Tetrabutylammonium-chloride-glycerol of deep eutectic solvent functionalized MnO2: a novel mimic enzyme for the quantitative and qualitative colorimetric detection of l-cysteine

Abstract

L-Cysteine is a common amino acid that plays an important role in human livelihood and production. Therefore, a novel method for the simultaneous quantitative and qualitative determination of L-cysteine by a colorimetric detection system is proposed. As a viable oxidase mimic, [N₄₄₄₄]Cl-G/MnO₂, which consisted of MnO₂ nanosheets functionalized by a tetrabutylammonium chloride–glycerol ([N₄₄₄₄]Cl-G) based deep eutectic solvent (DES) was fabricated. Owing to the oxidation of MnO₂ nanosheets, [N₄₄₄₄]Cl-G/MnO₂ could oxidize the colorless 3,3′,5,5′-tetramethylbenzidine (TMB) into a blue product (oxTMB) with the characteristic UV–vis spectrum absorbance at 652 nm. The oxidation of TMB by DES/MnO₂ was inhibited when L-cysteine was introduced, and the absorbance decreased proportionally with the increase in L-cysteine concentration. Due to this inhibition effect, a colorimetric detection system ([N₄₄₄₄]Cl-G/MnO₂-TMB) was developed for the quantitative determination of L-cysteine. Under optimal conditions, the assay showed good linearity over the concentration range of 0.125–2.00 μg mL⁻¹ with a low detection limit of 5.96 ng mL⁻¹. A study of the inhibition mechanism demonstrated that the sulfhydryl group of L-cysteine could decompose [N₄₄₄₄]Cl-G/MnO₂ into Mn²⁺, thus limiting the conversion of TMB to oxTMB. In addition, the [N₄₄₄₄]Cl-G/MnO₂-TMB system was used in test strips for the visual qualitative detection of L-cysteine. The selectivity and test strip results demonstrated the high selectivity, simple operation, and rapid response of the [N₄₄₄₄]Cl-G/MnO₂-TMB system for the qualitative detection of L-cysteine. Given the satisfying performance of the detection strategy, colorimetric sensing based on the [N₄₄₄₄]Cl-G/MnO₂-TMB system is considered to have prospective application value in the quantitative and qualitative detection of L-cysteine.