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Glutathione Regulated Inner filter effect of MnO nanosheets on Boron Nitride Quantum Dots for Sensitive Assay Chao Peng, Huanhuan Xing, Xiushuang Fan, Yuan Xue, Jing Li, and Erkang Wang Anal. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.analchem.8b05961 • Publication Date (Web): 08 Apr 2019 Downloaded from http://pubs.acs.org on April 9, 2019

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Analytical Chemistry

Glutathione Regulated Inner filter effect of MnO2 nanosheets on Boron Nitride Quantum Dots for Sensitive Assay

Chao Peng, a, b Huanhuan Xing, a, b Xiushuang Fan, c Yuan Xue, a, b Jing Li, a, b * Erkang Wang a, b *

a. State Key Laboratory of Electroanalytical Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, Jilin, 130022, China. b. University of Science and Technology of China, Hefei, Anhui, 230029, China. c. Department of Anesthesiology, The First Hospital of Jilin University, Changchun, Jilin, 130021, China. Corresponding

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Analytical Chemistry 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ABSTRACT Glutathione (GSH) can help the body maintain the function of the normal immune system and its level change associates with varieties of diseases. For achieving the ultrasensitive assay of GSH, a “switch on” nanosensor is designed based on GSH regulated the inner filter effect (IFE) of MnO2 nanosheets (MnO2 NS) on boron nitride quantum dots (BNQDs). Here, the fluorescence of BNQDs is quenched efficiently in the presence of redoxable MnO2 NS due to the superior light absorption capability. While the introduction of GSH can trigger the decomposition of MnO2 to Mn2+ and weaken the IFE, causing the partial fluorescence recovery. The recovered fluorescence is dependent on the concentration of GSH. Under the optimal conditions, this sensing platform shows the response to GSH in the range of 0.5 to 250 μM with the detection limit of 160 nM. Based on the GSH activated reduction of MnO2 NS, the MnO2 NS/BNQDs nanoprobes exhibit good selectivity to GSH. The practical application of the proposed system is demonstrated by detecting the GSH in human plasma samples with satisfied results.

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INTRODUCTION Glutathione (GSH) as one important non-protein biothiol in eukaryotic cells, plays crucial roles in multiple physiological functions, such as the cellular antioxidant defense system, regulation of cell growth and protein function. The concentration of GSH ranges from 1 to 15 mM1 in human cells and its aberrant level is closely related to many diseases, such as acquired immune deficiency syndrome, human immunodeficiency virus, Alzheimer's disease, diabetes and cancer.2-4 Developing a reliable sensing platform for monitoring the GSH has drawn considerable attention. Up to date, many methods have been reported for detecting GSH, such as high performance liquid chromatography-ultraviolet,5 electrochemiluminescence (ECL),6 photoelectrochemistry,7 surface enhanced Raman scattering,8 mass spectrometry,9 fluorescence spectroscopy and enzyme-linked immunosorbent assay.10, 11 Compared with other methods, fluorescence analysis with high sensitivity,12 simple operation, non-destructy13 and low cost14 has been attracted more and more interest for high-performance GSH sensing platform. For the most of fluorescence GSH assays, “signal-on” sensing based on competition mechanism is often employed via the strong affinity between GSH and quenchers such as metal ions,12 oxidants15 and nanomaterials16 in combination with the fluorescent nanoprobes. And more and more efforts have been made for exploring fluorescent nanoprobes for the assays of GSH including transition metal quantum dots (QDs),17 C-dots,18 silver and gold nanoclusters,19, graphitic-C3N4

13

20

upconversion nanoparticles,21

and persistent luminescence nanoparticles.22 For example, Lin’s

group utilized the biocompatible graphene QDs as nanoprobes to construct a “turn-off-on” nanosensor for GSH detection and intracellular imaging23 based on the quenching effects of MnO2 NS. MnO2 NS with thin layer structure, high specific surface area and superior light absorption capacity show high promising potential as fluorescence quenchers. Moreover, the recognized reaction between GSH and MnO2 makes the MnO2 NS more popular in the GSH sensing. Although good achievements 3



