Materials Science and Engineering College, Guilin University of Technology, Key Laboratory of New Processing Technology for Nonferrous Materials, Ministry of Education, Guangxi Key Laboratory of Optical and Electronic Materials and Devices, Guangxi Collaborative Innovation Center for Exploration of Hidden Nonferrous Metal Deposits and Development of New Materials, Guilin University of Technology, 541004 Guilin, China.
Federal Institute for Materials Research and Testing (BAM), 12489 Berlin, Germany.
J Mater Chem B. 2020 Aug 5;8(30):6481-6489. doi: 10.1039/d0tb00088d.
Light-induced NO release based on exogenous NO donors has attracted substantial attention in clinical applications; the induction light source usually converts near-infrared light to blue or ultraviolet light. However, the low efficiency of near-infrared light-assisted chemical light energy conversion remains a challenge, especially for NaYF4:Yb3+/Tm3+ photoconverting near-infrared light to ultraviolet (UV) and blue light. In this paper, a luminescence-enhanced strategy is reported by doping Ca2+ into NaYF4:Yb3+/Tm3+ and coating it with NaGdF4 through a two-step solvothermal method. Then, UCNPs modified with methyl-β-cyclodextrin (M-β-CD) are loaded on a ruthenium nitrosyl complex [(3)Ru(NO)(Cl)] as nitric oxide release-molecules (NORMs). X-ray diffraction (XRD) and energy-dispersive X-ray spectroscopy (EDS) data demonstrated that Ca2+ was successfully doped into NaYF4:Yb3+/Tm3+ nanoparticles as the core, and a pure hexagonal phase, NaYF4, was obtained from the doping of Ca2+. TEM revealed that the crystallinity was significantly improved after Ca2+ doping, and the core-shell structure was successfully synthesized, with NaGdF4 directionally grown on the NaYF4:Ca/Yb/Tm core. Fluorescence tests showed that, especially in the ultraviolet and blue light excitation wavelength regions, the UC emission intensity of the Ca-doped NaYF4:Yb3+/Tm3+@NaGdF4 core-shell UCNPs increased by 302.95 times vs. NaYF4:Yb3+/Tm3+ UCNPs. Finally, the release of NO was tested by the Griess method. Under 980 nm irradiation, the cell viability distinctly decreased with increasing UCNPs@M-β-CD-NORMs concentration. This study shows that NORM release of NO is triggered by enhanced up-converted UV and blue light, which can be used for the development of UV photo-sensitive drugs.
基于外源性一氧化氮供体的光诱导一氧化氮释放引起了临床应用的广泛关注；诱导光源通常将近红外光转换为蓝光或紫外线。然而，近红外光辅助化学光能量转换的效率仍然是一个挑战，特别是对于将 NaYF4：Yb3+/Tm3+近红外光转换为紫外线（UV）和蓝光的光转换。在本文中，通过两步溶剂热法将 Ca2+掺杂到 NaYF4：Yb3+/Tm3+中并涂覆 NaGdF4，报道了一种发光增强策略。然后，用甲基-β-环糊精（M-β-CD）修饰上 UCNPs 负载在钌亚硝酰配合物[(3)Ru(NO)(Cl)]上作为一氧化氮释放分子（NORMs）。X 射线衍射（XRD）和能谱（EDS）数据表明，Ca2+成功地掺杂到 NaYF4：Yb3+/Tm3+纳米粒子作为核，通过掺杂 Ca2+得到了纯六方相 NaYF4。TEM 显示，掺杂 Ca2+后结晶度显著提高，并成功合成了核壳结构，NaGdF4 定向生长在 NaYF4：Ca/Yb/Tm 核上。荧光测试表明，特别是在紫外和蓝光激发波长区域，掺杂 Ca 的 NaYF4：Yb3+/Tm3+@NaGdF4 核壳 UCNPs 的 UC 发射强度比 NaYF4：Yb3+/Tm3+ UCNPs 增加了 302.95 倍。最后，通过格里斯法测试了 NO 的释放。在 980nm 照射下，随着 UCNPs@M-β-CD-NORMs 浓度的增加，细胞活力明显降低。本研究表明，NO 的 NORM 释放是由增强的上转换紫外和蓝光触发的，可用于开发对紫外线敏感的药物。
