Skip to main content
SpringerLink
Log in

Fluorometric determination of mercury(II) based on dual-emission metal-organic frameworks incorporating carbon dots and gold nanoclusters

  • Original Paper
  • Published:
Microchimica Acta Aims and scope Submit manuscript

Abstract

Carbon dots and gold nanoclusters co-encapsulated by zeolitic imidazolate framework-8 (CDs/AuNCs@ZIF-8) have been obtained at room temperature. The composite has been applied to the ratiometric fluorescence determination of mercury(II). The composite shows fluorescence emission maxima at 440 and 640 nm under 360 nm excitation, due to the CDs and AuNCs, respectively (associated quantum yields were 18% and 17%, respectively). In the presence of Hg2+, the fluorescence at about 640 nm is quenched, while the fluorescence at about 440 nm is unaffected. The CDs/AuNCs@ZIF-8 composite allows the sensitive detection of Hg2+, with the fluorescence intensity ratio (I640/I440) decreasing linearly with Hg2+ concentration over the range 3–30 nM. The fluorescence emission of the composite changes color from red to blue with increasing Hg2+ under UV excitation, which can easily be discerned visually. This visual detection of Hg2+ is due to the high fluorescence quantum yields of the CDs and AuNCs and the ~ 200 nm separation between the two emission maxima.

(A) Schematic diagram showing the operating principle of the determination for Hg(II). (B) Digital graph of the solutions in absence and presence of 30 nM Hg(II) under a portable UV lamp

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4

Similar content being viewed by others

References

  1. Erxleben H, Ruzicka J (2005) Atomic absorption spectroscopy for mercury, automated by sequential injection and miniaturized in lab-on-valve system. Anal Chem 77(16):5124–5128. https://doi.org/10.1021/ac058007s

    Article  CAS  PubMed  Google Scholar 

  2. Hong YS, Rifkin E, Bouwer EJ (2011) Combination of diffusive gradient in a thin film probe and IC-ICP-MS for the simultaneous determination of CH3Hg+ and Hg2+ in oxic water. Environ Sci Technol 45(15):6429–6436. https://doi.org/10.1021/es200398d

    Article  CAS  PubMed  Google Scholar 

  3. Zhang Z, Tang A, Liao S, Chen P, Wu Z, Shen G, Yu R (2011) Oligonucleotide probes applied for sensitive enzyme-amplified electrochemical assay of mercury(II) ions. Biosens Bioelectron 26(7):3320–3324. https://doi.org/10.1016/j.bios.2011.01.006

    Article  CAS  PubMed  Google Scholar 

  4. Sener G, Uzun L, Denizli A (2014) Lysine-promoted colorimetric response of gold nanoparticles: a simple assay for ultrasensitive mercury (II) detection. Anal Chem 86(1):514–520. https://doi.org/10.1021/ac403447a

    Article  CAS  PubMed  Google Scholar 

  5. Tyrakowski CM, Snee PT (2014) Ratiometric CdSe/ZnS quantum dot protein sensor. Anal Chem 86(5):2380–2386. https://doi.org/10.1021/ac4040357

    Article  CAS  PubMed  Google Scholar 

  6. Niu W, Shan D, Zhu R, Deng S, Cosnier S, Zhang X (2016) Dumbbell-shaped carbon quantum dots/AuNCs nanohybrid as an efficient ratiometric fluorescent probe for sensing cadmium (II) ions and l-ascorbic acid. Carbon 96:1034–1042. https://doi.org/10.1016/j.carbon.2015.10.051

    Article  CAS  Google Scholar 

  7. Xie H, Dong J, Duan J, Waterhouse GIN, Hou J, Ai S (2018) Visual and ratiometric fluorescence detection of Hg2+ based on a dual-emission carbon dots-gold nanoclusters nanohybrid. Sensors Actuators B Chem 259:1082–1089. https://doi.org/10.1016/j.snb.2017.12.149

    Article  CAS  Google Scholar 

  8. Wang L, Cao H, He Y, Pan C, Sun T, Zhang X, Wang C, Liang G (2019) Facile preparation of amino-carbon dots/gold nanoclusters FRET ratiometric fluorescent probe for sensing of Pb2+/Cu2+. Sensors Actuators B Chem 282:78–84. https://doi.org/10.1016/j.snb.2018.11.058

    Article  CAS  Google Scholar 

  9. Wang R, Wang X, Sun Y (2017) Aminophenol-based carbon dots with dual wavelength fluorescence emission for determination of heparin. Microchim Acta 184:187–193. https://doi.org/10.1007/s00604-016-2009-y

    Article  CAS  Google Scholar 

  10. Hua J, Jiao Y, Wang M, Yang Y (2018) Determination of norfloxacin or ciprofloxacin by carbon dots fluorescence enhancement using magnetic nanoparticles as adsorbent. Microchim Acta 185:137–145. https://doi.org/10.1007/s00604-018-2685-x

