scholarly journals Oxovanadium(V/IV) Complexes as Redox Mediators for Biofuel Cells: Physical, Magnetic, and Electrochemical Characterization, DFT and Molecular Docking

Compounds ◽  
2021 ◽  
Vol 1 (1) ◽  
pp. 15-28
Author(s):  
Natsuki Katsuumi ◽  
Hiba Sehimi ◽  
Sayantan Pradhan ◽  
Sanyobi Kim ◽  
Tomoyuki Haraguchi ◽  
...  

Based on the potential redox and catalytic ability of oxovanadium complexes, our goal was to characterize the physical properties of two such complexes to be used as mediators for laccase. Computational studies, TD-DFT calculations and docking simulations were performed to elucidate the interaction between laccase and the two anionic complexes (aquabis(oxalato)oxidovanadate(IV) (1) and bis(oxalato)dioxidovanadate(V)) (2), respectively. Electrochemical measurements carried out on anion complexes of 1 and 2 docked into laccase were compared to laccase alone, showing changes in oxidation-reduction potential and current value, especially with the oxovanadium anion of 2. Since both internal tiny magnetic fields of ferromagnetic catalysts and external applied magnetic fields were found in previous investigations to constitute effective ways to improve the oxygen transfer rate, the magnetic susceptibility was measured. A valence change proneness was confirmed with higher valence for the oxovanadium anion of 2, which is in accordance with the electrochemical results.

1960 ◽  
Vol 38 (3) ◽  
pp. 399-407 ◽  
Author(s):  
Rudolf Kaul ◽  
Michael Shaw

Extracts of healthy and rusted leaves of Little Club and Khapli wheats were made under anaerobic conditions. Oxidation–reduction potentials in the extracts were measured at two different levels both in the presence and in the absence of both methylene blue and riboflavin as redox mediators. At the lower level (i.e. in the absence of mediators) a reversible rise in potential was noted during the course of rust infection on Little Club; with Khapli the rise was similar but was not reversed. The response to rust infection of resistant and susceptible plants was also reflected in characteristic changes in the average potentials at higher levels (i.e. in the presence of mediators). After infection the oxidation–reduction balance of susceptible tissue was reorganized by the introduction of new systems which were found in the reduced state only. After infection the oxidation–reduction potential of resistant tissue was only poorly poised as indicated by a rise in the average potentials and as demonstrated by oxidation– reduction titrations.The results are discussed and the possibility is considered that a rust-induced catalyst may “short circuit” the chain of hydrogen transport, thus initiating all the observed redox changes.


2021 ◽  
Vol 14 (1) ◽  
Author(s):  
Adnan Kadić ◽  
Anikó Várnai ◽  
Vincent G. H. Eijsink ◽  
Svein Jarle Horn ◽  
Gunnar Lidén

Abstract Background Biochemical conversion of lignocellulosic biomass to simple sugars at commercial scale is hampered by the high cost of saccharifying enzymes. Lytic polysaccharide monooxygenases (LPMOs) may hold the key to overcome economic barriers. Recent studies have shown that controlled activation of LPMOs by a continuous H2O2 supply can boost saccharification yields, while overdosing H2O2 may lead to enzyme inactivation and reduce overall sugar yields. While following LPMO action by ex situ analysis of LPMO products confirms enzyme inactivation, currently no preventive measures are available to intervene before complete inactivation. Results Here, we carried out enzymatic saccharification of the model cellulose Avicel with an LPMO-containing enzyme preparation (Cellic CTec3) and H2O2 feed at 1 L bioreactor scale and followed the oxidation–reduction potential and H2O2 concentration in situ with corresponding electrode probes. The rate of oxidation of the reductant as well as the estimation of the amount of H2O2 consumed by LPMOs indicate that, in addition to oxidative depolymerization of cellulose, LPMOs consume H2O2 in a futile non-catalytic cycle, and that inactivation of LPMOs happens gradually and starts long before the accumulation of LPMO-generated oxidative products comes to a halt. Conclusion Our results indicate that, in this model system, the collapse of the LPMO-catalyzed reaction may be predicted by the rate of oxidation of the reductant, the accumulation of H2O2 in the reactor or, indirectly, by a clear increase in the oxidation–reduction potential. Being able to monitor the state of the LPMO activity in situ may help maximizing the benefit of LPMO action during saccharification. Overcoming enzyme inactivation could allow improving overall saccharification yields beyond the state of the art while lowering LPMO and, potentially, cellulase loads, both of which would have beneficial consequences on process economics.


Author(s):  
Kamil Gill ◽  
Michal Kups ◽  
Patryk Harasny ◽  
Tomasz Machalowski ◽  
Marta Grabowska ◽  
...  

Since varicocele is so common in infertile men, this study intends to analyse the relationships between varicocele and conventional semen characteristics, sperm nuclear DNA dispersion and oxidation-reduction potential (ORP) in semen. Varicocele-positive and varicocele-negative infertile men (study groups) showed significantly lower standard sperm parameters and higher sperm DNA fragmentation (SDF) and ORP in semen than healthy volunteers and subjects with proven fertility (control groups). A lower proportion of low SDF levels (0–15% SDF) and higher incidence of high SDF levels (>30% SDF), as well as a higher prevalence of high ORP values (>1.37 mV/106 sperm/mL), were found in the study groups vs. the control groups. Moreover, infertile men had significantly lower odds ratios (ORs) for low SDF levels and significantly higher ORs for high SDF levels and high ORP. SDF and ORP were negatively correlated with sperm number, morphology, motility and vitality. Furthermore, a significant positive correlation was found between SDF and ORP. The obtained results suggest that disorders of spermatogenesis may occur in varicocele-related infertility. These abnormalities are manifested not only by reduced standard semen parameters but also by decreased sperm DNA integrity and simultaneously increased oxidative stress in semen.


2013 ◽  
Vol 813 ◽  
pp. 519-524
Author(s):  
Sang An Ha ◽  
Jei Pil Wang

A purpose of the present study is to derive optimum study factors for removal of heavy metals using combined alternating current electric/magnetic field and electric membranes for the area contaminated with heavy metals in soil or underground water. ORP (Oxidation Reduction Potential) analysis was conducted to determine an intensity of tendency for oxidation or reduction of the samples contaminated with heavy metals, and electrical membrane treatment was used with adjustment of concentrations and voltages of liquid electrode (Na2SO4) to derive a high removal rate. Removal constants were analyzed to be 0.0417, 0.119, 0.1594 when the voltages were 5V, 10V, 15V, respectively, and treatment efficiency was shown to increase as the liquid electrode concentration was increased. Keywords: heavy metals, electric/magnetic field, ORP, electrical membrane


1984 ◽  
Vol 224 (2) ◽  
pp. 577-580 ◽  
Author(s):  
M Madden ◽  
S M Lau ◽  
C Thorpe

Pig kidney general acyl-CoA dehydrogenase is markedly stabilized against loss of flavin and activity in 7.3 M-urea or at 60 degrees C upon reduction with sodium dithionite or octanoyl-CoA. Electron transferring flavoprotein is similarly stabilized, whereas egg white riboflavin-binding protein loses flavin more readily on reduction. These and other data support the anticipated correlation between the kinetic stability of the holoproteins and the oxidation-reduction potential of their bound flavins.


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