Skip to main content
SpringerLink
Log in

Polydopamine coated copper nanoclusters with aggregation-induced emission for fluorometric determination of phosphate ion and acid phosphatase activity

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

Abstract

The preparation of aggregation-induced emission-type copper nanoclusters (CuNCs) capped with polydopamine (PDA) is described. PDA was formed via in situ polymerization of dopamine in the presence of alkaline polyethylenimine. The PDA-capped CuNCs (PDA-CuNCs) exhibit orange fluorescence with maximal emission at 580 nm upon excitation at 340 nm, a storage stability of at least 2 weeks, and a quantum yield (QY) of 2.54% in aqueous solution. The QY is 28-fold higher than that of sole CuNCs. The fluorescence of the PDA-CuNCs is quenched by Fe3+ ion while it is recovered by PO43− due to its stronger affinity for Fe3+. On this basis, a fluorometric phosphate assay was developed that has a 1.5 nM detection limit and a linear range over 0.003–70 μM. The method was satisfactorily applied to the determination of phosphate in local tap water and human sera, and the results agreed well with those obtained by a colorimetric method. In the presence of acid phosphatase (ACP), PO43− is produced by the catalytic hydrolysis of adenosine triphosphate (ACP substrate). Thus, a fluorogenic assay for screening ACP activity was established. Response is linear over the activity range 0.0012–25 U L−1, with a detection limit of 0.001 U L−1 (at S/N = 3).

We proposed an effective polydopamine-templating strategy for the in situ synthesis of highly emissive and stable CuNCs and demonstrated its use as an ion-driven fluorescence switch for the determination of phosphate and acid phosphatase activity.

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

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

Similar content being viewed by others

References

  1. Shigeo N, Shintaro Y, Daisuke K, Mitsuru Y, Takashi S (2012) Newly development of phosphate binders in hyperphosphatemic patients with kidney dysfunction. Clin Calcium 22:1557–1566

    Google Scholar 

  2. Ménesguen A, Desmit X, Dulière V, Lacroix G, Thouvenin B, Thieuc V, Dussauze M (2018) How to avoid eutrophication in coastal seas? A new approach to derive river-specific combined nitrate and phosphate maximum concentrations. Sci Total Environ 628–629:400–414

    Article  Google Scholar 

  3. Spangler C, Schaeferling M, Wolfbeis OS (2008) Fluorescent probes for micro determination of inorganic, phosphates and biophosphates. Microchim Acta 161:1–39

    Article  CAS  Google Scholar 

  4. Zhang J, Wang S, Liu C, He G, Peng T (2018) A novel turn-on fluorescent probe for highly selective detection of phosphate ion in living cell. Chin J Chem 36:1179–1181

    Article  CAS  Google Scholar 

  5. Xu JY, Zhou Y, Cheng GF, Dong MT, Liu SX, Huang CB (2015) Carbon dots as a luminescence sensor for ultrasensitive detection of phosphate and their bioimaging properties. Luminescence 30:411–415

    Article  CAS  Google Scholar 

  6. Zou WS, Kong WL, Zhao QC, Zhang J, Zhao X, Zhao D, Wang YQ (2019) A composite consisting of bromine-doped carbon dots and ferric ions as a fluorescent probe for determination and intracellular imaging of phosphate. Microchim Acta 186:576

  7. Cao H, Chen Z, Huang Y (2015) Copper nanocluster coupling europium as an off-to-on fluorescence probe for the determination of phosphate ion in water samples. Talanta 143:450–456

    Article  CAS  Google Scholar 

  8. Ding SN, Li CM, Gao BH, Kargbo O, Wan N, Chen X, Zhou C (2014) Probing phosphate ion via the europium (III)-modulated fluorescence of gold nanoclusters. Microchim Acta 181:1957–1963

    Article  CAS  Google Scholar 

  9. Han MS, Kim DH (2002) Naked-eye detection of phosphate ions in water at physiological pH: a remarkably selective and easy-to-assemble colorimetric phosphatesensing probe. Angew Chem Int Ed 41:3809–3811

    Article  CAS  Google Scholar 

  10. Jońca J, Fernández VL, Thouron D, Paulmier A, Graco M, Garçon V (2011) Phosphate determination in seawater: toward an autonomous electrochemical method. Talanta 87:161–167

