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WS2 quantum dots-MnO2 nanosheet system for use in ratiometric fluorometric/scattered light detection of glutathione

Microchimica Acta volume 187, Article number: 344 (2020) Cite this article

Abstract

Based on WS2 quantum dots (QDs) as fluorescent signals and MnO2 nanosheets as second-order scattering (SOS) signals, a combination of fluorescence and scattered light was used to construct a ratio sensing platform for glutathione (GSH) detection. When MnO2 nanosheets are added to WS2 QDs, the fluorescence of WS2 QDs is quenched by MnO2 nanosheets through IFE. Large-sized MnO2 nanosheets increase the SOS of the system and gradually approach the fluorescence. After adding GSH to WS2 QDs-MnO2, the MnO2 nanosheets were decomposed into Mn2+. The disappearance of the characteristic absorption peak of the MnO2 nanosheets suppressed the IFE to WS2 QDs, resulting in the fluorescence recovery of WS2 QDs. The reduction in size of MnO2 nanosheets after decomposition results in a decrease in the SOS of the system. Therefore, the ratio detection of GSH is obtained through the fluorescence and SOS dual signal response. Under optimal experimental conditions, the value of F406/S648 is linearly related to the GSH concentration in the range 0 to 60 μM, and the limit of detection (LOD) of GSH is 0.12 μM. In addition, the system is also used for the determination of GSH in real water samples and human serum, with good analytical results.

Schematic principle of fluorescence/scattered light system based on WS2 QDs-MnO2 for GSH ratiometric detection.

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References

  1. Li S, Wang L, Zhang X, Chai H, Huang Y (2018) A Co, N co-doped hierarchically porous carbon hybrid as a highly efficient oxidase mimetic for glutathione detection. Sensors and Actuators B: Chemical

  2. Li J, Rao X, Xiang F, Wei J, Yuan M, Liu Z (2018) A photoluminescence “switch-on” nanosensor composed of nitrogen and sulphur co-doped carbon dots and gold nanoparticles for discriminative detection of glutathione. Analyst 143(9):2083–2089

    CAS  PubMed  Article  Google Scholar 

  3. Han L, Liu SG, Zhang XF, Tao BX, Li NB, Luo HQ (2018) A sensitive polymer dots-manganese dioxide fluorescent nanosensor for “turn-on” detection of glutathione in human serum. Sensors Actuators B Chem 258:25–31

    CAS  Article  Google Scholar 

  4. Gao Y, Wu K, Li H, Chen W, Fu M, Yue K, Zhu X, Liu Q (2018) Glutathione detection based on peroxidase-like activity of Co3O4–Montmorillonite nanocomposites. Sensors Actuators B Chem 273:1635–1639

    CAS  Article  Google Scholar 

  5. Yan F, Bai Z, Zu F, Zhang Y, Sun X, Ma T, Chen L (2019) Yellow-emissive carbon dots with a large stokes shift are viable fluorescent probes for detection and cellular imaging of silver ions and glutathione. Mikrochim Acta 186(2):113

    PubMed  Article  CAS  Google Scholar 

  6. Yang X-F, Huang Q, Zhong Y, Li Z, Li H, Lowry M, Escobedo JO, Strongin RM (2014) A dual emission fluorescent probe enables simultaneous detection of glutathione and cysteine/homocysteine. Chem Sci 5(6):2177–2183

    CAS  PubMed  PubMed Central  Article  Google Scholar 

  7. He L, Xu Q, Liu Y, Wei H, Tang Y, Lin W (2015) Coumarin-based turn-on fluorescence probe for specific detection of glutathione over cysteine and homocysteine. ACS Appl Mater Interfaces 7(23):12809–12813

    CAS  PubMed  Article  Google Scholar 

  8. Huang Y, Zhou J, Feng H, Zheng J, Ma H-M, Liu W, Tang C, Ao H, Zhao M, Qian Z (2016) A dual-channel fluorescent chemosensor for discriminative detection of glutathione based on functionalized carbon quantum dots. Biosens Bioelectron 86:748–755

    CAS  PubMed  Article  Google Scholar 

  9. Lee PT, Goncalves LM, Compton RG (2015) Electrochemical determination of free and total glutathione in human saliva samples. Sensors Actuators B Chem 221:962–968

