Recent Advance of Biological Molecular Imaging Based on Lanthanide-Doped Upconversion-Luminescent Nanomaterials
"> Graphical abstract
"> Figure 1
<p>The structure and optical properties of upconversion nanoparticles (UCNPs): (<b>a</b>) Scheme illustration of the structure and components of the UCNPs; (<b>b</b>–<b>e</b>) Upconversion multicolor tuning in Ln<sup>3+</sup>-doped cubic NaYF<sub>4</sub> UCNPs. Room temperature UCNP emission spectra of (<b>b</b>) NaYF<sub>4</sub>:Yb/Er (18/2 mol%), (<b>c</b>) NaYF<sub>4</sub>:Yb/Tm (20/0.2 mol%), (<b>d</b>) NaYF<sub>4</sub>:Yb/Er (25–60/2 mol%), and (<b>e</b>) NaYF<sub>4</sub>:Yb/Tm/Er (20/0.2/0.2–1.5 mol%) particles in ethanol solutions (10 mM). The spectra in (<b>d</b>) and (<b>e</b>) were normalized to Er<sup>3+</sup> 660 nm and Tm<sup>3+</sup> 480 nm emissions, respectively; (<b>f</b>) The proposed energy transfer mechanisms showing the upconversion processes in Er<sup>3+</sup>, Tm<sup>3+</sup>, and Yb<sup>3+</sup> doped crystals under 980 nm diode laser excitation. The dashed-dotted, dashed, dotted and full arrows represent photon excitation, energy transfer, multiphoton relaxation, and emission processes, respectively. Only visible and NIR emissions are shown here. (<b>g</b>) Upconversion multicolor fine-tuning through the use of lanthanide-doped NaYF<sub>4</sub> nanoparticles with varied dopant ratios. Adapted with permission from references [<a href="#B33-nanomaterials-04-00129" class="html-bibr">33</a>,<a href="#B34-nanomaterials-04-00129" class="html-bibr">34</a>,<a href="#B35-nanomaterials-04-00129" class="html-bibr">35</a>] and [<a href="#B39-nanomaterials-04-00129" class="html-bibr">39</a>], respectively. NIR, near-infrared. Copyright: American Chemical Society, 2008; Royal Society of Chemistry, 2009; and John Wiley and Sons, 2013.</p> "> Figure 2
<p>Surface functionalization of UCNPs and their functional groups for biological applications. Adapted with permission and modified from references [<a href="#B27-nanomaterials-04-00129" class="html-bibr">27</a>,<a href="#B28-nanomaterials-04-00129" class="html-bibr">28</a>,<a href="#B29-nanomaterials-04-00129" class="html-bibr">29</a>,<a href="#B30-nanomaterials-04-00129" class="html-bibr">30</a>,<a href="#B31-nanomaterials-04-00129" class="html-bibr">31</a>]. Copyright: Royal Society of Chemistry, 2013.</p> "> Figure 3
<p><span class="html-italic">In vivo</span> imaging of living rats with quantum dots (QDs) injected into the translucent skin of the foot (<b>a</b>) showing fluorescence, but not through thicker skin of the back (<b>b</b>) or abdomen (<b>c</b>), NaYF<sub>4</sub>:Yb/Er nanoparticles injected below the abdominal skin (<b>d</b>), thigh muscles (<b>e</b>) or below the skin of the back (<b>f</b>) show luminescence. QDs on a black disk in (<b>a</b>,<b>b</b>) are used as the control. Adapted with permission from reference [<a href="#B83-nanomaterials-04-00129" class="html-bibr">83</a>]. Copyright: Elsevier, 2008.</p> "> Figure 4
<p><span class="html-italic">In vivo</span> imaging of a mouse with the injection of UCNPs: intact mouse (<b>left</b>); the same mouse after dissection (<b>right</b>). The red color indicates emission from UCNPs; green and black show the background, as indicated by the arrows. The inset presents the photoluminescence spectra corresponding to the spectrally unmixed components of the multispectral image obtained with the Maestro system. Adapted with permission from reference [<a href="#B78-nanomaterials-04-00129" class="html-bibr">78</a>]. Copyright: American Chemical Society, 2008.</p> "> Figure 5
<p>UCNPs for cellular labeling and <span class="html-italic">in vivo</span> tracking analysis. (<b>a</b>) Confocal UCNP imaging (<b>left</b>) and its overlay with a bright field image (<b>right</b>) of cells stained with 200 μg mL<sup>−1</sup> NaLuF<sub>4</sub> UCNPs for 3 h at 37 °C. (<b>b</b>) <span class="html-italic">In vivo</span> UCNPs imaging of athymic nude mice after subcutaneous injection of 50 human nasopharyngeal epidermal carcinoma KB cells (<b>left</b>) and tail-vein injection of 1000 KB cells (<b>right</b>). The KB cells were pre-incubated with 200μg mL<sup>−1</sup> NaLuF4 UCNPs for 3 h at 37 °C before injection. (<b>c</b> and <b>d</b>) <span class="html-italic">In vivo</span> detection of UCNP-labeled mMSCs (an exogenous contast agent to track mouse Mesenchymal Stem Cells). (<b>c</b>) An upconversion luminescence image of a mouse subcutaneously injected with various numbers of mouse mesenchymal stem cells (1 × 10<sup>5</sup>) labeled with UCNPs. (<b>d</b>) Quantification of UCNPs luminescence signals in (<b>c</b>). Adapted with permission from references [<a href="#B87-nanomaterials-04-00129" class="html-bibr">87</a>,<a href="#B89-nanomaterials-04-00129" class="html-bibr">89</a>], respectively. UCL, upconversion luminescence. Copyright: American Chemical Society, 2011; and Elsevier, 2012.</p> "> Figure 6
