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Microchimica Acta

, 186:806 | Cite as

A “turn off-on” fluorescent nanoprobe consisting of CuInS2 quantum dots for determination of the activity of β-glucosidase and for inhibitor screening

  • Ziping LiuEmail author
  • Ye Tian
  • Yang Han
  • Edith Bai
  • Yanan Li
  • Zhiwei Xu
  • Shasha Liu
Original Paper
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Abstract

A fluorescent “turn off-on” nanoprobe is described for highly sensitive and selective determination of the activity of the enzyme β-glucosidase (β-Glu). Firstly, cysteine modified CuInS2 quantum dots (Cys-CuInS2 QDs) were prepared from indium(III) and copper(II) salts and the presence of thiourea. The red fluorescence of the Cys-CuInS2 QDs, with excitation/emission maxima at 590/656 nm, is quenched by Cu(II). However, in the presence of β-Glu and the cyanogenic glycoside, enzymatic hydrolysis leads to the formation of cyanide. The latter competitively binds to Cu(II) owing to its high affinity for cyanide. This restores the fluorescence of the Cys-CuInS2 QDs. Under the optimum conditions, fluorescence increases linearly in the 0.5–700 U·L−1 β-Glu activity range. The detection limit is 0.2 U·L−1. The nanoprobe was applied to analyze spiked soil samples, and satisfactory results were obtained. The average recoveries of β-Glu were in the range of 96–103%, and the RSD was lower than 4.0%. The fluorescent probe can also be used to screen for β-Glu inhibitors as demonstrated for castanospermine as an example.

Graphical abstract

Schematic representation of the fluorescent nanoprobe for β-glucosidase activity detection and inhibitor screening by taking advantage of the fluorescence (FL) “turn-off” and “turn-on” feature of cysteine capped CuInS2 quantum dots (Cys-CuInS2 QDs).

Keywords

Fluorescence Cys-CuInS2 QDs Cyanogenic glycoside Amygdalin Cyanide Castanospermine Enzyme activity Soil Competitively binds Cu(II) 

Notes

Acknowledgements

This work was funded by the China Postdoctoral Science Foundation (No. 2018 M631850), the Fundamental Research Funds for the Central Universities (Nos. 2412018QD019 and 2412018ZD012), the National Natural Science Foundation of China (No. 41301364) and Science and Technology Research Project of Jilin Province (No. JJKH20190283KJ).

Compliance with ethical standards

Conflict of interest

The authors declare that they have no competing interests.

Supplementary material

604_2019_3918_MOESM1_ESM.docx (481 kb)
ESM 1 (DOCX 481 kb)

