Interfacing non-enzymatic catalysis with living microorganisms

Abstract

This review highlights recent advances in the field of biocompatible chemistry. It focusses on the combined use of non-enzymatic catalysis and microbial metabolism to support cellular function and to synthesise high value chemicals.

Extracellular Electron Transfer Enables Cellular Control of Cu(I)-Catalyzed Alkyne–Azide Cycloaddition

“…Furthermore, in negative controls involving the ΔMtr-pathway knockout or E. coli , we did not observe a complete arrest of CuAAC conversion. It is likely that Cu­(II) reduction is tied to other electron transport or reduction pathways such as extracellular flavins, glutathione, ,, and copper nanoparticle formation . Despite the presence of some background reduction, our results indicate that conversion is primarily controlled by the Mtr-pathway.…”

“…Recently, we and others have connected cellular metabolism to exogenous synthetic reactions via hydrogen generation, the secretion of reactive cellular metabolites, and extracellular electron transfer (EET). 10 − 14 Among these approaches, EET is particularly advantageous, because it provides a tunable protein bridge between central carbon metabolism and extracellular redox reactions, including those controlled via metal catalysts. Specifically, EET in the model electroactive bacterium Shewanella oneidensis (wild-type MR-1) is regulated through a set of well-defined heme-containing cytochromes in the Mtr-pathway (metal-reducing pathway).…”

“…Recently, we and others have connected cellular metabolism to exogenous synthetic reactions via hydrogen generation, the secretion of reactive cellular metabolites, and extracellular electron transfer (EET). − Among these approaches, EET is particularly advantageous, because it provides a tunable protein bridge between central carbon metabolism and extracellular redox reactions, including those controlled via metal catalysts. Specifically, EET in the model electroactive bacterium Shewanella oneidensis (wild-type MR-1) is regulated through a set of well-defined heme-containing cytochromes in the Mtr-pathway (metal-reducing pathway). − This pathway allows S. oneidensis to use oxidized metal ions, including organometallic catalysts, as terminal electron acceptors under anaerobic conditions. − Indeed, bacterial reduction of metals including iron­(III) and copper­(II) by E. coli and S. oneidensis has previously been used to perform atom-transfer radical polymerization (ATRP), − and transcriptional regulation of specific EET proteins in S. oneidensis has enabled dynamic control over metal reduction and resulting catalysis. , Given these results, we hypothesized that additional synthetic reactions involving the Cu­(II/I) redox couple could be metabolically controlled using EET from S. oneidensis .…”

Hydrodechlorination of Aryl Chlorides Under Biocompatible Conditions

“…We set out to create a biocompatible chemical reaction to reduce C–Cl bonds on aryl chlorides. We envisioned that such a reaction would have applications in wastewater treatment, synthetic biology, semisynthesis, and green chemistry methods. A biocompatible reaction is one that can be carried out in the presence of living cells .…”

Enzymatic Catalysis Conceptual Study

“…It is essential to remember that enzymes are proteins, which catalyze specific reactions. [1][2][3][4][5][6][7] Enzymes are particularly important in organic chemistry because they speed up reactions, they offer mild reactions conditions, and a unique selectivity. Their meaningful is also due to fact that the applications of emzymes have been developed into scientific research not only in academic settings, but also for industrial quantities namely the enzymatic synthesis of methane whose reactions mechanisms have recently been reported by our group (Scheme 1).…”