<p>(<b>a</b>) Scheme of the synthesis of UCNP-Arginine-Glycine-Asparatic (RGD). (<b>b</b>) Time-dependent <span class="html-italic">in vivo</span> upconversion luminescence imaging of subcutaneous U87 MG (left hind leg, indicated by short arrows) and MCF-7 (Michigan Cancer Foundation-7) tumor (right hind leg, indicated by long arrows) borne by athymic nude mice after intravenous injection of UCNP-RGD over a 24 h period. UCNP-RGD conjugate was prepared from UCNP-OA complex (OA: Oleylamine). All images were acquired under the same instrumental conditions (power ≈ 80 mW cm<sup>-2</sup> and temperature ≈ 21.5 °C on the surface of the mouse). Adapted with permission from reference [<a href="#B92-nanomaterials-04-00129" class="html-bibr">92</a>]. Copyright: American Chemical Society, 2009.</p> "> Figure 7
<p>The design for photo-controlled Dox delivery through mesoporous silica coated UCNPs conjugated with folic acid. Adapted with permission from reference [<a href="#B73-nanomaterials-04-00129" class="html-bibr">73</a>]. Copyright: John Wiley and Sons, 2013.</p> "> Figure 8
<p>Bioluminescent images of firefly luciferase (fLuc) activity in living mice that were treated with D-luciferin. (<b>a</b>) Experimental design for uncaging D-luciferin and subsequent bioluminescence through the use of photo-caged core-shell upconversion nanoparticles. (<b>b</b>) <b>Left</b>: injection with D-luciferin (20 μM, 20 μL); <b>right</b>: injection with photo-caged nanoparticles without NIR light irradiation. (<b>c</b>) <b>Left</b>: injection with photo-caged nanoparticles and irradiation with UV light for 10 min; <b>right</b>: injection with photo-caged nanoparticles and irradiation with NIR light for 1 h. Adapted with permission from reference [<a href="#B62-nanomaterials-04-00129" class="html-bibr">62</a>]. Copyright: John Wiley and Sons, 2012.</p> "> Figure 9
<p>Live-cell apoptosis imaging for NIR irradiation of Pt(IV)-probe UCNPs@SiO<sub>2</sub> (15 µM) incubated cells: (<b>a</b>) schematic illustration of NIR light activation of platinum(IV) prodrug and intracellular apoptosis imaging through upconversion nanoparticles; (<b>b</b>) A2780 cells; and (<b>c</b>) cisplatin resistant A2780cis cells. (blue: DAPI (4,6-Diamidino-2-phenylindole); green: Annexin V; red: Cy5.) Quantitative flow cytometric analysis of (<b>d</b>) A2780 and (<b>e</b>) A2780cis cells treated with different concentrations of Pt(IV)-probe UCNPs@SiO<sub>2</sub> (10, 15 and 20 µM, respectively) and 1 h NIR irradiation. Cells treated with Ac-DEVD (Aspartic acid-Glutamic acid-Valine-Aspartic acid)-CHO (20 µM) inhibitor and NIR irradiation of cells without Pt(IV)-probe UCNP incubation were used as controls. Adapted with permission from reference [<a href="#B102-nanomaterials-04-00129" class="html-bibr">102</a>]. Copyright: John Wiley and Sons, 2013.</p> "> Figure 10
<p><span class="html-italic">In vivo</span> Single Photon Emission Tomography (SPECT)/Optical imaging study after intravenous injection of <sup>153</sup>Sm-UCNPs. (<b>a</b>) Whole-body three-dimensional projection, (<b>b</b>) coronal, (<b>c</b>) sagittal and (<b>d</b>) transversal images acquired at 1 h and (<b>e</b>) whole-body three-dimensional projection images acquired at 24 h are shown respectively. The arrows in the inset point to the liver (L) and spleen (S). (<b>f</b>) <span class="html-italic">In vivo</span> upconversion luminescence imaging of the Kunming mouse 1 h after tail vein injection of the <sup>153</sup>Sm-UCNPs (20 mg/kg). Adapted with permission from reference [<a href="#B105-nanomaterials-04-00129" class="html-bibr">105</a>]. Copyright: Elsevier, 2013.</p> "> Figure 11
<p>(<b>I</b>) A whole-body imaging of UCNPs@SiO<sub>2</sub>-GdDTPA (Diethylenetriaminepentaacetic Acid) for 10 min. (<b>I-A</b>) <span class="html-italic">In vivo</span> imaging of the sacrificed nude mouse after injection with UCNPs@SiO<sub>2</sub>-GdDTPA for 10 min. (<b>I-B</b>) <span class="html-italic">Ex vivo</span> imaging of nude mouse. (<b>I-C</b>) <span class="html-italic">Ex vivo</span> imaging of viscera. All images were acquired under the same instrumental conditions, and the power density of the 980 nm laser is 150 mW cm<sup>−2</sup>. (<b>II</b>) The application of <span class="html-italic">in vivo</span> CT imaging in Kunming mice. (<b>II-A</b>, <b>B</b> and <b>C</b>) serials coronal CT images of Kunming mouse at different layer after injection with UCNPs@SiO<sub>2</sub>-GdDTPA. (<b>II-E</b>, <b>F</b> and <b>G</b>) partial enlarged CT view of abdomen. (<b>III</b>) The application of <span class="html-italic">in vivo</span> MRI imaging of the Kunming mice. (<b>III-A</b>) T<sub>1</sub>-weighted