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Folic acid-conjugated chromium(III) doped nanoparticles consisting of mixed oxides of zinc, gallium and tin, and possessing near-infrared and long persistent phosphorescence for targeted imaging of cancer cells

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Abstract

Folic acid-conjugated luminescent nanomaterials have long been widely used in targeted bioimaging, often simultaneously acting as vehicles for drug delivery. They often require, however, intense light sources for photoexcitation, and this often results in photobleaching, strong luminescence background, and strong light scattering. This article describes the preparation of nanoparticles (NPs) of the type Zn1.1Ga1.8Sn0.1O4 doped with Cr(III) ions and surface-modified with folic acid. The functionalization of the NPs was monitored via measurement of zeta potentials, FTIR spectra and thermogravimetry. Cell viability and biocompatibility were tested using the MTT kit. The NPs have a size of 220 nm and were characterized by dynamic X-ray diffraction, light scattering, field emission scanning electron microscopy and high-resolution transmission electron microscopy. After annealing the NPs for 10 min at 300 °C and irradiating them with 254 nm light for 10 min, they display deep red emission that persists for up to 10 h. The NPs are easily dispersed, small-sized, and crystalline. In our perception, the new material with its long decay time offers quite novel features in terms of targeted optical imaging in providing high resolution, weak disturbance by background luminescence, and the absence of light scattering. They were successfully applied to image MCF-7 and A549 cells.

Folic acid-conjugated nanoparticles of the type Zn1.1Ga1.8Sn0.1O4:Cr3+ are presented that are easily dispersible, small-sized (100 nm), and well crystallized. They display a phosphorescence in the NIR that persists for >10 h after excitation and were used to image MCF-7 and A549 cells.

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References

  1. Ahmed E, Morton SW, Hammond PT, Swager TM (2013) Fluorescent multiblock pi-conjugated polymer nanoparticles for in vivo tumor targeting. Adv Mater 25:4504–4510

    Article  CAS  Google Scholar 

  2. Abdukayum A, Chen JT, Zhao Q, Yan XP (2013) 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 135:14125–14133

    Article  CAS  Google Scholar 

  3. Chen C, Ke J, Zhou XE, Yi W, Brunzelle JS, Li J, Yong EL, Xu HE, Melcher K (2013) Structural basis for molecular recognition of folic acid by folate receptors. Nature 500:486–489

    Article  CAS  Google Scholar 

  4. Huang P, Bao L, Zhang C, Lin J, Luo T, Yang D, He M, Li Z, Gao G, Gao B, Fu S, Cui D (2011) Folic acid-conjugated silica-modified gold nanorods for X-ray/CT imaging-guided dual-mode radiation and photo-thermal therapy. Biomaterials 32:9796–9809

    Article  CAS  Google Scholar 

  5. Pan J, Feng SS (2009) Targeting and imaging cancer cells by folate-decorated, quantum dots (QDs)- loaded nanoparticles of biodegradable polymers. Biomaterials 30:1176–1183

    Article  CAS  Google Scholar 

  6. Chen L, Han H (2014) Recent advances in the use of near-infrared quantum dots as optical probes for bioanalytical, imaging and solar cell application. Microchim Acta 181:1485–1495

    Article  CAS  Google Scholar 

  7. Zheng C, Zheng M, Gong P, Jia D, Zhang P, Shi B, Sheng Z, Ma Y, Cai L (2012) Indocyanine green-loaded biodegradable tumor targeting nanoprobes for in vitro and in vivo imaging. Biomaterials 33:5603–5609

    Article  CAS  Google Scholar 

  8. Gabizon A, Horowitz AT, Goren D, Tzemach D, Shmeeda H, Zalipsky S (2003) In vivo fate of folate-targeted polyethylene-glycol liposomes in tumor-bearing mice. Clin Cancer Res 9:6551–6559

