Synthesis Optimization of BaGdF5:x%Tb3+ Nanophosphors for Tunable Particle Size

X-ray photodynamic therapy (XPDT) is aimed at the treatment of deep-located malignant tumors thanks to the high penetration depth of X-rays. In XPDT therapy, it is necessary to use materials that effectively absorb X-rays and convert them into visible radiation-nanophosphors. Rare-earth elements, fluorides, in particular, doped BaGdF5, are known to serve as efficient nanophosphor. On the other hand, the particle size of nanophosphors has a crucial impact on biodistribution, cell uptake, and cytotoxicity. In this work, we investigated various Tb:Gd ratios in the range from 0.1 to 0.5 and optimized the terbium content to achieve the maximum luminescence under X-ray excitation. The effect of temperature, composition of the ethylene glycol/water solvent, and the synthesis technique (solvothermal and microwave) on the size of the nanophosphors was explored. It was found that the synthesis techniques and the solvent composition had the greatest influence on the averaged particle size. By varying these two parameters, it is possible to tune the size of the nanophosphor particles, which make them suitable for biomedical applications.

[1]  Alexander Soldatov,et al.  BaGdF5 Nanophosphors Doped with Different Concentrations of Eu3+ for Application in X-ray Photodynamic Therapy , 2021, International journal of molecular sciences.

[2]  Alexander Soldatov,et al.  The Rare-Earth Elements Doping of BaGdF5 Nanophosphors for X-ray Photodynamic Therapy , 2021, Nanomaterials.

[3]  Rahul Singh,et al.  Phase and photoluminescence analysis of dual-colour emissive Eu3+-doped ZrO2 nanoparticles for advanced security features in anti-counterfeiting , 2021, Colloids and Surfaces A: Physicochemical and Engineering Aspects.

[4]  Thanh Chung Pham,et al.  Recent Strategies to Develop Innovative Photosensitizers for Enhanced Photodynamic Therapy. , 2021, Chemical reviews.

[5]  Yanhua Song,et al.  Ionic liquid/H2O two-phase synthesis and luminescence properties of BaGdF5:RE3+ (RE = Ce/Dy/Eu/Yb/Er) octahedra , 2020 .

[6]  Q. Shi,et al.  Temperature dependent quantum cutting in cubic BaGdF5:Eu3+ nanophosphors , 2020 .

[7]  A. K. Narula,et al.  Luminescence sensitization of Ln3+ impurity ions in BaGdF5 host matrix: Structural investigation, color tunable luminescence and energy transfer , 2020 .

[8]  Jianhua Liu,et al.  Synthesis of PEGylated BaGdF5 Nanoparticles as Efficient CT/MRI Dual-modal Contrast Agents for Gastrointestinal Tract Imaging , 2020 .

[9]  A. Soldatov,et al.  Nanocomposites for X-Ray Photodynamic Therapy , 2020, International journal of molecular sciences.

[10]  V. Butova,et al.  X-RAY NANOPHOSPHORS BASED ON BaGdF5 FOR X-RAY PHOTODYNAMIC THERAPY IN ONCOLOGY , 2020, Nanotechnologies in Russia.

[11]  Stacy Gates-Rector,et al.  The Powder Diffraction File: a quality materials characterization database , 2019, Powder Diffraction.

[12]  F Levi,et al.  European cancer mortality predictions for the year 2019 with focus on breast cancer. , 2019, Annals of oncology : official journal of the European Society for Medical Oncology.

[13]  A. Grumezescu,et al.  Neuronanomedicine: An Up-to-Date Overview , 2019, Pharmaceutics.

[14]  J. del-Castillo,et al.  Energy transfer and tunable emission in BaGdF5: RE3+ (RE= Ce, Tb, Eu) nano-glass-ceramics , 2019, Journal of Alloys and Compounds.

[15]  D M Parkin,et al.  Estimating the global cancer incidence and mortality in 2018: GLOBOCAN sources and methods , 2018, International journal of cancer.