MR images of liver after injection with UCNPs@SiO<sub>2</sub>-GdDTPA for 0, 30 and 120 min (<b>III-B</b>) T<sub>1</sub> distribution images of liver after injection with UCNPs@SiO<sub>2</sub>-GdDTPA for 0, 30 and 120 min. (<b>III-C</b>) Local colorized T<sub>1</sub>-weighted MR images of liver after injection with UCNPs@SiO<sub>2</sub>-GdDTPA for 0, 30 and 120 min. (<b>III-D</b>) T<sub>1</sub>-weighted MR images of spleen after injection with UCNPs@SiO<sub>2</sub>-GdDTPA for 0, 30 and 120 min. (<b>III-E</b>) T<sub>1</sub> distribution images of spleen after injection with UCNPs<b>@</b>SiO<sub>2</sub>-GdDTPA for 0, 30 and 120 min. (<b>III-F</b>) Local colorized T<sub>1</sub>-weighted MR images of spleen after injection with UCNPs@SiO<sub>2</sub>-GdDTPA for 0, 30 and 120 min. Adapted with permission from reference [<a href="#B85-nanomaterials-04-00129" class="html-bibr">85</a>]. Copyright: Elsevier, 2012.</p> "> Figure 12
<p>Absorption of water in the NIR and the integration scheme of the Nd<sup>3+</sup>→Yb<sup>3+</sup> energy transfer (ET) process by introducing the Nd<sup>3+</sup>/Yb<sup>3+</sup> co-doped shell. The resulting Nd<sup>3+</sup>→Yb<sup>3+</sup>→activator ET could extend the effective excitation bands for conventional Yb<sup>3+</sup>-sensitized UCNPs. Featuring lower water absorptions, these alternative excitation bands are expected to minimize the tissue overheating effect caused by NIR laser exposure (the blue line represents the absorption spectrum of water). Adapted with permission from reference [<a href="#B113-nanomaterials-04-00129" class="html-bibr">113</a>]. Copyright: American Chemical Society, 2013.</p> "> Figure 13
<p><span class="html-italic">In vitro</span> and <span class="html-italic">in vivo</span> heating effect induced by laser irradiation. (<b>a</b>,<b>b</b>) HEK (Human Embryonic Kidney) 293T cells after 5 min irradiation of 980 nm (<b>a</b>) and a 808 nm laser (<b>b</b>). Living cells and dead cells were stained with calcein AM (Acetomethoxy) and propidium iodide, respectively. (<b>c</b>,<b>d</b>) Infrared thermal image of a nude mouse during continuous (<b>c</b>) 980 nm laser irradiation for 50 s and (<b>d</b>) 808 nm laser irradiation for 300 s. Irradiation spots are denoted with the white arrows. Adapted with permission from reference [<a href="#B113-nanomaterials-04-00129" class="html-bibr">113</a>]. Copyright: American Chemical Society, 2013.</p> ">
Abstract
:1. Introduction
2. Synthesis, Surface Functionalization and Biocompatibility of Lanthanide UCNPs
3. Lanthanide UCNPs for Optical Imaging
4. Doped Lanthanide UCNPs for Multimodality Imaging
5. Summary and Perspectives
Acknowledgments
Conflicts of Interest
References
- Achilefu, S. Introduction to concepts and strategies for molecular imaging. Chem. Rev. 2010, 110, 2575–2578. [Google Scholar] [CrossRef]
- He, X.; Gao, J.; Gambhir, S.S.; Cheng, Z. Near-infrared fluorescent nanoprobes for cancer molecular imaging: Status and challenges. Trends Mol. Med. 2010, 12, 574–583. [Google Scholar]
- Hildebrandt, I.J.; Gambhir, S.S. Molecular imaging applications for immunology. Clin. Immunol. 2004, 2, 210–224. [Google Scholar] [CrossRef]
- Weissleder, R.; Pittet, M.J. Imaging in the era of molecular oncology. Nature 2008, 452, 580–589. [Google Scholar] [CrossRef]
- Jiang, T.T.; Xing, B.G; Rao, J.H. Recent development of biological reporter technology for detecting gene expression. Biotech. Genet. Eng. Rev. 2008, 25, 41–75. [Google Scholar] [CrossRef]
- Massoud, T.F.; Gambhir, S.S. Molecular imaging in living subjects: Seeing fundamental biological processes in a new light. Genes Dev. 2003, 17, 545–580. [Google Scholar] [CrossRef]
- Willmann, J.K.; van Bruggen, N.; Dinkelborg, L.M.; Gambhir, S.S. Molecular imaging in drug development. Nat. Rev. Drug Discov. 2008, 7, 591–607. [Google Scholar] [CrossRef]
- Mullard, A. Molecular imaging as a de-risking tool: Coming into focus? Nat. Rev. Drug Discov. 2013, 12, 251–252. [Google Scholar] [CrossRef]
- Hastings, J.W. Chemistries and colors of bioluminescent reactions: A review. Gene 1996, 173, 5–11. [Google Scholar] [CrossRef]
- Leoning, A.M.; Wu, A.M.; Gambhir, S.S. Red-shifted Renilla reniformis luciferase variants for imaging in living subjects. Nat. Methods 2007, 4, 641–643. [Google Scholar] [CrossRef]
- Contag, C.H.; Bachmann, M.H. Advances in in vivo bioluminescence imaging of gene expression. Annu. Rev. Biomed. Eng. 2002, 4, 235–260. [Google Scholar] [CrossRef]
- Ray, P.; Gambhir, S.S. Noninvasive imaging of molecular events with bioluminescent reporter genes in living subjects. Methods Mol. Biol. 2007, 411, 131–144. [Google Scholar] [CrossRef]