    CAS  Google Scholar 

  9. Yi Z, Zeng S, Lu W, Wang H, Rao L, Liu H, Hao J (2014) Synergistic dual-modality in vivo upconversion luminescence/X-ray imaging and tracking of amine-functionalized NaYbF4:Er nanoprobes. ACS Appl Mater Interfaces 6:3839–3846

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

  11. Yoo MK, Park IK, Lim HT, Lee SJ, Jiang HL, Kim YK, Choi YJ, Cho MH, Cho CS (2012) Folate-PEG-superparamagnetic iron oxide nanoparticles for lung cancer imaging. Acta Biomater 8:3005–3013

    Article  CAS  Google Scholar 

  12. Shin SJ, Beech JR, Kelly KA (2013) Targeted nanoparticles in imaging: paving the way for personalized medicine in the battle against cancer. Integr Biol (Camb) 5:29–42

    Article  CAS  Google Scholar 

  13. Yang Y (2014) Upconversion nanophosphors for use in bioimaging, therapy, drug delivery and bioassays. Microchim Acta 181:263–294

    Article  CAS  Google Scholar 

  14. Xia HX, Yang XQ, Song J-T, Chen J, Zhang MZ, Yan DM, Zhang L, Qin MY, Bai LY, Zhao YD, Ma ZY (2014) Folic acid-conjugated silica-coated gold nanorods and quantum dots for dual-modality CT and fluorescence imaging and photothermal therapy. J Mater Chem B 2:1945–1953

    Article  CAS  Google Scholar 

  15. Fischer CR, Groehn V, Reber J, Schibli R, Ametamey SM, Müller C (2013) Improved PET imaging of tumors in mice using a novel (18) F-folate conjugate with an albumin-binding entity. Mol Imaging Biol 15:649–654

    Article  Google Scholar 

  16. Sun L, Wei Z, Chen H, Liu J, Guo J, Cao M, Wen T, Shi L (2014) Folic acid-functionalized up-conversion nanoparticles: toxicity studies in vivo and in vitro and targeted imaging applications. Nanoscale 6:8878–8883

    Article  CAS  Google Scholar 

  17. Pan YJ, Li D, Jin S, Wei C, Wu KY, Guo J, Wang CC (2013) Folate-conjugated poly(N-(2-hydroxypropyl)methacrylamide-co-methacrylic acid) nanohydrogels with pH/redox dual-stimuli response for controlled drug release. Polym Chem 4:3545–3553

    Article  CAS  Google Scholar 

  18. Ye C, Wang YQ, Li CG, Yu J, Hu YZ (2014) Preparation of liposomes loaded with quantum dots, fluorescence resonance energy transfer studies, and near-infrared in-vivo imaging of mouse tissue. Microchim Acta 180:117–125

    Article  Google Scholar 

  19. Bessière A, Sharma SK, Basavaraju N, Priolkar KR, Binet L, Viana B, Bos AJJ, Maldiney T, Richard C, Scherman D, Gourier D (2014) Storage of visible light for long-lasting phosphorescence in chromium-doped zinc gallate. Chem Mater 26:1365–1373

    Article  Google Scholar 

  20. Maldiney T, Byk G, Wattier N, Seguin J, Khandadash R, Bessodes M, Richard C, Scherman D (2012) Synthesis and functionalization of persistent luminescence nanoparticles with small molecules and evaluation of their targeting ability. Int J Pharm 423:102–107

    Article  CAS  Google Scholar 

  21. Li Y, Zhou S, Li Y, Sharafudeen K, Ma Z, Dong G, Peng M, Qiu J (2014) Long persistent and photo-stimulated luminescence in Cr3+-doped Zn–Ga–Sn–O phosphors for deep and reproducible tissue imaging. J Mater Chem C 2:2657–2663

    Article  CAS  Google Scholar 

  22. Sharma SK, Gourier D, Viana B, Maldiney T, Teston E, Scherman D, Richard C (2014) Persistent luminescence of AB2O4:Cr3+ (A=Zn, Mg, B=Ga, Al) spinels: New biomarkers for in vivo imaging. Opt Mater 36:1901–1906

