Facile Fabrication of Hierarchical MOF-Metal Nanoparticle Tandem Catalysts for the Synthesis of Bioactive Molecules
Facile Fabrication of Hierarchical MOF-Metal Nanoparticle Tandem Catalysts for the Synthesis of Bioactive Molecules
复制标题
轻松制备多级 MOF-金属纳米颗粒串联催化剂，用于合成生物活性分子。
DOI：
10.1021/acsami.0c05344
复制
发表时间：
2020-05-20
影响因子：
9.5
通讯作者：
Huang, Wenyu
中科院分区：
文献类型：
--
作者：
Chen, Jingwen;Zhang, Biying;Huang, Wenyu
具有永久孔隙结构的多功能金属-有机骨架（MOFs）是有机转化的理想催化剂。在此，我们报告了用碱性脂肪胺基团和聚乙烯吡咯烷酮封端的铂纳米颗粒（Pt NPs）官能化的分级MOF的构建。有机配体的合成后共价修饰增加了MOF中的基本位点密度，同时引入中孔以产生分级多孔结构。该多功能MOF能够催化连续的Knoevenagel缩合-氢化-分子内环化反应。通过负载在MOF上的Pt NPs将硝基独特地选择性还原为中间体羟胺，然后与氰基进行分子内环化，提供了优于喹啉的不常见喹啉N-氧化物的优异产率（高达92%）。Pt纳米颗粒上的分级MOF和聚乙烯吡咯烷酮封端剂协同促进底物的富集，从而在还原-分子内环化反应中产生高活性。生物活性测试表明，所合成的喹啉氮氧化物对肺癌细胞的增殖有明显的抑制作用。我们的研究结果表明，在温和的条件下，MOF催化直接合成生物活性分子的可行性。
Multifunctional metal-organic frameworks (MOFs) that possess permanent porosity are promising catalysts in organic transformation. Herein, we report the construction of a hierarchical MOF functionalized with basic aliphatic amine groups and polyvinylpyrrolidone-capped platinum nanoparticles (Pt NPs). The postsynthetic covalent modification of organic ligands increases basic site density in the MOF and simultaneously introduces mesopores to create a hierarchically porous structure. The multifunctional MOF is capable of catalyzing a sequential Knoevenagel condensation-hydrogenation-intramolecular cyclization reaction. The unique selective reduction of the nitro group to intermediate hydroxylamine by Pt NPs supported on MOF followed by intramolecular cyclization with a cyano group affords an excellent yield (up to 92%) to the uncommon quinoline N-oxides over quinolines. The hierarchical MOF and polyvinylpyrrolidone capping agent on Pt NPs synergistically facilitate the enrichment of substrates and thus lead to high activity in the reduction-intramolecular cyclization reaction. The bioactivity assay indicates that the synthesized quinoline N-oxides evidently inhibit the proliferation of lung cancer cells. Our findings demonstrate the feasibility of MOF-catalyzed direct synthesis of bioactive molecules from readily available compounds under mild conditions.