    Article  CAS  Google Scholar 

  11. Cheng J, Xu YL, Zhou D (2019) Novel carbon quantum dots can serve as an excellent adjuvant for the gp85 protein vaccine against avian leukosis virus subgroup J in chickens. Poult Sci 98(11):5315–5320. https://doi.org/10.3382/ps/pez313

    Article  CAS  PubMed  Google Scholar 

  12. Chen T, Hu Y, Cen Y, Chu X, Lu Y (2013) A dual-emission fluorescent nanocomplex of gold-cluster-decorated silica particles for live cell imaging of highly reactive oxygen species. J Am Chem Soc 135(31):11595–11602. https://doi.org/10.1021/ja4035939

    Article  CAS  PubMed  Google Scholar 

  13. Zhou H, Long JR, Yaghi OM (2012) Introduction to metal-organic frameworks. Chem Rev 112(2):673–674. https://doi.org/10.1021/cr300014x

    Article  CAS  PubMed  Google Scholar 

  14. Park KS, Ni Z, Côté AP, Choi JY, Huang R, Uribe-Romo FJ, Chae HK, O’Keeffe M, Yaghi OM (2006) Exceptional chemical and thermal stability of zeolitic imidazolate frameworks. Proc Natl Acad Sci 103(27):10186–10191. https://doi.org/10.1073/pnas.0602439103

    Article  CAS  PubMed  Google Scholar 

  15. Liang K, Ricco R, Doherty CM, Styles MJ, Bell S, Kirby N, Mudie S, Haylock D, Hill AJ, Doonan CJ (2015) Biomimetic mineralization of metal-organic frameworks as protective coatings for biomacromolecules. Nat Commun 6:7240. https://doi.org/10.1038/ncomms8240

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  16. Chen W, Vázquez-González M, Zoabi A, Abu-Reziq R, Willner I (2018) Biocatalytic cascades driven by enzymes encapsulated in metal-organic framework nanoparticles. Nat Catal 1(9):689–695. https://doi.org/10.1038/s41929-018-0117-2

    Article  CAS  Google Scholar 

  17. Selvaprakash K, Chen Y (2014) Using protein-encapsulated gold nanoclusters as photoluminescent sensing probes for biomolecules. Biosens Bioelectron 61:88–94. https://doi.org/10.1016/j.bios.2014.04.055

    Article  CAS  PubMed  Google Scholar 

  18. Song W, Liang R, Wang Y, Zhang L, Qiu J (2015) Green synthesis of peptide-templated gold nanoclusters as novel fluorescence probes for detecting protein kinase activity. Chem Commun 51(49):10006–10009. https://doi.org/10.1039/C5CC02280K

    Article  CAS  Google Scholar 

  19. Wang L, Jiang X, Zhang M, Yang M, Liu Y-N (2017) In situ assembly of Au nanoclusters within protein hydrogel networks. Chem Asian J 12(18):2374–2378. https://doi.org/10.1002/asia.201700915

    Article  CAS  PubMed  Google Scholar 

  20. Xie J, Zheng Y, Ying JY (2009) Protein-directed synthesis of highly fluorescent gold nanoclusters. J Am Chem Soc 131(3):888–889. https://doi.org/10.1021/ja806804u

    Article  CAS  PubMed  Google Scholar 

  21. Xie J, Zheng Y, Ying JY (2010) Highly selective and ultrasensitive detection of Hg2+ based on fluorescence quenching of Au nanoclusters by Hg2+-Au+ interactions. Chem Commun 46(6):961–963. https://doi.org/10.1039/B920748A

    Article  CAS  Google Scholar 

  22. Zhu S, Meng Q, Wang L, Zhang J, Song Y, Jin H, Zhang K, Sun H, Wang H, Yang B (2013) Highly photoluminescent carbon dots for multicolor patterning, sensors, and bioimaging. Angew Chem Int Edit 52(14):3953–3957. https://doi.org/10.1002/anie.201300519

    Article  CAS  Google Scholar 

  23. Xu X, Yan B (2016) Fabrication and application of a ratiometric and colorimetric fluorescent probe for Hg2+ based on dual-emissive metal-organic framework hybrids with carbon dots and Eu3+. J Mater Chem C 4(7):1543–1549. https://doi.org/10.1039/C5TC04002G

    Article  CAS  Google Scholar 

  24. Wu X, Ge J, Yang C, Hou M, Liu Z (2015) Facile synthesis of multiple enzyme-containing metal-organic frameworks in a biomolecule-friendly environment. Chem Commun 51(69):13408–13411. https://doi.org/10.1039/c5cc05136c

    Article  CAS  Google Scholar 

  25. Ma Y, Xu G, Wei F, Cen Y, Xu X, Shi M, Cheng, Chai Y, Sohail M, Hu Q (2018) One-pot synthesis of a magnetic, ratiometric fluorescent nanoprobe by encapsulating Fe3O4 magnetic nanoparticles and dual-emissive rhodamine B modified carbon dots in metal-organic framework for enhanced HClO sensing. ACS Appl Mater Interfaces 10(24):20801–20805. https://doi.org/10.1021/acsami.8b05643

