Nature uses its own sophisticated catalysts, namely enzymes, to carry out numerous biochemical reactions sustaining life. Besides enzymes, innovative man-made catalysts — capable of synthesizing functional molecules such as therapeutic drugs and bioimaging probes locally inside living cells from simple and non-toxic precursors via various bond forming/breaking reactions — can lead to the discovery of side-effect-free drugs and ultraprecise diagnosis and also contribute as synthetic toolkit to chemical biologists. To realize such versatile and efficient biorthogonal reactions — rational, customizable and biocompatible designs of catalysts which can provide high catalytic efficacy, tolerance to complex biological media and facility to remotely control or stimulate reaction rates should be synthesized. Unfortunately, most of the reported biorthogonal catalysts take rather long reaction times and realize the products in poor yields and don’t offer any plug-in to remotely trigger or promote sluggish intracellular reactions, which is a serious bottle-neck for their advancement to extensive applications. Our new plasmonically integrated nanoreactors (PINERs) can perform highly accelerated catalytic reactions in living cells by using NIR-light as harmless and efficient energy source. The bi-component design of PINER (overall size ca. 100 nm) consists of compartmentalized and selectively accessible noble metal (Au/Pd/Pt) catalytic nanocrystals (size ca. 2 nm), proximally interfaced with a plasmonic corona having multiple closely spaced Au-nanospheroids (size ca. 15 nm). Plasmonic Au-nanospheroids act as optical nano-antennae which can efficiently concentrate remotely exposed NIR light and convert the absorbed photonic energy to highly localized heat and generate reactive charge-carriers; and these plasmon-induced effects dramatically stimulate the reactions taking place on proximal catalytic nanocrystals in PINER, without any unintentional adverse effects on living cells.

Remotely operable and highly functional plasmonic nanoreactors for NIR-light-induced bioorthogonal catalysis in living cells

2019 Fall National Meeting

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