Placing metal complexes in macromolecular scaffolds has shown its usefulness in improving catalytic activity for synthetic purposes and reactions in biological environments. Here, we show that a star polymer scaffold with a dense shell and a concentrated ligand core can be readily synthesized from an integrated polymerization-crosslinking process mediated directly by a tris-triazole ligand. The straightforward synthesis can give well-defined polymeric nanoparticles with a core–shell structure, with a dense polymeric shell protecting the ligands in the core that are readily available for metal coordination. Using copper and palladium catalyst as examples, we show that those macromolecular Cu and Pd catalysts can mediate aqueous “click” reactions and propargyl carbamate deprotection, respectively. The scaffolds not only grant protection and stabilization of the catalytic centers, but, more importantly, they also can be tuned to promote reactions in different cellular locations in mammalian cells, and the localization of the products are guided by either the catalytic scaffold or specially designed substrates.

中文翻译：

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在细胞环境中催化或底物引导的致密壳高分子支架

将金属络合物放置在大分子支架中已显示出其在改善用于合成目的和在生物环境中反应的催化活性方面的有用性。在这里，我们表明，具有致密壳和浓配体核的星形聚合物支架可以很容易地由直接由三三唑配体介导的集成聚合-交联过程合成。简单的合成方法可以得到具有核-壳结构的明确定义的聚合物纳米颗粒，并具有致密的聚合物壳来保护核中的配体，这些配体可用于金属配位。以铜和钯催化剂为例，我们表明那些大分子的铜和钯催化剂可以分别介导水性“喀哒”反应和炔丙基氨基甲酸酯脱保护。