    Article  CAS  PubMed  Google Scholar 

  26. Hou J, Li J, Sun J, Ai S, Wang M (2014) Nitrogen-doped photoluminescent carbon nanospheres: green, simple synthesis via hair and application as a sensor for Hg2+ ions. RSC Adv 4(70):37342. https://doi.org/10.1039/c4ra04209c

    Article  CAS  Google Scholar 

  27. Xiong H, Wang W, Liang J, Wen W, Zhang X, Wang S (2017) A convenient purification method for metal nanoclusters based on pH-induced aggregation and cyclic regeneration and its applications in fluorescent pH sensors. Sensors Actuators B Chem 239:988–992. https://doi.org/10.1016/j.snb.2016.08.114

    Article  CAS  Google Scholar 

  28. Yan X, Li H, Jin R, Zhao X, Liu F, Lu G (2019) Sensitive sensing of enzyme-regulated biocatalytic reactions using gold nanoclusters-melanin-like polymer nanosystem. Sensors Actuators B Chem 279:281–288. https://doi.org/10.1016/j.snb.2018.10.009

    Article  CAS  Google Scholar 

  29. Hou J, Dong J, Zhu H, Teng X, Ai S, Mang M (2015) A simple and sensitive fluorescent sensor for methyl parathion based on l-tyrosine methyl ester functionalized carbon dots. Biosens Bioelectron 68:20–26. https://doi.org/10.1016/j.bios.2014.12.037

    Article  CAS  PubMed  Google Scholar 

  30. Li B, Ma H, Zhang B, Qian J, Cao T, Feng H, Qin W (2019) Dually emitting carbon dots as fluorescent probes for ratiometric fluorescent sensing of pH values, mercury(II), chloride and Cr(VI) via different mechanisms. Microchim Acta 186(6):34. https://doi.org/10.1007/s00604-019-3437-2

    Article  CAS  Google Scholar 

  31. Ke CB, Lu TL, Chen JL (2019) Excitation-independent dual emissions of carbon dots synthesized by plasma irradiation of ionic liquids: ratiometric fluorometric determination of norfloxacin and mercury(II). Microchim Acta 186(6):376. https://doi.org/10.1007/s00604-019-3505-7

    Article  CAS  Google Scholar 

  32. Gao Y, Liu M, Yue X, Du J (2019) Ratiometric fluorometric determination of mercury(II) by exploiting its quenching effect on glutathione-stabilized and tetraphenylporphyrin modified gold nanoclusters. Microchim Acta 186(5):30. https://doi.org/10.1007/s00604-019-3405-x

    Article  CAS  Google Scholar 

Download references

Funding

This work was supported by the National Natural Science Foundation of China (41771342, 31872889), the Natural Science Foundation of Shandong Province, China (ZR2019MD025, ZR2017BB064), the Key R&D Program of Shandong Province, China (2018YYSP029), the “13th Five-Year” National Key R&D Program of China (2017YFD0801504), and the Funds of Shandong Double Tops Program, China (SYL2017XTTD01). GINW received funding support from the MacDiarmid Institute for Advanced Materials and Nanotechnology, the Dodd Walls Centre for Photonic and Quantum Technologies, and the Ministry of Business Innovation and Employment (MBIE) Catalyst Fund, Contract MAUX1609: “Disruptive Technologies from Metal-Organic Frameworks.”

Author information

Authors and Affiliations

  1. College of Food Science and Engineering, Shandong Agricultural University, Taian, 271018, Shandong, People’s Republic of China

    Manli Guo, Jingtian Chi & Xiangyang Li

  2. College of Chemistry and Material Science, Shandong Agricultural University, Taian, 271018, Shandong, People’s Republic of China

    Yijing Li, Geoffrey I. N. Waterhouse, Shiyun Ai & Juying Hou

  3. School of Chemical Sciences, The University of Auckland, Auckland, 1142, New Zealand

    Geoffrey I. N. Waterhouse

Authors
  1. Manli Guo
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Jingtian Chi
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Yijing Li
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Geoffrey I. N. Waterhouse
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Shiyun Ai
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Juying Hou
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Xiangyang Li
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding authors

Correspondence to Juying Hou or Xiangyang Li.

Ethics declarations

Conflict of interest

The authors declare that they have no competing interests.

Additional information

Publisher’s note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Manli Guo and Jingtian Chi are co-first authors.

Electronic supplementary material

ESM 1

(DOCX 1701 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Guo, M., Chi, J., Li, Y. et al. Fluorometric determination of mercury(II) based on dual-emission metal-organic frameworks incorporating carbon dots and gold nanoclusters. Microchim Acta 187, 534 (2020). https://doi.org/10.1007/s00604-020-04508-z

Download citation

  • Received:

  • Accepted:

  • Published:

  • DOI: https://doi.org/10.1007/s00604-020-04508-z

Keywords

Search

Navigation