Bringing fluorine into the (essential) chemistry of bacteria
Fluorine (F) is a key element for the synthesis of molecules broadly used in medicine, agriculture and material applications. ‘Decorating’ organic structures with F atoms onto is a unique strategy for tuning molecular properties—yet organofluorines are rarely found in Nature, and approaches to integrate fluorometabolites into the core biochemistry of living cells are scarce. In this talk, I will also discuss how synthetic metabolism can be implemented to expand the chemical landscape of bacteria, thus providing alternative biosynthetic strategies for fluorinated building-blocks. Such general approach will be illustrated by showing how synthetic gene circuits can be engineered in the platform bacterium Pseudomonas putida for organofluorine biosynthesis. To this end, fluoride-responsive riboswitches, orthogonal RNA polymerases and novel fluorinating enzymes mined from extreme environments were combined to drive in vivo biofluorination reactions. Biosynthesis of fluoronucleotides and fluorosugars in engineered P. putida is demonstrated with mineral fluoride both as the only F source (i.e. as a substrate of the pathway) and as inducer of the synthetic circuit. Building on these results, prospects for bioproduction of fluorinated building blocks and materials will be likewise discussed at the light of ‘F-addiction’ strategies.
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