As trategy called ultramicroporous building unit (UBU) is introduced. It allows the creation of hierarchical biporous features that work in tandem to enhance gas uptake capacity and separation. Smaller pores from UBUs promote selectivity,w hile larger inter-UBUp acking pores increase uptake capacity.T he effectiveness of this UBUs trategy is shown with ac obalt MOF (denoted SNNU-45) in which octahedral cages with 4.5 pore sizeserve as UBUs.The C 2 H 2 uptake capacity at 1atm reaches 193.0 cm 3 g À1 (8.6 mmol g À1 ) at 273 Kand 134.0 cm 3 g À1 (6.0 mmol g À1 )at298 K. Suchhigh uptake capacity is accompanied by ahigh C 2 H 2 /CO 2 selectivity of up to 8.5 at 298 K. Dynamic breakthrough studies at room temperature and 1atm show aC 2 H 2 /CO 2 breakthrough time up to 79 min g À1 ,among top-performing MOFs.Grand canonical Monte Carlo simulations agree that ultrahigh C 2 H 2 /CO 2 selectivity is mainly from UBUultramicropores,while packing pores promote C 2 H 2 uptake capacity.
High gas‐uptake capacity is desirable for many reasons such as gas storage and sequestration. Moreover, ultrahigh capacity can enable a practical separation process by mitigating the selectivity factor that sometimes compromises separation efficiency. Herein, a single‐walled nickel–organic framework with an exceptionally high gas capture capability is reported. For example, C2H4 and C2H6 uptake capacities are at record‐setting levels of 224 and 289 cm3 g−1 at 273 K and 1 bar (169 and 110 cm3 g−1 at 298 K and 1 bar), respectively. Such ultrahigh capacities for both gases give rise to an excellent separation performance, as shown for C2H6/C2H4 with breakthrough times of 100, 60 and 30 min at 273, 283 and 298 K and under 1 atm. This new material is also shown to readily remove ethylene released from fruits, and once again, its ultrahigh capacity plays a key role in the extraordinary length of time achieved in the preservation of the fruit freshness.
The major obstacles of anti‐PD therapy in metastatic tumors are limited drug delivery in primary tumors and metastatic foci, and the lack of tumor‐infiltrating lymphocytes (TILs). Here, the authors constructed a novel cellular membrane nanovesicles platform (M/IR NPs) based on homologous targeting and near‐infrared (NIR) responsive release strategy to potentiate PD‐1/PD‐L1 blockade therapy against metastatic tumors. In tumor‐bearing mice, biomimetic M/IR NPs targeted both primary tumors and their lung metastases. Upon laser irradiation, M/IR NPs reduced cancer‐associated fibroblasts (CAFs) in tumor microenvironment, thus increasing the penetration of TILs. When shed from homologous tumor cell membranes, positively charged nanoparticles (IR NPs) core can capture released tumor‐associated antigens, thereby enhancing the antigen‐presenting ability of DCs to activate cytotoxic T lymphocytes. When the photothermal conversion temperature under NIR‐laser is higher than 42 °C, M/IR NPs initiated the rupture of cell membranes and the responsive release of PD‐1/PD‐L1 inhibitor BMS, which significantly attenuated tumor‐associated immunosuppression and synergistically induced T cellular immunity to inhibit the tumor growth and metastasis. Overall, biomimetic M/IR NPs can improve the targeting and therapeutic efficacy of anti‐PD therapy in primary tumors and metastases, opening up a new avenue for the diagnosis and treatment of metastatic tumors in the future.
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