References

  1. 1.
    Zeng ZH, Mizukami S, Kikuchi K (2012) Simple and real-time colorimetric assay for glycosidases activity using functionalized gold nanoparticles and its application for inhibitor screening. Anal Chem 84:9089–9095CrossRefGoogle Scholar
  2. 2.
    Cairns JRK, Mahong B, Baiya S, Jeon JS (2015) β-Glucosidases: multitasking, moonlighting or simply misunderstood? Plant Sci 241:246–259CrossRefGoogle Scholar
  3. 3.
    Bi YH, Zhu C, Wang ZY, Luo HZ, Fu RP, Zhao XJ, Zhao XJ, Jiang L (2019) Purification and characterization of a glucose-tolerant β-glucosidase from black plum seed and its structural changes in ionic liquids. Food Chem 274:422–428CrossRefGoogle Scholar
  4. 4.
    Lillelund VH, Jensen HH, Liang X, Bols M (2002) Recent developments of transition-state analogue glycosidase inhibitors of non-natural product origin. Chem Rev 102:515–553CrossRefGoogle Scholar
  5. 5.
    Chróst RJ, Overbeck J (1990) Substrate-ectoenzyme interaction: significance of β-glucosidase activity for glucose metabolism by aquatic bacteria. Arch Hydrobiol Beih Ergebn Limnol 34:93–98Google Scholar
  6. 6.
    Gil-Sotres F, Trasar-Cepeda C, Leiros MC, Seoane S (2005) Different approaches to evaluating soil quality using biochemical properties. Soil Biol Biochem 37:877–887CrossRefGoogle Scholar
  7. 7.
    Yan JL, Pan GX, Li LQ, Quan GX, Ding C, Luo AL (2010) Adsorption, immobilization, and activity of β-glucosidase on different soil colloids. J Colloid Interf Sci 348:565–570CrossRefGoogle Scholar
  8. 8.
    Sazawa K, Kuramitz H (2015) Hydrodynamic voltammetry as a rapid and simple method for evaluating soil enzyme activities. Sensors 15:5331–5343CrossRefGoogle Scholar
  9. 9.
    Trasar-Cepeda C, Leiro’s MC, Gil-Sotres F (2008) Hydrolytic enzyme activities in agricultural and forest soils. Some implications for their use as indicators of soil quality. Soil Biol Biochem 40:2146–2155CrossRefGoogle Scholar
  10. 10.
    Stege PW, Messina GA, Bianchi G, Olsina RA, Raba J (2010) Determination of β-glucosidase activity in soils with a bioanalytical sensor modified with multiwalled carbon nanotubes. Anal Bioanal Chem 397:1347–1353CrossRefGoogle Scholar
  11. 11.
    Kwan DH, Chen HM, Ratananikom K, Hancock SM, Watanabe Y, Kongsaeree PT, Samuels AL, Withers SG (2011) Self-immobilizing fluorogenic imaging agents of enzyme activity. Angew Chem Int Ed 50:300–303CrossRefGoogle Scholar
  12. 12.
    Huang S, Yang EL, Yao JD, Liu Y, Xiao Q (2018) Carbon dots doped with nitrogen and boron as ultrasensitive fluorescent probes for determination of α-glucosidase activity and its inhibitors in water samples and living cells. Microchim Acta 185:394CrossRefGoogle Scholar
  13. 13.
    Yan S, Wu G (2011) Prediction of michaelis-menten constant of beta-glucosidases using nitrophenyl-beta-D-glucopyranoside as substrate. Protein Pept Lett 18:1053–1057CrossRefGoogle Scholar
  14. 14.
    Watanabe A, Suzuki M, Ujiie S, Gomi K (2016) Purification and enzymatic characterization of a novel β-1,6-glucosidase from Aspergillus oryzae. J Biosci Bioeng 121:259–264CrossRefGoogle Scholar
  15. 15.
    Serdiuk IE, Reszka M, Myszka H, Krzyminski K, Liberek B, Roshal AD (2016) Flavonol-based fluorescent indicator for determination of β-glucosidase activity. RSC Adv 6:42532–42536CrossRefGoogle Scholar
  16. 16.
    Jawaid AM, Chattopadhyay S, Wink DJ, Page LE, Snee PT (2013) Cluster-seeded synthesis of doped CdSe:Cu4 quantum dots. ACS Nano 7:3190–3197CrossRefGoogle Scholar
  17. 17.
    Ma Q, Li Y, Lin ZH, Tang GC, Su XG (2013) A novel ascorbic acid sensor based on the Fe3+/Fe2+ modulated photoluminescence of CdTe quantum dots@SiO2 nanobeads. Nanoscale 5:9726–9731CrossRefGoogle Scholar
  18. 18.
