Springer Nature is making SARS-CoV-2 and COVID-19 research free. View research | View latest news | Sign up for updates

Preparation of nonconjugated fluorescent polymer nanoparticles for use as a fluorescent probe for detection of 2,4,6-trinitrophenol

  • 128 Accesses

Abstract

Water-soluble nonconjugated fluorescent polymer nanoparticles (NFPNs) were prepared from branched polyethylenimine (PEI) and citric acid through an amide condensation reaction in the aqueous phase. The NFPNs were characterized using a transmission electron microscope, Fourier transform infrared (FTIR) spectroscopy, and X-ray photoelectron spectra (XPS). The NFPN fluorescence (with excitation/emission peaks at 360/450 nm) was quenched by 2,4,6-trinitrophenol (TNP) at trace concentrations through the inner filter effect and the formation of self-assembled non-fluorescent Meisenheimer complexes of TNP on the NFPN surfaces through acid–base interactions. The complexes effectively enriched TNP from the bulk solution on the NFPN surfaces through acid–base interactions, and the strong overlap between NFPN excitation and TNP absorption peaks contributed to NFPNs having good sensitivity and selectivity for TNP. The method was selective for TNP and was not sensitive to other interfering species. The calibration plot of log(F0/F) versus TNP concentration shows a linear relationship (R2 = 0.999) for TNP concentration in the range of 0.5–150 μM. The detection limit for TNP was 0.7 μM. The assay was successfully used to determine TNP in spiked lake water samples, and the recoveries were 96.6–102.7%.

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

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

References

  1. 1.

    Peng D, Zhang L, Li FF, Cui WR, Liang RP, Qiu JD. Facile and green approach to the synthesis of boron nitride quantum dots for 2,4,6-Trinitrophenol sensing. ACS Appl Mater Interfaces. 2018;10(8):7315–23.

  2. 2.

    Sun X, Ma X, Kumar CV, Lei Y. Protein-based sensitive, selective and rapid fluorescence detection of picric acid in aqueous media. Anal Methods. 2014;6(21):8464–8.

  3. 3.

    Luo Z, Liu B, Si S, Lin Y, Luo CS, Pan C, et al. A fluorescent chemosensor based on nonplanar donor-acceptor structure for highly sensitive and selective detection of picric acid in water. Dyes Pigments. 2017;143:463–9.

  4. 4.

    Liu S, Shi F, Chen L, Su X. Bovine serum albumin coated CuInS2 quantum dots as a near-infrared fluorescence probe for 2,4,6-trinitrophenol detection. Talanta. 2013;116:870–5.

  5. 5.

    Ho MY, D'Souza N, Migliorato P. Electrochemical aptamer-based sandwich assays for the detection of explosives. Anal Chem. 2012;84(84):4245–7.

  6. 6.

    Patel R, Bothra S, Kumar R, Crisponi G, Sahoo SK. Pyridoxamine driven selective turn-off detection of picric acid using glutathione stabilized fluorescent copper nanoclusters and its applications with chemically modified cellulose strips. Biosens Bioelectron. 2018;102:196–203.

  7. 7.

    Wang M, Fu Q, Zhang K, Wan Y, Wang L, Gao M, et al. A magnetic and carbon dot based molecularly imprinted composite for fluorometric detection of 2,4,6-trinitrophenol. Microchim Acta. 2019;186(2):86.

  8. 8.

    Deng X, Huang X, Wu D. Forster resonance-energy-transfer detection of 2,4,6-trinitrophenol using copper nanoclusters. Anal Bioanal Chem. 2015;407(16):4607–13.

  9. 9.

    Zhang F, Zhang G, Yao H, Wang Y, Chu T, Yang Y. A europium (III) based nano-flake MOF film for efficient fluorescent sensing of picric acid. Microchim Acta. 2017;184(4):1207–13.

  10. 10.

    Ahmed M, Hameed S, Ihsan A, Naseer MM. Fluorescent thiazol-substituted pyrazoline nanoparticles for sensitive and highly selective sensing of explosive 2,4,6-trinitrophenol in aqueous medium. Sensors Actuat B: Chem. 2017;248:57–62.

  11. 11.

    Sukhanov PT, Kushnir AA, Churilina EV, Maslova NV, Shatalov GV. Chromatographic determination of nitrophenols in aqueous media after two-stage preconcentration using an N-vinylpyrrolidone-based polymer. J Anal Chem. 2017;72(4):468–72.

