Reagentless Detection of Low-Molecular-Weight Triamterene Using Self-Doped TiO2 Nanotubes

  • Felipe F. Hudari
    Felipe F. Hudari
    São Paulo State University (Unesp), Institute of Chemistry, Araraquara, São Paulo, Brazil
  • Guilherme G. Bessegato
    Guilherme G. Bessegato
    São Paulo State University (Unesp), Institute of Chemistry, Araraquara, São Paulo, Brazil
  • Flávio C. Bedatty Fernandes
    Flávio C. Bedatty Fernandes
    São Paulo State University (Unesp), Institute of Chemistry, Araraquara, São Paulo, Brazil
  • Maria V. B. Zanoni*
    Maria V. B. Zanoni
    São Paulo State University (Unesp), Institute of Chemistry, Araraquara, São Paulo, Brazil
    *E-mail: [email protected]
  • , and 
  • Paulo R. Bueno*
    Paulo R. Bueno
    São Paulo State University (Unesp), Institute of Chemistry, Araraquara, São Paulo, Brazil
    *E-mail: [email protected]. Tel.: +55 16 3301 9642. Fax: +55 16 3322 2308.
Cite this: Anal. Chem. 2018, 90, 12, 7651–7658
Publication Date (Web):May 16, 2018
https://doi.org/10.1021/acs.analchem.8b01501
Copyright © 2018 American Chemical Society
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Abstract

TiO2 nanotube electrodes were self-doped by electrochemical cathodic polarization, potentially converting Ti4+ into Ti3+, and thereby increasing both the normalized conductance and capacitance of the electrodes. One-hundred (from 19.2 ± 0.1 μF cm−2 to 1.9 ± 0.1 mF cm−2 for SD-TNT) and two-fold (from ∼6.2 to ∼14.4 mS cm–2) concomitant increases in capacitance and conductance, respectively, were achieved in self-doped TiO2 nanotubes; this was compared with the results for their undoped counterparts. The increases in the capacitance and conductance indicate that the Ti3+ states enhance the density of the electronic states; this is attributed to an existing relationship between the conductance and capacitance for nanoscale structures built on macroscopic electrodes. The ratio between the conductance and capacitance was used to detect and quantify, in a reagentless manner, the triamterene (TRT) diuretic by designing an appropriate doping level of TiO2 nanotubes. The sensitivity was improved when using immittance spectroscopy (Patil et al. Anal. Chem.2015, 87, 944–950; Bedatty Fernandes et al. Anal. Chem.2015, 87, 12137–12144) (2.4 × 106 % decade–1) compared to cyclic voltammetry (5.8 × 105 % decade–1). Furthermore, a higher linear range from 0.5 to 100 μmol L–1 (5.0 to 100 μmol L–1 for cyclic voltammetry measurements) and a lower limit-of-detection of approximately 0.2 μmol L–1 were achieved by using immittance function methodology (better than the 4.1 μmol L–1 obtained by using cyclic voltammetry).

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The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.analchem.8b01501.

  • Cyclic voltammograms; Bode and Nyquist plots in the presence of the interferents hydrochlorothiazide and furosemide; Impedance-derived analytical curves for hydrochlorothiazide and furosemide; Nyquist capacitive and Bode plot for real and imaginary components obtained in the presence of TRT (PDF).

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