have been made, there are still many problems with above-mentioned sensors, such as difficulty in preparation of raw materials or fluorescent nanoprobes and relatively low overlapped efficiency between accepter and donor. Developing the new fluorescent nanoprobes with convenient synthesis process, excellent photoluminescence stability, high biocompatibility and suitable emission wavelength to improve the analytical performance for sensing GSH is very significant in biological applications, especially for the IFE based sensing strategy. In recent years, BNQDs as the green alternative to the transition metal QDs with unique physical and chemical properties such as good chemical stability, low toxicity,24 favorable biocompatibility and excellent photoluminescence stability25 have exhibited promising potential in the practical applications such as ECL coreactant,26 bioimaging,23 optoelectronics and biomedical devices.24 Notably, BNQDs-based applications are still in their infancy, especially in the fabrication of biosensors. Inspired by the unique feature of BNQDs and MnO2 NS, we combine them in one matrix and design a “switch-on” nanosensor for the ultrasensitive assay of GSH (Scheme 1). Here, highly fluorescent BNQDs with the maximum emission wavelength of 380 nm are successfully synthesized via a one-spot hydrothermal method by simple mixing of boric acid and ammonia. MnO2 NS are synthesized by ultrasonic reduction of KMnO4 in 2-(N-morpholino) ethanesulfonic acid (MES) buffer solution. The adsorption of redoxable MnO2 NS with maximum absorption center 380 nm overlaps well with the emission spectrum of BNQDs, which endows them as the good acceptor of fluorescent nanoprobes of BNQDs to quench the fluorescence efficiently based on the IFE. While the existence of GSH can activate the fluorescence again as a result of the decomposition of MnO2 to Mn2+ and oxidation of GSH to GSSH, which provides the basis for the GSH sensing. The combination of BNQDs and MnO2 NS makes the sensing more sensitive (The limit of detection (LOD) = 160 nM) and the introduction of BNQDs enabled the detection of GSH with low cost due to the convenient synthesis process. The successful practical application in human serum samples suggests the great potential in the biological application of disease monitoring and clinical diagnosis. 4


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EXPERIMENTAL SECTION Chemicals and Reagents. All the chemicals are used as received without any further purification, KMnO4, KCl, HCl, KH2PO4, K2HPO4•3H2O are bought from Beijing Chemical Reagent Company (Beijing, China). L-glutathione reduced (GSH) is purchased from Sigma-Aldrich Chemical Co (Milwaukee, WI), MES is purchased from Bioengineering Engineering Shanghai Co., Ltd. and boric acid is bought from Xilong Chemical Co., Ltd. (Guangdong). The deionized water (18.2 MΩ cm-1) purified by a Milli-Q system (Millipore, Bedford, MA) is used to prepare all the solutions. Apparatus. Transmission electron microscopy (TEM) is taken by a JEM-2010 (HR) microscope operated at 200 kV. X-ray photoelectron spectroscopy (XPS) is obtained from an ESCALAB-MKⅡX-ray photoelectron spectroscope (VG Scientific, UK). The fluorescence spectra are obtained from Cary Eclipse fluorescence spectrophotometer (Agilent Technologies) and UV-vis spectra are recorded using the Cary 500 scan UV-vis spectrometer (Varian). Preparation of BNQDs. The BNQDs are synthesized via a simple one-spot hydrothermal method according to the previous work.26, 27 Briefly, 0.4 g of boric acid is dissolved in 10 ml of distilled water, then 0.8 mL of ammonia is added into the above solution. The mixture is heated in a Teflon-equipped stainless-steel autoclave at 200 °C for 12 h. Preparation of MnO2 NS. The MnO2 NS are prepared according to previous reports.21, 28 Typically, 1 mL KMnO4 (10 mM) is added into 10 mL MES buffer (0.01 M). Then the mixture keeps sonication for 30 min by ultrasonic cell crusher with an output power of 400 W. The MnO2 NS are obtained after centrifugation under 10000 rpm for 10 min and wash with distilled water for many times. The purified MnO2 NS 5



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are dispersed in distilled water for further use and stored at 4 °C. The final concentration of MnO2 NS is 41.2 μM for the subsequent GSH detection experiments according to the results from inductively coupled plasma-mass spectrometry. Detection of GSH. Different concentration of GSH is added into 40 μL MnO2 NS and 10 μL BNQDs mixture for 6 min at room temperature. Then, the above mixture is diluted to 400 μL with phosphate buffer solution (10 mM, pH 3.5) and fluorescence

spectra

of

the

nanoprobes

are

collected

on

fluorescence

spectrophotometer with excitation wavelength at 310 nm. Detecting GSH in human plasma samples. The human plasma samples are provided by the First Hospital of Jilin University. The pre-treatment of plasma is according to the literature.15, 29 Briefly, the plasma is centrifuged at 12000 rpm for 20 min to remove insoluble matter. The supernatant is collected and dilute 6 times with a phosphate buffer solution of pH 6.0 for subsequent analysis. Then the total GSH concentrations are determined by standard addition method.

