Silica Jar-with-Lid as Chemo-Enzymatic Nano-Compartment for Enantioselective Synthesis inside Living Cells

Seonock Kim, Dr. Nitee Kumari, Jongwon Lim, Dr. Sateesh Dubbu, Dr. Amit Kumar, Prof. In Su Lee  

 Nanodevices, harvesting the power of synthetic catalysts and enzymes to perform enantioselective synthesis inside cell, have never been reported. Here, we synthesized round bottom jar-like silica nanostructures (SiJARs) with a chemo-responsive metal-silicate lid. This was isolated as an intermediate structure during highly controlled solid-state nanocrystal-conversion at the arc-section of silica shell. Different catalytic noble metals (Pt, Pd, Ru) were selectively modified on the lid-section through galvanic reactions. And, lid aperture-opening was regulated by mild acidic conditions or intracellular environment which accommodated the metal nanocrystals and enzymes, and in turn created an open-mouth nanoreactor. Distinct from the free enzymes, SiJARs performed asymmetric aldol reactions with high activity and enantioselectivity (yield >99%, ee = 95%) and also functioned as the artificial catalytic organelles inside living cells. This work bridges the enormous potential of sophisticated nanocrystal-conversion chemistry and advanced platforms for new-to-nature catalysis.   https://doi.org/10.1002/anie.202103165