Skip to main content
Log in

The determination of copper ions based on sensitized chemiluminescence of silver nanoclusters

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

Abstract

We report on the first application of novel, water-soluble and fluorescent silver nanoclusters (Ag NCs) in a chemiluminescent (CL) detection system. A method has been developed for the determination of copper(II) ion that is based on the fact that the weak CL resulting from the redox reaction between Ce(IV) ion and sulfite ion is strongly enhanced by the Ag NCs and that the main CL signals now originate from Ag NCs. UV-visible spectra, CL spectra and fluorescent (FL) spectra were acquired to investigate the enhanced CL mechanism. It is proposed that the electronic energy of the excited state intermediate SO2* that originates from the CL reaction is transferred to Ag NCs to form an electronically excited NC whose emission is observed. In addition, it is found that copper(II) is capable of inhibiting the CL of the nanoclusters system, but not if other common metal ions are present. The detection of copper(II) is achieved indirectly by measuring the CL intensity of Ag NCs. Under the optimized experimental conditions, a linear relationship does exist between the intensity of CL and the concentrations of copper(II) in the range of 0.2 nM to 0.1 mΜ. The detection limit is 0.12 nM. The method is applied to the determination of copper(II) ion in tap water with satisfactory results.

We report the first application of novel, water-soluble and fluorescent silver nanoclusters in a chemiluminescent detection system. It was found that Ag NCs acted as the luminophor and energy acceptor. A method has been developed for the determination of copper(II) ion that is based on the fact that the capable of inhibiting the CL of the nanoclusters system.

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

Access this article

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

Instant access to the full article PDF.

Fig. 1
Scheme 1
Fig. 2
Fig. 3
Fig. 4

Similar content being viewed by others

References

  1. Toby S (1984) Chemiluminescence in the reactions of ozon. Chem Rev 84:277–285

    Article  CAS  Google Scholar 

  2. Lin JM, Yamada M (2000) Chemiluminescent reaction of fluorescent organic compounds with KHSO5 using cobalt(II) as catalyst and its first application to molecular imprinting. Anal Chem 72:1148–1155

    Article  CAS  Google Scholar 

  3. Juan AO, Francisco JB, Manuel C, Fernando DR (2004) Application of lanthanide-sensitised chemiluminescence to the determination of levofloxacin, moxifloxacin and trovafloxacin in tablets. Microchim Acta 144:207–213

    Article  Google Scholar 

  4. Han HY, He ZK, Zeng YE (2006) Chemiluminescence method for the determination of glutathione in human serum using the Ru(phen) 2+3 –KMnO4 system. Microchim Acta 155:431–434

    Article  CAS  Google Scholar 

  5. Godlewska-Żyłkiewicz B, Malejko J, Leśniewska B, Kojło A (2008) Assessment of immobilized yeast for the separation and determination of platinum in environmental samples by flow-injection chemiluminescence and electrothermal atomic absorption spectrometry. Microchim Acta 163:327–334

    Article  Google Scholar 

  6. Li SF, Tao SJ, Wang FF, Hong JG, Wei XW (2010) Chemiluminescence reactions of luminol system catalyzed by nanoparticles of a gold/silver alloy. Microchim Acta 169:73–78

    Article  CAS  Google Scholar 

  7. Wang X, Zhao HC, Nie LH, Jin LP, Zhang ZL (2001) Europium sensitized chemiluminescense determination of rufloxacin. Anal Chim Acta 445:169–175

    Article  CAS  Google Scholar 

  8. Liu WB, Huang YM (2004) Cerium(IV)-based chemiluminescence of phentolamine sensitized by rhodamine 6 G. Anal Chim Acta 506:183–187

    Article  CAS  Google Scholar 

  9. Yu J, Choi S, Dickson RM (2009) Shuttle-based fluorogenic silver-cluster biolabels. Angew Chem Int Ed 48:318–320

    Article  CAS  Google Scholar 

  10. Vosch T, Antoku Y, Hsiang J, Richards CI, Gonzalez JI, Dickson RM (2007) Strongly emissive individual DNA-encapsulated Ag nanoclusters as single-molecule fluorophores. Proc Natl Acad Sci 104:12616–12621

    Article  CAS  Google Scholar 

  11. Xie JP, Zheng YG, Ying JY (2009) Protein-directed synthesis of highly fluorescent gold nanoclusters. J Am Chem Soc 131:888–889

    Article  CAS  Google Scholar 

  12. Patel SA, Richards CI, Hsiang JC, Dickson RM (2008) Water-soluble Ag nanoclusters exhibit strong two-photon-induced fluorescence. J Am Chem Soc 130:11602–11603

    Article  CAS  Google Scholar 

  13. Yu J, Patel SA, Dickson RM (2007) In vitro and intracellular production of peptide-encapsulated fluorescent silver nanoclusters. Angew Chem Int Ed 46:2028–2030

    Article  CAS  Google Scholar 

  14. Lin CAJ, Yang TY, Lee CH, Huang SH, Sperling RA, Zanella M, Li JK, Shen JL, Wang HH, Yeh HI, Parak WJ, Chang WH (2009) Synthesis, characterization, and bioconjugation of fluorescent gold nanoclusters toward biological labelin applications. Nano 3:3395–401