RESULTS AND DISCUSSION Characterization of the BNQDs and MnO2 NS. The synthesis of BNQDs is achieved via a facile one-spot hydrothermal treatment of boric acid and ammonia. The TEM image in Figure 1A indicates that the as-prepared BNQDs exhibit good monodispersity with a mean size of 2 nm and are easily dispersed in the aqueous medium. The optical properties of BNQDs are collected using fluorescence spectra (Figure 1B). Strong emission is observed at 380 nm under an excitation of 310 nm. Under the UV light, the as-prepared BNQDs emit strong blue light (inset of Figure 1B). All these results confirm the success synthesis of the fluorescent BNQDs. The MnO2 NS are synthesized via a top-down sonication and characterized using TEM and XPS. As shown in Figure 1C, lamellar structure of MnO2 NS is observed, exhibiting the characteristic two-dimension morphology. As depicted in Figure 1D, the XPS of MnO2 NS presents two peaks locating at 642.0 eV and 653.9 eV, corresponding to Mn 2p3/2 and Mn 2p1/2 of MnO2 respectively, which is consistent with previous reported literature,30 revealing the formation of MnO2 NS. 6


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Detection Strategy of GSH. To clearly demonstrate the quenching effect induced by MnO2 NS, the UV-vis absorption of MnO2 NS is collected (Figure 2A). The MnO2 NS exhibit a superior light absorption capability ranging from 200 to 600 nm with the maximum absorption center at 380 nm, which overlaps well with the emission spectrum of BNQDs (em=380 nm). This is the prerequisite for the IFE (Figure 2B, red line). To confirm the GSH regulated IFE of MnO2 NS on BNQDs, the control experiments are carried out (Figure 2B). When there is only GSH, no change in the fluorescence intensity is observed, indicating the good photostability of BNQDs and low interaction between GSH and BNQDs. As expected, the introduction of MnO2 NS quenches the fluorescence of BNQDs effectively. After adding GSH into the BNQDs-MnO2 NS system, it will react with redoxable MnO2 NS to produce Mn2+ (Equation 1) and fluorescence of BNQDs is recovered. In the previous work,23, 27 Lin and Liu’s group investigated the effect of metal ions on BNQDs and found that the Mn2+ cannot induce any fluorescence intensity change. Therefore, the recovered fluorescence is mainly attributed to the MnO2 NS releasing from the surface of BNQDs. Here, the redoxable MnO2 NS act as two roles, one is the energy acceptor, the other is the recognizer for GSH. The GSH regulated IFE provides the basis for the quantification of GSH. 2GSH  MnO 2  2H    GSSG  Mn 2  H 2 O (1)

Optimization of experimental conditions. In order to obtain high performance of the “switch-on” nanosensor, the incubation conditions including reaction time and pH are investigated. As shown in Figure 3A, the fluorescence intensity of BNQDs at 380 nm gradually increases with the extension of the reaction time between GSH and BNQDs-MnO2 NS fluorescent probes in the presence of 62.5 μM GSH. When the reaction time reaches 6 min, the recovered fluorescence intensity of BNQDs reaches the maximum and therefore 6 min is chosen for the subsequent GSH detection experiments. The pH of the reaction solution has a great influence on the recovered fluorescence intensity of BNQDs.23 10 mM phosphate solution of pH from 3.0-6.0 mixed with BNQDs is used for the investigation of pH effect and the final pH is 7



