Centro Singular de Investigación en Química Biolóxica e Materiais Moleculares (CiQUS), Departamento de Física de Partículas, Universidade de Santiago de Compostela, 15782 Santiago de Compostela, Spain.
Centro Singular de Investigación en Química Biolóxica e Materiais Moleculares (CiQUS), Departamento de Bioquímica y Biología Molecular, Universidade de Santiago de Compostela, 15782 Santiago de Compostela, Spain.
ACS Nano. 2021 Oct 26;15(10):16924-16933. doi: 10.1021/acsnano.1c07983. Epub 2021 Oct 18.
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.
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）驱动光热环化反应。作为概念验证，我们选择了一种分子内环化反应，该反应基于吡啶对亲电碳的亲核攻击，该过程需要高活化能，并且通常通过在约 90°C 的温度下加热在体相溶液中实现。核壳纳米反应器（NR）的设计包括一个金纳米星核，该核嵌入在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，NR 的基于 MOF 的外壳允许反应物有效地扩散到等离子体腔内，在腔内，它们在近红外照射下发生转化。光热驱动的反应能够在细胞内生成可通过荧光显微镜跟踪的环状荧光产物。该策略可能有不同类型的应用，例如用于前药的时空激活。
