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Microchimica Acta

, 186:41 | Cite as

Alginate capped and manganese doped ZnS quantum dots as a phosphorescent probe for time-resolved detection of copper(II)

  • Wen-Sheng ZouEmail author
  • Ming-Yue Deng
  • Ya-Qin Wang
  • Xiaoli ZhaoEmail author
  • Wei-Hua LiEmail author
  • Xian-Huai Huang
Original Paper
  • 283 Downloads

Abstract

A method is described for the detection of Cu(II). It is based on the use of a room-temperature phosphorescent probe consisting of alginate-capped and manganese(II)-doped ZnS quantum dots. The carboxy groups at the surface of the probe strongly coordinate Cu(II) to form a complex. As a result, the 4T1-6A1 transition of the Mn(II) ions in the probe is quenched, and the long decay time (~2.1 ms in the unquenched state) is accordingly reduced. At excitation/emission wavelengths of 316/590 nm and a delay time of 0.1 ms, the probe shows a linear response in the 0.01 to 12 μM Cu(II) concentration range. The detection limit is 6.0 nM and the RSD is 3.2% (for n = 5).

Graphical Abstract

A two-step procedure is described to synthesize alginate capped manganese doped ZnS QDs. These coordinate with Cu(II) to form an absorbent complex and can be used as a phosphorescent probe for time-resolved detection of Cu(II).

Keywords

Room-temperature phosphorescence (RTP) Alginate Stokes shift Long lifetime 

Notes

Acknowledgement

This work was supported by Natural Science Foundation of China (21506002, 41673131). The authors also thanked Anhui key project of research and development plan (1704a0902006), major science and technology project of Anhui Province (17030801028) and major project of Department of Education of Anhui province (KJ2018A0513) for financial supports.

Compliance with ethical standards

The author(s) declare that they have no competing interests.

Supplementary material

604_2018_3165_MOESM1_ESM.docx (1.1 mb)
ESM 1 (DOCX 1.13 mb)