  12. 12.

    Zhou H, Zhang Z, Jiang C, Guan G, Zhang K, Mei Q, et al. Trinitrotoluene explosive lights up ultrahigh Raman scattering of nonresonant molecule on a top-closed silver nanotube Array. Anal Chem. 2011;83(18):6913–7.

  13. 13.

    Tanwar AS, Hussain S, Malik AH, Afroz MA, Iyer PK. Inner filter effect based selective detection of Nitroexplosive-picric acid in aqueous solution and solid support using conjugated polymer. ACS Sens. 2016;1(8):1070–7.

  14. 14.

    Tanwar AS, Adil LR, Afroz MA, Iyer PK. Inner filter effect and resonance energy transfer based attogram level detection of N\nitroexplosive picric acid using dual emitting cationic conjugated Polyfluorene. ACS Sens. 2018;3(8):1451–61.

  15. 15.

    Liu J, Liu G, Liu W, Wang Y, Xu M, Wang B. Turn-on fluorometric β-carotene assay based on competitive host-guest interaction between rhodamine 6G and β-carotene with a graphene oxide functionalized with a β-cyclodextrin-modified polyethyleneimine. Microchim Acta. 2016;183(3):1161–8.

  16. 16.

    Sun B, Zhao B, Wang D, Wang Y, Tang Q, Zhu S, et al. Fluorescent non-conjugated polymer dots for targeted cell imaging. Nanoscale. 2016;8(18):9837–41.

  17. 17.

    Zhu S, Song Y, Shao J, Zhao X, Yang B. Non-conjugated polymer dots with crosslink-enhanced emission in the absence of fluorophore units. Angew Chem Int Ed. 2015;54(49):14626–37.

  18. 18.

    Luo D, Liu SG, Li NB, Luo HQ. Water-soluble polymer dots formed from polyethylenimine and glutathione as a fluorescent probe for mercury(II). Mikrochim Acta. 2018;185(6):284.

  19. 19.

    Liu J, Liu G, Liu W, Wang Y. Turn-on fluorescence sensor for the detection of heparin based on rhodamine B-modified polyethyleneimine-graphene oxide complex. Biosens Bioelectron. 2015;64:300–5.

  20. 20.

    Liu J, Liu X, Luo H, Gao Y. One-step preparation of nitrogen-doped and surface-passivated carbon quantum dots with high quantum yield and excellent optical properties. RSC Adv. 2014;4(15):7648.

  21. 21.

    Liu J, Wang L, Bao H. A novel fluorescent probe for ascorbic acid based on seed-mediated growth of silver nanoparticles quenching of carbon dots fluorescence. Anal Bioanal Chem. 2019;411(4):877–83.

  22. 22.

    Gao L, Ju L, Cui H. Chemiluminescent and fluorescent dual-signal graphene quantum dots and their application in pesticide sensing arrays. J Mater Chem C. 2017;5(31):7753–8.

  23. 23.

    Sinduja B, John SA. Silver nanoparticles capped with carbon dots as a fluorescent probe for the highly sensitive “off-on” sensing of sulfide ions in water. Anal Bioanal Chem. 2019;411(12):2597–605.

  24. 24.

    Zhao L, Li H, Xu Y, Liu H, Zhou T, Huang N, et al. Selective detection of copper ion in complex real samples based on nitrogen-doped carbon quantum dots. Anal Bioanal Chem. 2018;410(18):4301–9.

  25. 25.

    Zuo P, Liu J, Guo H, Wang C, Liu H, Zhang Z, Liu Q. Multifunctional N,S co-doped carbon dots for sensitive probing of temperature, ferric ion, and methotrexate. Anal Bioanal Chem 2019;411(8):1647–1657.

  26. 26.

    Liu SG, Liu T, Li N, Geng S, Lei JL, Li NB, et al. Polyethylenimine-derived fluorescent nonconjugated polymer dots with reversible dual-signal pH response and logic gate operation. J Phys Chem C. 2017;121(12):6874–83.

  27. 27.

    Vallan L, Urriolabeitia EP, Ruiperez F, Matxain JM, Canton-Vitoria R, Tagmatarchis N, et al. Supramolecular-enhanced charge transfer within entangled polyamide chains as the origin of the universal blue fluorescence of polymer carbon dots. J Am Chem Soc. 2018;140(40):12862–9.