    CAS  Article  Google Scholar 

  10. Ge J, Cai R, Chen X, Wu Q, Zhang L, Jiang Y, Cui C, Wan S, Tan W (2019) Facile approach to prepare HSA-templated MnO2 nanosheets as oxidase mimic for colorimetric detection of glutathione. Talanta 195:40–45

    CAS  PubMed  Article  Google Scholar 

  11. Ouyang L, Zhu L, Jiang J, Tang H (2014) A surface-enhanced Raman scattering method for detection of trace glutathione on the basis of immobilized silver nanoparticles and crystal violet probe. Anal Chim Acta 816:41–49

    CAS  PubMed  Article  Google Scholar 

  12. Bigdeli A, Ghasemi F, Abbasi-Moayed S, Shahrajabian M, Fahimi-Kashani N, Jafarinejad S, Farahmand Nejad MA, Hormozi-Nezhad MR (2019) Ratiometric fluorescent nanoprobes for visual detection: design principles and recent advances - a review. Anal Chim Acta 1079:30–58

    CAS  PubMed  Article  Google Scholar 

  13. Ma Z, Wu T, Li P, Liu M, Huang S, Li H, Zhang Y, Yao S (2019) A dual (colorimetric and fluorometric) detection scheme for glutathione and silver (I) based on the oxidase mimicking activity of MnO2 nanosheets. Mikrochim Acta 186(8):498

    PubMed  Article  CAS  Google Scholar 

  14. Xu X, He L, Long Y, Pan S, Liu H, Yang J, Hu X (2019) S-doped carbon dots capped ZnCdTe quantum dots for ratiometric fluorescence sensing of guanine. Sensors Actuators B Chem 279:44–52

    CAS  Article  Google Scholar 

  15. Chen S, Jia Y, Zou GY, Yu YL, Wang JH (2019) A ratiometric fluorescent nanoprobe based on naphthalimide derivative-functionalized carbon dots for imaging lysosomal formaldehyde in HeLa cells. Nanoscale 11(13):6377–6383

    CAS  PubMed  Article  Google Scholar 

  16. Yan F, Zu F, Xu J, Zhou X, Bai Z, Ma C, Luo Y, Chen L (2019) Fluorescent carbon dots for ratiometric detection of curcumin and ferric ion based on inner filter effect, cell imaging and PVDF membrane fouling research of iron flocculants in wastewater treatment. Sensors Actuators B Chem 287:231–240

    CAS  Article  Google Scholar 

  17. Jin H, Baek B, Kim D, Wu F, Batteas JD, Cheon J, Son DH (2017) Effects of direct solvent-quantum dot interaction on the optical properties of colloidal monolayer WS2 quantum dots. Nano Lett 17(12):7471–7477

    CAS  PubMed  Article  Google Scholar 

  18. Cheng G, Li B, Zhao C, Yan X, Wang H, Lau KM, Wang J (2018) Interfacially bound exciton state in a hybrid structure of monolayer WS2 and InGaN quantum dots. Nano Lett 18(9):5640–5645

    CAS  PubMed  Article  Google Scholar 

  19. Srivastava M, Tiwari P, Mall VK, Srivastava SK, Prakash R (2019) Voltammetric determination of the antimalarial drug chloroquine using a glassy carbon electrode modified with reduced graphene oxide on WS2 quantum dots. Microchim Acta 186(7):415

    Article  CAS  Google Scholar 

  20. Fang Y, Pan J, Zhang D, Wang D, Hirose HT, Terashima T, Uji S, Yuan Y, Li W, Tian Z, Xue J, Ma Y, Zhao W, Xue Q, Mu G, Zhang H, Huang F (2019) Discovery of superconductivity in 2M WS2 with possible topological surface states. Adv Mater 31(30):e1901942

    PubMed  Article  CAS  Google Scholar 

  21. Dhenadhayalan N, Lin KC, Saleh TA (2019) Recent advances in functionalized carbon dots toward the design of efficient materials for sensing and catalysis applications. Small:e1905767

  22. Chen J, Meng H, Tian Y, Yang R, Du D, Li Z, Qu L, Lin Y (2019) Recent advances in functionalized MnO2 nanosheets for biosensing and biomedicine applications. Nanoscale Horizons 4(2):321–338