References

  1. 1.
    Gözde Ö, Sezin E, Dotse SC, Merve F, Çagdas B, Fatma T, Sezgin B (2017) Sensitive determination of copper in water samples using dispersive liquid-liquid microextraction-slotted quartz tube-flame atomic absorption spectrometry. Microchem J 132:406–410CrossRefGoogle Scholar
  2. 2.
    Lin TW, Huang SD (2001) Direct and simultaneous determination of copper, chromium, aluminum, and manganese in urine with a multielement graphite furnace atomic absorption spectrometer. Anal Chem 73:4319–4325CrossRefGoogle Scholar
  3. 3.
    Wu J, Boyle EA (1997) Low blank preconcentration technique for the determination of lead, copper, and cadmium in small-volume seawater samples by isotope dilution ICPMS. Anal Chem 69:2464–2470CrossRefGoogle Scholar
  4. 4.
    Becker JS, Matusch A, Depboylu C, Dobrowolska J, Zoriy MV (2007) Quantitative imaging of selenium, copper, and zinc in thin sections of biological tissues (slugs-genus arion) measured by laser ablation inductively coupled plasma mass spectrometry. Anal Chem 79:6074–6080CrossRefGoogle Scholar
  5. 5.
    Otero-Romani J, Moreda-Pineiro A, Bermejo-Barrera A, Bermejo-Barrera P (2005) Evaluation of commercial C18 cartridges for trace elements solid phase extraction from seawater followed by inductively coupled plasma-optical emission spectrometry determination. Anal Chim Acta 536:213–218CrossRefGoogle Scholar
  6. 6.
    Liu Y, Liang P, Guo L (2005) Nanometer titanium dioxide immobilized on silica gel as sorbent for preconcentration of metal ions prior to their determination by inductively coupled plasma atomic emission spectrometry. Talanta 68:25–30CrossRefGoogle Scholar
  7. 7.
    Casey WQ, David MC, Daniel DM-L, Thomas R III, John V, Charles SH (2018) Solid-phase extraction coupled to a paper-based technique for trace copper detection in drinking water. Environ Sci Technol 52:3567–3573CrossRefGoogle Scholar
  8. 8.
    Jonathon D, Joed EO-S, Timothy NL (2017) Copper sensing in alkaline electrolyte using anodic stripping voltammetry by means of a lead mediator. Electroanal 29:2685–2688CrossRefGoogle Scholar
  9. 9.
    Ding C, Zhu A, Tian Y (2014) Functional surface engineering of C-dots for fluorescent biosensing and in vivo bioimaging. Acc Chem Res 47:20–30CrossRefGoogle Scholar
  10. 10.
    Saleem M, Rafiq M, Hanif M, Shaheen MA, Seo S-Y (2018) A brief review on fluorescent copper sensor based on conjugated organic dyes. J Fluoresc 28:97–165CrossRefGoogle Scholar
  11. 11.
    Zhao C, Liu B, Bi X, Liu D, Pan C, Wang L, Pang Y (2016) A novel flavonoid-based bioprobe for intracellular recognition of Cu2+ and its complex with Cu2+ for secondary sensing of pyrophosphate. Sens Actuators B 229:131–137CrossRefGoogle Scholar
  12. 12.
    Li Y, Zhao Y, Chan W, Wang Y, You Q, Liu C, Zheng J, Li J, Yang S, Yang R (2015) Selective tracking of lysosomal Cu2+ ions using simultaneous target- and location-activated fluorescent nanoprobes. Anal Chem 87:584–591CrossRefGoogle Scholar
  13. 13.
    Han Y, Ding C, Zhou J, Tian Y (2015) Single probe for imaging and biosensing of pH, Cu2+ ions, and pH/Cu2+ in live cells with ratiometric fluorescence signals. Anal Chem 87:5333–5339CrossRefGoogle Scholar
  14. 14.
    Gao N, Yang W, Nie H, Gong Y, Jing J, Gao L, Zhang X (2017) Turn-on theranostic fluorescent nanoprobe by electrostatic self-assembly of carbon dots with doxorubicin for targeted cancer cell imaging, in vivo hyaluronidase analysis, and targeted drug delivery. Biosens Bioelectron 96:300–307CrossRefGoogle Scholar
  15. 15.
    Hamd-Ghadareh S, Salimi A, Fathi F, Bahrami S (2017) An amplified comparative fluorescence resonance energy transfer immunosensing of CA125 tumor marker and ovarian cancer cells using green and economic carbon dots for bio-applications in labeling, imaging and sensing. Biosens Bioelectron 96:308–316CrossRefGoogle Scholar
  16. 16.
    Zou W-S, Zhao Q-C, Zhang J, Chen X-M, Wang X-F, Zhao L, Chen S-H, Wang Y-Q (2017) Enhanced photoresponsive polyethyleneimine/citric acid co-carbonized dots for facile and selective sensing and intracellular imaging of cobalt ions at physiologic pH. Anal Chim Acta 970:64–72CrossRefGoogle Scholar
  17. 17.
