Upconverting NIR Photons for Bioimaging
<p>Typical upconversion spectra of β-NaYF<sub>4</sub>:20%Yb, 2%Er (dark green) and β-NaYF<sub>4</sub>:20%Yb, 0.5%Tm (blue).</p> "> Figure 2
<p>Upconversion process of Nd/Yb/Er(Tm) tri-dopants system with 800 nm excitation. Reproduced with permission from [<a href="#B12-nanomaterials-05-02148" class="html-bibr">12</a>]. Copyright John Wiley & Sons, 2013.</p> "> Figure 3
<p>Upconversion emission spetra of (<b>a</b>) NaGdF<sub>4</sub>:25%Yb/0.3%Tm (15 nm) and (<b>b</b>) corresponding core-shell nanoparticles (20 nm) in nonylphenylether/ethanol/water solutions with different water ratio. Reproduced with permission from [<a href="#B23-nanomaterials-05-02148" class="html-bibr">23</a>]. Copyright John Wiley & Sons, 2010.</p> "> Figure 4
<p>Heteroshell structure of α-NaYbF<sub>4</sub>:Tm@CaF<sub>2</sub>. (<b>a</b>)TEM, (<b>b</b>) high-angle annular dark-field STEM, (<b>c</b>) linear EDX scanning of a single UCNP and (<b>d</b>) corresponding elemental ratio analysis. Reproduced with permission from [<a href="#B24-nanomaterials-05-02148" class="html-bibr">24</a>]. Copyright John Wiley & Sons, 2013.</p> "> Figure 5
<p>Bright upconversion under 800 nm excitation by engineering core@shell@shell structure. (<b>a</b>) Simplied energy-level diagrams depicting the energy transfer between Nd, Yb, and Er ions upon 800 nm excitation. (<b>b</b>) Schematic illustration of the proposed energy transfer mechanisms in the quenching-shield sandwich-structured UCNPs, (<b>c</b>) upconversion emission spectra of the as-synthesized UCNPs. Reproduced with permission from [<a href="#B25-nanomaterials-05-02148" class="html-bibr">25</a>]. Copyright John Wiley & Sons, 2014.</p> "> Figure 6
<p>(<b>a</b>) Schematic design of tuning the Nd-sensitized upconversion process through nanostructural engineering. (<b>b</b>) Emisssion spectra of the multishelled nanoparticles under excitation at 808 and 976 nm, respectively. Inset: digital camera photograph of corresponding solution sample. Reproduced with permission from [<a href="#B27-nanomaterials-05-02148" class="html-bibr">27</a>]. Copyright John Wiley & Sons, 2013.</p> "> Figure 7
<p>(<b>a</b>) Illustration of two-way photoswitching of spiropyran by using UCNPs with dual NIR excitations. (<b>b</b>) Tm<sup>3+</sup> and Er<sup>3+</sup> emissions from the UCNPs under 808 nm and 980 nm excitations and the evolution of the UV-vis absorption spectrum of the photoisomerization. (<b>c</b>) Kinetic monitoring of the photoswitching reaction. The red line shows the kinetics of the reaction of merocyanine to spiropyran. (<b>d</b>) Dual NIR-driven photoswitching of spiropyran over many cycles in THF/methanol (9/1, <span class="html-italic">v</span>/<span class="html-italic">v</span>) solution by monitoring the absorbance of merocyanine at 560 nm. Reproduced with permission from [<a href="#B28-nanomaterials-05-02148" class="html-bibr">28</a>]. Copyright John Wiley & Sons, 2014.</p> "> Figure 8
<p>Scheme of the phase transition and ligand exchange procedure by using NOBF<sub>4</sub>. Reprinted with the permission with permission from [<a href="#B32-nanomaterials-05-02148" class="html-bibr">32</a>]. Copyright American Chemical Society, 2011.</p> "> Figure 9
<p>Upconverted luminescence of individual water-soluble upconverting nanoparticles (UCNPs). (<b>A</b>) Confocal upconverted luminescent image of individual amphiphilic polymer-coated UCNPs (schematically shown in the <span class="html-italic">Inset</span>) sparsely dispersed on a clean coverglass. The laser power is approximately 10 mW, equivalent to approximately 5 × 10<sup>6</sup> W/cm<sup>2</sup>. Some of the bright luminescent spots represent multiple UCNPs within the diffraction limited area, generating saturated “white” spots in the image. (<b>B</b>) A histogram of integrated emission intensity from over 200 upconverted luminescent spots, suggesting that most of the luminescent spots are from single polymer-coated UCNPs. The data were analyzed from confocal upconverted luminescent images over a 75 × 75 μm area, and the number of saturated “white” spots was shown in the histogram as a blue bar. Such single water-soluble UCNPs also exhibit exceptional photostability (<b>C</b>) and non-blinking behavior (<b>D</b>) Reprinted with the permission from [<a href="#B3-nanomaterials-05-02148" class="html-bibr">3</a>]. Copyright American Chemical Society, 2009.</p> "> Figure 10