- Wehrman, T.S.; von Degenfeld, G.; Krutzik, P.O.; Nolan, G.P.; Blau, H.M. Luminescent imaging of beta-galactosidase activity in living subjects using sequential reporter-enzyme luminescence. Nature methods 2006, 3, 295–301. [Google Scholar] [CrossRef]
- Tung, C.H.; Zeng, Q.; Shah, K.; Kim, D.E.; Schellingerhout, D.; Weissleder, R. In vivo imaging of beta-galactosidase activity using far red fluorescent switch. Cancer Res. 2004, 6, 1579–1583. [Google Scholar]
- Shah, K.; Tung, C.H.; Breakefield, X.O.; Weissleder, R. In vivo imaging of S-TRAIL-mediated tumor regression and apoptosis. Mol. Ther. 2005, 11, 926–931. [Google Scholar] [CrossRef]
- Zhou, W.; Valley, M.P.; Shultz, J.; Hawkins, E.M.; Bernad, L.; Good, T.; Good, D.; Riss, T.L.; Klaubert, D.H.; Wood, K.V. New bioluminogenic substrates for monoamine oxidase assays. J. Am. Chem. Soc. 2006, 128, 3122–3123. [Google Scholar] [CrossRef]
- Rao, J.; Dragulescu-Andrasi, A.; Yao, H. Fluorescent imaging in vivo: Recent advances. Curr. Opin. Biotech. 2007, 18, 17–25. [Google Scholar] [CrossRef]
- Licha, K.; Olbrich, C. Optical imaging in drug discovery and diagnostic applications. Adv. Drug Deliv. Rev. 2005, 57, 1087–1108. [Google Scholar]
- Stefflova, K.; Chen, J.; Zheng, G. Using molecular beacons for cancer imaging and treatment. Front Biosci. 2007, 12, 4709–4721. [Google Scholar] [CrossRef]
- Escobedo, J.O.; Rusin, O.; Lim, S.; Strongin, R.M. NIR dyes for bioimaging applications. Curr. Opin. Chem. Biol. 2010, 184, 64–71. [Google Scholar]
- Shao, Q.; Yang, Y.M.; Xing, B.G. Chemistry of Optical Imaging Probes. In Molecular Imaging Probes for Cancer Research; World Science: British Columbia, Canada, 2010. [Google Scholar]
- Rothman, D.M.; Shults, M.D.; Imperiali, B. Chemical approaches for investigating phosphorylation in signal transduction networks. Trends Cell Biol. 2005, 15, 502–510. [Google Scholar] [CrossRef]
- Lawrence, D.S. The preparation and in vivo applications of caged peptides and proteins. Curr. Opin. Chem. Biol. 2005, 9, 570–575. [Google Scholar] [CrossRef]
- Erathodiyil, N.; Ying, J.Y. Functionalization of inorganic nanoparticles for bioimaging applications. Acc. Chem. Res. 2011, 44, 925–935. [Google Scholar] [CrossRef]
- Gao, J.H.; Chen, X.Y.; Cheng, Z. Near-infrared quantum dots as optical probes for tumor imaging. Curr. Top. Med. Chem. 2010, 10, 1147–1157. [Google Scholar] [CrossRef]
- Cai, W.B.; Chen, X.Y. Nanoplatforms for targeted molecular imaging in living subjects. Small 2007, 3, 1840–1854. [Google Scholar] [CrossRef]
- Biju, V. Chemical modifications and bioconjugate reactions of nanomaterials for sensing, imaging, drug delivery and therapy. Chem. Soc. Rev. 2014, 43, 744–764. [Google Scholar] [CrossRef]
- Michalet, X.; Pinaud, F.F.; Bentolila, L.A.; Tsay, J.M.; Doose, S.; Li, J.; Sundaresan, G.; Wu, A.; Gambhir, S.S.; Weiss, S. Quantum dots for live cells, in vivo imaging, and diagnostics. Science 2005, 307, 538–544. [Google Scholar]
- Probst, C.E.; Zrazhevskiy, P.; Bagalkot, V.; Gao, X.H. Quantum dots as a platform for nanoparticle drug delivery vehicle design. Adv. Drug Deliv. Rev. 2013, 65, 703–718. [Google Scholar] [CrossRef]
- Biju, V.; Itoh, T.; Ishikawa, M. Delivering quantum dots to cells: Bioconjugated quantum dots for targeted and nonspecific extracellular and intracellular imaging. Chem. Soc. Rev. 2010, 39, 3031–3056. [Google Scholar] [CrossRef]
- Chi, X.; Huang, D.; Zhao, Z.; Zhou, Z.; Yin, Z.; Gao, J. Nanoprobes for in vitro diagnostics of cancer and infectious diseases. Biomaterials 2012, 33, 189–206. [Google Scholar] [CrossRef]
- Jayakumar, M.K.; Idris, N.M.; Zhang, Y. Remote activation of biomolecules in deep tissues using near-infrared-to-UV upconversion nanotransducers. Proc. Natl. Acad. Sci. USA 2012, 109, 8483–8488. [Google Scholar] [CrossRef]
- Wang, F.; Liu, X. Upconversion multicolor fine-tuning: Visible to near-infrared emission from lanthanide-doped NaYF4 nanoparticles. J. Am. Chem. Soc. 2008, 130, 5642–5643. [Google Scholar]
- Wang, F.; Liu, X. Recent advances in the chemistry of lanthanide-doped upconversion nanocrystals. Chem. Soc. Rev. 2009, 38, 976–989. [Google Scholar] [CrossRef]
- Haase, H.; Schafer, H. Upconverting nanoparticles. Angew. Chem. Int. Ed. 2011, 50, 5808–5829. [Google Scholar] [CrossRef]
- Mader, H.S.; Kele, P.; Saleh, S.M.; Wolfbeis, O.S. Upconverting luminescent nanoparticles for use in bioconjugation and bioimaging. Curr. Opin. Chem. Biol. 2010, 14, 582–596. [Google Scholar] [CrossRef]
- Feng, W.; Sun, L.D.; Zhang, Y.W.; Yan, C.H. Synthesis and assembly of rare earth nanostructures directed by the principle of coordination chemistry in solution-based process. Coordin. Chem. Rev. 2010, 254, 1038–1053. [Google Scholar] [CrossRef]
- Cheng, L.; Wang, C.; Liu, Z. Upconversion nanoparticles and their composite nanostructures for biomedical imaging and cancer therapy. Nanoscale 2013, 5, 23–37. [Google Scholar] [CrossRef]
