Crystal cell oriented-rotation triggered phase transition of porous upconversion nanocrystals synthesis in hydrothermal system.

The phase transition of upconversion nanocrystals (UNs) from cubic to hexagonal structure is of fundamental importance in improving the luminescence intensity by about one or two orders of magnitudes, but the mechanism is still not well understood and efforts to completely transfer the phase from cubic to hexagonal structure remains a difficult and challenging task. Here, we describe a hydrothermal system in which an anion induces the phase transition process to give simultaneous control over the size, morphology, phase and emission properties. We first confirm that the crystal cell oriented-rotation driven by an anion in a hydrothermal system promoted the phase transition, and the energy zones figure of the phase transition from cubic to hexagonal structure has been figured out. We have successfully applied the structural mechanics finite element calculations to validate the reaction process. We have also demonstrated that porous UNs can be rationally tuned in size (down to fifteen nanometers), phase (cubic or hexagonal) and emission properties at precisely defined conditions, and were effective for in vitro and in vivo CT imaging.

[1]  Daxiang Cui,et al.  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 , 2011 .

[2]  S. Feng,et al.  New materials in hydrothermal synthesis. , 2001, Accounts of chemical research.

[3]  Qing Peng,et al.  Enhanced catalytic activity of ceria nanorods from well-defined reactive crystal planes , 2005 .

[4]  M. Wuttig,et al.  Phase-change materials for rewriteable data storage. , 2007, Nature materials.

[5]  Mark E. Davis Ordered porous materials for emerging applications , 2002, Nature.

[6]  Jun Lin,et al.  Highly uniform and monodisperse beta-NaYF(4):Ln(3+) (Ln = Eu, Tb, Yb/Er, and Yb/Tm) hexagonal microprism crystals: hydrothermal synthesis and luminescent properties. , 2007, Inorganic chemistry.

[7]  D. Zhao,et al.  Formation of Hollow Upconversion Rare-Earth Fluoride Nanospheres: Nanoscale Kirkendall Effect During Ion Exchange , 2009 .

[8]  V. de Zea Bermudez,et al.  Progress on lanthanide-based organic-inorganic hybrid phosphors. , 2011, Chemical Society reviews.

[9]  Bin Chen,et al.  An Anion-Induced Hydrothermal Oriented-Explosive Strategy for the Synthesis of Porous Upconversion Nanocrystals , 2015, Theranostics.

[10]  Wenjun Yang,et al.  Synthesis, Characterization, and Biological Application of Size-Controlled Nanocrystalline NaYF4:Yb,Er Infrared-to-Visible Up-Conversion Phosphors , 2004 .

[11]  Yong Zhang,et al.  Upconversion fluorescence imaging of cells and small animals using lanthanide doped nanocrystals. , 2008, Biomaterials.

[12]  Xin Zhang,et al.  One-pot hydrothermal synthesis of lanthanide ions doped one-dimensional upconversion submicrocrystals and their potential application in vivo CT imaging. , 2013, Nanoscale.

[13]  Hui Guo,et al.  Mesoporous-silica-coated up-conversion fluorescent nanoparticles for photodynamic therapy. , 2009, Small.

[14]  Jun Lin,et al.  Synthesis of Magnetic, Up‐Conversion Luminescent, and Mesoporous Core–Shell‐Structured Nanocomposites as Drug Carriers , 2010 .

[15]  Qian Liu,et al.  A general strategy for biocompatible, high-effective upconversion nanocapsules based on triplet-triplet annihilation. , 2013, Journal of the American Chemical Society.

[16]  E. Roduner Size matters: why nanomaterials are different. , 2006, Chemical Society reviews.

[17]  Markus P. Hehlen,et al.  Hexagonal Sodium Yttrium Fluoride Based Green and Blue Emitting Upconversion Phosphors , 2004 .

[18]  Xun Wang,et al.  Fullerene-like rare-Earth nanoparticles. , 2003, Angewandte Chemie.

[19]  R. E. Thoma,et al.  Phase Equilibria in the System Sodium Fluoride-Yttrium Fluoride , 1963 .

[20]  Xiaogang Liu,et al.  Recent advances in the chemistry of lanthanide-doped upconversion nanocrystals. , 2009, Chemical Society reviews.

[21]  K. E. Easterling,et al.  Phase Transformations in Metals and Alloys (Revised Reprint) , 2009 .

[22]  Qing Peng,et al.  A general strategy for nanocrystal synthesis , 2005, Nature.