  28. 28.

    Tao S, Lu S, Geng Y, Zhu S, Redfern SAT, Song Y, et al. Design of metal-free polymer carbon dots: a new class of room-temperature phosphorescent materials. Angew Chem Int Ed Engl. 2018;57(9):2393–8.

  29. 29.

    Zhai W, Wang C, Yu P, Wang Y, Mao L. Single-layer MnO2 nanosheets suppressed fluorescence of 7-hydroxycoumarin: mechanistic study and application for sensitive sensing of ascorbic acid in vivo. Anal Chem. 2014;86(24):12206–13.

  30. 30.

    Ma Y, Chen Y, Liu J, Han Y, Ma S, Chen X. Ratiometric fluorescent detection of chromium(VI) in real samples based on dual emissive carbon dots. Talanta. 2018;185:249–57.

  31. 31.

    Ahmed GHG, Laíño RB, Calzón JAG, García MED. Highly fluorescent carbon dots as nanoprobes for sensitive and selective determination of 4-nitrophenol in surface waters. Microchim Acta. 2014;182(1–2):51–9.

  32. 32.

    Wei W, Lu R, Tang S, Liu X. Highly cross-linked fluorescent poly(cyclotriphosphazene-co-curcumin) microspheres for the selective detection of picric acid in solution phase. J Mater Chem A. 2015;3(8):4604–11.

  33. 33.

    Qi W, He H, Fu Y, Zhao M, Qi L, Hu L, et al. Water-dispersed fluorescent silicon nanodots as probes for fluorometric determination of picric acid via energy transfer. Microchim Acta. 2018;186(1):18.

  34. 34.

    Li L, Zhang Q, Ding Y, Cai X, Gu S, Cao Z. Application of l-cysteine capped core–shell CdTe/ZnS nanoparticles as a fluorescence probe for cephalexin. Anal Methods. 2014;6(8):2715–21.

  35. 35.

    Li L, Cheng Y, Ding Y, Lu Y, Zhang F. Application of thioglycolic acid capped nano-ZnS as a fluorescence probe for the determination of nevirapine. Anal Methods. 2012;4(12):4213.

  36. 36.

    Han Y, Chen Y, Feng J, Liu J, Ma S, Chen X. One-pot synthesis of fluorescent silicon nanoparticles for sensitive and selective determination of 2,4,6-trinitrophenol in aqueous solution. Anal Chem. 2017;89(5):3001–8.

  37. 37.

    Chen B, Chai S, Liu J, Liu C, Li Y, He J, et al. 2,4,6-Trinitrophenol detection by a new portable sensing gadget using carbon dots as a fluorescent probe. Anal Bioanal Chem. 2019;411(11):2291–300.

  38. 38.

    Yang G, Hu W, Xia H, Zou G, Zhang Q. Highly selective and reproducible detection of picric acid in aqueous media, based on a polydiacetylene microtube optical waveguide. J Mater Chem A. 2014;2(37):15560.

  39. 39.

    Bhalla V, Gupta A, Kumar M. Fluorescent nanoaggregates of pentacenequinone derivative for selective sensing of picric acid in aqueous media. Org Lett. 2012;14(12):3112–5.

  40. 40.

    Tian X, Qi X, Liu X, Zhang Q. Selective detection of picric acid by a fluorescent ionic liquid chemosensor. Sensors Actuat B: Chem. 2016;229:520–7.

Download references

Acknowledgments

This work was supported by the Natural Science Foundation of Anhui Province, China (1708085MB48) and the National Natural Science Foundation of China (21205002).

Author information

Correspondence to Jinshui Liu.

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.

Electronic supplementary material

ESM 1

(PDF 2.22 MB)

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Liu, J., Wu, F., Xie, A. et al. Preparation of nonconjugated fluorescent polymer nanoparticles for use as a fluorescent probe for detection of 2,4,6-trinitrophenol. Anal Bioanal Chem 412, 1235–1242 (2020). https://doi.org/10.1007/s00216-019-02360-6

Download citation

Keywords

  • Fluorescence
  • Nonconjugated fluorescent polymer nanoparticles
  • 2,4,6-Trinitrophenol
  • Inner filter effect