Silica Jar‐with‐Lid as Chemo‐Enzymatic Nano‐Compartment for Enantioselective Synthesis inside Living Cells. (24th June 2021)

• Record Type: Journal Article
• Authors: Kim, Seonock; Kumari, Nitee; Lim, Jongwon; Dubbu, Sateesh; Kumar, Amit; Lee, In Su
• Is Part Of: Angewandte Chemie. Volume 133:Number 30(2021)
• Page Start: 16473
• Page End: 16478
• Publication Date: 2021-06-24
• Subjects: chemo-enzyme hybrid -- enantioselective catalysis -- nanocatalyst -- nanocrystal conversion chemistry -- open-mouth nanoreactor; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.202103165
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: 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 (SiJAR s) 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, SiJAR s 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. Abstract : Round bottom jar‐like silica nanostructure (SiJAR) fitted with a Mn‐silicate lid was fabricated through the highly controlled thermal solid‐state conversion of a MnO nanocrystal at the inside of hollow SiO2 shell. The lid aperture‐opening created an open‐mouth nanoreactor accommodating catalytic metal nanocrystals and enzymes, which performed asymmetric aldol reactions with high activity and enantioselectivity inside living cells.