    Article  Google Scholar 

  11. Liu R, Wang C, Hu J, Su Y, Lv Y (2018) DNA-templated copper nanoparticles: versatile platform for label-free bioassays. TrAC Trends Anal Chem 105:436–452

    Article  CAS  Google Scholar 

  12. Wang ZG, Chen BK, Rogach AL (2017) Synthesis, optical properties and applications of light-emitting copper nanoclusters. Nanoscale Horiz 2:135–146

    Article  CAS  Google Scholar 

  13. Jia X, Li J, Wang EK (2013) Cu nanoclusters with aggregation induced emission enhancement. Small 9:3873–3879

    Article  CAS  Google Scholar 

  14. Hu X, Liu X, Zhang X, Cao H, Huang Y (2019) MnO2 nanowires tuning of photoluminescence of alloy Cu/Ag NCs and thiamine enables a ratiometric fluorescent sensing of glutathione. Sensors Actuators B Chem 286:476–482

    Article  CAS  Google Scholar 

  15. Hu X, Liu X, Zhang X, Chai H, Huang Y (2018) One-pot synthesis of the CuNCs/ZIF-8 nanocomposites for sensitively detecting H2O2 and screening of oxidase activity. Biosens Bioelectron 105:65–70

    Article  CAS  Google Scholar 

  16. Liu Y, Ai K, Lu L (2014) Polydopamine and its derivative materials: synthesis and promising applications in energy, environmental, and biomedical fields. Chem Rev 114:5057–5115

    Article  CAS  Google Scholar 

  17. Bai YT, Zhang B, Chen L, Lin ZJ, Zhang XM, Ge DT, Shi W, Sun YA (2018) Facile one-pot synthesis of polydopamine carbon dots for photothermal therapy. Nanoscale Res Lett 13:287

    Article  Google Scholar 

  18. Nurunnabi M, Khatun Z, Nafiujjaman M, Lee DG, Lee YK (2013) Surface coating of graphene quantum dots using mussel-inspired polydopamine for biomedical optical imaging. ACS Appl Mater Interfaces 5:8246–8253

    Article  CAS  Google Scholar 

  19. Tao Y, Li M, Ren J, Qu X (2015) Metal nanoclusters: novel probes for diagnostic and therapeutic applications. Chem Soc Rev 44:8636–8663

    Article  CAS  Google Scholar 

  20. Vilar-Vidal N, Blanco MC, López-Quintela MA, Rivas J, Serra C (2010) Electrochemical synthesis of very stable photoluminescent copper clusters. J Phys Chem C 114:15924–15930

    Article  CAS  Google Scholar 

  21. Li XG, Zhang F, Gao Y, Zhou QM, Zhao Y, Li Y, Huo JZ, Zhao XJ (2016) Facile synthesis of red emitting 3-aminophenylboronic acid functionalized copper nanoclusters for rapid, selective and highly sensitive detection of glycoproteins. Biosens Bioelectron 86:270–276

    Article  CAS  Google Scholar 

  22. Ho CC, Ding SJ (2013) The pH-controlled nanoparticles size of polydopamine for anti-cancer drug delivery. J Mater Sci Mater Med 24:2381–2390

    Article  CAS  Google Scholar 

  23. Liu Q, Pu ZH, Asiri AM, Al-Youbi AO, Sun XP (2014) Polydopamine nanospheres: a biopolymer-based fluorescent sensing platform for DNA detection. Sensors Actuators B Chem 191:567–571

    Article  CAS  Google Scholar 

  24. Bernsmann F, Ball V, Addiego F, Ponche A, Michel M, Gracio JJDA, Ruch D (2011) Dopamine-melanin film deposition depends on the used oxidant and buffer solution. Langmuir 27:2819–2825

    Article  CAS  Google Scholar 

  25. Wu ZN, Liu JL, Gao Y, Liu HW, Li TT, Zou HY, Wang ZG, Zhang K, Wang Y, Zhang H, Yang B (2015) Assembly-induced enhancement of Cu nanoclusters luminescence with mechanochromic property. J Am Chem Soc 137:12906–12913

    Article  CAS  Google Scholar 

  26. Krogsgaard M, Behrens MA, Pedersen JS, Birkedal H (2013) Self-healing mussel-inspired multi-pH-responsive hydrogels. Biomacromolecules 14:297–301

    Article  CAS  Google Scholar 

  27. Cao H, Chen Z, Zheng H, Huang Y (2014) Copper nanoclusters as a highly sensitive and selective fluorescence sensor for ferric ions in serum and living cells by imaging. Biosens Bioelectron 62:189–195

