We describe a microporous plasmonic nanoreactor to carry out designed near-infrared (NIR)-driven photothermal cyclizations inside living cells. As a proof of concept, we chose an intramolecular cyclization that is based on the nucleophilic attack of a pyridine onto an electrophilic carbon, a process that requires high activation energies and is typically achieved in bulk solution by heating at ∼90 °C. The core–shell nanoreactor (NR) has been designed to include a gold nanostar core, which is embedded within a metal–organic framework (MOF) based on a polymer-stabilized zeolitic imidazole framework-8 (ZIF-8). Once accumulated inside living cells, the MOF-based cloak of NRs allows an efficient diffusion of reactants into the plasmonic chamber, where they undergo the transformation upon near-IR illumination. The photothermal-driven reaction enables the intracellular generation of cyclic fluorescent products that can be tracked using fluorescence microscopy. The strategy may find different type of applications, such as for the spatio-temporal activation of prodrugs.

中文翻译：

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使用基于金属-有机框架的纳米反应器在活细胞中进行等离子体辅助热环化

我们描述了一种微孔等离子体纳米反应器，用于在活细胞内进行设计的近红外 (NIR) 驱动的光热环化。作为概念证明，我们选择了基于吡啶亲核攻击亲电碳的分子内环化，该过程需要高活化能，通常通过在约 90 °C 下加热在本体溶液中实现。核壳纳米反应器 (NR) 设计为包含金纳米星核，该核嵌入基于聚合物稳定的沸石咪唑骨架 8 (ZIF-8) 的金属有机骨架 (MOF) 中。一旦在活细胞内积累，基于 MOF 的 NRs 斗篷允许反应物有效扩散到等离子体室中，在那里它们在近红外照射下进行转化。光热驱动的反应能够在细胞内产生循环荧光产物，可以使用荧光显微镜进行追踪。该策略可以找到不同类型的应用，例如用于前药的时空激活。