    Michalet X, Pinaud FF, Bentolila LA, Tsay JM, Doose S, Li JJ, Sundaresan G, Wu AM, Gambhir SS, Weis SS (2005) Quantum dots for live cells, in vivo imaging, and diagnostics. Science 307:538–544CrossRefGoogle Scholar
  18. 18.
    Gedda G, Lee C-Y, Lin Y-C, Wu H-F (2016) Green synthesis of carbon dots from prawn shells for highly selective and sensitive detection of copper ions. Sens Actuators B 224:396–403CrossRefGoogle Scholar
  19. 19.
    Dong Y, Wang R, Li G, Chen C, Chi Y, Chen G (2012) Polyamine-functionalized carbon quantum dots as fluorescent probes for selective and sensitive detection of copper ions. Anal Chem 84:6220–6224CrossRefGoogle Scholar
  20. 20.
    Qu Q, Zhu A, Shao X, Shi G, Tian Y (2012) Development of a carbon quantum dots-based fluorescent Cu2+ probe suitable for living cell imaging. Chem Commun 48:5473–5475CrossRefGoogle Scholar
  21. 21.
    Lin X, Gao G, Zheng L, Chi Y, Chen G (2014) Encapsulation of strongly fluorescent carbon quantum dots in metal-organic frameworks for enhancing chemical sensing. Anal Chem 86:1223–1228CrossRefGoogle Scholar
  22. 22.
    Zong J, Yang X, Trinchi A, Hardin S, Cole I, Zhu Y, Li C, Muster T, Wei G (2014) Carbon dots as fluorescent probes for “off-on” detection of Cu2+ and L-cysteine in aqueous solution. Biosens Bioelectron 51:330–335CrossRefGoogle Scholar
  23. 23.
    Zou W-S, Zhao Q-C, Kong W-L, Wang X-F, Chen X-M, Zhang J, Wang Y-Q (2018) Multi-level fluorescent logic gate based on polyamine coated carbon dots capable of responding to four stimuli. Chem Eng J 337:471–479CrossRefGoogle Scholar
  24. 24.
    Li C, Liu J, Alonso S, Li F, Zhang Y (2012) Upconversion nanoparticles for sensitive and in-depth detection of Cu2+ ions. Nanoscale 4:6065–6071CrossRefGoogle Scholar
  25. 25.
    Zhou J, Liu Z, Li F (2012) Upconversion nanophosphors for small-animal imaging. Chem Soc Rev 41:1323–1349CrossRefGoogle Scholar
  26. 26.
    Shu T, Su L, Wang J, Lu X, Liang F, Li C, Zhang X (2016) Value of the debris of reduction sculpture: thiol etching of Au nanoclusters for preparing water-soluble and aggregation-induced emission-active Au(I) complexes as phosphorescent copper ion sensor. Anal Chem 88:6071–6077CrossRefGoogle Scholar
  27. 27.
    You Y, Han Y, Lee Y-M, Park SY, Nam W, Lippard SJ (2011) Phosphorescent sensor for robust quantification of copper(II) ion. J Am Chem Soc 133:11488–11491CrossRefGoogle Scholar
  28. 28.
    Wang Y-Q, Zou W-S (2011) 3-Aminopropyltriethoxysilane-functionalized manganese doped ZnS quantum dots for room-temperature phosphorescence sensing ultratrace 2,4,6-trinitrotoluene in aqueous solution. Talanta 85:469–475CrossRefGoogle Scholar
  29. 29.
    Zou W-S, Sheng D, Ge X, Qiao J-Q, Lian H-Z (2011) Room-temperature phosphorescence (RTP) chemosensor and Rayleigh scattering (RS) chemodosimeter dual-recognition probe for TNT based on Mn-doped ZnS quantum dots. Anal Chem 83:30–37CrossRefGoogle Scholar
  30. 30.
    Martinsen A, SkjBk-Braek G, Smidsrs¢d O (1989) Alginate as immobilization material: I. correlation between chemical and physical properties of alginate gel beads. Biotechnol Bioeng 33:79–89CrossRefGoogle Scholar
  31. 31.
    Morris ER, Rees DA, Thom D, Boyd J (1978) Chiroptical and stoichiometric evidence of a specific, primary dimerisation process in alginate gelation. Carbohydr Res 66:145–154CrossRefGoogle Scholar
  32. 32.
    Grant GT, Morris ER, Rees DA, Smith PJC, Thom D (1973) Biological interactions between polysaccharides and divalent cations: the egg-box model. FEBS Lett 32:195–198CrossRefGoogle Scholar
  33. 33.
    Shao N, Zhang Y, Cheung SM, Yang RH, Chan WH, Mo T, Li KA, Liu F (2005) Copper ion-selective fluorescent sensor based on the inner filter effect using a spiropyran derivative. Anal Chem 77:7294–7303CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Austria, part of Springer Nature 2018

Authors and Affiliations

  1. 1.Anhui Key Laboratory of Water Pollution Control and Wastewater Reuse, and Key Laboratory of Functional Molecule Design and Interface ProcessAnhui Jianzhu UniversityHefeiPeople’s Republic of China
  2. 2.State Key Laboratory of Environmental Criteria and Risk AssessmentChinese Research Academy of Environmental SciencesBeijingChina

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