    Article  CAS  Google Scholar 

  23. Su Q, Li C, Wang J (2014) Some interesting phenomena in the study of rare earth long lasting phosphors. Opt Mater 36:1894–1900

    Article  CAS  Google Scholar 

  24. Pan Z, Lu YY, Liu F (2012) Sunlight-activated long-persistent luminescence in the near-infrared from Cr3+-doped zinc gallogermanates. Nat Mater 11:58–63

    Article  CAS  Google Scholar 

  25. Li Y, Li YY, Sharafudeen K, Dong GP, Zhou SF, Ma ZJ, Peng MY, Qiu JR (2014) A strategy for developing near infrared long-persistent phosphors: taking MAlO3:Mn4+, Ge4+ (M=La, Gd) as an example. J Mater Chem C 2:2019–2027

    Article  CAS  Google Scholar 

  26. Peng C, Qin J, Zhou B, Chen Q, Shen M, Zhu M, Lu X, Shi X (2013) Targeted tumor CT imaging using folic acid-modified PEGylated dendrimer-entrapped gold nanoparticles. Polym Chem 4:4412–4424

    Article  CAS  Google Scholar 

  27. Maldiney T, Bessiere A, Seguin J, Teston E, Sharma SK, Viana B, Bos AJ, Dorenbos P, Bessodes M, Gourier D, Scherman D, Richard C (2014) The in vivo activation of persistent nanophosphors for optical imaging of vascularization, tumours and grafted cells. Nat Mater 13:418–426

    Article  CAS  Google Scholar 

  28. Li Y, Du X, Sharafudeen K, Liao C, Qiu J (2014) A long persistent phosphor based on recombination centers originating from Zn imperfections. Spectrochim Acta A Mol Biomol Spectrosc 123:7–11

    Article  CAS  Google Scholar 

  29. Sun L, Liu T, Qiu Y, Liu J, Li F, Shi L, Wolfbeis OS (2014) Direct formation of mesoporous upconverting nanoparticles for bioimaging of living cells. Microchim Acta 181:775–782

    Article  CAS  Google Scholar 

  30. Müller C, Reber J, Schlup C, Leamon CP, Schibli R (2013) In vitro and in vivo evaluation of an innocuous drug cocktail to improve the quality of folic acid targeted nuclear imaging in preclinical research. Mol Pharm 10:967–974

    Article  Google Scholar 

  31. Li Y, Zhou S, Dong G, Peng M, Wondraczek L, Qiu J (2014) Anti-stokes fluorescent probe with incoherent excitation. Sci Rep 4:4059(1)–4059(6)

    Google Scholar 

  32. Van den Eeckhout K, Smet PF, Poelman D (2010) Persistent luminescence in Eu2+-Doped compounds: a review. Materials (Basel) 3:2536–2566

    Article  Google Scholar 

  33. Zhuang Y, Ueda J, Tanabe S (2013) 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 1:7849–7855

    Article  CAS  Google Scholar 

Download references

Acknowledgments

This work was financially supported by the National Natural Science Foundation of China (Grant Nos. 51132004, 51322208, 51102096, 51302087), Guangdong Natural Science Foundation (Grant Nos. S2011030001349, S20120011380, S2013050014549), National Basic Research Program of China (2011CB808102).

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Correspondence to Jianrong Qiu.

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Li, Y., Chen, R., Li, Y. et al. Folic acid-conjugated chromium(III) doped nanoparticles consisting of mixed oxides of zinc, gallium and tin, and possessing near-infrared and long persistent phosphorescence for targeted imaging of cancer cells. Microchim Acta 182, 1827–1834 (2015). https://doi.org/10.1007/s00604-015-1486-8

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  • DOI: https://doi.org/10.1007/s00604-015-1486-8

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