6.0-9.0, When the original pH is 3.5, the recovery reaches the maximum, which is different from the reported system.23. Since the synthesis of BNQDs is obtained using hydrothermal reaction of boric acid and ammonia and the pH of reaction solution is alkaline after the formation of BNQDs. Therefore, adding the above phosphate solution to the above GSH analysis system, the final pH is 6.5 and it is consistent with the other systems as shown in the Figure 3B.23 Selectivity studies for GSH. Good selectivity is important character for evaluating the constructed nanosensor. The influence of some common substance including K+, Ca2+, Na+, Zn2+, Mn2+, histidine (His), glutamic acid (Glu), cysteine (Cys), homocysteine (Hcy), vitamin C (Vc), bovine serum albumin (BSA) and glucose are recorded. As shown in the Figure 4, when interference substance with the same concentration to GSH is added to the system (BNQDs-MnO2-GSH as blank), the recovered fluorescence intensity of BNQDs does not change (less than 7% fluctuation) for other molecules except Vc (here, F and F0 refer to the fluorescence intensity of BNQDs-MnO2 in the presence and absence of GSH, respectively). Although Vc as a reductant leads to the fluorescence intensity change of BNQDs-MnO2-GSH (about 12% fluctuation), its concentration in plasma is much smaller than that of GSH31, 32 and therefore the influence of Vc can be negligible for GSH determination. To avoid the interference from high concentration of reductant in the real samples, separation processes are suggested. Detection of GSH. Under the optimized condition, different concentration of GSH is introduced and the fluorescence emission of BNQDs gradually recoveries as the concentration of GSH varies from 0.5-250 μM (Figure 5A). As indicated in Figure 5B, the recovered ratio of (F-F0)/F0 is proportional to the GSH concentration ((F-F0)/F0 represents the fluorescence recovery ratio) in two different linear concentration ranges. When the GSH range is 0.5-12.5 μM, it follows the equation 2 ([GSH] is the concentration of GSH), when the GSH ranging from 12.5 -100 μM, Equation 3 is used. This phenomenon was also noted in the Liu’s work.33 The difference in linear slope between the two GSH concentration ranges may be due to the different reaction states of the probes and GSH. The LOD can reach 160 nM based 8


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on the S/N = 3. Table 1 compares analytical performance between other methods and the present system. It is worth noting that sensitivity of this nanosensor is found to be lower than that obtained using other nanoprobes based IFE. Moreover, the synthesis of the photostable and biocompatible fluorescent probes is very convenient and construction of sensing platform system is very simple, endowing it as ideal candidate for fluorescence sensors.

F - F0  0.0169[GSH]  0.109 （2） F0 F - F0  0.00925[GSH]  0.206 （3） F0 Detecting GSH in human plasma samples. In order to verify the feasibility of the fluorescence “switch-on” sensor, the detection of GSH in actual human plasma samples using the present nanosensor is carried out. When we utilize the present platform for the determination, sample is pre-diluted with 10 mM phosphate buffer solution to be consistent with the dynamic range of our assay. And the standard addition method is employed for the recovery test and the average recovery is 101.26 % and 100.95 %, respectively (Table 2) which indicates the potential of BNQDs-MnO2 NS probes for GSH measuring even in complicated biological environments.

CONCLUSIONS In summary, we successfully construct a fluorescence “switch-on” nanosensor via a simple method, in which BNQDs and MnO2 NS are used as fluorescent donors and quenchers, respectively. When MnO2 NS are assembled on the surface of BNQDs, the fluorescence intensity of BNQDs is effectively quenched by the MnO2 NS based on the IFE. However, the presence of GSH would regulate the IFE by triggering MnO2 to Mn2+ and the fluorescence intensity of BNQDs is restored. More importantly, the fluorescence “switch-on” sensor has low detection limit, wide detection range and selectivity, which exhibits satisfied results in practical application for detecting GSH. 9



It indicates that the present system using biocompatible BNQDs as fluorescent probes holds potential prospects in the biomedical field.

ACKNOWLEDGMENT The National Natural Science Foundation of China (Grant No. 21427811), MOST China (No. 2016YFA0203200), Youth Innovation Promotion Association CAS (No.2016208), Jilin Provincial Science Technology Development Plan Project (No.20170101194JC).

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Scheme 1. Schematic principle of GSH regulated inner filter effect of MnO2 NS on BNQDs for sensing.

Figure 1. (A) TEM image of BNQDs; (B) Excitation (red line) and emission (black line) spectra of BNQDs, The inset of (B) is photograph of the BNQDs solution taken 11



under 365nm UV light; (C) TEM image of MnO2 NS; (D) XPS spectra of MnO2 NS.

Figure 2. (A) UV-vis absorption of spectrum of the MnO2 NS (red line) and the fluorescence emission spectrum of BNQDs (black line); (B) Fluorescence spectra of BNQDs (black line), BNQDs-GSH (green line), BNQDs-MnO2 (red line) and BNQDs-MnO2-GSH (blue line).

Figure 3. (A) The effect of reaction time on the recovered fluorescence intensity of BNQDs-MnO2 system in the presence of 62.5 μM GSH; (B) The effect of supporting pH on the fluorescence intensity of BNQDs-MnO2 probes in the presence of 62.5 μM GSH.

