Key Laboratory of Mesoscopic Chemistry (Ministry of Education), State Key Laboratory of Coordination Chemistry, and School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210023, People's Republic of China.
State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, People's Republic of China.
ACS Appl Mater Interfaces. 2023 Jun 7;15(22):27264-27276. doi: 10.1021/acsami.3c02052. Epub 2023 May 29.
A new universal strategy for silane functionalization of metal-organic frameworks (MOFs) was developed. It was demonstrated that silanes were coupled both with terminal hydroxyl (OH) groups and with bridging OH groups of metal-oxo clusters of MOFs through condensation reactions between the silanols of hydrolyzed silanes and the terminal/bridging OH groups to form metal-O-Si bonds. A wide variety of functionalization of MOFs with conventional silanes can be realized by combining synthesis reactions in the solution phase and chemical modifications on the surface. Multivalent supramolecular nanovalves based on the host-guest chemistry of cyclodextrin polymer (CDP) and benzimidazole stalks silanized on the nanoscale MOF (NMOF) surface were successfully constructed. The CDP-valved NMOFs showed the excellent performance of low pH- and α-amylase-responsive controlled drug release. In vitro and in vivo results demonstrated that the CDP-valved NMOFs had a significant inhibitory effect on tumor growth and almost no damage/toxicity to normal tissues. The silanization strategy is universal and opens up a new way for the functionalization of MOFs, which are endowed with a wide variety of applications spanning gas storage, chemical sensing, adsorption and separation, heterogeneous catalysis, and drug delivery.
开发了一种用于金属有机骨架（MOF）硅烷功能化的新通用策略。通过水解硅烷的硅醇与末端/桥接 OH 基团之间的缩合反应，证明硅烷与 MOF 的金属氧簇的末端 OH 基团和桥接 OH 基团偶联，形成金属-O-Si 键。通过在溶液相中进行合成反应和在表面进行化学修饰，可以实现 MOF 与传统硅烷的各种功能化。成功构建了基于环糊精聚合物（CDP）主客体化学和纳米尺度 MOF（NMOF）表面硅烷化苯并咪唑支链的多价超分子纳米阀。CDP 阀控 NMOFs 表现出对低 pH 和α-淀粉酶响应的控释药物释放的优异性能。体外和体内结果表明，CDP 阀控 NMOFs 对肿瘤生长具有显著的抑制作用，对正常组织几乎没有损伤/毒性。硅烷化策略具有通用性，为 MOF 的功能化开辟了新途径，使其在气体储存、化学传感、吸附和分离、多相催化以及药物输送等方面具有广泛的应用。