    Google Scholar 

  15. Triulzi RC, Micic M, Giordani S, Serry M, Chiou WA, Leblanc RM (2006) Immunoasssay based on the antibody-conjugated PAMAM-dendrimer-gold quantum dot complex. Chem Commun 48:5068–5070

    Article  Google Scholar 

  16. Huang CC, Yang Z, Lee KH, Chang HT (2007) Synthesis of highly fluorescent gold nanoparticles for sensing mercury(II). Angew Chem Int Ed 46:6824–6828

    Article  CAS  Google Scholar 

  17. Huang CC, Chiang CK, Lin ZH, Lee KH, Chang HT (2008) Bioconjugated gold nanodots and nanoparticles for protein assays based on photoluminescence quenching. Anal Chem 80:1497–1504

    Article  CAS  Google Scholar 

  18. Zheng J, Dickson RM (2002) Individual water-soluble dendrimer-encapsulated silver nanodot fluorescence. J Am Chem Soc 124:13982–13983

    Article  CAS  Google Scholar 

  19. Petty JT, Zheng J, Hud NV, Dickson RM (2004) DNA-templated Ag nanocluster formation. J Am Chem Soc 126:5207–5212

    Article  CAS  Google Scholar 

  20. Ritchie CM, Johnsen KR, Kiser JR, Antoku Y, Dickson RM, Petty JT (2007) g Nanocluster formation using a cytosine oligonucleotide template. J Phys Chem C 111:175–181

    Article  CAS  Google Scholar 

  21. Shen Z, Duan H, Frey H (2007) Water-soluble fluorescent Ag nanoclusters obtained from multiarm star poly(acrylic acid) as “Molecular Hydrogel” templates. Adv Mater 19:349–352

    Article  CAS  Google Scholar 

  22. Shang L, Dong SJ (2008) Silver nanocluster-based fluorescent sensors for sensitive detection of Cu(II). J Mater Chem 18:1–6

    Article  Google Scholar 

  23. Shang L, Dong SJ (2008) Facile preparation of water-soluble fluorescent silver nanoclusters using a polyelectrolyte template. Chem Commun 9:1088–1090

    Article  Google Scholar 

  24. Cui H, Zhang ZF, Shi MJ, Xu Y, Wu YL (2005) Light emission of gold nanoparticles induced by the Reaction of bis(2, 4, 6-trichlorophenyl) oxalate and hydrogen peroxide. Anal Chem 77:6402–6406

    Article  CAS  Google Scholar 

  25. Takeuchi K, Ibusuki T (1985) Determiomation of traces of hydrogensulfite by chemiluminescence with cerium(IV) sulfate as the reagent. Anal Chim Acta 174:359–363

    Article  CAS  Google Scholar 

  26. Huang YM, Zhang C, Zhang XR, Zhang ZJ (1999) Chemiluminescence of sulfite based on auto-oxidation sensitized by rhodamine 6 G. Anal Chim Acta 391:95–100

    Article  CAS  Google Scholar 

  27. Yu XJ, Jiang ZH, Wang QJ, Guo YS (2010) Silver nanoparticle-based chemiluminescence enhancement for the determination of norfloxacin. Microchim Acta 171:17–22

    Article  CAS  Google Scholar 

  28. Zheng J, Nicovich PR, Dickson RM (2007) Highly fluorescent noble-metal quantum dots. Annu Rev Phys Chem 58:409–431

    Article  CAS  Google Scholar 

  29. Sorouraddin MH, Manzoori JL, Iranifam M (2005) Determination of copper(II) based on its catalytic effect on thiosemicarbazide–H2O2–CTMAB chemiluminescence reaction. Talanta 66:1117–1121

    Article  CAS  Google Scholar 

Download references

Acknowledgements

This research was supported by the National Natural Science Foundation of China (No. 20505004), Outstanding Adult-young Scientific Research Encouraging Foundation of Shandong Province (No. 2008BS03015) and the Doctoral Found of QUST (No. 0022235).

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Xijuan Yu.

Electronic supplementary material

Below is the link to the electronic supplementary material.

Fig. S1

Effect of Ag NCs concentration on the CL intensity, Ce(IV): 0.7 mM; Na2SO3: 0.6 mM; H2SO4: 45 mM (DOC 42 kb)

Fig. S2

Effect of Ce(IV) concentration on the CL intensity, Ag nanoclusters: 11 μM; Na2SO3: 0.6 mM; H2SO4: 45 mM. (DOC 37 kb)

Fig. S3

Effect of Na2SO3 concentration on the CL intensity, Ag nanoclusters:11 μM; Ce(IV): 0.5 mM; H2SO4: 45 mM. (DOC 41 kb)

Rights and permissions

Reprints and permissions

About this article

Cite this article

Yu, X., Wang, Q. The determination of copper ions based on sensitized chemiluminescence of silver nanoclusters. Microchim Acta 173, 293–298 (2011). https://doi.org/10.1007/s00604-011-0549-8

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s00604-011-0549-8

Keywords

Navigation