- Gu, Z.; Yan, L.; Tian, G.; Li, S.; Chai, Z.; Zhao, Y. Recent advances in design and fabrication of upconversion nanoparticles and their safe theranostic applications. Adv. Mater. 2013, 25, 3758–3779. [Google Scholar] [CrossRef]
- Liu, Y.; Tu, D.; Zhu, H.; Chen, X. Lanthanide-doped luminescent nanoprobes: Controlled synthesis, optical spectroscopy, and bioapplications. Chem. Soc. Rev. 2013, 42, 6924–6958. [Google Scholar] [CrossRef]
- Wang, F.; Banerjee, D.; Liu, Y.; Chen, X.; Liu, X. Upconversion nanoparticles in biological labeling, imaging, and therapy. Analyst 2010, 135, 1839–1854. [Google Scholar] [CrossRef]
- Cheng, L.; Yang, K.; Li, Y.; Chen, J.; Wang, C.; Shao, M.; Lee, S.T.; Liu, Z. Facile preparation of multifunctional upconversion nanoprobes for multimodal imaging and dual-targeted photothermal therapy. Angew. Chem. Int. Ed. 2011, 50, 7385–7390. [Google Scholar]
- Zhou, J.; Liu, Z.; Li, F. Upconversion nanophosphors for small-animal imaging. Chem. Soc. Rev. 2012, 41, 1323–1349. [Google Scholar] [CrossRef]
- Yi, G.S.; Chow, G.M. Synthesis of hexagonal-phase NaYF4:Yb,Er and NaYF4:Yb,Tm nanocrystals with efficient up-conversion fluorescence. Adv. Funct. Mater. 2006, 16, 2324–2329. [Google Scholar] [CrossRef]
- Wang, F.; Han, Y.; Lim, C.S.; Lu, Y.; Wang, J.; Xu, J.; Chen, H.; Zhang, C.; Hong, M.; Liu, X. Simultaneous phase and size control of upconversion nanocrystals through lanthanide doping. Nature 2010, 463, 1061–1065. [Google Scholar] [CrossRef]
- Mai, H.X.; Zhang, Y.W.; Si, R.; Yan, Z.G.; Sun, L.D.; You, L.P.; Yan, C.H. High-quality sodium rare-earth fluoride nanocrystals: Controlled synthesis and optical properties. J. Am. Chem. Soc. 2006, 128, 6426–6436. [Google Scholar]
- Zhang, Y.W.; Sun, X.; Si, R.; You, L.P.; Yan, C.H. Single-crystalline and monodisperse LaF3 triangular nanoplates from a single-source precursor. J. Am. Chem. Soc. 2005, 127, 3260–3261. [Google Scholar]
- Mai, H.X.; Zhang, Y.W.; Sun, L.D.; Yan, C.H. Highly efficient multicolor up-conversion emissions and their mechanisms of monodisperse NaYF4:Yb,Er core and core/shell-structured nanocrystals. J. Phys. Chem. C 2007, 111, 13721–13729. [Google Scholar] [CrossRef]
- Mai, H.X.; Zhang, Y.W.; Sun, L.D.; Yan, C.R. Size- and phase-controlled synthesis of monodisperse NaYF4:Yb,Er nanocrystals from a unique delayed nucleation pathway monitored with upconversion spectroscopy. J. Phys. Chem. C 2007, 111, 13730–13739. [Google Scholar]
- Wang, X.; Zhuang, J.; Peng, Q.; Li, Y. A general strategy for nanocrystal synthesis. Nature 2005, 437, 121–124. [Google Scholar] [CrossRef]
- Wang, L.; Li, P.; Zhuang, J.; Bai, F.; Feng, J.; Yan, X.; Li, Y. Carboxylic acid enriched nanospheres of semiconductor nanorods for cell imaging. Angew. Chem. Int. Ed. 2008, 47, 1054–1057. [Google Scholar]
- Wang, M.; Liu, J.L.; Zhang, Y.X.; Hou, W.; Wu, X.L.; Xu, S.K. Two-phase solvothermal synthesis of rare-earth doped NaYF4 upconversion fluorescent nanocrystals. Mater. Lett. 2009, 63, 325–327. [Google Scholar] [CrossRef]
- Sun, Y.J.; Chen, Y.; Tian, L.J.; Yu, Y.; Kong, X.G.; Zhao, J.W.; Zhang, H. Controlled synthesis and morphology dependent upconversion luminescence of NaYF4:Yb,Er nanocrystals. Nanotechnology 2007, 18, 275609–275617. [Google Scholar] [CrossRef]
- Tian, G.; Gu, Z.J.; Zhou, L.J.; Yin, W.Y.; Liu, X.X.; Yan, L.; Jin, S.; Ren, W.L.; Xing, G.M.; Li, S.J.; et al. Mn2+ Dopant-controlled synthesis of NaYF4:Yb/Er upconversion nanoparticles for in vivo imaging and drug delivery. Adv. Mater. 2012, 24, 1226–1231. [Google Scholar] [CrossRef]
- Stouwdam, J.W.; van Veggel, F.C.J.M. Near-infrared emission of redispersible Er3+, Nd3+, and Ho3+ doped LaF3 nanoparticles. Nano. Lett. 2002, 2, 733–737. [Google Scholar] [CrossRef]
- Patra, A.; Friend, C.S.; Kapoor, R.; Prasad, P.N. Upconversion in Er3+:ZrO2 nanocrystals. J. Phys. Chem. B 2002, 106, 1909–1912. [Google Scholar]
- Vetrone, F.; Boyer, J.C.; Capobianco, J.A.; Speghini, A.; Bettinelli, M. Significance of Yb3+ concentration on the upconversion mechanisms in codoped Y2O3:Er3+, Yb3+ nanocrystals. J. Appl. Phys. 2004, 96, 661–667. [Google Scholar] [CrossRef]
- Xu, L.L.; Yu, Y.N.; Li, X.G.; Somesfalean, G.; Zhang, Y.G.; Gao, H.; Zhang, Z.G. Synthesis and upconversion properties of monoclinic Gd2O3:Er3+ nanocrystals. Opt. Mater. 2008, 30, 1284–1288. [Google Scholar] [CrossRef]
- Kong, W.J.; Shan, J.; Ju, Y.G. Flame synthesis and effects of host materials on Yb3+/Er3+ co-doped upconversion nanophosphors. Mater. Lett. 2010, 64, 688–691. [Google Scholar] [CrossRef]
- Qin, X.; Yokomori, T.; Ju, Y.G. Flame synthesis and characterization of rare-earth (Er3+, Ho3+, and Tm3+) doped upconversion nanophosphors. Appl. Phys. Lett. 2007, 90, 073104. [Google Scholar] [CrossRef]
