Skip to main content
SpringerLink
Log in

Silica shell-assisted synthetic route for mono-disperse persistent nanophosphors with enhanced in vivo recharged near-infrared persistent luminescence

  • Research Article
  • Published:
Nano Research Aims and scope Submit manuscript

Abstract

Near-infrared (NIR) persistent-luminescence nanoparticles have emerged as a new class of background-free contrast agents that are promising for in vivo imaging. The next key roadblock is to establish a robust and controllable method for synthesizing monodisperse nanoparticles with high luminescence brightness and long persistent duration. Herein, we report a synthesis strategy involving the coating/etching of the SiO2 shell to obtain a new class of small NIR highly persistent luminescent ZnGa2O4:Cr3+,Sn4+ (ZGOCS) nanoparticles. The optimized ZGOCS nanoparticles have an excellent size distribution of ~15 nm without any agglomeration and an NIR persistent luminescence that is enhanced by a factor of 13.5, owing to the key role of the SiO2 shell in preventing nanoparticle agglomeration after annealing. The ZGOCS nanoparticles have a signal-to-noise ratio ~3 times higher than that of previously reported ZnGa2O4:Cr3+ (ZGC-1) nanoparticles as an NIR persistent-luminescence probe for in vivo bioimaging. Moreover, the persistent-luminescence signal from the ZGOCS nanoparticles can be repeatedly re-charged in situ with external excitation by a white lightemitting diode; thus, the nanoparticles are suitable for long-term in vivo imaging applications. Our study suggests an improved strategy for fabricating novel high-performance optical nanoparticles with good biocompatibility.

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

Similar content being viewed by others

References

  1. Van den Eeckhout, K.; Poelman, D.; Smet, P. F. Persistent luminescence in non-Eu2+-doped compounds: A review. Materials 2013, 6, 2789–2818.

    Article  Google Scholar 

  2. Hölsä, J. Persistent luminescence beats the afterglow: 400 years of persistent luminescence. Electrochem. Soc. Interface 2009, 18, 42–45.

    Google Scholar 

  3. Pan, Z. W.; Lu, Y.-Y.; Liu, F. Sunlight-activated longpersistent luminescence in the near-infrared from Cr3+-doped zinc gallogermanates. Nat. Mater. 2012, 11, 58–63.

    Article  Google Scholar 

  4. le Masne de Chermont, Q.; Chanéac, C.; Seguin, J.; Pellé, F.; Maîtrejean, S.; Jolivet, J.-P.; Gourier, D.; Bessodes, M.; Scherman, D. Nanoprobes with near-infrared persistent luminescence for in vivo imaging. Proc. Natl. Acad. Sci. USA 2007, 104, 9266–9271.

    Article  Google Scholar 

  5. Debasu, M. L.; Ananias, D.; Pinho, S. L. C.; Geraldes, C. F. G. C.; Carlos, L. D.; Rocha, J. (Gd, Yb, Tb)PO4 up-conversion nanocrystals for bimodal luminescence–MR imaging. Nanoscale 2012, 4, 5154–5162.

  6. Maldiney, T.; Bessiè re, A.; Seguin, J.; Teston, E.; Sharma, S. K.; Viana, B.; Bos, A. J. J.; Dorenbos, P.; Bessodes, M.; Gourier, D. et al. The in vivo activation of persistent nanophosphors for optical imaging of vascularization, tumours and grafted cells. Nat. Mater. 2014, 13, 418–426.

    Article  Google Scholar 

  7. Tavares, A. J.; Chong, L.; Petryayeva, E.; Algar, W. R.; Krull, U. J. Quantum dots as contrast agents for in vivo tumor imaging: Progress and issues. Anal. Bioanal. Chem. 2011, 399, 2331–2342.

    Article  Google Scholar 

  8. Smith, A. M.; Mancini, M. C.; Nie, S. M. Bioimaging: Second window for in vivo imaging. Nat. Nanotechnol. 2009, 4, 710–711.

    Article  Google Scholar 

  9. Weissleder, R.; Ntziachristos, V. Shedding light onto live molecular targets. Nat. Med. 2003, 9, 123–128.

    Article  Google Scholar 

  10. Liu, Q.; Sun, Y.; Li, C. G.; Zhou, J.; Li, C. Y.; Yang, T. S.; Zhang, X. Z.; Yi, T.; Wu, D. M.; Li, F. Y. 18F-labeled magnetic-upconversion nanophosphors via rare-earth cationassisted ligand assembly. ACS Nano 2011, 5, 3146–3157.

