Flavin secretion of Clostridium acetobutylicum in a bioelectrochemical system - Is an iron limitation involved?

A flavin-based extracellular electron transfer mechanism (EET) has recently been described for the gram-positive Listeria monocytogenes. The gram-positive, solvent producing Clostridium acetobutylicum is a known flavin producer. Since flavin secretion in C. acetobutylicum can be triggered by a low-iron environment, the interaction of iron with an electrochemical system as well as the consequences for flavin production are investigated. It is shown that iron adsorbs onto the electrode's surface in the form of iron phosphorus compounds but that this iron is still bioavailable. Moreover, a shift in the flavin spectrum of the supernatant from high flavin mononucleotide percentages of 59% to high riboflavin (43-45%) and flavin adenine dinucleotide (FAD, 40-48%) content can be seen by limiting or omitting the iron source from the culture medium. When additionally an electric potential of -600 mV vs. Ag/AgCl (saturated KCl) is applied, the same overall trend is obtained but an increase in flavin concentration and especially in the FAD share between 6 and 27% is observed. This study is a first hint that a flavin-based EET might also take place in solventogenic Clostridia and highlights the importance of further investigation of flavin production and their involvement in EET mechanisms in different species.

Increased Biobutanol Production by Mediator-Less Electro-Fermentation.

A future bio-economy should not only be based on renewable raw materials but also in the raise of carbon yields of existing production routes. Microbial electrochemical technologies are gaining increased attention for this purpose. In this study, the electro-fermentative production of biobutanol with C. acetobutylicum without the use of exogenous mediators is investigated regarding the medium composition and the reactor design. It is shown that the use of an optimized synthetic culture medium allows higher product concentrations, increased biofilm formation, and higher conductivities compared to a synthetic medium supplemented with yeast extract. Moreover, the optimization of the reactor system results in a doubling of the maximum product concentrations for fermentation products. When a working electrode is polarized at -600 mV vs. Ag/AgCl, a shift from butyrate to acetone and butanol production is induced. This leads to an increased final solvent yield of YABE = 0.202 g g-1 (control 0.103 g g-1 ), which is also reflected in a higher carbon efficiency of 37.6% compared to 23.3% (control) as well as a fourfold decrease in simplified E-factor to 0.43. The results are promising for further development of biobutanol production in bioelectrochemical systems in order to fulfil the principles of Green Chemistry.