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1.0

(F-F0)/F0

0.5

V c G lu BS A G Cy lu s co s Bl e an k

nS O N 4 aC C l aC l2 K C Zn l C l2 H is H cy

0.0 M

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


Figure 4. The relative fluorescence intensity of BNQDs-MnO2 in the presence of the interfering substances and GSH using same concentration of 62.5 μM. F and F0 are fluorescence intensity of BNQDs-MnO2 probes in the presence and absence of GSH, respectively.

Figure 5. (A) Fluorescence of BNQDs-MnO2 probes with different concentrations of GSH. The concentrations of GSH are 0.5, 1.25, 2.5, 6.25, 12.5, 25, 50, 75, 100, 125 and 250 μM; (B) Relationship between fluorescence intensity recovered ratio and the GSH concentration. Table 1. Comparison of other Fluorescence Methods for GSH Sensing. Probes Linear range LOD Ref PDA 0-350 μM 1.5 μM 34 nanoparticles-MnO2 Carbon dots (CD)-MnO2 1-200 μM 0.6 μM 35 GQDs-MnO2 1-1000 μM 0.45 μM 36 AuNC@BSA-MnO2 0-500 μM 20 μM 37 g-C3N4-MnO2 200-500 μM 0.2 μM 13 MnO2-modified UCNPs not given 0.9 μM 21 13



BNQDs-MnO2

0.5-100 μM

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0.16 μM

Table 2. Recovery Test Results of GSH in human plasma samples. Added GSH Measured GSH Recovery (μM) (μM) (%) 10 10.29 102.9 10.42 104.2 9.63 96.3 20 20.75 103.75 20.16 100.80 19.66 98.30

14


This work

RSD (n=3) 4.19

2.70

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Yield Gold Nanocluster Probe for Ultrasensitive Glutathione Detection. Biosens. Bioelectron. 2018, 105, 71-76. 30. Yan, X.; Song, Y.; Wu, X. L.; Zhu, C. Z.; Su, X. G.; Du, D.; Lin, Y. H. Oxidase-Mimicking Activity of Ultrathin MnO2 Nanosheets in Colorimetric Assay of Acetylcholinesterase Activity. Nanoscale 2017, 9, 2317-2323. 31. Wang, Y. H.; Jiang, K.; Zhu, J. L.; Zhang, L.; Lin, H. W. A FRET-Based Carbon Dot-MnO2 Nanosheet Architecture for Glutathione Sensing in Human Whole Blood Samples. Chem. Commun. 2015, 51, 12748-12751. 32. Michelet, F.; Gueguen, R.; Leroy, P.; Wellman, M.; Nicolas, A.; Siest, G. Blood and Plasma Glutathione Measured in Healthy Subjects by HPLC: Relation to Sex, Aging, Biological Variables, and Life Habits. Clin. Chem. 1995, 41, 1509-1517. 33. Mi, Y. Y.; Lei, X. X.; Han, H. Y.; Liang, J. G.; Liu, L. Z. A Sensitive Label-Free FRET Probe for Glutathione Based on CdSe/ZnS Quantum Dots and MnO2 Nanosheets. Anal. Methods 2018, 10, 4170-4177. 34. Kong, X. J.; Wu, S.; Chen, T. T.; Yu, R. Q.; Chu, X. MnO2-Induced Synthesis of Fluorescent Polydopamine Nanoparticles for Reduced Glutathione Sensing in Human Whole Blood. Nanoscale 2016, 8, 15604-15610. 35. Xu, Y.; Chen, X.; Chai, R.; Xing, C. F.; Li, H. R.; Yin, X. B. A Magnetic/Fluorometric Bimodal Sensor Based on a Carbon Dots-MnO2 Platform for Glutathione Detection. Nanoscale 2016, 8, 13414-13421. 36. Liu, Z. E.; Cai, X. H.; Lin, X. F.; Zheng, Y. J. ; Wu, Y. T.; Chen, P. P.; Weng, S. H.; Lin, L. Q.; Lin, X. H. Signal-on Fluorescent Sensor Based on GQDs-MnO2 Composite for Glutathione. Anal. Methods 2016, 8, 2366-2374. 37. Lin, S. C.; Cheng, H. J.; Ouyang, Q. R.; Wei, H. Deciphering the Quenching Mechanism of 2D MnO2 Nanosheets towards Au Nanocluster Fluorescence to Design Effective Glutathione Biosensors. Anal. Methods 2016, 8, 3935-3940.

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Glutathione Regulated Inner Filter Effect of MnO2 Nanosheets on

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