    Article  Google Scholar 

  11. Zhou, B.; Shi, B. Y.; Jin, D. Y.; Liu, X. G. Controlling upconversion nanocrystals for emerging applications. Nat. Nanotechnol. 2015, 10, 924–936.

    Article  Google Scholar 

  12. Yang, D. M.; Ma, P. A.; Hou, Z. Y.; Cheng, Z. Y.; Li, C. X.; Lin, J. Current advances in lanthanide ion (Ln3+)-based upconversion nanomaterials for drug delivery. Chem. Soc. Rev. 2015, 44, 1416–1448.

    Article  Google Scholar 

  13. Chan, C. F.; Xie, C.; Tsang, M. K.; Lear, S.; Dai, L. X.; Zhou, Y.; Cicho, J.; Karbowiak, M.; Hreniak, D.; Lan, R. F. The effects of morphology and linker length on the properties of peptide–lanthanide upconversion nanomaterials as G2 phase cell cycle inhibitors. Eur. J. Inorg. Chem. 2015, 2015, 4539–4545.

    Article  Google Scholar 

  14. Gallo, J.; Alam, I. S.; Jin, J. F.; Gu, Y.-J.; Aboagye, E. O.; Wong, W.-T.; Long, N. J. PET imaging with multimodal upconversion nanoparticles. Dalton Trans. 2014, 43, 5535–5545.

  15. Chen, C.-W.; Lee, P.-H.; Chan, Y.-C.; Hsiao, M.; Chen, C.-H.; Wu, P. C.; Wu, P. R.; Tsai, D. P.; Tu, D. T.; Chen, X. Y. et al. Plasmon-induced hyperthermia: Hybrid upconversion NaYF4:Yb/Er and gold nanomaterials for oral cancer photothermal therapy. J. Mater. Chem. B 2015, 3, 8293–8302.

    Article  Google Scholar 

  16. Geißler, D.; Charbonnière, L. J.; Ziessel, R. F.; Butlin, N. G.; Löhmannsröben, H. G.; Hildebrandt, N. Quantum dot biosensors for ultrasensitive multiplexed diagnostics. Angew. Chem., Int. Ed. 2010, 49, 1396–1401.

    Article  Google Scholar 

  17. Luo, S. L.; Zhang, E. L.; Su, Y. P.; Cheng, T. M.; Shi, C. M. A review of NIR dyes in cancer targeting and imaging. Biomaterials 2011, 32, 7127–7138.

    Article  Google Scholar 

  18. Yahia-Ammar, A.; Nonat, A. M.; Boos, A.; Rehspringer, J.-L.; Asfari, Z.; Charbonnière, L. J. Thin-coated water soluble CdTeS alloyed quantum dots as energy donors for highly efficient FRET. Dalton Trans. 2014, 43, 15583–15592.

    Article  Google Scholar 

  19. Dai, W. B.; Lei, Y. F.; Ye, S.; Song, E. H.; Chen, Z.; Zhang, Q. Y. Mesoporous nanoparticles Gd2O3@ mSiO2/ ZnGa2O4:Cr3+,Bi3+ as multifunctional probes for bioimaging. J. Mater. Chem. B 2016, 4, 1842–1852.

    Article  Google Scholar 

  20. Shi, J. P.; Sun, X.; Li, J. L.; Man, H. Z.; Shen, J. S.; Yu, Y. K.; Zhang, H. W. Multifunctional near infrared-emitting longpersistence luminescent nanoprobes for drug delivery and targeted tumor imaging. Biomaterials 2015, 37, 260–270.

    Article  Google Scholar 

  21. Teston, E.; Richard, S.; Maldiney, T.; Lièvre, N.; Wang, G. Y.; Motte, L.; Richard, C.; Lalatonne, Y. Non-aqueous sol–gel synthesis of ultra small persistent luminescence nanoparticles for near-infrared in vivo imaging. Chem.—Eur. J. 2015, 21, 7350–7354.

    Article  Google Scholar 

  22. Srivastava, B. B.; Kuang, A. X.; Mao, Y. B. Persistent luminescent sub-10 nm Cr doped ZnGa2O4 nanoparticles by a biphasic synthesis route. Chem. Commun. 2015, 51, 7372–7375.