- Ma, P.; Xiao, H.; Li, X.; Li, C.; Dai, Y.; Cheng, Z.; Jing, X.; Lin, J. Rational design of multifunctional upconversion nanocrystals/polymer nanocomposites for cisplatin(IV) delivery and biomedical imaging. Adv. Mater. 2013, 25, 4898–4905. [Google Scholar] [CrossRef]
- Yang, Y.; Shao, Q.; Deng, R.; Wang, C.; Teng, X.; Cheng, K.; Cheng, Z.; Huang, L.; Liu, Z.; Liu, X.; et al. In vitro and in vivo uncaging and bioluminescence imaging by using photocaged upconversion nanoparticles. Angew. Chem. Int. Ed. 2012, 51, 3125–3129. [Google Scholar] [CrossRef]
- Liu, J.N.; Bu, W.; Pan, L.M.; Zhang, S.; Chen, F.; Zhou, L.; Zhao, K.L.; Peng, W.; Shi, J. Simultaneous nuclear imaging and intranuclear drug delivery by nuclear-targeted multifunctional upconversion nanoprobes. Biomaterials 2012, 33, 7282–7290. [Google Scholar] [CrossRef]
- Xiong, L.; Yang, T.; Yang, Y.; Xu, C.; Li, F. Long-term in vivo biodistribution imaging and toxicity of polyacrylic acid-coated upconversion nanophosphors. Biomaterials 2010, 31, 7078–7085. [Google Scholar] [CrossRef]
- Rantanen, T.; Jarvenpaa, M.L.; Vuojola, J.; Kuningas, K.; Soukka, T. Fluorescence-quenching-based enzyme-activity assay by using photon upconversion. Angew. Chem. Int. Ed. 2008, 47, 3811–3813. [Google Scholar] [CrossRef]
- Naccache, R.; Vetrone, F.; Mahalingam, V.; Cuccia, L.A.; Capobianco, J.A. Controlled synthesis and water dispersibility of hexagonal phase NaGdF4:Ho3+/Yb3+ nanoparticles. Chem. Mater. 2009, 21, 717–723. [Google Scholar] [CrossRef]
- Bogdan, N.; Vetrone, F.; Ozin, G.A.; Capobianco, J.A. Synthesis of ligand-free colloidally stable water dispersible brightly luminescent lanthanide-doped upconverting nanoparticles. Nano. Lett. 2011, 11, 835–840. [Google Scholar] [CrossRef]
- Chen, J.; Guo, C.R.; Wang, M.; Huang, L.; Wang, L.P.; Mi, C.C.; Li, J.; Fang, X.X.; Mao, C.B.; et al. Controllable synthesis of NaYF4:Yb,Er upconversion nanophosphors and their application to in vivo imaging of Caenorhabditis elegans. J. Mater. Chem. 2011, 21, 2632–2638. [Google Scholar] [CrossRef]
- Zhou, H.P.; Xu, C.H.; Sun, W.; Yan, C.H. Clean and flexible modification strategy for carboxyl/aldehyde-functionalized upconversion nanoparticles and their optical applications. Adv. Funct. Mater. 2009, 19, 3892–3900. [Google Scholar] [CrossRef]
- Chen, Z.; Chen, H.; Hu, H.; Yu, M.; Li, F.; Zhang, Q.; Zhou, Z.; Yi, T.; Huang, C. Versatile synthesis strategy for carboxylic acid-functionalized upconverting nanophosphors as biological labels. J. Am. Chem. Soc. 2008, 130, 3023–3029. [Google Scholar]
- Wang, L.Y.; Yan, R.X.; Hao, Z.Y.; Wang, L.; Zeng, J.H.; Bao, J.; Wang, X.; Peng, Q.; Li, Y.D. Fluorescence resonant energy transfer biosensor based on upconversion-luminescent nanoparticles. Angew. Chem. Int. Edit. 2005, 44, 6054–6057. [Google Scholar]
- Bao, Y.; Luu, Q.A.N.; Lin, C.K.; Schloss, J.M.; May, P.S.; Jiang, C.Y. Layer-by-layer assembly of freestanding thin films with homogeneously distributed upconversion nanocrystals. J. Mater. Chem. 2010, 20, 8356–8361. [Google Scholar]
- Yang, Y.M.; Velmurugan, B.; Liu, X.; Xing, B. NIR photoresponsive crosslinked upconverting nanocarriers toward selective intracellular drug release. Small 2013, 9, 2937–2944. [Google Scholar] [CrossRef]
- Yang, Y.M.; Liu, F.; Liu, X.G.; Xing, B.G. NIR light controlled photorelease of siRNA and its targeted intracellular delivery based on upconversion nanoparticles. Nanoscale 2013, 5, 231–238. [Google Scholar] [CrossRef]
- Cao, T.; Yang, Y.; Gao, Y.; Zhou, J.; Li, Z.; Li, F. High-quality water-soluble and surface-functionalized upconversion nanocrystals as luminescent probes for bioimaging. Biomaterials 2011, 32, 2959–2968. [Google Scholar] [CrossRef]
- Nichkova, M.; Dosev, D.; Gee, S.J.; Hammock, B.D.; Kennedy, I.M. Microarray immunoassay for phenoxybenzoic acid using polymer encapsulated Eu:Gd2O3 nanoparticles as fluorescent labels. Anal. Chem. 2005, 77, 6864–6873. [Google Scholar] [CrossRef]
- Peer, D.; Karp, J.M.; Hong, S.; FaroKHzad, O.C.; Margalit, R.; Langer, R. Nanocarriers as an emerging platform for cancer therapy. Nat. Nanotechnol. 2007, 2, 751–760. [Google Scholar] [CrossRef]
- Nyk, M.; Kumar, R.; Ohulchanskyy, T.Y.; Bergey, E.J.; Prasad, P.N. High contrast in vitro and in vivo photoluminescence bioimaging using near infrared to near infrared up-conversion in Tm3+ and Yb3+ doped fluoride nanophosphors. Nano Lett. 2008, 8, 3834–3838. [Google Scholar] [CrossRef]
- Xing, H.Y.; Zheng, X.P.; Ren, Q.G.; Bu, W.B.; Ge, W.Q.; Xiao, Q.F.; Zhang, S.J.; Wei, C.Y.; Qu, H.Y.; Wang, Z.; et al. Computed tomography imaging-guided radiotherapy by targeting upconversion nanocubes with significant imaging and radiosensitization enhancements. Sci. Rep.-UK 2013, 3, 1–9. [Google Scholar]
