Abstract: Rare earth upconversion nanoparticles have attracted considerable attention in the fields of display, detection, especially biomedicine because they can convert near infrared light into visible light. However, due to the limitation of upconversion luminescence mechanism and the electron transition characteristics of rare earth ions , the fluorescence quantum yield of rare earth upconversion nanoparticles is very low, which greatly limits theirs development. Therefore, it is very important to improve the luminescence efficiency of rare earth upconversion nanoparticles. Coating shell layer on rare earth upconversion nanoparticles by preparing core-shell structured materials can inhibit the surface quenching of rare earth materials, passivate lattice defects of the inner-core surface, isolate the interference of external adverse factors, which greatly improve the efficiency of transformation on the luminescence. Meanwhile, it can bring a series of excellent performance. For example, coating single-layer shell can change the material surface hydrophobicity; coating multilayer shells can prepare multifunctional nanocomposites with diagnostic and therapeutic function. Based onthe characteristics of rare earth ions and upconversion luminescence, the defects of rare earth upconversion nanoparticles were analyzed. This paper also focused on the advantages and disadvantages of several kinds of the preparation methods of core-shell structured nanomaterials which were widely studied in recent years, including inert core-shell structure, active core-shell structure and multilayer core-shell structure. The structural characteristics and application status of three types of core-shell structures were summarized. And their effects of core-shell structure on the luminescence of upconversion nanoparticles were discussed. We pointed out that the main effects of the inert shell on the fluorescence of the rare earth upconversion nanoparticles, including isolating the external environment interference and reducing the surface activity of the materials. Coating active shell on the surface can introduce new functions by doping different ions in the shell. Multi-layer shell can not only effectively prevent ion transition and reduce fluorescence quenching, but also provide new ideas for the preparation of integrated nanometer treatment platform for diagnosis and treatment by making full use of the advantages of rare earth materials and various treatment methods. Finally , we reviewed the applications of rare earth upconversion nanoparticles with core-shell-structure in deep tissue imaging, multi-mode imaging, drug delivery, photothermal therapy and photodynamic therapy. And we also pointed out the existing problems in development of core-shell-structured materials. For example, the bonding strength between shell and core was not easy to control; the optimum shell coating thickness was not uncertain; and the materials were not still industrialized. In the future, the emphasis should be put on exploring the mechanism of core-shell structure and seeking for more efficient methods of shell preparation based on the principles, in order to further expand the application of core-shell structured rare earth upconversion nanomaterials in biomedical fields.
Auzel F. Chemical Reviews, 2004, 104(1), 139.2 Ma W J, You F T, Peng H S, et al. Journal of Physics, 2017, 66(10), 307 (in Chinese).马文君, 由芳田, 彭洪尚, 等.物理学报, 2017, 66(10), 307.3 Feng A L, You M L, Tian L M, et al. Scientific Reports, 2015, 5(10), 7779.4 Sun R J, Qiu P Y, Zhang C L, et al. CIESC Journal, 2014 (7), 2620 (in Chinese).孙容瑾, 邱培宇, 张春雷, 等.化工学报, 2014 (7), 2620.5 Binnemans K. Chemical Reviews, 2009, 109(9), 4283.6 Benelle C, Gatteschi D. Chemical Reviews, 2002, 102(6), 2369.7 Wu F. The luminescence dynamics in lanthanide doped upconversion core/shell nanoparticles. Doctoral thesis, Changchun Institute of Optics, Fine Mechanics and Physics Chinese Academy of Science, China, 2015 (in Chinese).吴飞. 核壳结构的纳米稀土上转换荧光材料发光动力学研究. 