    Article  Google Scholar 

  23. Li, Y.; Li, Y. Y.; Chen, R. C.; Sharafudeen, K.; Zhou, S. F.; Gecevicius, M.; Wang, H. H.; Dong, G. P.; Wu, Y. L.; Qin, X. X. et al. Tailoring of the trap distribution and crystal field in Cr3+-doped non-gallate phosphors with near-infrared long-persistence phosphorescence. NPG Asia Mater. 2015, 7, e180.

    Article  Google Scholar 

  24. Zhuang, Y. X.; Ueda, J.; Tanabe, S. Tunable trap depth in Zn(Ga1-xAlx)2O4:Cr,Bi red persistent phosphors: Considerations of high-temperature persistent luminescence and photostimulated persistent luminescence. J. Mater. Chem. C 2013, 1, 7849–7855.

    Article  Google Scholar 

  25. Maldiney, T.; Richard, C.; Seguin, J.; Wattier, N.; Bessodes, M.; Scherman, D. Effect of core diameter, surface coating, and PEG chain length on the biodistribution of persistent luminescence nanoparticles in mice. ACS Nano 2011, 5, 854–862.

    Article  Google Scholar 

  26. Li, Y.; Gecevicius, M.; Qiu, J. R. Long persistent phosphors—From fundamentals to applications. Chem. Soc. Rev. 2016, 45, 2090–2136.

    Article  Google Scholar 

  27. Maldiney, T.; Rémond, M.; Bessodes, M.; Scherman, D.; Richard, C. Controlling aminosilane layer thickness to extend the plasma half-life of stealth persistent luminescence nanoparticles in vivo. J. Mater. Chem. B 2015, 3, 4009–4016.

    Article  Google Scholar 

  28. Abdukayum, A.; Chen, J.-T.; Zhao, Q.; Yan, X.-P. Functional near infrared-emitting Cr3+/Pr3+ Co-doped zinc gallogermanate persistent luminescent nanoparticles with superlong afterglow for in vivo targeted bioimaging. J. Am. Chem. Soc. 2013, 135, 14125–14133.

    Article  Google Scholar 

  29. Wang, F.; Wang, J.; Liu, X. G. Direct evidence of a surface quenching effect on size-dependent luminescence of upconversion nanoparticles. Angew. Chem., Int. Ed. 2010, 122, 7618–7622.

    Article  Google Scholar 

  30. Li, Z. J.; Zhang, Y. W.; Wu, X.; Huang, L.; Li, D. S.; Fan, W.; Han, G. Direct aqueous-phase synthesis of sub-10 nm “luminous pearls” with enhanced in vivo renewable nearinfrared persistent luminescence. J. Am. Chem. Soc. 2015, 137, 5304–5307.

    Article  Google Scholar 

  31. Zhou, W. L.; Zou, R.; Yang, X. F.; Huang, N. Y.; Huang, J. J.; Liang, H. B.; Wang, J. Core-decomposition-facilitated fabrication of hollow rare-earth silicate nanowalnuts from core–shell structures via the Kirkendall effect. Nanoscale 2015, 7, 13715–13722.

    Article  Google Scholar 

  32. Pinho, S. L. C.; Pereira, G. A.; Voisin, P.; Kassem, J.; Bouchaud, V.; Etienne, L.; Peters, J. A.; Carlos, L.; Mornet, S.; Geraldes, C. F. et al. Fine tuning of the relaxometry of Fe2O3@SiO2 nanoparticles by tweaking the silica coating thickness. ACS Nano 2010, 4, 5339–5349.

    Article  Google Scholar 

  33. Gallo, J.; Alam, I. S.; Lavdas, I.; Wylezinska-Arridge, M.; Aboagye, E. O.; Long, N. J. RGD-targeted MnO nanoparticles as T1 contrast agents for cancer imaging—The effect of PEG length in vivo. J. Mater. Chem. B 2014, 2, 868–876.

    Article  Google Scholar 

  34. Bessière, A.; Jacquart, S.; Priolkar, K.; Lecointre, A.; Viana, B.; Gourier, D. ZnGa2O4:Cr3+: A new red long-lasting phosphor with high brightness. Opt. Express 2011, 19, 10131–10137.

    Article  Google Scholar 

  35. Allix, M.; Chenu, S.; Véron, E.; Poumeyrol, T.; Kouadri-Boudjelthia, E. A.; Alahraché, S.; Porcher, F.; Massiot, D.; Fayon, F. Considerable improvement of long-persistent luminescence in germanium and tin substituted ZnGa2O4. Chem. Mater. 2013, 25, 1600–1606.

