None of the currently commercialized shielding materials in Generation IV nuclear energy systems are satisfactory in their performance. Developing a candidate neutron shielding material with good heat resistance and high strength is a challenging task. In this work, various gadolinium metal–organic frameworks (Gd-MOFs) with obvious advantages, such as porous structures, organic surfaces and strong neutron-absorbing nuclei, were synthesized to constrain polyimide (PI) chains. A series of Gd-MOF/PI conjugates were subsequently assessed for their thermal stability, mechanical properties and neutron shielding performance. The increase of the Gd-MOF content improved the thermal neutron shielding ability but slightly reduced the fast neutron shielding ability. Compared with those of pure PI, the Gd-MOF/PI films demonstrate a higher glass transition temperature (Tg), which is considered the gold standard of engineering plastics. It was also observed that the tensile strength directly correlates with the Gd-MOF content, which continuously increases until a maximum is reached, and then subsequently decreases. Furthermore, the high-temperature tensile test showed that these tunable Gd-MOF/PI films are intact and robust, indicating their potential application for neutron shielding materials in Generation IV nuclear energy systems.
With the increasing demand for on-site detection, the current approach of building dual-emission or multi-emission luminescence sensors based on metal-organic frameworks (MOFs) which possess the capacity of self-reference for numerous non-analyte factors falls short of meeting sensing requirements. Therefore, we have designed a novel strategy for constructing wavelength shift-based luminescence sensor named Eu/Gd(TCPP), which exhibits dual-emitting from metal ions Eu 3+ and flexible rotating aggregation-induced emission (AIE) ligands H 4 TCPP (2,3,5,6-tetrakis(4-carboxyphenyl)pyrazine). This sensor was prepared by a simple, green and fast plasma synthesis method. It's worth noting that the fluorescence emission of Eu/Gd(TCPP) shows a specific wavelength shift from ligand peak, and a visual color change from red to blue within a pH range of 4 to 3. Moreover, various characterization data verified that the luminescence switching mechanism of Eu/Gd(TCPP) was attributed to the H + -induced collapse of the Eu/Gd(TCPP) crystal structure, followed by untwisting of free ligands that lose rigid MOFs confinement. This hindered the antenna effect from H 4 TCPP to Ln 3+ ions and restricted the rotation emission of ligand, resulting in the red-shifting of the ligand emission and corresponding luminescence switching. By tactfully utilizing the short-range pH response property of Eu/Gd(TCPP), highly sensitive and selective on-site visual detection of acidic aspartic acid can be achieved.
Yuda Zhu,Nini Xin,Zi Qiao,Suping Chen,Lingwan Zeng,Yusheng Zhang,Dan Wei,Jing Sun,Hongsong Fan
Bioactive metal–organic frameworks (bio-MOFs) built from biofunctional metal ions and linkers show a new strategy to construct multifunctional theranostic platforms. Herein, a bio-MOF is synthetized via the self-assembling of Fe 3+ ions and doxorubicin hydrochloride (DOX) molecules. Then, through a stepwise assembly strategy, another bio-MOFs structure consisting of Gd 3+ ions and 1,3,5-benzenetricarboxylic acid (H 3 BTC) is wrapped on the surfaces of Fe-DOX nanoparticles, followed by adsorbing photosensitizer indocyanine green (ICG). Specifically, the Gd-MOF shell structure can not only act as a contrast agent for magnetic resonance imaging (MRI), but also provides protection for Fe-DOX cores, controlling the release of DOX. The photoacoustic and photothermal imaging (PAI and PTI) methods are successfully introduced to the platform by loading ICG, providing potential applications for multimodal biological imaging. The in vitro and in vivo outcomes indicate that the Fe-DOX@Gd-MOF-ICG nanoplatform exhibits outstanding synergistic antitumor performance via MR/PA/PT imaging guided chemotherapy, photothermal and photodynamic combination therapy. The work may encourage further exploration of bio-MOFs based multifunctional theranostic platforms for multimodal imaging guided compound antitumor therapy, which will open an avenue of MOFs toward biological applications.
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