Thioester synthesis through geoelectrochemical CO2 fixation on Ni sulfides

A prevailing scenario of the origin of life postulates thioesters as key intermediates in protometabolism, but there is no experimental support for the prebiotic CO2 fixation routes to thioesters. Here we demonstrate that, under a simulated geoelectrochemical condition in primordial ocean hydrothermal systems (–0.6 to –1.0 V versus the standard hydrogen electrode), nickel sulfide (NiS) gradually reduces to Ni0, while accumulating surface-bound carbon monoxide (CO) due to CO2 electroreduction. The resultant partially reduced NiS realizes thioester (S-methyl thioacetate) formation from CO and methanethiol even at room temperature and neutral pH with the yield up to 35% based on CO. This thioester formation is not inhibited, or even improved, by 50:50 coprecipitation of NiS with FeS or CoS (the maximum yields; 27 or 56%, respectively). Such a simple thioester synthesis likely occurred in Hadean deep-sea vent environments, setting a stage for the autotrophic origin of life.

Performance Analysis of Biocathode in Bioelectrochemical CO2 Reduction

Microbial electrosynthesis (MES) biogas upgrading is done via reduction of carbon dioxide to methane through electroactive microbial catalysis. The baseline MES mode of operation showed about a 39% increase in the methane production rate compared to the open circuit mode of operation. MES is capable of producing acetic acid at relatively more negative potential (−0.80 to –0.90 V vs. Standard Hydrogen Electrode (SHE)) than the potential at which it produces methane (−0.65 V vs. SHE). The optimum pH for enhancing the electroactive acetogens is found to be around 6.8–7.0 while a pH of around 7.0–7.5 enhances the electroactive methanogens performance. The biocathode adaptation test reveals that 45% of the methane was produced through the electrochemical pathway with a coulombic efficiency of 100% while maintaining heterotrophic efficiency above 99%.

Tactic Response ofShewanella oneidensisMR-1 toward Insoluble Electron Acceptors

ABSTRACTExoelectrogenic bacteria are defined by their ability to respire on extracellular and insoluble electron acceptors and have applications in bioremediation and microbial electrochemical systems (MESs), while playing important roles in biogeochemical cycling.Shewanella oneidensisMR-1, which has become a model organism for the study of extracellular respiration, is known to display taxis toward insoluble electron acceptors, including electrodes. Multiple mechanisms have been proposed for MR-1’s tactic behavior, and, here, we report on the role of electrochemical potential by video microscopy cell tracking experiments in three-electrode electrochemical cells. MR-1 trajectories were determined using a particle tracking algorithm and validated with Shannon’s entropy method. Tactic response by MR-1 in the electrochemical cell was observed to depend on the applied potential, as indicated by the average velocity and density of motile (>4 µm/s) MR-1 close to the electrode (<50 µm). Tactic behavior was observed at oxidative potentials, with a strong switch between the potentials −0.15 to −0.25 V versus the standard hydrogen electrode (SHE), which coincides with the reduction potential of flavins. The average velocity and density of motile MR-1 close to the electrode increased when riboflavin was added (2 µM), but were completely absent in a ΔmtrC/ΔomcAmutant of MR-1. Besides flavin’s function as an electron mediator to support anaerobic respiration on insoluble electron acceptors, we propose that riboflavin is excreted by MR-1 to sense redox gradients in its environment, aiding taxis toward insoluble electron acceptors, including electrodes in MESs.IMPORTANCEPrevious hypotheses of tactic behavior of exoelectrogenic bacteria are based on techniques that do not accurately control the electrochemical potential, such as chemical-in-plug assays or microscopy tracking experiments in two-electrode cells. Here, we have revisited previous experiments and, for the first time, performed microscopy cell-tracking experiments in three-electrode electrochemical cells, with defined electrode potentials. Based on these experiments, taxis toward electrodes is observed to switch at about −0.2 V versus standard hydrogen electrode (SHE), coinciding with the reduction potential of flavins.

A two-dimensional layered CdS/C2N heterostructure for visible-light-driven photocatalysis

A CdS/C2N heterojunction possesses a type-II band alignment with respect to the standard hydrogen electrode potentials.