Fabricating ultralow-power-excitable lanthanide-doped inorganic nanoparticles with anomalous thermo-enhanced photoluminescence behavior

具有反常热增强发光且可超低功率激发的稀土掺杂无机纳米颗粒

Trivalent lanthanide(Ln^(3+))-doped luminescent nanoparticles(NPs)have been extensively investigated as deep-tissue-penetration visual bioimaging agents owing to their exceptional upconversion and near-infrared(NIR)luminescence upon irradiation of NIR light.However,in most cases,the power density of irradiation used for in vivo biological imaging is much higher than that of the reported maximum permissible exposure(MPE)value of NIR light,which inevitably does great damage to the living organisms under study and thus impedes the plausible clinical applications.Herein,by using a facile syringe pump-aided shell epitaxial growth method,we construct for the first time a new class of Ln^(3+)-doped KMgF_(3):Yb/Er@KMgF_(3)core-shell NPs that can be activated by utilizing a 980-nm xenon lamp or diode laser with an ultralow excitation power density down to 0.08 mW cm^(−2),a value that is approximately 4 orders of magnitude lower than the MPE value set by the American National Standards Institute(ANSI)for safe bioimaging in vivo.By combining the comparative spectroscopic investigations with atomic-resolved spherical aberration corrected transmission electron microscopy(AC-TEM)characterization,we find that the reduced crystallographic defects are the primary cause underlying such an ultralow-power-excitable feature of the KMgF_(3):Yb/Er@KMgF_(3)core-shell NPs.And,by the same token,the resultant KMgF_(3):Yb/Er@KMgF_(3)core-shell NPs also exhibit an anomalous thermo-enhanced photoluminescence(PL)behavior coupled with an excellent photothermal stability that cannot occur in other Ln^(3+)-doped core-shell NPs.These findings described here unambiguously pave a new way to prepare high-quality Ln^(3+)-doped luminescent NPs with desirable ultralow-power-excitable capability and photothermal stability for future biomedical applications.

稀土掺杂的纳米发光颗粒因其具有优异的上转换和近红外发光性能,被当作生物深层组织影像剂广泛研究.但是,目前用于生物体内成像材料的辐照功率密度远高于近红外光辐照生物组织安全阈值,阻碍了其临床应用.在此,我们利用注射泵辅助壳层外延生长的方法,首次构建了一类可低功率激发的稀土掺杂核壳结构纳米颗粒(KMgF_(3):Yb/Er@KMgF_(3)).该纳米颗粒可通过氙灯或者功率密度低至0.08 mW cm^(−2)的980 nm激光器激发,这比美国国家标准协会设定的生物体内成像安全阈值低约4个数量级.基于光谱对比和原子级高分辨球差透射电镜的研究,我们发现KMgF_(3):Yb/Er@KMgF_(3)纳米颗粒可超低功率激发的主要原因是晶体缺陷的减少.另外,所得的核壳结构纳米颗粒还表现出异常的热增强光致发光行为以及优异的光热稳定性.本论文的这些发现为制备可超低功率激发而且具有良好光热稳定性的稀土掺杂无机纳米荧光探针奠定了良好的基础.