Distinct roles of pH and organic ligands in the dissolution of goethite by cysteine.

Electron shuttles such cysteine play an important role in Fe cycle and its availability in soils, while the roles of pH and organic ligands in this process are poorly understood. Herein, the reductive dissolution process of goethite by cysteine were explored in the presence of organic ligands. Our results showed that cysteine exhibited a strong reactivity towards goethite - a typical iron minerals in paddy soils with a rate constant ranging from 0.01 to 0.1 hr-1. However, a large portion of Fe(II) appeared to be "structural species" retained on the surface. The decline of pH was favorable to generate more Fe(II) ions and enhancing tendency of Fe(II) release to solution. The decline of generation of Fe(II) by increasing pH was likely to be caused by a lower redox potential and the nature of cysteine pH-dependent adsorption towards goethite. Interestingly, the co-existence of oxalate and citrate ligands also enhanced the rate constant of Fe(II) release from 0.09 to 0.15 hr-1; nevertheless, they negligibly affected the overall generation of Fe(II) in opposition to the pH effect. Further spectroscopic evidence demonstrated that two molecules of cysteine could form disulfide bonds (S-S) to generate cystine through oxidative dehydration, and subsequently, inducing electron transfer from cysteine to the structural Fe(III) on goethite; meanwhile, those organic ligands act as Fe(II) "strippers". The findings of this work provide new insights into the understanding of the different roles of pH and organic ligands on the generation and release of Fe induced by electron shuttles in soils.

Enhancement of bioelectricity generation by cofactor manipulation in microbial fuel cell.

Microbial fuel cells (MFCs) are promising for harnessing bioenergy from various organic wastes. However, low electricity power output (EPT) is one of the major bottlenecks in the practical application of MFCs. In this study, EPT improvement by cofactor manipulation was explored in the Pseudomonas aeruginosa-inoculated MFCs. By overexpression of nadE (NAD synthetase gene), the availability of the intracellular cofactor pool (NAD(H/(+))) significantly increased, and delivered approximately three times higher power output than the original strain (increased from 10.86 µW/cm(2) to 40.13 µW/cm(2)). The nadE overexpression strain showed about a onefold decrease in charge transfer resistance and higher electrochemical activity than the original strain, which should underlie the power output improvement. Furthermore, cyclic voltammetry, HPLC, and LC-MS analysis showed that the concentration of the electron shuttle (pyocyanin) increased approximately 1.5 fold upon nadE overexpression, which was responsible for the enhanced electrochemical activity. Thus, the results substantiated that the manipulation of intracellular cofactor could be an efficient approach to improve the EPT of MFCs, and implied metabolic engineering is of great potential for EPT improvement.