Electrochemical chiral sensing of tryptophan enantiomers by using 3D nitrogen-doped reduced graphene oxide and self-assembled polysaccharides

Abstract

A chiral sensor is described for the enantioselective recognition of L- and D-tryptophan (Trp). The sensor is based on the use of (a) Cu(II) ions coordinated with β-cyclodextrin (Cu-β-CD) that was self-assembled with carboxymethyl cellulose (CD-Cu-CMC) as a chiral selector, (b) of N-doped reduced graphene oxide (N-rGO) as substrate materials, and (c) of differential pulse voltammetry that was used for enantiorecognition. The 3D N-rGO was prepared by using reduced graphene oxide and pyrrole as the starting materials. Electrostatic interaction occurs between the carboxy groups of CMC and Cu(II) ions in Cu-β-CD. The FT-IR, SEM, XRD and XPS techniques showed that 3D N-rGO and the CD-Cu-CMC composite were successfully synthesized. The 3D N-rGO enabled the immobilization of the chiral selector (CD-Cu-CMC) and improves the active areas. A glassy carbon electrode was modified with N-rGO/CD-Cu-CMC and then showed a stronger electrochemical signal for L-Trp than for D-Trp, typically at a working potential of around 0.78 V (vs. SCE). UV-vis spectroscopy proved that CD-Cu-CMC has a higher affinity for D-Trp. The enantioselectivity for D-Trp over L-Trp is 4.72. The modified electrode had a limit of detection of 0.063 μM and 0.0035 μM for L-Trp and D-Trp, respectively, with a linear response range of 0.01 mM to 5 mM. The sensor was used to detect Trp (D- or L-Trp) in spiked real human urine and human serum protein samples.

Schematic representation of an electrochemical chirality sensor based on the merits of N-rGO and CD-Cu-CMC. It involves the preparation of a chiral selector and a substrate material. N-Doped graphene oxide (N-rGO) was prepared by using graphene oxide (GO) and pyrrole as precursor. The combination of carboxymethyl cellulose (CMC) with Cu-β-CD leads to a novel self-assembly framework.

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Acknowledgements

This work was funded by the National Natural Science Foundation of China (51262027), the State Key Laboratory of Solidification Processing in NWPU (SKLSP201754), the Science and Technology Project Gansu Province (17YF1GA017), the Research Project of Higher Education in Gansu Province (2017A-002), and the Science and Technology Project Gansu Province (17JR5RA082).

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Correspondence to Zunli Mo.

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Niu, X., Yang, X., Mo, Z. et al. Electrochemical chiral sensing of tryptophan enantiomers by using 3D nitrogen-doped reduced graphene oxide and self-assembled polysaccharides. Microchim Acta 186, 557 (2019). https://doi.org/10.1007/s00604-019-3682-4

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Keywords

  • Enantioselective recognition
  • Electrochemical sensor
  • 3D Nitrogen-doped reduced graphene oxide
  • Differential pulse voltammetry
  • Chiral selector