<p>Example of lanthanide-doped UCNPs of core-shell structures with NIR-to-NIR optical transitions and their application for small animal imaging studies plus illustration showing the better penetration of NIR light in contrast with visible light. Reprinted with permission from [<a href="#B5-nanomaterials-05-02148" class="html-bibr">5</a>]. Copyright American Chemical Society, 2012.</p> "> Figure 11
<p>Illustration scheme for UCNP-RGD and <span class="html-italic">in vivo</span> upconversion luminescence imaging of subcutaneous U87MG tumor (left hind leg) and MCF-7 tumor (right hind leg) after intravenous injection of UCNP-RGD conjugate over 24-hour period. (<b>a</b>,<b>d</b>,<b>g</b>) bright field, (<b>b</b>,<b>e</b>,<b>h</b>) upconversion images, (<b>c</b>,<b>f</b>,<b>i</b>) overlay of the corresponding bright field images with the upconversion ones. (<b>a</b>–<b>c</b>), (<b>d</b>–<b>f</b>), and (<b>g</b>–<b>i</b>) are taken at 1, 4 and 24 h postinjection, respectively. Reprinted with permission from [<a href="#B35-nanomaterials-05-02148" class="html-bibr">35</a>]. Copyright American Chemical Society, 2009.</p> "> Figure 12
<p>Schematic illustration of antigen-loaded UCNPs for dendritic cell stimulation, tracking, and vaccination in immunotherapy. Reprinted with permission from [<a href="#B39-nanomaterials-05-02148" class="html-bibr">39</a>]. Copyright American Chemical Society, 2015.</p> "> Figure 13
<p>Scheme of real-time monitoring of ATP-responsive drug release using mesoporous-silica-coated multicolor upconversion nanoparticles. Reprinted with permission from [<a href="#B41-nanomaterials-05-02148" class="html-bibr">41</a>]. Copyright American Chemical Society, 2015.</p> "> Figure 14
<p>Schematic drawing of FRET-based UCNPs/siRNA-BOBO-3 complex system. siRNA are stained with BOBO-3 dyes, and the stained siRNA are attached to the surface of NaYF<sub>4</sub>:Yb,Er nanoparticles. Upon excitation of the nanoparticles at 980 nm, energy is transferred from the donor (UCNPs) to the acceptor (BOBO-3). Reprinted with permission from [<a href="#B42-nanomaterials-05-02148" class="html-bibr">42</a>]. Copyright American Chemical Society, 2010.</p> "> Figure 15
<p>(<b>a</b>) <span class="html-italic">In vivo</span> volume of tumors exposed to various controls and ALA-UCNPs with red and near-infrared irradiation (0.5 W/cm<sup>2</sup>) in simulated deep tumors, (<b>b</b>) scheme of the simulated deep tumor PDT process. Reprinted with permission from [<a href="#B51-nanomaterials-05-02148" class="html-bibr">51</a>]. Copyright American Chemical Society, 2014.</p> "> Figure 16
<p>Schematic illustration of the NIR-driven reactive oxygen species generation by the use of UCNP/TiO<sub>2</sub>. Reprinted with permission from [<a href="#B55-nanomaterials-05-02148" class="html-bibr">55</a>]. Copyright American Chemical Society, 2015.</p> "> Figure 17
<p>(<b>a</b>) Illustration of nano-carriers for enhanced photothermal ablation and radiotherapy synergistic therapy; (<b>b</b>) photographs of mice in 30, 60, 90 and 120 days of treatment, showing complete eradication of the tumor and no visible recurrences of the tumors in at least 120 days. Reprinted with permission from [<a href="#B59-nanomaterials-05-02148" class="html-bibr">59</a>]. Copyright American Chemical Society, 2013.</p> ">
Abstract
:1. Introduction
2. Engineering of UCNPs for Biomedical Applications
2.1. Basic Mechanism of UCNPs
2.2. Synthesis of UCNPs
2.3. UCNPs with Core@Shell Structures
2.4. Surface Modification for Upconversion Enhancing and Bio-Conjugation
3. UCNPs as Imaging Contrast Reagents
4. UCNPs as Imaging Guidable Delivery Nanoplatform
4.1. UCNPs as in Vivo Traceable Drug Carriers
4.2. Light Controllable Drug Release Based on UCNPs
4.3. UCNPs for Gene Delivery
5. UCNPs as Phototherapeutic Reagents
5.1. Photodynamic Therapy
5.2. Photothermal Therapy
6. Conclusion and Prospects
Acknowledgments
Author Contributions
Conflicts of Interest
References
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Li, Z.; Zhang, Y.; La, H.; Zhu, R.; El-Banna, G.; Wei, Y.; Han, G. Upconverting NIR Photons for Bioimaging. Nanomaterials 2015, 5, 2148-2168. https://doi.org/10.3390/nano5042148
Li Z, Zhang Y, La H, Zhu R, El-Banna G, Wei Y, Han G. Upconverting NIR Photons for Bioimaging. Nanomaterials. 2015; 5(4):2148-2168. https://doi.org/10.3390/nano5042148
Chicago/Turabian StyleLi, Zhanjun, Yuanwei Zhang, Hieu La, Richard Zhu, Ghida El-Banna, Yuzou Wei, and Gang Han. 2015. "Upconverting NIR Photons for Bioimaging" Nanomaterials 5, no. 4: 2148-2168. https://doi.org/10.3390/nano5042148