Carbon nanotubes and graphene modified screen-printed carbon electrodes as sensitive sensors for the determination of phytochelatins in plants using liquid chromatography with amperometric detection

• A new HPLC method with amperometric detection was tested for phytochelatin analyses.
• The conventional glassy carbon electrode was compared with screen-printed electrodes.
• Carbon nanotubes and graphene modifications were made to improve the SPCE sensitivity.
• The CNT–SPCE has been used to analyze several thiols in plants treated with Hg or Cd.

Nanomaterials are of great interest for the development of electrochemical sensors. Multi-walled carbon nanotubes and graphene were used to modify the working electrode surface of different screen-printed carbon electrodes (SPCE) with the aim of improving the sensitivity of the SPCE and comparing it with the conventional glassy carbon electrode. To assay the usability of these sensors, a HPLC methodology with amperometric detection was developed to analyze several phytochelatins in plants of Hordeum vulgare and Glycine max treated with Hg(II) or Cd(II) giving detection limits in the low μmol L−1 range.Phytochelatins are low molecular weight peptides with the general structure γ-(Glu-Cys)n-Gly (n = 2–5) which are synthesized in plants in the presence of heavy metal ions. These compounds can chelate heavy metal ions by the formation of complexes which, are transported to the vacuoles, where the toxicity is not threatening. For this reason phytochelatins are essential in the detoxification of heavy metal ions in plants.The developed HPLC method uses a mobile phase of 1% of formic acid in water with KNO3 or NaCl (pH = 2.00) and 1% of formic acid in acetonitrile. Electrochemical detection at different carbon-based electrodes was used. Among the sensors tested, the conventional glassy carbon electrode offers the best sensitivity although modification improves the sensitivity of the SPCE. Glutathione and several isoforms of phytochelatin two were found in plant extracts of both studied species.