- Lim, S.F.; Riehn, R.; Ryu, W.S.; Khanarian, N.; Tung, C.K.; Tank, D.; Austin, R.H. In vivo and scanning electron microscopy imaging of up-converting nanophosphors in Caenorhabditis elegans. Nano Lett. 2006, 6, 169–174. [Google Scholar] [CrossRef]
- Wang, K.; Ma, J.B.; He, M.; Gao, G.; Xu, H.; Sang, J.; Wang, Y.X.; Zhao, B.Q.; Cui, D.X. Toxicity assessments of near-infrared upconversion luminescent LaF3:Yb,Er in early development of zebrafish embryos. Theranostics 2013, 3, 258–266. [Google Scholar] [CrossRef]
- Mitsunaga, M.; Ogawa, M.; Kosaka, N.; Rosenblum, L.T.; Choyke, P.L.; Kobayashi, H. Cancer cell-selective in vivo near infrared photoimmunotherapy targeting specific membrane molecules. Nat. Med. 2011, 17, 1685–1691. [Google Scholar] [CrossRef]
- Chatterjee, D.K.; Rufaihah, A.J.; Zhang, Y. Upconversion fluorescence imaging of cells and small animals using lanthanide doped nanocrystals. Biomaterials 2008, 29, 937–943. [Google Scholar] [CrossRef]
- Zhou, J.; Sun, Y.; Du, X.; Xiong, L.; Hu, H.; Li, F. Dual-modality in vivo imaging using rare-earth nanocrystals with near-infrared to near-infrared (NIR-to-NIR) upconversion luminescence and magnetic resonance properties. Biomaterials 2010, 31, 3287–3295. [Google Scholar]
- Xia, A.; Chen, M.; Gao, Y.; Wu, D.; Feng, W.; Li, F. Gd3+ complex-modified NaLuF4-based upconversion nanophosphors for trimodality imaging of NIR-to-NIR upconversion luminescence, X-ray computed tomography and magnetic resonance. Biomaterials 2012, 33, 5394–5405. [Google Scholar] [CrossRef]
- Xing, H.; Bu, W.; Ren, Q.; Zheng, X.; Li, M.; Zhang, S.; Qu, H.; Wang, Z.; Hua, Y.; Zhao, K.; et al. A NaYbF4:Tm3+ nanoprobe for CT and NIR-to-NIR fluorescent bimodal imaging. Biomaterials 2012, 33, 5384–5393. [Google Scholar] [CrossRef]
- Liu, Q.; Sun, Y.; Yang, T.; Feng, W.; Li, C.; Li, F. Sub-10 nm hexagonal lanthanide-doped NaLuF4 upconversion nanocrystals for sensitive bioimaging in vivo. J. Am. Chem. Soc. 2011, 133, 17122–17125. [Google Scholar] [CrossRef]
- Yang, T.; Sun, Y.; Liu, Q.; Feng, W.; Yang, P.; Li, F. Cubic sub-20 nm NaLuF4-based upconversion nanophosphors for high-contrast bioimaging in different animal species. Biomaterials 2012, 33, 3733–3742. [Google Scholar] [CrossRef]
- Wang, C.; Cheng, L.; Xu, H.; Liu, Z. Towards whole-body imaging at the single cell level using ultra-sensitive stem cell labeling with oligo-arginine modified upconversion nanoparticles. Biomaterials 2012, 33, 4872–4881. [Google Scholar] [CrossRef]
- Chari, R.V. Targeted cancer therapy: Conferring specificity to cytotoxic drugs. Acc. Chem. Res. 2008, 41, 98–107. [Google Scholar] [CrossRef]
- Xiong, L.Q.; Chen, Z.G.; Yu, M.X.; Li, F.Y.; Liu, C.; Huang, C.H. Synthesis, characterization, and in vivo targeted imaging of amine-functionalized rare-earth up-converting nanophosphors. Biomaterials 2009, 30, 5592–5600. [Google Scholar] [CrossRef]
- Xiong, L.; Chen, Z.; Tian, Q.; Cao, T.; Xu, C.; Li, F. High contrast upconversion luminescence targeted imaging in vivo using peptide-labeled nanophosphors. Anal. Chem. 2009, 81, 8687–8694. [Google Scholar] [CrossRef]
- Danhier, F.; Le Breton, A.; Préat, V. RGD-based strategies to target alpha(v) beta(3) integrin in cancer therapy and diagnosis. Mol. Pharm. 2012, 9, 2961–2973. [Google Scholar] [CrossRef]
- Li, Y.; Jing, C.; Zhang, L.; Long, Y.T. Resonance scattering particles as biological nanosensors in vitro and in vivo. Chem. Soc. Rev. 2012, 41, 632–642. [Google Scholar] [CrossRef]
- Cai, W.; Chen, X. Anti-angiogenic cancer therapy based on integrin alphavbeta3 antagonism. Anticancer Agents Med. Chem. 2006, 6, 407–428. [Google Scholar] [CrossRef]
- Meyer, A.; Auernheimer, J.; Modlinger, A.; Kessler, H. Targeting RGD recognizing integrins: Drug development, biomaterial research, tumor imaging and targeting. Curr. Pharm. Des. 2006, 12, 2723–2747. [Google Scholar] [CrossRef]
- Yu, X.F.; Sun, Z.; Li, M.; Xiang, Y.; Wang, Q.Q.; Tang, F.; Wu, Y.; Cao, Z.; Li, W. Neurotoxin-conjugated upconversion nanoprobes for direct visualization of tumors under near-infrared irradiation. Biomaterials 2010, 31, 8724–8731. [Google Scholar]
- Shao, Q.; Xing, B. Photoactive molecules for applications in molecular imaging and cell biology. Chem. Soc. Rev. 2010, 39, 2835–2846. [Google Scholar]
- Mayer, G.; Heckel, A. Biologically active molecules with a “light switch”. Angew. Chem. Int. Ed. 2006, 45, 4900–4921. [Google Scholar]
- Lee, H.; Larson, D.R.; Lawrence, D.S. Illuminating the chemistry of life: Design, synthesis, and applications of “caged” and related photoresponsive compounds. ACS Chem. Biol. 2009, 4, 409–427. [Google Scholar] [CrossRef]
- Young, D.D.; Deiters, A. Photochemical control of biological processes. Org. Biomol. Chem. 2007, 5, 999–1005. [Google Scholar] [CrossRef]