[16]  M Vermandel,et al.  Using X-rays in photodynamic therapy: an overview , 2018, Photochemical & photobiological sciences : Official journal of the European Photochemistry Association and the European Society for Photobiology.

[17]  Juyoung Yoon,et al.  Innovative Strategies for Hypoxic-Tumor Photodynamic Therapy. , 2018, Angewandte Chemie.

[18]  Guorong Jia,et al.  Active targeted dual-modal CT/MR imaging of VX2 tumors using PEGylated BaGdF5 nanoparticles conjugated with RGD , 2018 .

[19]  Juyoung Yoon,et al.  Supramolecular photosensitizers rejuvenate photodynamic therapy. , 2018, Chemical Society reviews.

[20]  C. A. Chang,et al.  Lanthanide-Doped Core-Shell-Shell Nanocomposite for Dual Photodynamic Therapy and Luminescence Imaging by a Single X-ray Excitation Source. , 2018, ACS applied materials & interfaces.

[21]  Liang Jiang,et al.  Manipulating upconversion emission of cubic BaGdF5:Ce3+/Er3+/Yb3+ nanocrystals through controlling Ce3+ doping , 2017 .

[22]  Jinxian Wang,et al.  Eu3+/Tb3+ doped cubic BaGdF5 multifunctional nanophosphors: Multicolor tunable luminescence, energy transfer and magnetic properties , 2017 .

[23]  Kevin W. Eliceiri,et al.  ImageJ2: ImageJ for the next generation of scientific image data , 2017, BMC Bioinformatics.

[24]  Jinxian Wang,et al.  Dual-mode, tunable color, enhanced upconversion luminescence and magnetism of multifunctional BaGdF5:Ln(3+) (Ln = Yb/Er/Eu) nanophosphors. , 2016, Physical chemistry chemical physics : PCCP.

[25]  Chengyi Xu,et al.  White light-emitting, tunable color luminescence, energy transfer and paramagnetic properties of terbium and samarium doped BaGdF5 multifunctional nanomaterials , 2016 .

[26]  Ye Sheng,et al.  BaGdF5:Dy(3+),Tb(3+),Eu(3+) multifunctional nanospheres: paramagnetic, luminescence, energy transfer, and tunable color. , 2016, Physical chemistry chemical physics : PCCP.

[27]  N. Thadhani,et al.  Synthesis and characterization of a BaGdF5:Tb glass ceramic as a nanocomposite scintillator for x-ray imaging , 2016, Nanotechnology.

[28]  Witold Lojkowski,et al.  Effect of Water Content in Ethylene Glycol Solvent on the Size of ZnO Nanoparticles Prepared Using Microwave Solvothermal Synthesis , 2016 .

[29]  Xinyang Zhang,et al.  Optimization of upconversion luminescence of Nd(3+)-sensitized BaGdF5-based nanostructures and their application in dual-modality imaging and drug delivery. , 2016, Dalton transactions.

[30]  F. Cussó,et al.  Ligand-Free Synthesis of Tunable Size Ln:BaGdF₅ (Ln = Eu³⁺ and Nd³⁺) Nanoparticles: Luminescence, Magnetic Properties, and Biocompatibility. , 2016, Langmuir : the ACS journal of surfaces and colloids.

[31]  T. Grzyb,et al.  Synthesis, characterization, and cytotoxicity in human erythrocytes of multifunctional, magnetic, and luminescent nanocrystalline rare earth fluorides , 2015, Journal of Nanoparticle Research.

[32]  Zhijun Wang,et al.  Luminescence and energy transfer of Eu2+/Tb3+/Eu3+ in LiBaBO3 phosphors with tunable-color emission , 2015 .

[33]  Huibi Xu,et al.  A novel deep photodynamic therapy modality combined with CT imaging established via X-ray stimulated silica-modified lanthanide scintillating nanoparticles. , 2015, Chemical communications.

