Fluorinated Hafnium and Zirconium Coenable the Tunable Biodegradability of Core-Multishell Heterogeneous Nanocrystals for Bioimaging.

Upconversion (UC)/downconversion (DC)-luminescent lanthanide-doped nanocrystals (LDNCs) with near-infrared (NIR, 650-1700 nm) excitation have been gaining increasing popularity in bioimaging. However, conventional NIR-excited LDNCs cannot be degraded and eliminated eventually in vivo owing to intrinsic "rigid" lattices, thus constraining clinical applications. A biodegradability-tunable heterogeneous core-shell-shell luminescent LDNC of Na3HfF7:Yb,Er@Na3ZrF7:Yb,Er@CaF2:Yb,Zr (abbreviated as HZC) was developed and modified with oxidized sodium alginate (OSA) for multimode bioimaging. The dynamic "soft" lattice-Na3Hf(Zr)F7 host and the varying Zr4+ doping content in the outmoster CaF2 shell endowed HZC with tunable degradability. Through elaborated core-shell-shell coating, Yb3+/Er3+-coupled UC red and green and DC second near-infrared (NIR-II) emissions were, respectively, enhanced by 31.23-, 150.60-, and 19.42-fold when compared with core nanocrystals. HZC generated computed tomography (CT) imaging contrast effects, thus enabling NIR-II/CT/UC trimodal imaging. OSA modification not only ensured the exemplary biocompatibility of HZC but also enabled tumor-specific diagnosis. The findings would benefit the clinical imaging translation of LDNCs.

Nano-photosensitizers with gallic acid-involved Fe-O-Cu "electronic storage station" bridging ligand-to-metal charge transfer for efficient catalytic theranostics.

NH2-MIL-88B (Fe) (MOF) is a promising photocatalytic material for antitumor therapy because of its distinctive electronic structure. However, inadequate separation of photo-generated electrons and slow reaction rate in low/high-valence iron (Fe) cycles limit their clinical application. In the present study, "electronic storage station" as a ligand-to-metal charge transfer bridge bond was constructed to inhibit recombination of electron/hole under 650 nm laser irradiation. Cupric (Cu) ions and gallic acid (GA) were self-assembled into a MOF (denoted as CGMOF) to create an FeO(GA)Cu bridge bond. GA, characterized by robust electron delocalization and abundant electron-donating groups, significantly enhances electron transfer efficiency for photodynamic therapy (PDT). CGMOF can respond to endogenous glutathione and release cuprous ions, accelerating the iron ion/ferrous ion cycles for chemodynamic therapy (CDT). The released Fe species can serve as T2-weighted magnetic resonance imaging contrast. Extended X-ray absorption fine structure spectra confirmed the presence of GA-containing FeOCu bonds in CGMOF. Furthermore, a series of photo-electrochemical tests confirmed that the formation of FeO(GA)Cu bond prominently elevated the redox capacity and increased the carrier density of CGMOF by 2.74-fold compared to that of MOF. In addition, cinnamaldehyde was grafted onto CGMOF for tumor-responsive hydrogen peroxide self-supply. Concurrently, hyaluronic acid was surface-modified to achieve the targeted delivery of nano-photosensitizers. In summary, this study presents an innovative approach for engineering Fe-based metal-organic frameworks for synergetic PDT/CDT applications.

Realizing the full reservoir operation potential during the 2020 Yangtze river floods.

Five severe floods occurred in the Yangtze River Basin, China, between July and August 2020, and the Three Gorges Reservoir (TGR) located in the middle Yangtze River experienced the highest inflow since construction. The world's largest cascade-reservoir group, which counts for 22 cascade reservoirs in the upper Yangtze River, cooperated in real time to control floods. The cooperation prevented evacuation of 600,000 people and extensive inundations of farmlands and aquacultural areas. In addition, no water spillage occurred during the flood control period, resulting in a world-record annual output of the TGR hydropower station. This work describes decision making challenges in the cooperation of super large reservoir groups based on a case-study, controlling the 4th and 5th floods (from Aug-14 to Aug-22), the efforts of technicians, multi-departments, and the state, and reflects on these. To realize the full potential of reservoir operation for the Yangtze River Basin and other basins with large reservoir groups globally, we suggest: (i) improve flood forecast accuracy with a long leading time; (ii) strengthen and further develop ongoing research on reservoir group cooperation; and (iii) improve and implement institutional mechanisms for coordinated operation of large reservoir groups.