RT Journal Article T1 Plasmonic-assisted thermocyclizations in living cells using metal−organic framework based nanoreactors A1 Carrillo Carrión, Carolina A1 Martínez González, Raquel A1 Polo Tobajas, Ester A1 Tomás Gamasa, María A1 Destito, Paolo A1 Ceballos Guzmán, Manuel A1 Pelaz García, Beatriz A1 López García, Fernando A1 Mascareñas Cid, José Luis A1 Pino González de la Higuera, Pablo Alfonso del K1 Bio-orthogonal chemistry K1 Nanocomposites K1 Thermoplasmonics K1 Intracellular thermocyclization K1 Thermolabile protecting groups AB 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 PB ACS SN 1936-0851 YR 2021 FD 2021 LK http://hdl.handle.net/10347/27035 UL http://hdl.handle.net/10347/27035 LA eng NO ACS Nano 2021, 15, 16924−16933 NO The authors thank the financial support of the MCIN/AEI (PID2020-119206RB-I00, PID2019-108624RB-I00, CTQ2017-84767-P, RYC-2017-23457, RYC-2019-028238-I, RTI2018-093813-J-I00), the Xunta de Galicia (ED431F 2017/02, 2021-CP054, ED431C-2021/25, Centro Singular de Investigación de Galicia Accreditation 2019−2022, and ED431G 2019/03), the European Union (European Regional Development Fund − ERDF; H2020-MSCA-IF grant agreement no. 749667; H2020-MSCA-ITN grant agreement no. 860942; H2020-FET-Open grant agreement No. 899612; and INTERREG V-A Spain−Portugal, project 0624_2IQBIONEURO_6_E), and the European Research Council (starting grant no. 950421, advanced grant no. 340055). The support of the orfeo-cinqa network (CTQ2016-81797-REDC) is also kindly acknowledged DS Minerva RD 22 abr 2026