Microchimica Acta

, 186:630 | Cite as

Core-shell upconversion nanoparticles of type NaGdF4:Yb,Er@NaGdF4:Nd,Yb and sensitized with a NIR dye are a viable probe for luminescence determination of the fraction of water in organic solvents

  • Wen Wang
  • Mingying Zhao
  • Lun WangEmail author
  • Hongqi ChenEmail author
Original Paper


Lanthanide-doped core-shell upconversion nanoparticles (UCNPs) of type NaGdF4:Yb,Er@NaGdF4:Yb,Nd were prepared by the co-precipitation method. The luminescence intensity was further enhanced by adding the sensitizer dye IR-808. If water is added to organic solvents [such as N,N-dimethylformamide (DMF), dimethyl sulfoxide, methanol, acetone, acetonitrile, and ethanol] containing the probe, its luminescence intensity peaking at 545 nm is reduced. The decrease is linearly related to the percentage of water in the respective organic solvent. Water fractions ranging from 0.05% to 10% (volume %) can be sensitively detected, and the detection limit is 0.018% of water in DMF. The detection scheme is mainly attributed to the fact that the transfer of energy from the near-infrared light (NIR) dye to the UCNPs is strongly reduced in the presence of traces of water.

Graphical abstract

The near infrared dye (IR-808) transfer efficiency to NaGdF4:Yb, Er@NaGdF4:Yb, Nd upconversion nanoparticles in water is far less than that in organic phase. Several methods for determination of trace water in organic solvents were developed by using this effect.


Upconversion nanoparticles Dye sensitization Luminescent probe Water fraction 



This work was financially supported by natural science foundation of China (21675002), the education commission natural science foundation of Anhui Province (KJ2017ZD25), foundation for innovation team of bioanalytical chemistry and Special and Excellent Research Fund of Anhui Normal University.

Compliance with ethical standards

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

Supplementary material

604_2019_3744_MOESM1_ESM.doc (1.6 mb)
ESM 1 (DOC 1620 kb)


