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

Cetinkaya A., Kaya S. I., Atici E. B., Corman M. E., UZUN L., ÖZKAN S. A.

ANALYTICAL AND BIOANALYTICAL CHEMISTRY, vol.414, no.28, pp.8023-8033, 2022 (SCI-Expanded) identifier identifier identifier

  • Publication Type: Article / Article
  • Volume: 414 Issue: 28
  • Publication Date: 2022
  • Doi Number: 10.1007/s00216-022-04335-6
  • Journal Indexes: Science Citation Index Expanded (SCI-EXPANDED), Scopus, Academic Search Premier, Aerospace Database, Aqualine, Aquatic Science & Fisheries Abstracts (ASFA), Artic & Antarctic Regions, BIOSIS, Biotechnology Research Abstracts, CAB Abstracts, Chemical Abstracts Core, Chimica, Communication Abstracts, Compendex, EMBASE, Food Science & Technology Abstracts, MEDLINE, Metadex, Pollution Abstracts, Veterinary Science Database, DIALNET, Civil Engineering Abstracts
  • Page Numbers: pp.8023-8033
  • Keywords: Tiotropium bromide, Molecularly imprinted polymer, Photopolymerization, Voltammetry, Drug analysis, RP-HPLC METHOD, HUMAN PLASMA, FORMOTEROL FUMARATE, VALIDATION
  • Ankara University Affiliated: Yes


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.