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. 2025 Mar 31;17(7):946.
doi: 10.3390/polym17070946.

Highly Sensitive Oxytetracycline Detection Using QCM and Molecularly Imprinted Polymers with Deep Eutectic Solvents

Cheng Chen  1 , Liling Wang  1 , Lin Xu  1 , Houjun Wang  2 , Peng Ye  2 , Shuang Liao  2 , Feng Tan  1
Affiliations

Highly Sensitive Oxytetracycline Detection Using QCM and Molecularly Imprinted Polymers with Deep Eutectic Solvents

Cheng Chen et al. Polymers (Basel). .

Abstract

This study presents an efficient method for detecting oxytetracycline, which is critical in environmental monitoring and food safety. A highly sensitive detection platform was developed by combining molecularly imprinted polymers (MIPs) with silica as a carrier, modified with deep eutectic solvents (DES), and a quartz crystal microbalance (QCM) sensor. The MIPs were specifically designed to target oxytetracycline hydrochloride, using SiO2 as the carrier, DES as the functional monomer, N, N-methylenebisacrylamide as the crosslinker, and ammonium persulfate as the initiator. The MIPs exhibited an adsorption capacity of 27.23 mg/g for oxytetracycline hydrochloride. After modification of the MIPs onto a gold electrode surface, a QCM-based sensor platform was constructed. The sensor demonstrated an exceptionally low detection limit of 0.019 ng/mL for oxytetracycline and exhibited excellent sensitivity in tap water. Furthermore, the sensor maintained over 90% detection performance after two weeks of room-temperature storage, indicating its stability. This method provides a rapid, highly sensitive approach for oxytetracycline detection, with potential for future improvements and widespread application in antibiotic testing.

Keywords: antibiotics; biosensors; deep eutectic solvents; molecularly imprinted polymer; quartz crystal microbalance.

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Conflict of interest statement

The authors declare they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

Figures

Scheme 1
Scheme 1
DES-SiO2-MIP-QCM sensor construction and OTC detection.
Figure 1
Figure 1
SEM images of DES-SiO2-MIP at different magnifications. (A) 104 × (B) 5 × 104 ×. (C) SEM images of SiO2. (D) SEM images of DES-SiO2-NIP.
Figure 2
Figure 2
Structural characterization of materials. (A) XRD patterns, (B) FTIR spectra, (C) XPS total spectrum, and (D) the relative concentration changes of each element of SiO2, DES-SiO2-NIP, and DES-SiO2-MIP. (E) C 1s, (F) O 1s, (G) Si 2p, and (H) N 1s of DES-SiO2-MIP.
Figure 3
Figure 3
Surface Characterization of DES-SiO2-MIP-QCM Sensors. Contact angle of (A) bare chip, (B) DES-SiO2-NIP-QCM, and (C) DES-SiO2-MIP-QCM. AFM 3D images of (D) bare chip, (E) DES-SiO2-NIP-QCM, (F) DES-SiO2-MIP-QCM before elution, and (G) DES-SiO2-MIP-QCM.
Figure 4
Figure 4
Investigation of the adsorption properties of DES-SiO2-MIP. (A) Selection of eluent. (B) Optimization of adsorption temperature and time. (C) Linear curve of OTC standard solution. (D) Adsorption saturation curves for DES-SiO2-NIP and DES-SiO2-MIP.
Figure 5
Figure 5
Testing fit of adsorption isotherms for the OTC imprinted sensor. (A) Langmuir, (B) Freundlich, (C) Elovich, and (D) Redlich–Peterson.
Figure 6
Figure 6
Detection performance of DES-SiO2-MIP-QCM sensors. (A) Frequency shift of the sensor with the different additions of DES-SiO2-MIP. (B) Linear curve of DES-SiO2-NIP-QCM and DES-SiO2-MIP-QCM for OTC detection. (C) A partially enlarged view of the linear curve in (B). (D) The selective adsorption of DES-SiO-MIP-QCM (at three concentrations). (E) The selective adsorption of DES-SiO2-NIP-QCM (at three concentrations).
Figure 7
Figure 7
(A) The frequency changes in the adsorption-elution-re-adsorption experiments of six parallel sensors. (B) The relative activity corresponding to A. (C) Elution stability and (D) temporal stability of the DES-SiO2-MIP-QCM.
See this image and copyright information in PMC

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