- Min, Y.; Li, J.; Liu, F.; Yeow, E.K.; Xing, B. Near-infrared light-mediated photoactivation of a platinum antitumor prodrug and simultaneous cellular apoptosis imaging by upconversion-luminescent nanoparticles. Angew. Chem. Int. Ed. 2014, 53, 1012–1016. [Google Scholar] [CrossRef]
- Cheng, L.; Yang, K.; Li, Y.; Zeng, X.; Shao, M.; Lee, S.T.; Liu, Z. Multifunctional nanoparticles for upconversion luminescence/MR multimodal imaging and magnetically targeted photothermal therapy. Biomaterials 2012, 33, 2215–2222. [Google Scholar] [CrossRef]
- He, M.; Huang, P.; Zhang, C.; Hu, H.; Bao, C.; Gao, G.; He, R.; Cui, D. Dual phase-controlled synthesis of uniform lanthanide-doped NaGdF4 upconversion nanocrystals via an OA/ionic liquid two-phase system for in vivo dual-modality imaging. Adv. Funct. Mater. 2011, 21, 4470–4477. [Google Scholar] [CrossRef]
- Sun, Y.; Yu, M.; Liang, S.; Zhang, Y.; Li, C.; Mou, T.; Yang, W.; Zhang, X.; Li, B.; Huang, C.; et al. Fluorine-18 labeled rare-earth nanoparticles for positron emission tomography (PET) imaging of sentinel lymph node. Biomaterials 2011, 32, 2999–3007. [Google Scholar] [CrossRef]
- Yang, Y.; Sun, Y.; Cao, T.; Peng, J.; Liu, Y.; Wu, Y.; Feng, W.; Zhang, Y.; Li, F. Hydrothermal synthesis of NaLuF4:153Sm,Yb,Tm nanoparticles and their application in dual-modality upconversion luminescence and SPECT bioimaging. Biomaterials 2013, 34, 774–783. [Google Scholar] [CrossRef]
- Zhou, J.; Yu, M.; Sun, Y.; Zhang, X.; Zhu, X.; Wu, Z.; Wu, D.; Li, F. Fluorine-18-labeled Gd3+/Yb3+/Er3+ co-doped NaYF4 nanophosphors for multimodality PET/MR/UCL imaging. Biomaterials 2011, 32, 1148–1156. [Google Scholar] [CrossRef]
- Xing, H.; Bu, W.; Zhang, S.; Zheng, X.; Li, M.; Chen, F.; He, Q.; Zhou, L.; Peng, W.; Hua, Y.; et al. Multifunctional nanoprobes for upconversion fluorescence, MR and CT trimodal imaging. Biomaterials 2012, 33, 1079–1089. [Google Scholar] [CrossRef]
- Chen, G.; Ohulchanskyy, T.Y.; Kachynski, A.; Agren, H.; Prasad, P.N. Intense visible and near-infrared upconversion photoluminescence in colloidal LiYF4:Er3+ nanocrystals under excitation at 1490 nm. ACS Nano 2011, 5, 4981–4986. [Google Scholar]
- Idris, N.M.; Gnanasammandhan, M.K.; Zhang, J.; Ho, P.C.; Mahendran, R.; Zhang, Y. In vivo photodynamic therapy using upconversion nanoparticles as remote-controlled nanotransducers. Nat. Med. 2012, 18, 1580–1585. [Google Scholar] [CrossRef]
- Wang, C.; Tao, H.Q.; Cheng, L.; Liu, Z. Near-infrared light induced in vivo photodynamic therapy of cancer based on upconversion nanoparticles. Biomaterials 2011, 32, 6145–6154. [Google Scholar]
- Cui, S.; Yin, D.; Chen, Y.; Di, Y.; Chen, H.; Ma, Y.; Achilefu, S.; Gu, Y. In vivo targeted deep-tissue photodynamic therapy based on near-infrared light triggered upconversion nanoconstructure. ACS Nano 2013, 7, 676–688. [Google Scholar]
- Zhan, Q.; Qian, J.; Liang, H.; Somesfalean, G.; Wang, D.; He, S.; Zhang, Z.; Andersson-Engels, S. Using 915 nm laser excited Tm3+/Er3+/Ho3+ doped NaYbF4 upconversion nanoparticles for in vitro and deeper in vivo bioimaging without overheating irradiation. ACS Nano 2011, 5, 3744–3757. [Google Scholar]
- Wang, Y.F.; Liu, G.Y.; Sun, L.D.; Xiao, J.W.; Zhou, J.C.; Yan, C.H. Nd3+-sensitized upconversion nanophosphors: Efficient in vivo bioimaging probes with minimized heating effect. ACS Nano 2013, 7, 7200–7206. [Google Scholar]
- Zou, W.; Visser, C.; Maduro, J.A.; Pshenichnikov, M.S.; Hummelen, J.C. Broadband dye-sensitized upconversion of near-infrared light. Nat. Photon. 2012, 6, 560–564. [Google Scholar] [CrossRef]
- Shen, J.; Chen, G.; Vu, A.-M.; Fan, W.; Bilsel, O.S.; Chang, C.-C.; Han, G. Engineering the upconversion nanoparticle excitation wavelength: Cascade sensitization of tri-doped upconversion colloidal nanoparticles at 800 nm. Adv. Opt. Mater. 2013, 1, 644–650. [Google Scholar] [CrossRef]
- Xie, X.; Gao, N.; Deng, R.; Sun, Q.; Xu, Q.H.; Liu, X. Mechanistic investigation of photon upconversion in Nd3+-sensitized core-shell nanoparticles. J. Am. Chem. Soc. 2013, 135, 12608–12611. [Google Scholar]
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Min, Y.; Li, J.; Liu, F.; Padmanabhan, P.; Yeow, E.K.L.; Xing, B. Recent Advance of Biological Molecular Imaging Based on Lanthanide-Doped Upconversion-Luminescent Nanomaterials. Nanomaterials 2014, 4, 129-154. https://doi.org/10.3390/nano4010129
Min Y, Li J, Liu F, Padmanabhan P, Yeow EKL, Xing B. Recent Advance of Biological Molecular Imaging Based on Lanthanide-Doped Upconversion-Luminescent Nanomaterials. Nanomaterials. 2014; 4(1):129-154. https://doi.org/10.3390/nano4010129
Chicago/Turabian StyleMin, Yuanzeng, Jinming Li, Fang Liu, Parasuraman Padmanabhan, Edwin K. L. Yeow, and Bengang Xing. 2014. "Recent Advance of Biological Molecular Imaging Based on Lanthanide-Doped Upconversion-Luminescent Nanomaterials" Nanomaterials 4, no. 1: 129-154. https://doi.org/10.3390/nano4010129