博士学位论文, 中国科学院研究生院(长春光学精密机械与物理研究所), 2015.8 Soukka T, Rantanen T, Kuningas K. Annals of the New York Academy of Sciences, 2008, 1130(1), 188.9 Dong H, Su L D, Yan C H. Chemical Society Reviews, 2015, 44(6), 1608.10 Stouwdam J W, Van Veggel F. Nano Letters, 2002, 2(7), 733.11 Yi G S, Chow G M. Journal of Materials Chemistry, 2005, 15(41), 4460.12 Yi G S, Chow G M. Advanced Functional Materials, 2006, 16(18), 2324.13 Mai H X, Zhang Y W, Si R, et al. Journal of the American Chemical Society, 2006, 128(19), 6426.14 Liu C, Wang H, Li X, et al. Journal of Materials Chemistry, 2009, 19(21), 3546.15 Wang F, Chatterjee D K, Li Z Q, et al. Nanotechnology, 2006, 17(23), 5786.16 Liu Y X, Pisarski W A, Zeng S J, et al. Optics Express, 2009, 17(11), 9089.17 Wang F, Banerjee D, Liu Y S, et al. Analyst, 2010, 135(8), 1839.18 Weissleder R. Nature Biotechnology, 2001, 19(4), 316.19 Chen G Y, Ohulchanskyy T Y, Liu S, et al. ACS Nano, 2012, 6(4), 2969.20 Ntziachristos V, Ripoll J, Wang L H V, et al. Nature Biotechnology, 2005, 23(3), 313.21 Feng A L, Lin M, Tian L M, et al. Rsc Advances, 2015, 5(94), 76825.22 Chen G Y, Qiu H L, Prasad P N, et al. Chemical Reviews, 2014, 114(10), 5161.23 Boyer J C, Van Veggel F. Nanoscale, 2010, 2(8), 1417.24 Kompe K, Borchert H, Storz J, et al. Angewandte Chemie-International Edition, 2003, 42(44), 5513.25 Yi G S, Chow G M. Chemistry of Materials, 2007, 19(3), 341.26 Chen M L, Ma Y, Li M Y. Materials Letters, 2014, 114, 80.27 Chen G Y, Agren H, Ohulchanskyy T Y, et al. Chemical Society Reviews, 2015, 44(6), 1680.28 Huang P, Zheng W, Zhou S, et al. Angewandte Chemie-International Edition, 2014, 53(5), 1252.29 Li Z, Zhang Y, Shuter B, et al. Langmuir, 2009, 25(20), 12015.30 Yu S X, Wang Z Q, Cao R J, et al. Journal of Fluorine Chemistry, 2017, 200, 77.31 Peng Y Q, Li Z H, Liu Z E, et al. Scientia Sinica(Chimica) , 2015,45(11), 1159 (in Chinese).彭叶青, 李志豪, 刘子恩, 等.中国科学:化学, 2015, 45(11), 1159.32 Cheng L, Yang K, Li Y G, et al.Angewandte Chemie-International Edition, 2011, 50(32), 7385.33 Du Y P, Sun X, Zhang Y W, et al. Crystal Growth & Design, 2009, 9(4), 2013.34 Schafer H, Ptacek P, Zerzouf O, et al. Advanced Functional Materials, 2008, 18(19), 2913.35 Yi G S, Peng Y F, Gao Z Q. Chemistry of Materials, 2011, 23(11), 2729.36 Ouyang J, Yin D G, Cao X Z, et al. Dalton Transactions, 2014, 43(37), 14001.37 Stecher J T, Rohlfing A B, Therine M J. Nanomaterials, 2014, 4(1), 69.38 Wong H T, Vetrone F, Naccache R, et al. Journal of Materials Chemistry, 2011, 21(41), 16589.39 Zhang F, Chen R C, Li X M, et al. Nano Letters, 2012, 12(6), 2852.40 Wang Y F, Sun L D, Xiao J W, et al. Chemistry-A European Journal, 2012, 18(18), 5558.41 Ghosh P, Oliva J, De La Rose E, et al. Journal of Physical Chemistry C, 2008, 112(26), 9650.42 Guo H, Li Z Q, Qian H S, et al. Nanotechnology, 2010, 21(12), 6.43 Chen F, Zhang S J, Bu W B, et al. Chemistry-A European Journal, 2012, 18(23), 7082.44 Wang C, Xu L G, Xu J T, et al. Dalton Transactions, 2017, 46(36), 12147.45 Qiu H L, Yang C H, Shao W, et al. Nanomaterials, 2014, 4(1), 55.46 Qiao X F, Zhou J C, Xiao J W, et al. Nanoscale, 2012, 4(15), 4611.47 Song L Z, Zhao N, Xu F J. Advanced Functional Materials, 2017, 27(32), 10.48 Robinson J T, Hong G S, Liang Y Y, et al. Journal of the American Chemical Society, 2012, 134(25), 10664.49 Fukumura D A I, Duda D G, Munn L L, et al. Microcirculation, 2010, 17(3), 206.50 Chen G Y, Shen J, Ohulchanskyy T Y, et al. ACS Nano, 2012, 6(9), 8280.51 Zhong Y T, Tian G, Gu Z J, et al. Advanced Materials, 2014, 26(18), 2831.52 Shankar L K, Menkens A, Sullivan D C. Molecular Imaging in Oncology, Humana Press, US, 2008.53 Xia A, Gao Y, Zhou J, et al. Biomaterials, 2011, 32(29), 7200.54 Zhu X J, Zhou J, Chen M, et al. Biomaterials, 2012, 33(18), 4618.55 Sun Y, Zhu X J, Peng J J, et al. ACS Nano, 2013, 7(12), 11290.56 Zhang F, Braun G B, Pallaoro A, et al. Nano Letters, 2012, 12(1), 61.57 Kang X J, Cheng Z Y, Li C X, et al. Journal of Physical Chemistry C, 2011, 115(32), 15801.58 Cheng L, Yang K, Li Y G, et al. Biomaterials, 2012, 33(7), 2215.59 Dong B A, Xu S, Sun J A, et al. Journal of Materials Chemistry, 2011, 21(17), 6193.60 Kalka K, Merk H, Mukhtar H. Journal of the American Academy of Dermatology, 2000, 42(3), 389.61 Brown S B, Brown E A, Walker I. Lancet Oncology, 2004, 5(8), 497.62 Konan Y N, Gurny R, All Mann E. Journal of Photochemistry & Photo-biology, B: Biology, 2002, 66(2), 89.63 Wang C, Tao H Q, Cheng L, et al. Biomaterials, 2011, 32(26), 6145.64 Idris N M, Gnanasammandhan M K, Zhang J, et al. Nature Medicine, 2012, 18(10), 1580.