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A semi-covalent molecularly imprinted electrochemical sensor for rapid and selective detection of tiotropium bromide

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Abstract

Tiotropium bromide (TIO) is a long-acting bronchodilator used in the treatment of chronic obstructive pulmonary disease (COPD) and asthma. Specifically, it is used to prevent patients from worsening breathing difficulties. In this study, a new TIO-imprinted electrochemical sensor was designed to detect TIO in serum and pharmaceutical samples. Methacryloyl-L-histidine-cobalt(II) [MAH-Co(II)] has been used as a metal-chelating monomer for synthesizing selective molecularly imprinted polymer (MIP). MIP film has been developed on glassy carbon electrodes using MAH-Co(II) as the functional monomer, 2-hydroxyethyl methacrylate (HEMA) as the basic monomer, and ethylene glycol dimethacrylate (EGDMA) as the cross-linker in the photopolymerization method. The surface characterization of the developed MAH-Co(II)@MIP/GCE electrochemical sensor was done using scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR). Also, the electrochemical behavior of the sensor was provided by differential pulse voltammetry (DPV), cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS) techniques. Under optimized experimental conditions, the linearity range was in the range of 10–100 fM, and the limit of detection (LOD) and limit of quantitation (LOQ) values were calculated as 2.73 fM and 9.75 fM, respectively. The MAH-Co(II)@MIP/GCE sensor was used to precisely determine TIO in capsule and commercial serum samples. The results demonstrated that the MIP could specifically recognize TIO compared to structurally related drugs and could be reliably applied to the direct determination of drugs from real samples.

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Funding

Ahmet Cetinkaya received financial support from the Council of Higher Education 100/2000 (YOK) under the special 100/2000 scholarship program and the Scientific and Technological Research Council of Turkey (TUBITAK) under the BIDEB/2211-A Ph.D. and ARDEB/1004 Ph.D. Scholarship Programmes.

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Authors and Affiliations

  1. Faculty of Pharmacy, Department of Analytical Chemistry, Ankara University, Ankara, Turkey

    Ahmet Cetinkaya & Sibel A. Ozkan

  2. Gülhane Faculty of Pharmacy, Department of Analytical Chemistry, University of Health Sciences, Ankara, Turkey

    S. Irem Kaya

  3. R&D Center, DEVA Holding A.S., Tekirdağ, Turkey

    Esen Bellur Atici

  4. Gülhane Faculty of Pharmacy, Department of Biochemistry, University of Health Sciences, Ankara, Turkey

    M. Emin Çorman

  5. Faculty of Science, Department of Chemistry, Hacettepe University, Ankara, Turkey

    Lokman Uzun

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  1. Ahmet Cetinkaya
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  2. S. Irem Kaya
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  4. M. Emin Çorman
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  5. Lokman Uzun
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  6. Sibel A. Ozkan
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Correspondence to Sibel A. Ozkan.

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Cetinkaya, A., Kaya, S.I., Atici, E.B. et al. A semi-covalent molecularly imprinted electrochemical sensor for rapid and selective detection of tiotropium bromide. Anal Bioanal Chem 414, 8023–8033 (2022). https://doi.org/10.1007/s00216-022-04335-6

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  • DOI: https://doi.org/10.1007/s00216-022-04335-6

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