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Electrochemical and electronic detection of biomarkers in serum: a systematic comparison using aptamer-functionalized surfaces

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Abstract

Sensitive and selective detection of biomarkers in serum in a short time has a significant impact on health. The enormous clinical importance of developing reliable methods and devices for testing serum levels of cardiac troponin I (cTnI), which are directly correlated to acute myocardial infarction (AMI), has spurred an unmatched race among researchers for the development of highly sensitive and cost-effective sensing formats to be able to differentiate patients with early onset of cardiac injury from healthy individuals with a mean cTnI level of 26 pg mL−1. Electronic- and electrochemical-based detection schemes allow for fast and quantitative detection not otherwise possible at the point of care. Such approaches rely largely on voltammetric and field-effect-based readouts. Here, we systematically investigate electric and electrochemical point-of-care sensors for the detection of cTnI in serum samples by using the same surface receptors, cTnI aptamer-functionalized CVD graphene-coated interdigated gold electrodes. The analytical performances of both sensors are comparable with a limit of detection (LoD) of 5.7 ± 0.6 pg mL−1(electrochemical) and 3.3 ± 1.2 pg mL−1 (electric). However, both sensors exhibit different equilibrium dissociation constant (KD) values between the aptamer-linked surface receptor and the cTnI analyte, being 160 pg mL−1 for the electrochemical and about three times lower for the electrical approach with KD = 51.4 pg mL−1. This difference is believed to be related to the use of a redox mediator in the electrochemical sensor for readout. The ability of the redox mediator to diffuse from the solution to the surface via the cTnI/aptamer interface is hindered, correlating to higher KD values. In contrast, the electric readout has the advantage of being label-free with a sensing limitation due to ionic strength effects, which can be limited using poly(ethylene) glycol surface ligands.

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Acknowledgements

Financial support from the Centre National de la Recherche Scientifique (CNRS), the University of Lille, the Hauts-de-France region and the CPER “Photonics for Society” is gratefully acknowledged. Financial support came further from the FFG, Austria, within the Comet program.

Conflict of interest

The authors declare no competing interests.

S. Szunerits is editor of Analytical and Bioanalytical Chemistry but was not involved in the peer review of this paper.

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Author notes

  1. Vladyslav Mishyn and Teresa Rodrigues contributed equally to this work.

Authors and Affiliations

  1. Univ. Lille, CNRS, Centrale Lille, Univ. Polytechnique Hauts-de-France, UMR 8520 - IEMN, 59000, Lille, France

    Vladyslav Mishyn, Teresa Rodrigues, Henri Happy, Rabah Boukherroub & Sabine Szunerits

  2. Biosensor Technologies, Austrian Institute of Technology, Konrad-Lorenz-Strasse 24, 3430, Tulln, Austria

    Teresa Rodrigues, Patrik Aspermair & Wolfgang Knoll

  3. Univ. Rennes, CNRS, ISCR –UMR 6226, Campus de Beaulieu, F-35000, Rennes, France

    Yann R. Leroux

  4. Univ. Lille, Inserm, CHU Lille, Institut Pasteur de Lille, U1011- EGID, 59000, Lille, France

    Laura Butruille, Eloise Woitrain & David Montaigne

  5. Department of Scientific Coordination and Management, Danube Private University, 3500, Krems, Austria

    Wolfgang Knoll

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  1. Vladyslav Mishyn
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  2. Teresa Rodrigues
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Corresponding authors

Correspondence to Vladyslav Mishyn, Teresa Rodrigues or Sabine Szunerits.

Additional information

Published in the topical collection featuring Promising Early-Career(Bio)Analytical Researchers with guest editors Antje J. Baeumner, María C. Moreno-Bondi, Sabine Szunerits, and Qiuquan Wang.

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Mishyn, V., Rodrigues, T., Leroux, Y.R. et al. Electrochemical and electronic detection of biomarkers in serum: a systematic comparison using aptamer-functionalized surfaces. Anal Bioanal Chem 414, 5319–5327 (2022). https://doi.org/10.1007/s00216-021-03658-0

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  • DOI: https://doi.org/10.1007/s00216-021-03658-0

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