An electrochemical sensor based on cellulose nanocrystal for the enantioselective discrimination of chiral amino acids

doi:10.1016/j.ab.2016.05.022

Analytical Biochemistry

Volume 508, 1 September 2016, Pages 50-57

https://doi.org/10.1016/j.ab.2016.05.022 Get rights and content

Abstract

A novel electrochemical sensor based on 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO)-oxidized cellulose nanocrystals (TOCNCs) and l-cystines (l-Cys) modified Au electrode (TOCNC/l-Cys/Au) has been fabricated for detection and discrimination of the enantiomers of phenylalanine (Phe), leucine (Leu), and valine (Val). The three amino acids are in connection with metabolism diseases. The TOCNC/l-Cys/Au electrode exhibited obvious peak current difference for the amino acid enantiomers by cyclic voltammetry (CV) and differential pulse voltammetry (DPV). The TOCNCs on the electrode surface expressed different interactions with d- and l-amino acids, so the electrochemical recognitions of the three amino acid enantiomers were achieved. TOCNCs were characterized by Fourier transform infrared (FT-IR) and scanning electron microscopy (SEM). The modified electrodes were characterized by SEM and electrochemical techniques. According to DPV, peak currents of the two enantiomers decreased linearly with their concentrations. Furthermore, satisfactory results were obtained when this electrode was applied to measure the d- and l-Phe mixture. The experimental results show that TOCNCs are suitable material for chiral sensor. The contrast of serum sample of healthy people and patients with type 2 diabetes also was proposed, and significant difference was exhibited on the modified electrode. This work is significant for the screening, diagnosis, and treatment of multiple metabolic diseases.

Section snippets

Chemicals and apparatus

All chemicals were of analytical grade and used without further purification. Microcrystalline cellulose, d- and l-Phe, d- and l-Leu, d- and l-Val, K₃[Fe(CN)₆], and K₄[Fe(CN)₆] were purchased from Sinoreagent. N-Hydroxysuccinimide (NHS), 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (EDC), and sodium bromide were purchased from J&K Chemical. H₂SO₄ was purchased from CdKelong. l-Cys was purchased from Shanghai Kangda Amino Acids. All aqueous solution was freshly prepared using deionized water.

Characterization of prepared CNC and TOCNC

SEM images of CNCs and TOCNCs are shown in Fig. 1A and B. CNCs and TOCNCs self-assembled to be an ordered helical structure, which was called chiral nematic and was a notable feature of cellulose [25]. Compared with CNCs, TOCNCs remained the structure of CNCs and expressed a tighter and neater arrangement. Fig. 1C shows FT-IR spectroscopy of CNCs and TOCNCs. The absorption bands at 3350 and 2900 cm⁻¹ were assigned to O single bond H stretching vibration and CH stretching vibration, respectively. The peaks

Conclusion

In this study, TOCNC/l-Cys/Au electrodes have been fabricated for detection and discrimination of Phe, Leu, and Val enantiomers, which are biomarkers of certain metabolic diseases. The modified electrodes realized the determination of a single enantiomer and chiral recognition of enantiomers, and both of them obtained good results. The recognition mechanism is that TOCNCs showed a stronger adsorption to d-amino acids than to l-amino acids, creating a clear difference in peak current between l-

Acknowledgments

This work was supported by the National Natural Science Foundation of China (21405161, 21405162, 21575115, 21327005, and 21175108); the Program for Chang Jiang Scholars and Innovative Research Team, Ministry of Education, China (IRT1283).

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An electrochemical sensor based on cellulose nanocrystal for the enantioselective discrimination of chiral amino acids

Abstract

Section snippets

Chemicals and apparatus

Characterization of prepared CNC and TOCNC

Conclusion

Acknowledgments

Cell Metab.

Anal. Biochem.

J. Chromatogr. B

Biosens. Bioelectron.

Biosens. Bioelectron.

Anal. Biochem.

J. Food Compos. Anal.

J. Pharm. Biomed.

Anal. Chem.

Carbohydr. Polym

Chirality, photochemistry, and the detection of amino acids in interstellar ice analogues and comets

Chem. Soc. Rev.

Photoluminescent sensing for acidic amino acids based on the disruption of graphene quantum dots/europium ions aggregates

Biosens. Bioelectron.

Recent progress in fluorescent and colorimetric chemosensors for detection of amino acids

Chem. Soc. Rev.

Hyperglycemia and a common variant of GCKR are associated with the levels of eight amino acids in 9,369 Finnish men

Diabetes

Metabolic signatures of insulin resistance in 7,098 young adults

Diabetes