Citation: . Switch-on fluorescence sensor for ascorbic acid detection based on MoS₂ quantum dots-MnO₂ nanosheets system and its application in fruit samples[J]. Chinese Chemical Letters, ;2017, 28(2): 338-344. doi: 10.1016/j.cclet.2016.10.003 shu

Switch-on fluorescence sensor for ascorbic acid detection based on MoS₂ quantum dots-MnO₂ nanosheets system and its application in fruit samples

Received Date: 25 July 2016
Revised Date: 6 September 2016
Accepted Date: 12 September 2016
Available Online: 8 February 2016

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In this work, molybdenum disulfide quantum dots (MoS₂ QDs) were firstly prepared by hydrothermal method using sodium molybdate and glutathione as precursors, and applied in ascorbic acid detection. When joining MnO₂ nanosheets into MoS₂ QDs solution, they produced an obvious fluorescence quenching, which should be due to inner filter effect (IFE). Meanwhile, the fluorescent probe was formed. Interestingly, we found that this quenching phenomenon disappeared with the addition of ascorbic acid. In other words, the fluorescence gradually restored. This recovery phenomenon is mainly due to the reduction effect of ascorbic acid for MnO₂ nanosheets. Under the optimum conditions, the limit of detection (LOD) of 39 nmol/L for ascorbic acid was achieved with a linear range of 0.33-5.00 μmol/L. The repeatability was better than 5.0% for ascorbic acid in both standard and fruit samples (n=3). Moreover, the as-fabricated fluorescent sensing system was successfully employed to detect the ascorbic acid levels in hawthorn and jujube with satisfactory results.
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Figure 1. The TEM images (A) and the size distribution (B) of MoS₂ QDs.

Figure 2. The TEM image of the MnO₂ nanosheets.

Figure 3. High-resolution peak-fitting XPS spectra of the Mo3d (A) and S_2p (B) regions for MoS₂ QDs.

Figure 4. UV-vis absorption (red line) and fluorescence emission (blue line) spectra of the MoS₂QDs.Insetisthe photographofMoS₂QDs dispersionsolutionunder visible light and UV light (365nm).

Figure 5. (A) Fluorescence emission (FL) spectra of the MoS₂ QDs under different excitation wavelength. (B) The time-resolved luminescence spectra of MoS₂ QDs.

Scheme1. Schematic illustration of the principle of MoS₂ QDs-MnO₂ nanosheets system based chemosensor for ascorbic acid (AA).

Figure 6. The UV-vis absorption of MnO₂ nanosheets (red line) and the fluorescence spectra of MoS₂ QDs (black line for excitation and blue line for emission).

Figure 7. Effects of (A) pH of buffer solution and (B) concentration of MnO₂ nanosheets on fluorescence restoration. ΔF = F-F₀, where F and F0 are the fluorescence intensities of MoS₂ QDs-MnO₂ nanosheets system in the presence and absence of ascorbic acid. (C, D) Relationship between fluorescence intensity and incubation time of quenching and restoration, respectively. Experimental conditions: 0.2 mol/L PBS buffer, 5.0 μmol/L ascorbic acid.

Figure 8. (A) Fluorescence emission spectra of MoS₂ QDs with increasing concentration of ascorbic acid (0.33, 0.66, 1.00, 2.00, 5.00, 20.00 μmol/L). (B) Relationship between ΔF/F₀ and the concentration of ascorbic acid. The fluorescence emission intensity at 430 nm was measured with an excitation of 360 nm. The error bar represents the average value ± the relative standard deviation (n= 3).

Figure 9. (A) Fluorescence emission intensity of MoS₂ QDs-MnO₂ nanosheets system to 0.5 mmol/L ascorbic acid (AA) and 13 other analytes (10-fold concentration of AA). (B) Fluorescence emission intensity of MoS₂ QDs-MnO₂ nanosheets system to AA and 13 other analytes (0.5 mmol/L) in the presence of AA (0.5 mmol/L). The 13 potential interferences are: Na⁺, Mg²⁺, Cl^-, citric acid (CA), vitamin B1 (VB1), glutathione (GSH), cysteine (Cys), lysine (Lys), glutamic acid (Glu), histidine (His), tryptophan (Try), serine (Ser), alanine (Ala), respectively. The error bar represents the average value ± the relative standard deviation (n= 3).

Switch-on fluorescence sensor for ascorbic acid detection based on MoS2 quantum dots-MnO2 nanosheets system and its application in fruit samples

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通讯作者: 陈斌, bchen63@163.com

Switch-on fluorescence sensor for ascorbic acid detection based on MoS₂ quantum dots-MnO₂ nanosheets system and its application in fruit samples