  1. 1.
    Wang L, Li Y (2007) Luminescent coordination compound nanospheres for water determination. Small 3(7):1218–1221. CrossRefPubMedGoogle Scholar
  2. 2.
    Gao F, Luo F, Chen X, Yao W, Yin J, Yao Z, Wang L (2009) Fluorometric determination of water in organic solvents using europium ion-based luminescent nanospheres. Microchim Acta 166(1–2):163–167. CrossRefGoogle Scholar
  3. 3.
    Kang E, Park HR, Yoon J, Yu H-Y, Chang S-K, Kim B, Choi K, Ahn S (2018) A simple method to determine the water content in organic solvents using the 1 H NMR chemical shifts differences between water and solvent. Microchem J 138:395–400. CrossRefGoogle Scholar
  4. 4.
    Ohira S, Miki Y, Matsuzaki T, Nakamura N, Sato YK, Hirose Y, Toda K (2015) A fiber optic sensor with a metal organic framework as a sensing material for trace levels of water in industrial gases. Anal Chim Acta 886:188–193. CrossRefPubMedGoogle Scholar
  5. 5.
    Huang D, Bing Y, Yi H, Hong W, Lai C, Guo Q, Niu C (2015) An optical-fiber sensor based on time-gated fluorescence for detecting water content in organic solvents. Anal Methods 7(11):4621–4628. CrossRefGoogle Scholar
  6. 6.
    Wang X-Y, Niu C-G, Hu L-Y, Huang D-W, Wu S-Q, Zhang L, Wen X-J, Zeng G-M (2017) A fluorescent ratiometric sensor based on covalent immobilization of chalcone derivative and porphyrin zinc for detecting water content in organic solvents. Sensors Actuators B Chem 243:1046–1056. CrossRefGoogle Scholar
  7. 7.
    Ye C, Qin Y, Huang P, Chen A, Wu FY (2018) Facile synthesis of carbon nanodots with surface state-modulated fluorescence for highly sensitive and real-time detection of water in organic solvents. Anal Chim Acta 1034:144–152. CrossRefPubMedGoogle Scholar
  8. 8.
    Wu JX, Yan B (2017) A dual-emission probe to detect moisture and water in organic solvents based on green-Tb(3+) post-coordinated metal-organic frameworks with red carbon dots. Dalton Trans 46(21):7098–7105. CrossRefPubMedGoogle Scholar
  9. 9.
    Zhou Y, Zhang D, Xing W, Cuan J, Hu Y, Cao Y, Gan N (2019) Ratiometric and turn-on luminescence detection of water in organic solvents using a responsive europium-organic framework. Anal Chem 91:4845–4851. CrossRefPubMedGoogle Scholar
  10. 10.
    Chen L, Ye JW, Wang HP, Pan M, Yin SY, Wei ZW, Zhang LY, Wu K, Fan YN, Su CY (2017) Ultrafast water sensing and thermal imaging by a metal-organic framework with switchable luminescence. Nat Commun 8:15985. CrossRefPubMedPubMedCentralGoogle Scholar
  11. 11.
    Dantan N, Frenzel W, Küppers S (2000) Determination of water traces in various organic solvents using Karl Fischer method under FIA conditions. Talanta 52(1):101–109. CrossRefPubMedGoogle Scholar
  12. 12.
    Xu BQ, Rao CQ, Cui SF, Wang J, Wang JL, Liu LP (2018) Determination of trace water contents of organic solvents by gas chromatography-mass spectrometry-selected ion monitoring. J Chromatogr A 1570:109–115. CrossRefPubMedGoogle Scholar
  13. 13.
    Guo S, Xie X, Huang L, Huang W (2016) Sensitive water probing through nonlinear photon Upconversion of lanthanide-doped nanoparticles. ACS Appl Mater Interfaces 8(1):847–853. CrossRefPubMedGoogle Scholar
  14. 14.
    Liu S, De G, Xu Y, Wang X, Liu Y, Cheng C, Wang J (2018) Size, phase-controlled synthesis, the nucleation and growth mechanisms of NaYF4:Yb/Er nanocrystals. J Rare Earths 36(10):1060–1066. CrossRefGoogle Scholar
  15. 15.
    Wang X, Yang J, Sun X, Yu H, Yan F, Meguellati K, Cheng Z, Zhang H, Yang YW (2018) Facile surface functionalization of upconversion nanoparticles with phosphoryl pillar[5] arenes for controlled cargo release and cell imaging. Chem Commun (Camb) 54(92):12990–12993. CrossRefGoogle Scholar
  16. 16.
    Dai Y, Bi H, Deng X, Li C, He F, Ma P, Yang P, Lin J (2017) 808 nm near-infrared light controlled dual-drug release and cancer therapy in vivo by upconversion mesoporous silica nanostructures. J Mater Chem B 5(11):2086–2095. CrossRefGoogle Scholar
  17. 17.
    Zhang T, Lin H, Cui L, An N, Tong R, Chen Y, Yang C, Li X, Liu J, Qu F (2016) Near infrared light triggered reactive oxygen species responsive upconversion nanoplatform for drug delivery and photodynamic therapy. Eur J Inorg Chem 2016(8):1206–1213. CrossRefGoogle Scholar
  18. 18.
    Zhang Y, Yu Z, Li J, Ao Y, Xue J, Zeng Z, Yang X, Tan TT (2017) Ultrasmall-superbright neodymium-upconversion nanoparticles via energy migration manipulation and lattice modification: 808 nm-activated drug release. ACS Nano 11(3):2846–2857. CrossRefPubMedGoogle Scholar
  19. 19.
    Yang G, Yang D, Yang P, Lv R, Li C, Zhong C, He F, Gai S, Lin J (2015) A single 808 nm near-infrared light-mediated multiple imaging and photodynamic therapy based on titania coupled upconversion nanoparticles. Chem Mater 27(23):7957–7968. CrossRefGoogle Scholar
  20. 20.
    Xu F, Zhao Y, Hu M, Zhang P, Kong N, Liu R, Liu C, Choi SK (2018) Lanthanide-doped core-shell nanoparticles as a multimodality platform for imaging and photodynamic therapy. Chem Commun (Camb) 54(68):9525–9528. CrossRefGoogle Scholar
  21. 21.
    Ding X, Liu J, Liu D, Li J, Wang F, Li L, Wang Y, Song S, Zhang H (2017) Multifunctional core/satellite polydopamine@Nd3+−sensitized upconversion nanocomposite: a single 808 nm near-infrared light-triggered theranostic platform for in vivo imaging-guided photothermal therapy. Nano Res 10(10):3434–3446. CrossRefGoogle Scholar
  22. 22.
    Wang X, Valiev RR, Ohulchanskyy TY, Agren H, Yang C, Chen G (2017) Dye-sensitized lanthanide-doped upconversion nanoparticles. Chem Soc Rev 46(14):4150–4167. CrossRefPubMedGoogle Scholar
  23. 23.
    Chen G, Damasco J, Qiu H, Shao W, Ohulchanskyy TY, Valiev RR, Wu X, Han G, Wang Y, Yang C, Agren H, Prasad PN (2015) Energy-cascaded Upconversion in an organic dye-sensitized core/shell fluoride nanocrystal. Nano Lett 15(11):7400–7407. CrossRefPubMedPubMedCentralGoogle Scholar
  24. 24.
    Yin D, Liu Y, Tang J, Zhao F, Chen Z, Zhang T, Zhang X, Chang N, Wu C, Chen D, Wu M (2016) Huge enhancement of upconversion luminescence by broadband dye sensitization of core/shell nanocrystals. Dalton Trans 45(34):13392–13398. CrossRefPubMedGoogle Scholar
  25. 25.
    Hazra C, Ullah S, Serge Correales YE, Caetano LG, Ribeiro SJL (2018) Enhanced NIR-I emission from water-dispersible NIR-II dye-sensitized core/active shell upconverting nanoparticles. J Mater Chem C 6(17):4777–4785. CrossRefGoogle Scholar
  26. 26.
    Zou X, Xu M, Yuan W, Wang Q, Shi Y, Feng W, Li F (2016) A water-dispersible dye-sensitized upconversion nanocomposite modified with phosphatidylcholine for lymphatic imaging. Chem Commun (Camb) 52(91):13389–13392. CrossRefGoogle Scholar
  27. 27.
    Xu J, Gulzar A, Liu Y, Bi H, Gai S, Liu B, Yang D, He F, Yang P (2017) Integration of IR-808 sensitized upconversion nanostructure and MoS2 nanosheet for 808 nm NIR light triggered phototherapy and bioimaging. Small 13(36):1701841. CrossRefGoogle Scholar
  28. 28.
    Andresen E, Resch-Genger U, Schaferling M (2019) Surface modifications for photon-Upconversion-based energy-transfer Nanoprobes. Langmuir 35(15):5093–5113. CrossRefPubMedGoogle Scholar

Copyright information

© Springer-Verlag GmbH Austria, part of Springer Nature 2019

Authors and Affiliations

  1. 1.Anhui Key Laboratory of Chemo-Biosensing, Key Laboratory of Functional Molecular Solids, Ministry of Education, College of Chemistry and Materials ScienceAnhui Normal UniversityWuhuPeople’s Republic of China

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