    Liu ZP, Liu H, Wang L, Su XG (2016) A label-free fluorescence biosensor for highly sensitive detection of lectin based on carboxymethyl chitosan-quantum dots and gold nanoparticles. Anal Chim Acta 932:88–97CrossRefGoogle Scholar
  19. 19.
    Resch-Genger U, Grabolle M, Cavaliere-Jaricot S, Nitschke R, Nann T (2008) Quantum dots versus organic dyes as fluorescent labels. Nat Methods 5:763–775CrossRefGoogle Scholar
  20. 20.
    Ma Q, Su XG (2011) Recent advances and applications in QDs-based sensors. Analyst 136:4883–4893CrossRefGoogle Scholar
  21. 21.
    Liu ZP, Lin ZH, Liu LL, Su XG (2015) A convenient and label-free fluorescence “turn off–on” nanosensor with high sensitivity and selectivity for acid phosphatase. Anal Chim Acta 876:83–90CrossRefGoogle Scholar
  22. 22.
    Liu SY, Zhang H, Qiao Y, Su XG (2012) One-pot synthesis of ternary CuInS2 quantum dots with near-infrared fluorescence in aqueous solution. RSC Adv 2:819–825CrossRefGoogle Scholar
  23. 23.
    Chen J, Gao YC, Xu ZB, Wu GH, Chen YC, Zhu CQ (2006) A novel fluorescent array for mercury (II) ion in aqueous solution with functionalized cadmium selenide nanoclusters. Anal Chim Acta 577:77–84CrossRefGoogle Scholar
  24. 24.
    Dong YQ, Wang RX, Li GL, Chen CQ, Chi YW, Chen GN (2012) Polyamine-functionalized carbon quantum dots as fluorescent probes for selective and sensitive detection of copper ions. Anal Chem 84:6220–6224CrossRefGoogle Scholar
  25. 25.
    Noipa T, Tuntulani T, Ngeontae W (2013) Cu2+-modulated cysteamine-capped CdS quantum dots as a turn-on fluorescence sensor for cyanide recognition. Talanta 105:320–326CrossRefGoogle Scholar
  26. 26.
    Wang J, Li RS, Zhang HZ, Wang N, Zhang Z, Huang CZ (2017) Highly fluorescent carbon dots as selective and visual probes for sensing copper ions in living cells via an electron transfer process. Biosens Bioelectron 97:157–163CrossRefGoogle Scholar
  27. 27.
    Amilan Jose D, Elstner M, Schiller A (2013) Allosteric indicator displacement enzyme assay for a cyanogenic glycoside. Chem Eur J 19:14451–14457CrossRefGoogle Scholar
  28. 28.
    Xing PF, Xu YQ, Li HJ, Liu SH, Lu AP, Sun SG (2015) Ratiometric and colorimetric near-infrared sensors for multi-channel detection of cyanide ion and their application to measure β-glucosidase. Sci Rep 5(16528):1–6Google Scholar
  29. 29.
    Ganesh V, Calatayud Sanz MP, Mareque-Rivas JC (2007) Effective anion sensing based on the ability of copper to affect electron transport across self-assembled monolayers. Chem Commun 5010-5012Google Scholar
  30. 30.
    Zeng Q, Cai P, Li Z, Qin JG, Tang BZ (2008) An imidazole-functionalized polyacetylene: convenient synthesis and selective chemosensor for metal ions and cyanide. Chem Commun 0: 1094–1096Google Scholar
  31. 31.
    Saul R, Chambers JP, Molyneux RJ, Elbein AD (1983) Castanospermine, a tetrahydroxylated alkaloid that inhibits β-glucosidase and β-glucocerebrosidase. Arch Biochem Biophys 221:593–597CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Austria, part of Springer Nature 2019

Authors and Affiliations

  • Ziping Liu
    • 1
    • 2
    Email author
  • Ye Tian
    • 3
  • Yang Han
    • 2
  • Edith Bai
    • 1
    • 2
  • Yanan Li
    • 4
  • Zhiwei Xu
    • 1
  • Shasha Liu
    • 1
    • 2
  1. 1.Key Laboratory of Geographical Processes and Ecological Security in Changbai Mountains, Ministry of EducationNortheast Normal UniversityChangchunPeople’s Republic of China
  2. 2.College of Geographical SciencesNortheast Normal UniversityChangchunPeople’s Republic of China
  3. 3.Jilin Province Product Quality Supervision Testing InstituteChangchunPeople’s Republic of China
  4. 4.Key Laboratory for Vegetation Ecology, Ministry of Education, Institute of Grassland ScienceNortheast Normal UniversityJilin ProvinceChina

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