No abstract

Postsynthetic modification represents an efficient strategy for the fabrication of tunable metal−organic frameworks (MOFs) and derived highperformance functional materials. Herein, we report the synthesis of a mixed-linker zinc(II)-based double-layered MOF (dlMOF) with dual-emissive luminescence, which was further applied as a host matrix to fabricate highly tunable Ln@dlMOF materials (Ln = Eu, Tb, Eu/Tb). The emission characteristics of these materials can be readily modulated over a wide spectrum, including white light emission, by simply tuning the Eu 3+ /Tb 3+ molar ratio in EuTb@dlMOF. Furthermore, by virtue of the difference in thermal sensitivity between triple-emissive sources, the Eu 3+ / Tb 3+ -codoped thermometer EuTb@dlMOF exhibits real-time successive chromogenic switches from red (room temperature) to white (intermediate temperature) to blue/green (cryogenic temperature) emission in a wide temperature region. The versatile performance and the facile assembly from easily available linkers suggest that postsynthetic lanthanide encapsulation represents an efficient strategy for the future engineering of advanced photoluminescent materials with stimuli-responsive and thermochromic properties.

As a novel molecular and functional imaging modality, X-ray luminescence computed tomography (XLCT) has shown its potentials in biomedical and preclinic applications. However, there are still some limitations of X-ray-excited luminescent materials, such as low luminescence efficiency, poor biocompatibility, and cytotoxicity, making in vivo XLCT imaging quite challenging. In this study, for the very first time, we present on using sub-10 nm β-NaGdF:X% Eu nanoparticles with poly(acrylic acid) (PAA) surface modification, which demonstrate outstanding luminescence efficiency, uniform size distribution, water dispersity, and biosafety, as the luminescent probes for in vivo XLCT application. The pure hexagonal phase (β-) NaGdF has been successfully synthesized and characterized by X-ray powder diffraction (XRD) and transmission electron microscopy (TEM), and then the results of X-ray photoelectron spectroscopy (XPS), energy-dispersive X-ray spectrometry  (EDX), and elemental mapping further confirm Eu ions doped into NaGdF host. Under X-ray excitation, the β-NaGdF nanoparticles with a doping level of 15% Eu exhibited the most efficient luminescence intensity. Notably, the doping level of Eu has no effect on the crystal phase and morphology of the NaGdF-based host. Afterward, β-NaGdF:15% Eu nanoparticles were modified with PAA to enhance the water dispersity and biocompatibility. The compatibility of in vivo XLCT imaging using such nanoparticles was systematically studied via in vitro cytotoxicity, physical phantom, and in vivo imaging experiments. The ultralow cytotoxicity of PAA-modified nanoparticles, which is confirmed by over 80% cell viability of SH-SY5Y cells when treated by high nanoparticle concentration of 200 μg/mL, overcome the major obstacle for in vivo application. In addition, the high luminescence intensity of PAA-modified nanoparticles enables the location error of in vivo XLCT imaging less than 2 mm, which is comparable to that using commercially available bulk material YO:15% Eu. The proposed nanoparticles promote XLCT research into an in vivo stage. Further modification of these nanoparticles with biofunctional molecules could enable the potential of targeting XLCT imaging.

Cone beam X-ray luminescence computed tomography (CB-XLCT) has been proposed as a promising hybrid imaging technique. Though it has the advantage of fast imaging, the inverse problem of CB-XLCT is seriously ill-conditioned, making the image quality quite poor, especially for imaging multi-targets. To achieve fast imaging of multi-targets, which is essential for in vivo applications, a truncated singular value decomposition (TSVD) based sparse view CB-XLCT reconstruction method is proposed in this study. With the weight matrix of the CB-XLCT system being converted to orthogonal by TSVD, the compressed sensing (CS) based L-norm method could be applied for fast reconstruction from fewer projection views. Numerical simulations and phantom experiments demonstrate that by using the proposed method, two targets with different edge-to-edge distances (EEDs) could be resolved effectively. It indicates that the proposed method could improve the imaging quality of multi-targets significantly in terms of localization accuracy, target shape, image contrast, and spatial resolution, when compared with conventional methods.

X-ray excited photodynamic therapy (X-PDT), which utilizes X-rays as the energy source and X-ray luminescent nanoparticles (XLNPs) as the transducer to excite photosensitizers (PS), resolves the penetration problem of light in traditional PDT to enable the treatment of deepseated tumors. Nevertheless, the high X-ray dosage used in X-PDT hampers its potential applications in clinics. In this study, to alleviate the dose problem, β-NaLuF 4 :Tb 3+ spherical nanoparticles (NPs) with ultrastrong green X-ray excited optical luminescence (XEOL) due to the less nonradiative relaxation probability and high X-ray absorption mass coefficient, which perfectly matches the absorption spectrum of a photosensitizer named rose bengal (RB), were synthesized and employed as the energy transducer for X-PDT. After covalent conjugation of NPs with RB, high Forster resonant energy transfer (FRET) efficiency up to 94.29% was achieved, leading to high production of singlet oxygen. In vivo X-PDT efficacy was evaluated by nude mice with a HepG2 tumor xenograft. With excellent biocompatibility, the synthesized NPs−RB nanocomposite showed significant antitumor efficiency up to 80 ± 12.3% with a total X-ray dose of only 0.19 Gy, demonstrating the feasibility of low-dose X-PDT in vivo for the first time. The present work provides a promising platform for X-PDT in deep-seated tumors.