[23]  Qing Peng,et al.  Lanthanide-doped nanocrystals: synthesis, optical-magnetic properties, and applications. , 2011, Accounts of chemical research.

[24]  B. Wall,et al.  Rare-earth-doped biological composites as in vivo shortwave infrared reporters , 2013, Nature Communications.

[25]  Hajime Yamamoto,et al.  Luminescence processes in Tm3+‐ and Er3+‐ion‐activated, Yb3+‐ion‐sensitized infrared upconversion devices , 1993 .

[26]  Louis A. Cuccia,et al.  Controlled Synthesis and Water Dispersibility of Hexagonal Phase NaGdF4:Ho3+/Yb3+ Nanoparticles , 2009 .

[27]  Yadong Li,et al.  Effects of downconversion luminescent film in dye-sensitized solar cells , 2006 .

[28]  Renren Deng,et al.  Tuning upconversion through energy migration in core-shell nanoparticles. , 2011, Nature materials.

[29]  J. Hao,et al.  A strategy for simultaneously realizing the cubic-to-hexagonal phase transition and controlling the small size of NaYF4:Yb3+,Er3+ nanocrystals for in vitro cell imaging. , 2012, Small.

[30]  M. Oh,et al.  Facile Synthetic Route for Thickness and Composition Tunable Hollow Metal Oxide Spheres from Silica‐Templated Coordination Polymers , 2011, Advanced materials.

[31]  T. Kijima,et al.  Rare Earth (Er, Tm, Yb, Lu) Oxide Nanotubes Templated by Dodecylsulfate Assemblies , 2002 .

[32]  D. Gerthsen,et al.  Nanoscale La(OH)3 hollow spheres and fine-tuning of its outer diameter and cavity size. , 2010, Small.

[33]  C. S. Lim,et al.  Simultaneous phase and size control of upconversion nanocrystals through lanthanide doping , 2010, Nature.

[34]  Guo Gao,et al.  Tuning lanthanide ion-doped upconversion nanocrystals with different shapes via a one-pot cationic surfactant-assisted hydrothermal strategy , 2014 .

[35]  Wei Feng,et al.  Sub-10 nm hexagonal lanthanide-doped NaLuF4 upconversion nanocrystals for sensitive bioimaging in vivo. , 2011, Journal of the American Chemical Society.

[36]  Wei Feng,et al.  Gd3+ complex-modified NaLuF4-based upconversion nanophosphors for trimodality imaging of NIR-to-NIR upconversion luminescence, X-Ray computed tomography and magnetic resonance. , 2012, Biomaterials.

[37]  Shanshan Huang,et al.  Facile and controllable synthesis of monodisperse CaF2 and CaF2:Ce3+/Tb3+ hollow spheres as efficient luminescent materials and smart drug carriers. , 2010, Chemistry.

[38]  Daxiang Cui,et al.  Folic acid-conjugated LaF3:Yb,Tm@SiO2 nanoprobes for targeting dual-modality imaging of upconversion luminescence and X-ray computed tomography. , 2012, The journal of physical chemistry. B.

[39]  Muthu Kumara Gnanasammandhan,et al.  In vivo photodynamic therapy using upconversion nanoparticles as remote-controlled nanotransducers , 2012, Nature Medicine.

[40]  Bin Chen,et al.  Hydrothermal Targeted‐Explosion Synthesis of Hollow/Porous Upconversion Nano‐ and Microcrystals with Potential for Luminescent Displays and Biological Imaging , 2015 .

[41]  Yun Sun,et al.  Dual-modality in vivo imaging using rare-earth nanocrystals with near-infrared to near-infrared (NIR-to-NIR) upconversion luminescence and magnetic resonance properties. , 2010, Biomaterials.

[42]  Guo Gao,et al.  Recent advances in lanthanide-doped upconversion nanomaterials: synthesis, nanostructures and surface modification. , 2013, Nanoscale.

[43]  M. Yoshio,et al.  La2O3 hollow nanospheres for high performance lithium-ion rechargeable batteries. , 2012, Chemical communications.

[44]  Gabor A. Somorjai,et al.  Formation of Hollow Nanocrystals Through the Nanoscale Kirkendall Effect , 2004, Science.

[45]  F. Auzel Upconversion and anti-Stokes processes with f and d ions in solids. , 2004, Chemical reviews.

[46]  Xun Wang,et al.  Synthesis of NaYF4 Nanocrystals with Predictable Phase and Shape , 2007 .

[47]  L. Archer,et al.  Hollow Micro‐/Nanostructures: Synthesis and Applications , 2008 .