Laccase mimetics as sensing elements for amperometric assay of 5-hydroxyindoleacetic acid in urine

Bioelectrochemistry. 2025 Feb:161:108839. doi: 10.1016/j.bioelechem.2024.108839. Epub 2024 Oct 24.

Abstract

Monitoring of the levels of 5-hydroxyindole-3-acetic acid (5-HIAA) is of significant importance for diagnostics of carcinoid tumors. We propose simple catalytic electrochemical sensors for the determination of 5-HIAA in urine using laccase and its mimetics. Laccase-like nanozymes (LacNZs) were synthesized via a chemical reduction, and resulting PtMn and MnO2 nanoflowers (NFs) demonstrated laccase-like activity similar to the laccase from the Trametes zonata. In addition, these LacNZs showed enhanced stability under a wide range of pH (3.0-7.5), temperatures (4-70 °C), and ionic strengths (up to 500 mM NaCl). The developed PtMn NF/graphite electrode, similar to a laccase/graphite electrode, can detect 5-HIAA with a high sensitivity (25 000 ± 12 A·M-1·m-2 and 1900 ± 9 A·M-1·m-2, respectively) and have linear ranges of 0.3 - 15 μM and 2 - 50 μM. The sensors work at low working potentials with a detection limit of 0.16 and 1.4 μM, covering the normal and pathologic ranges of 5-HIAA (1 - 50 μM) content in urine. They have been successfully applied to 5-HIAA assay in urine samples of people with various diseases and revealed good recovery values and reproducibility. Additionally, the LacNZ-sensor has the best stability and can be used up to 20 days.

Keywords: 5-Hydroxyindole-3-acetic acid assay; Amperometric sensor; Laccase; Laccase-like nanozyme; Nanoflowers.

MeSH terms

  • Biomimetic Materials / chemistry
  • Biosensing Techniques / methods
  • Electrochemical Techniques / methods
  • Electrodes
  • Humans
  • Hydroxyindoleacetic Acid* / urine
  • Laccase* / chemistry
  • Laccase* / metabolism
  • Limit of Detection*
  • Oxides / chemistry

Substances

  • Hydroxyindoleacetic Acid
  • Laccase
  • Oxides