    Article  Google Scholar 

  36. Lee, Y. E.; Norton, D. P.; Budai, J. D. Enhanced photoluminescence in epitaxial ZnGa2O4: Mn thin-film phosphors using pulsed-laser deposition. Appl. Phys. Lett. 1999, 74, 3155–3157.

    Article  Google Scholar 

  37. Kang, B. K.; Lim, H. D.; Mang, S. R.; Song, K. M.; Jung, M. K.; Yoon, D. H. Synthesis and characteristics of ZnGa2O4 hollow nanostructures via carbon@Ga(OH)CO3@Zn(OH)2 by a hydrothermal method. CrystEngComm 2015, 17, 2267–2272.

    Article  Google Scholar 

  38. Bessière, A.; Sharma, S. K.; Basavaraju, N.; Priolkar, K. R.; Binet, L.; Viana, B.; Bos, A. J. J.; Maldiney, T.; Richard, C.; Scherman, D. et al. Storage of visible light for long-lasting phosphorescence in chromium-doped zinc gallate. Chem. Mater. 2014, 26, 1365–1373.

    Article  Google Scholar 

  39. Maldiney, T.; Lecointre, A.; Viana, B.; Bessière, A.; Bessodes, M.; Gourier, D.; Richard, C.; Scherman, D. Controlling electron trap depth to enhance optical properties of persistent luminescence nanoparticles for in vivo imaging. J. Am. Chem. Soc. 2011, 133, 11810–11815.

    Article  Google Scholar 

  40. Li, Z. J.; Shi, J. P.; Zhang, H. W.; Sun, M. Highly controllable synthesis of near-infrared persistent luminescence SiO2/CaMgSi2O6 composite nanospheres for imaging in vivo. Opt. Express 2014, 22, 10509–10518.

    Article  Google Scholar 

  41. Jokerst, J. V.; Lobovkina, T.; Zare, R. N.; Gambhir, S. S. Nanoparticle PEGylation for imaging and therapy. Nanomedicine 2011, 6, 715–728.

    Article  Google Scholar 

Download references

Acknowledgements

This work was financially supported by the National Basic Research Program of China (No. 2014CB643801), the National Natural Science Foundation of China (Nos. 51572302 and 21271191), the Joint Funds of the National Natural Science Foundation of China and Guangdong Province (No. U1301242), Teamwork Projects of Guangdong Natural Science Foundation (No. S2013030012842), Guangdong Science & Technology Project (Nos. 2013B090800019 and 2015B090926011) and Natural Science Foundation of Guangdong Province (No. 2014A030313114).

Author information

Authors and Affiliations

  1. Ministry of Education Key Laboratory of Bioinorganic and Synthetic Chemistry, State Key Laboratory of Optoelectronic Materials and Technologies, KLGHEI of Environment and Energy Chemistry, School of Chemistry, Sun Yat-Sen University, Guangzhou, 510275, China

    Rui Zou, Junjian Huang, Lin Huang, Xuejie Zhang, Jing Wang & Qiang Su

  2. Key Lab of Urban Pollutant Conversion, Institute of Urban Environment, Chinese Academy of Sciences, Xiamen, 361021, China

    Junpeng Shi & Hongwu Zhang

  3. Department of Chemistry, Hong Kong Baptist University, Hong Kong, 999077, China

    Ka-Leung Wong

  4. Institute for Biomedical Materials and Devices (IBMD), Faculty of Science, University of Technology, Sydney, NSW, 2007, Australia

    Dayong Jin

Authors
  1. Rui Zou
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Junjian Huang
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Junpeng Shi
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Lin Huang
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Xuejie Zhang
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Ka-Leung Wong
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Hongwu Zhang
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Dayong Jin
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. Jing Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

  10. Qiang Su
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding authors

Correspondence to Ka-Leung Wong, Hongwu Zhang, Dayong Jin or Jing Wang.

Additional information

These authors contributed equally to this work.

Electronic supplementary material

12274_2016_1396_MOESM1_ESM.pdf

Silica shell-assisted synthetic route for mono-disperse persistent nanophosphors with enhanced in vivo recharged near-infrared persistent luminescence

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Zou, R., Huang, J., Shi, J. et al. Silica shell-assisted synthetic route for mono-disperse persistent nanophosphors with enhanced in vivo recharged near-infrared persistent luminescence. Nano Res. 10, 2070–2082 (2017). https://doi.org/10.1007/s12274-016-1396-z

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s12274-016-1396-z

Keywords

Search

Navigation