    CAS  PubMed  Article  Google Scholar 

  23. Liu Z, Zhang S, Lin H, Zhao M, Yao H, Zhang L, Peng W, Chen Y (2018) Theranostic 2D ultrathin MnO2 nanosheets with fast responsibility to endogenous tumor microenvironment and exogenous NIR irradiation. Biomaterials 155:54–63

    CAS  PubMed  Article  Google Scholar 

  24. Zhu S, Wang S, Xia M, Wang B, Huang Y, Zhang D, Zhang X, Wang G (2019) Intracellular imaging of glutathione with MnO2 Nanosheet@Ru(bpy)32+–UiO-66 nanocomposites. ACS Appl Mater Interfaces 11(35):31693–31699

    CAS  PubMed  Article  Google Scholar 

  25. Xiao T, Sun J, Zhao J, Wang S, Liu G, Yang X (2018) FRET effect between fluorescent polydopamine nanoparticles and MnO2 nanosheets and its application for sensitive sensing of alkaline phosphatase. ACS Appl Mater Interfaces 10(7):6560–6569

    CAS  PubMed  PubMed Central  Article  Google Scholar 

  26. Yan X, Song Y, Zhu C, Li H, Du D, Su X, Lin Y (2018) MnO2 nanosheet-carbon dots sensing platform for sensitive detection of organophosphorus pesticides. Anal Chem 90(4):2618–2624

    CAS  PubMed  PubMed Central  Article  Google Scholar 

  27. Liu Y, Zeng Z, Bloom B, Waldeck DH, Wei J (2018) Stable low-current electrodeposition of α-MnO2 on superaligned electrospun carbon nanofibers for high-performance energy storage. Small 14(3):1703237

    Article  CAS  Google Scholar 

  28. Thakkar D, Gevriya B, Mashru RC (2014) Study on interaction between palladium(capital I, Ukrainiancapital I, Ukrainian)-linezolid chelate with eosin by resonance Rayleigh scattering, second order of scattering and frequency doubling scattering methods using Taguchi orthogonal array design. Spectrochim Acta A Mol Biomol Spectrosc 122:75–81

    CAS  PubMed  Article  Google Scholar 

  29. Chen P, Liu S, Liu Z, Hu X (2011) Study on the ternary mixed ligand complex of palladium(II)-aminophylline-fluorescein sodium by resonance Rayleigh scattering, second-order scattering and frequency doubling scattering spectrum and its analytical application. Spectrochim Acta A Mol Biomol Spectrosc 78(1):518–522

    PubMed  Article  CAS  Google Scholar 

  30. Yan F, Sun Z, Ma T, Sun X, Xu J, Wang R, Chen L (2019) Ratiometric fluorescent nanoprobes based on resonance Rayleigh scattering and inner filter effect for detecting alizarin red and Pb2+. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy:117843

  31. Wu Z, Nan D, Yang H, Pan S, Liu H, Hu X (2019) A ratiometric fluorescence-scattered light strategy based on MoS2 quantum dots/CoOOH nanoflakes system for ascorbic acid detection. Anal Chim Acta 1091:59–68

    CAS  PubMed  Article  Google Scholar 

  32. Singh VK, Yadav MS, Mishra H, Kumar R, Tiwari RS, Pandey A, Srivastava A (2019) WS2 quantum dot graphene nanocomposite film for UV photodetection. ACS Applied Nano Materials 2(6):3934–3942

    CAS  Article  Google Scholar 

  33. Zhu Z, Lin X, Wu L, Zhao C, Zheng Y, Liu A, Lin L, Lin X (2018) “Switch-on” fluorescent nanosensor based on nitrogen-doped carbon dots-MnO2 nanocomposites for probing the activity of acid phosphatase. Sensors Actuators B Chem 274:609–615

    CAS  Article  Google Scholar 

  34. Peng C, Xing H, Fan X, Xue Y, Li J, Wang E (2019) Glutathione regulated inner filter effect of MnO2 nanosheets on boron nitride quantum dots for sensitive assay. Anal Chem 91(9):5762–5767

    CAS  PubMed  Article  Google Scholar 

  35. Zhang XL, Zheng C, Guo SS, Li J, Yang HH, Chen G (2014) Turn-on fluorescence sensor for intracellular imaging of glutathione using g-C(3)N(4) nanosheet-MnO(2) sandwich nanocomposite. Anal Chem 86(7):3426–3434

