Modulation of Molybdenum-Centered Redox Potentials and Electron-Transfer Rates by Sulfur versus Oxygen Ligation

2004 ◽  
Vol 43 (23) ◽  
pp. 7389-7395 ◽  
Author(s):  
Darrell Uhrhammer ◽  
Franklin A. Schultz
Keyword(s):  
Electron Transfer ◽  
Redox Potentials ◽  
Transfer Rates

scholarly journals Structure and function of Aspergillus niger laccase McoG

Biocatalysis ◽  
2017 ◽  
Vol 3 (1) ◽  
pp. 1-21 ◽  
Author(s):  
Marta Ferraroni ◽  
Adrie H. Westphal ◽  
Marco Borsari ◽  
Juan Antonio Tamayo-Ramos ◽  
Fabrizio Briganti ◽  
...  
Keyword(s):  
Crystal Structure ◽  
Electron Transfer ◽  
Aspergillus Niger ◽  
Structure And Function ◽  
Redox Potentials ◽  
Wild Type ◽  
Multicopper Oxidases ◽  
Transfer Rates ◽  
The Common ◽  
And Function

AbstractThe ascomycete Aspergillus niger produces several multicopper oxidases, but their biocatalytic properties remain largely unknown. Elucidation of the crystal structure of A. niger laccase McoG at 1.7 Å resolution revealed that the C-terminal tail of this glycoprotein blocks the T3 solvent channel and that a peroxide ion bridges the two T3 copper atoms. Remarkably, McoG contains a histidine (His253) instead of the common aspartate or glutamate expected to be involved in catalytic proton transfer with phenolic compounds. The crystal structure of H253D at 1.5 Å resolution resembles the wild type structure. McoG and the H253D, H253A and H253N variants have similar activities with 2,2’-azino-bis(3- ethylbenzothiazoline-6-sulphonic acid or N,N-dimethyl-p-phenylenediamine sulphate. However, the activities of H253A and H253N with 2-amino-4-methylphenol and 2-amino-4-methoxyphenol are strongly reduced compared to that of wild type. The redox potentials and electron transfer rates (k

scholarly journals Insight to Microbial Fe(III) Reduction Mediated by Redox-Active Humic Acids with Varied Redox Potentials

2021 ◽  
Vol 18 (13) ◽  
pp. 6807
Author(s):  
Jingtao Duan ◽  
Zhiyuan Xu ◽  
Zhen Yang ◽  
Jie Jiang
Keyword(s):  
Molecular Weight ◽  
Electron Transfer ◽  
Humic Acids ◽  
Weight Fraction ◽  
Electrochemical Analysis ◽  
Microbial Reduction ◽  
Redox Potentials ◽  
Groundwater Environment ◽  
Redox Active ◽  
Different Molecular Weight

Redox-active humic acids (HA) are ubiquitous in terrestrial and aquatic systems and are involved in numerous electron transfer reactions affecting biogeochemical processes and fates of pollutants in soil environments. Redox-active contaminants are trapped in soil micropores (<2 nm) that have limited access to microbes and HA. Therefore, the contaminants whose molecular structure and properties are not damaged accumulate in the soil micropores and become potential pollution sources. Electron transfer capacities (ETC) of HA reflecting redox activities of low molecular weight fraction (LMWF, <2.5) HA can be detected by an electrochemical method, which is related to redox potentials (Eh) in soil and aquatic environments. Nevertheless, electron accepting capacities (EAC) and electron donating capacities (EDC) of these LMWF HA at different Eh are still unknown. EDC and EAC of different molecular weight HA at different Eh were analyzed using electrochemical methods. EAC of LMWF at −0.59 V was 12 times higher than that at −0.49 V, while EAC increased to 2.6 times when the Eh decreased from −0.59 V to −0.69 V. Afterward, LMWF can act as a shuttle to stimulate microbial Fe(III) reduction processes in microbial reduction experiments. Additionally, EAC by electrochemical analysis at a range of −0.49–−0.59 V was comparable to total calculated ETC of different molecular weight fractions of HA by microbial reduction. Therefore, it is indicated that redox-active functional groups that can be reduced at Eh range of −0.49–−0.59 are available to microbial reduction. This finding contributes to a novel perspective in the protection and remediation of the groundwater environment in the biogeochemistry process.

Quantification of Electron Transfer Rates to a Solid Phase Electron Acceptor through the Stages of Biofilm Formation from Single Cells to Multicellular Communities

2010 ◽  
Vol 44 (7) ◽  
pp. 2721-2727 ◽  
Author(s):  
Jeffrey S. McLean ◽  
Greg Wanger ◽  
Yuri A. Gorby ◽  
Martin Wainstein ◽  
Jeff McQuaid ◽  
...  
Keyword(s):  
Electron Transfer ◽  
Electron Acceptor ◽  
Biofilm Formation ◽  
Solid Phase ◽  
Single Cells ◽  
Transfer Rates

scholarly journals The effects of the chemical environment of menaquinones in lipid monolayers on mercury electrodes on the thermodynamics and kinetics of their electrochemistry

2021 ◽  
Author(s):  
Karuppasamy Dharmaraj ◽  
Dirk Dattler ◽  
Heike Kahlert ◽  
Uwe Lendeckel ◽  
Felix Nagel ◽  
...  
Keyword(s):  
Electron Transfer ◽  
Rate Constants ◽  
Transfer Rate ◽  
Chemical Environment ◽  
Lipid Monolayers ◽  
Redox Potentials ◽  
Electron Transfer Rate ◽  
Thermodynamics And Kinetics ◽  
Mercury Electrodes ◽  
Kinetics Of

AbstractThe effects of the chemical environment of menaquinones (all-trans MK-4 and all-trans MK-7) incorporated in lipid monolayers on mercury electrodes have been studied with respect to the thermodynamics and kinetics of their electrochemistry. The chemical environment relates to the composition of lipid films as well as the adjacent aqueous phase. It could be shown that the addition of all-trans MK-4 to TMCL does not change the phase transition temperatures of TMCL. In case of DMPC monolayers, the presence of cholesterol has no effect on the thermodynamics (formal redox potentials) of all-trans MK-7, but the kinetics are affected. Addition of an inert electrolyte (sodium perchlorate; change of ionic strength) to the aqueous phase shifts the redox potentials of all-trans MK-7 only slightly. The formal redox potentials of all-trans MK-4 were determined in TMCL and nCL monolayers and found to be higher in nCL monolayers than in TMCL monolayers. The apparent electron transfer rate constants, transfer coefficients and activation energies of all-trans MK-4 in cardiolipins have been also determined. Most surprisingly, the apparent electron transfer rate constants of all-trans MK-4 exhibit an opposite pH dependence for TMCL and nCL films: the rate constants increase in TMCL films with increasing pH, but in nCL films they increase with decreasing pH. This study is a contribution to understand environmental effects on the redox properties of membrane bond redox systems. Graphical abstract

Four Aspects of the Distance Dependence of Electron-Transfer Rates

1982 ◽  
pp. 213-233 ◽  
Author(s):  
EPHRAIM BUHKS ◽  
RALPH G. WILKINS ◽  
STEPHAN S. ISIED ◽  
JOHN F. ENDICOTT
Keyword(s):  
Electron Transfer ◽  
Transfer Rates ◽  
Distance Dependence
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