Summary Translating the potential of transition metal catalysis to biological and living environments promises to have a profound impact in chemical biology and biomedicine. A major challenge in the field is the creation of metal-based catalysts that remain active over time. Here, we demonstrate that embedding a reactive metallic core within a microporous metal-organic framework-based cloak preserves the catalytic site from passivation and deactivation, while allowing a suitable diffusion of the reactants. Specifically, we report the fabrication of nanoreactors composed of a palladium nanocube core and a nanometric imidazolate framework, which behave as robust, long-lasting nanoreactors capable of removing propargylic groups from phenol-derived pro-fluorophores in biological milieu and inside living cells. These heterogeneous catalysts can be reused within the same cells, promoting the chemical transformation of recurrent batches of reactants. We also report the assembly of tissue-like 3D spheroids containing the nanoreactors and demonstrate that they can perform the reactions in a repeated manner.

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Translating the potential of thermoplasmonics to cell‐derived nanomaterials offers exciting opportunities to fabricate beyond state‐of‐art artificial biomimetic nanocomposites that upon illumination perform active tasks such as delivery of cargo in complex, dynamic media such as the cytosol of cells. Cell‐derived nanoparticles have shown stunning potential to implement cell‐specific functions, such as long blood circulation or targeting capabilities, into advanced drug delivery nanosystems. The biomimicry nanotechnology has now advanced to offer new and exciting opportunities to improve the commonly poor in vivo performance of most current nanomedicines, including evading the immune system and targeting specific tissues such as tumors, the latest remaining among the most wanted breakthroughs in nanomedicine. However, the use of cell‐derived nanocomposites as stimulus‐controlled drug delivery agents remains virtually unexplored. This study reports the fabrication of a plasmonic cell‐derived nanocomposite by integrating near‐infrared active gold nanorods in its structure. As a proof of concept, the plasmonic nanomembranes are loaded with cell non‐permeant antibodies, which upon near‐infrared stimulation can be released from the plasmonic nanomembranes into the cytosol of living cells, without impairing cell viability or the antibodies' function. These results set the stage for the development of photoactive cell‐derived nanocarriers, which in addition to cell‐specific functions promise straightforward access to spatiotemporal‐controlled intracellular delivery of antibodies.