules was prepared by sol-gel method, and the electrodes were modified with MIP to form an electrochemical luminescence sensor (MIP-ECL). This method simultaneously possesses ECL's advantage of high sensitivity and MIP's advantage of high selectivity. Moreover, the addition of carboxylated multi-walled carbon nanotubes (MWCNT-COOH) improved the functionalization of the gold electrode surface and increased the binding sites of MIP. Meanwhile, the good conductivity of MWCNTs promoted electron transfer and further improved the sensitivity of the sensor. The sensor showed a wide linear interval in which the E1 concentrations can range from 0.1 μg/L to 200 μg/L, along with a high linear correlation coefficient (R ² = 0.999). The linear regression equation of the sensor was Y = 243.64x-79.989, and the detection limit (LOD) was 0.0047 μg/L. To validate our sensor, actual samples were also measured by the reference method (LC-MS/MS), and it was found that the relative deviation of quantitative results of the two different methods was less than 4.1%. This indicates that the quantitative results obtained by this sensor are accurate and can be used for rapid in situ determination of E1 in clinical samples and environmental water.

Keywords: Estrone; LC-MS/MS; electrochemical luminescence sensor; environmental estrogen; human healthy risk assessment; molecular imprinting technique.

Grants and funding

The author(s) declare financial support was received for the research, authorship, and/or publication of this article. This work was supported by the Young and middle-aged teacher foundation of the Education Department of Fujian Province (grant number JAT200377], the start-up funds for new teachers in Fujian Police College, the Natural Science Foundation of Fujian Province (grant numbers 2022J01516 and 2023J05081), the Application innovation Program of The Ministry of Public Security of P.R.C. (grant number 2021YY21] and Special scientific research projects of Fujian Provincial Department of Finance for the directly affiliated institutions in 2020.