    CAS  PubMed  Article  Google Scholar 

  36. Cai QY, Li J, Ge J, Zhang L, Hu YL, Li ZH, Qu LB (2015) A rapid fluorescence "switch-on" assay for glutathione detection by using carbon dots-MnO2 nanocomposites. Biosens Bioelectron 72:31–36

    CAS  PubMed  PubMed Central  Article  Google Scholar 

  37. Lin S, Cheng H, Ouyang Q, Wei H (2016) Deciphering the quenching mechanism of 2D MnO2 nanosheets towards Au nanocluster fluorescence to design effective glutathione biosensors. Anal Methods 8(19):3935–3940

    Article  Google Scholar 

  38. Yan X, Song Y, Zhu C, Song J, Du D, Su X, Lin Y (2016) Graphene quantum dot-MnO2 nanosheet based optical sensing platform: a sensitive fluorescence "turn off-on" nanosensor for glutathione detection and intracellular imaging. ACS Appl Mater Interfaces 8(34):21990–21996

    CAS  PubMed  PubMed Central  Article  Google Scholar 

  39. Gu J, Hu D, Wang W, Zhang Q, Meng Z, Jia X, Xi K (2015) Carbon dot cluster as an efficient "off-on" fluorescent probe to detect Au(III) and glutathione. Biosens Bioelectron 68:27–33

    CAS  PubMed  Article  Google Scholar 

  40. Yan F, Ye Q, Xu J, He J, Chen L, Zhou X (2017) Carbon dots-bromoacetyl bromide conjugates as fluorescence probe for the detection of glutathione over cysteine and homocysteine. Sensors Actuators B Chem 251:753–762

    CAS  Article  Google Scholar 

  41. Wang Q, Wang C, Wang X, Zhang Y, Wu Y, Dong C, Shuang S (2019) Construction of CPs@MnO2–AgNPs as a multifunctional nanosensor for glutathione sensing and cancer theranostics. Nanoscale 11(40):18845–18853

    CAS  PubMed  Article  Google Scholar 

  42. Jiao Y, Gao Y, Meng Y, Lu W, Liu Y, Han H, Shuang S, Li L, Dong C (2019) One-step synthesis of label-free Ratiometric fluorescence carbon dots for the detection of silver ions and glutathione and cellular imaging applications. ACS Appl Mater Interfaces 11(18):16822–16829

    CAS  Article  PubMed  Google Scholar 

  43. Shamsipur M, Safavi A, Mohammadpour Z (2014) Indirect colorimetric detection of glutathione based on its radical restoration ability using carbon nanodots as nanozymes. Sensors Actuators B Chem 199:463–469

    CAS  Article  Google Scholar 

  44. Liu J, Meng L, Fei Z, Dyson PJ, Jing X, Liu X (2017) MnO2 nanosheets as an artificial enzyme to mimic oxidase for rapid and sensitive detection of glutathione. Biosens Bioelectron 90:69–74

    CAS  PubMed  Article  Google Scholar 

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Funding

The work was supported by the National Natural Science Foundation of China (51678409, 51638011, and 51578375), Tianjin Research Program of Application Foundation and Advanced Technology (19JCYBJC19800, 18JCYBJC87500, 15ZCZDSF00880), State Key Laboratory of Separation Membranes and Membrane Processes (Z1-201507), and the Program for Innovative Research Team in University of Tianjin (TD13-5042).

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  1. State Key Laboratory of Separation Membranes and Membrane Processes/National Center for International Joint Research on Separation Membranes, School of Chemistry and Chemical Engineering, Tiangong University, Tianjin, 300387, People’s Republic of China

    Fanyong Yan, Zhonghui Sun, Jinxia Xu, Hejing Li & Yuyang Zhang

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  1. Fanyong Yan
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  2. Zhonghui Sun
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Correspondence to Fanyong Yan.

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Yan, F., Sun, Z., Xu, J. et al. WS2 quantum dots-MnO2 nanosheet system for use in ratiometric fluorometric/scattered light detection of glutathione. Microchim Acta 187, 344 (2020). https://doi.org/10.1007/s00604-020-04318-3

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  • DOI: https://doi.org/10.1007/s00604-020-04318-3

Keywords

  • WS2 quantum dots
  • MnO2 nanosheets
  • Glutathione (GSH)
  • Fluorescence
  • Second-order scattering (SOS)
  • Ratiometric