    Article  CAS  Google Scholar 

  28. Rahnemaie R, Hiemstra T, Van Riemsdijk WH (2007) Geometry, charge distribution, and surface speciation of phosphate on goethite. Langmuir 23:3680–3689

    Article  CAS  Google Scholar 

  29. Dai C, Yang CX, Yan XP (2015) Ratiometric fluorescent detection of phosphate in aqueous solution based on near infrared fluorescent silver nanoclusters/metal-organic shell composite. Anal Chem 87:11455–11459

    Article  CAS  Google Scholar 

  30. Gao N, Huang J, Wang LY, Feng JY, Huang PC, Wu FY (2018) Ratiometric fluorescence detection of phosphate in human serum with a metal-organic frameworks-based nanocomposite and its immobilized agarose hydrogels. Appl Surf Sci 459:686–692

    Article  CAS  Google Scholar 

  31. Yam LT (1974) Clinical significance of the human acid phosphatases: a review. Am J Med 56:604–616

    Article  CAS  Google Scholar 

  32. Kong HY, Byun J (2013) Emerging roles of human prostatic acid phosphatase. Biomol Ther 21:10–20

    Article  CAS  Google Scholar 

  33. Qu ZY, Na WD, Liu XT, Liu H, Su XG (2018) A novel fluorescence biosensor for sensitivity detection of tyrosinase and acid phosphatase based on nitrogen-doped graphene quantum dots. Anal Chim Acta 997:52–59

    Article  CAS  Google Scholar 

  34. Guo P, Yan SY, Zhou YM, Wang CC, Xu XW, Weng XC, Zhou X (2013) A novel fluorescent “turn-off/turn-on” system for the detection of acid phosphatase activity. Analyst 138:3365–3367

    Article  CAS  Google Scholar 

  35. Shi FP, Zhang Y, Na WD, Zhang XY, Li Y, Su XG (2016) Graphene quantum dots as selective fluorescence sensor for the detection of ascorbic acid and acid phosphatase via Cr(VI)/Cr (III)-modulated redox reaction. J Mater Chem B 4:3278–3285

    Article  CAS  Google Scholar 

  36. Huang YY, Feng H, Liu WD, Zhou YY, Tang C, Ao H, Zhao MZ, Chen GL, Chen JR, Qian Z (2016) Luminescent aggregated copper nanoclusters nanoswitch controlled by hydrophobic interaction for real-time monitoring of acid phosphatase activity. Anal Chem 88:11575–11583

    Article  CAS  Google Scholar 

  37. Qian ZS, Chai LJ, Zhou Q, Huang YY, Tang C, Chen JR, Feng H (2015) Reversible fluorescent nanoswitch based on carbon quantum dots nanoassembly for real-time acid phosphatase activity monitoring. Anal Chem 87:7332–7339

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Key Laboratory of Eco-environments in Three Gorges Reservoir Region (Ministry of Education), College of Chemistry and Chemical Engineering, Southwest University, Chongqing, 400715, China

    Qianqian Du, Xiaodan Zhang & Yuming Huang

  2. Key Laboratory of Chongqing Inorganic Special Functional Materials, College of Chemistry and Chemical Engineering, Yangtze Normal University, Chongqing, 408100, China

    Haiyan Cao

Authors
  1. Qianqian Du
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Xiaodan Zhang
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Haiyan Cao
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Yuming Huang
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding authors

Correspondence to Haiyan Cao or Yuming Huang.

Ethics declarations

Ethical statement

The study was approved by the Ethics Committee of Southwest University, and all experiments were performed in compliance with guidelines of the Institute Ethics Committee. All the human serum samples were from Southwest University Hospital and treated according to the guidelines of the Institute Ethics Committee. All volunteers provided written informed consent prior to participation in the study.

Conflict of interest

The author(s) 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.

Electronic supplementary material

ESM 1

(DOC 11.5 mb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Du, Q., Zhang, X., Cao, H. et al. Polydopamine coated copper nanoclusters with aggregation-induced emission for fluorometric determination of phosphate ion and acid phosphatase activity. Microchim Acta 187, 357 (2020). https://doi.org/10.1007/s00604-020-04335-2

Download citation

  • Received:

  • Accepted:

  • Published:

  • DOI: https://doi.org/10.1007/s00604-020-04335-2

Keywords

Search

Navigation