摘要
针对现有磁-光双模态成像材料灵敏度低与穿透深度不足的缺陷,通过引入局域表面等离子体共振(LSPR)效应的隔层的方法,成功制备了新型Fe_3O_4@MoO_3@GdF_3:Eu~(3+)磁-光双模态成像材料. XRD分析结果表明, Fe_3O_4表面逐层包覆上了结晶良好的单斜晶系的MoO_3和正交晶系的GdF3:Eu3+纳米晶.荧光光谱分析表明,该材料具有良好的发光性,以593 nm附近的5D0→7F1磁偶极跃迁为最强发射峰.而该材料的磁饱和强度仍为25.9 emu/g. MTT和MRI分析结果表明, Fe_3O_4@MoO_3@GdF_3:Eu~(3+)磁-光双模态成像材料具有低毒性和较好的核磁共振成像效果.该方法将解决磁-光双模态成像材料性能方面的瓶颈问题,为推进该类材料在肿瘤精准诊疗和光学共聚焦显微技术中的应用提供理论依据和实验基础.
The probe plays a key role in the process of the tumor diagnosis and image guided accuracy surgery, but its single-function,weaker luminescent intensity and high cost limitits application. Therefore, development of new type high-performance and multi-functional imaging materials has become an important research topic in the field of chemistry, materials science, life science and medicine. In recent years, researchers have found that magnetic-luminescent bi-functional nanoparticles can provide high-resolution, high-contrast images for precision medicine and are crucial for imaging applications. Among them, the design and synthesis of Fe_3O_4@REL(rare earth luminescence) magnetic-luminescent bi-functional nanoparticles have become the focus of current research.In this work, we demonstrated the nonmetallic plasmon induced enhancement of luminescence in a core-shell structured material, consisting of Fe_3O_4 as the core, GdF3: Eu3+as the luminescence layer and MoO3 as the plasmonic layer. The novel Fe_3O_4@MoO_3@GdF_3:Eu~(3+)nanoparticles of MoO3 intermediate with local surface plasmon resonance(LSPR) effect were synthesized by solvothermal and precipitation method. And their structures, compositions and properties were analyzed.Enhancement mechanism of luminescence property and the interaction factors between the oxide layer and luminescence shell had been illuminated. The results of X-ray diffraction(XRD) analysis showed that the nanoparticles are composed of Fe33 O4, single monoclinic MoO3 and orthorhombic GdF3:Eu+. Transmission electron microscope(TEM) images showed that the obvious nanoparticles and MoO3 and GdF3:Eu3+are deposited on the surface of Fe3 O4 layer by layer. It showed that the shielding effect of homogeneous coating MoO3 spacer and the MoO3 with LSPR plays a role in enhancing the luminescence properties of the shell GdF3:Eu3+. The emission spectra showed that the strongest emission(593 nm) is due to the5 D0→7 F1 forced electric dipole transition, and the other emission bands are observed at 556, 616 and 692 nm for5 D0→7 Fn,5 D0→7 F2 and5 D0→7 F4, respectively. The magnetic measurement results showed that the Fe_3O_4@MoO_3@GdF_3:Eu~(3+)nanoparticles possess excellent magnetic responsivity(25.9 emu/g) and redispersibility. MTT assays showed that the nanoparticles almost have no cytotoxicity or side effects in living cells. The magnetic resonance imaging of the sample gradually enhanced with the increase of the concentration, indicating that the effect of magnetic resonance imaging was corresponding to the concentration. The T2 magnetic resonance imaging relaxation rate of the material was0.9813 mg-1 m-1 s-1.In summary, the core-shell structured Fe_3O_4@MoO_3@GdF_3:Eu~(3+)nanoparticles have been prepared by a facile method.The nanoparticles have high emission intensity and magnetisation saturation value. Compared with Fe3 O4@GdF3:Eu3+,luminescence intensity of Fe_3O_4@MoO_3@GdF_3:Eu~(3+)nanoparticles increased significantly. Therefore, the as-prepared core-shell structured bifunctional nanoparticles are feasibly applicable to simultaneous cell imaging and target drug delivery. This work can solve the property problem of the magnetic-luminescent bimodal imaging material and promote this kind of composite material applications in imaging and therapy of tumor, and optical confocal microscopy technology.
引文
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