[34]  R. Luque,et al.  Solvothermal synthesis of metal nanocrystals and their applications , 2015 .

[35]  Feng Liu,et al.  Nanoscintillator-mediated X-ray inducible photodynamic therapy for in vivo cancer treatment. , 2015, Nano letters.

[36]  An Xie,et al.  Controlled synthesis and optical properties of Ce3+/Tb3+ co-doped BaGdF5 nanocrystals , 2015, Rare Metals.

[37]  V. Petříček,et al.  Crystallographic Computing System JANA2006: General features , 2014 .

[38]  Xiaohu Liang,et al.  Effect of calcining temperature on particle size of hydroxyapatite synthesized by solid-state reaction at room temperature , 2013 .

[39]  Muriel Barberi-Heyob,et al.  X-ray-Induced singlet oxygen activation with nanoscintillator-coupled porphyrins , 2013 .

[40]  J. Werner,et al.  Reactive oxygen species in cancer biology and anticancer therapy. , 2013, Current medicinal chemistry.

[41]  J. Werner,et al.  Reactive Oxygen Species in the Immune System , 2013, International reviews of immunology.

[42]  Yongchao Jia,et al.  Inorganic-salt-induced morphological transformation and luminescent performance of GdF3 nanostructures. , 2013, Dalton transactions.

[43]  M. Valerio,et al.  The optical properties of Eu3+ doped BaAl2O4: A computational and spectroscopic study , 2012 .

[44]  Wing-Cheung Law,et al.  Core/shell NaGdF4:Nd(3+)/NaGdF4 nanocrystals with efficient near-infrared to near-infrared downconversion photoluminescence for bioimaging applications. , 2012, ACS nano.

[45]  Jiabiao Lian,et al.  Template-free solvothermal synthesis of ZnO nanoparticles with controllable size and their size-dependent optical properties , 2012 .

[46]  Jun Lin,et al.  Size and shape controllable synthesis and luminescent properties of BaGdF5:Ce3+/Ln3+ (Ln = Sm, Dy, Eu, Tb) nano/submicrocrystals by a facile hydrothermal process. , 2011, Nanoscale.

[47]  Dong Li,et al.  Preparation of starch-based nanoparticles through high-pressure homogenization and miniemulsion cross-linking: Influence of various process parameters on particle size and stability , 2011 .

[48]  Yongsheng Liu,et al.  A Strategy to Achieve Efficient Dual‐Mode Luminescence of Eu3+ in Lanthanides Doped Multifunctional NaGdF4 Nanocrystals , 2010, Advanced materials.

[49]  Markus Niederberger,et al.  Metal Oxide Nanoparticles in Organic Solvents: Synthesis, Formation, Assembly and Application , 2009 .

[50]  Yu-ran Luo,et al.  Comprehensive handbook of chemical bond energies , 2007 .

[51]  E. Diau,et al.  Visible quantum cutting through downconversion in green-emitting K2GdF5:Tb3+ phosphors , 2006 .

[52]  C. Xie,et al.  Controlled growth of ZnO by adding H2O , 2005 .

[53]  Jan Hrbáč,et al.  The influence of complexing agent concentration on particle size in the process of SERS active silver colloid synthesis , 2005 .

[54]  J. Boilot,et al.  Emission Processes in YVO4:Eu Nanoparticles , 2003 .

[55]  C. H. Kam,et al.  Enhancement of green emission from Tb3+:GdOBr phosphors with Ce3+ ion co-doping , 2001 .

[56]  J. Hölsä,et al.  Crystal fields in REOF : Eu3+(RE = La, Gd and Y) , 1995 .

[57]  E. Obermeier,et al.  Thermal, Conductivity, Density, Viscosity, and Prandtl-Numbers of Ethylene Glycol-Water Mixtures , 1984 .

[58]  R. D. Shannon Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides , 1976 .