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In coordination chemistry, 2,2′:6′,2″-terpyridine is a versatile and extensively studied tridentate ligand. Terpyridine forms stable complexes with a variety of metal ions through coordination sites provided by the three nitrogen atoms in its pyridine rings. This paper presents an electrochemical study on various bis(terpyridine)osmium(II) complexes, addressing the absence of a systematic investigation into their redox behavior. Additionally, a computational chemistry analysis was conducted on these complexes, as well as on eight previously studied osmium(II)-bipyridine and -phenanthroline complexes, to expand both the experimental and theoretical understanding. The experimental redox potentials, Hammett constants, and DFT-calculated energies show linear correlations due to the electron-donating or electron-withdrawing nature of the substituents, as described by the Hammett constants. These substituent effects cause shifts to lower or higher redox potentials, respectively. [ABSTRACT FROM AUTHOR]

Previously, we found that in the reaction center (RC) of the purple bacterium Cereibacter sphaeroides, formation of heterodimeric primary electron donor (P) caused by the substitution of His-L173 by Leu, was compensated by the second mutation Ile-L177 – His. Significant changes in the spectral properties, pigment composition, and redox potential of P observed in the H(L173)L RC, are restored to the corresponding characteristics of the native RC in the RC H(L173)L/I(L177)H, with the difference that the energy of the long-wavelength QY optical transition of P increases significantly (by ~75 meV). In this work, it was shown using light-induced difference FTIR spectroscopy that the homodimeric structure of P is preserved in the RC with double mutation with partially altered electronic properties: electronic coupling in the radical-cation of the P+ dimer is weakened and localization of the positive charge on one of its halves is increased. Results of the study of the triple mutant RC, H(L173)L/I(L177)H/F(M197)H, are consistent with the assumption that the observed changes in the P+ electronic structure, as well as considerable blue shift of the QY P absorption band in the RC H(L173)L/I(L177)H, are associated with modification of the spatial position and/or geometry of P. Using femtosecond transient absorption spectroscopy, it was shown that the mutant H(L173)L/I(L177)H RC retains a sequence of reactions P* → P+BA− → P+HA− → P+QA− with electron transfer rates and the quantum yield of the final state P+QA− close to those observed in the wild-type RC (P* is the singlet-excited state of P; BA, HA, and QA are molecules of bacteriochlorophyll, bacteriopheophytin, and ubiquinone in the active A-branch of cofactors, respectively). The obtained results, together with the previously published data for the RC with symmetrical double mutation H(M202)L/I(M206)H, demonstrate that by introducing additional point amino acid substitutions, photochemical activity of the isolated RC from C. sphaeroides could be maintained at a high level even in the absence of important structural elements – axial histidine ligands of the primary electron donor P. [ABSTRACT FROM AUTHOR]

Reductive dissolution of barium (Ba) sulfate in wetland soils may increase Ba bioavailability in the environment, yet no information is available regarding Ba remediation using biochar. This study investigated the effectiveness of sugarcane (Saccharum officinarum) straw biochar pyrolyzed at 350 °C (BC350), 550 °C (BC550), and 750 °C (BC750) in inhibiting barite dissolution and, consequently, Ba availability in a soil artificially spiked with barite and flooded for 365 days. Increasing pyrolysis temperature alters the carbon structure, and increases dehydration and depolymerization, resulting in more stable biochar that releases less DOC (8.6-fold decrease from BC350 to BC750). Additionally, high-temperature biochar (BC750) had 1.7 times higher carbon (C) content, 2.4 times higher ash content, and a 13.1 times greater specific surface area (SSA) than low-temperature biochar (BC350). Amending soil with BC750 increased pH but did not promote reducing conditions, and thus did not promote barite dissolution. Conversely, greater DOC in low-temperature biochar, particularly BC350, favored reducing conditions and increased barite dissolution by 23%, with BC550 also showing an 18% increase. This enhancement led to a greater pool of Ba sorbed into more labile exchangeable sites. In summary, pyrolysis temperature affects biochar attributes, which in turn influences the soil geochemical environment and Ba speciation. Low-temperature biochar (BC350) shows potential as an amendment to increase the bioavailable Ba pool in assisted remediation programs, such as biochar-assisted phytoremediation. Highlights: • Biochar pyrolysis temperature affected both redox potential and barite dissolution. • BC750 mitigated barite dissolution while modifying exchangeable sorption sites. • DOC release from low temperature biochar promoted barite reductive dissolution. • BC350 may enhance biochar-mediated phytoremediation applications. [ABSTRACT FROM AUTHOR]

Analysis of the structure of two-domain laccase ScaSL from Streptomyces carpinensis VKM Ac-1300 (with a middle-redox potential) revealed determinants that could affect the increased potential of ScaSL. Site-directed mutagenesis of the ScaSL laccase was carried out, and mutants H286A, H286T, H286W, and F232Y/F233Y were obtained. Replacement of His 286 with Ala led to a decrease in redox potential (0.45 V) and an increase in stability at pH 9 and 11; replacement with Thr led to an increase in redox potential (0.51 V) but to a decrease in the thermal stability of the protein; replacement with Trp did not affect the enzyme properties. Replacement of Phe residues 232 and 233 with Tyr led to a shift in enzyme activity to the acidic pH range without changing the redox potential and a decrease in the thermostability and pH stability of the enzyme. All mutants more efficiently oxidized phenolic substrate 2,6-DMP and were able to participate in direct electron transfer (DET) with MWCNT-modified electrodes. The F232Y/F233/Y mutant was unable to degrade triphenylmethane dyes without a mediator but showed a greater degree of decolorization of azo dyes in the presence of the mediator. The crystal structure of laccase with the highest potential was determined with high resolution. [ABSTRACT FROM AUTHOR]

Imine-bridged meso-meso and β-meso unsymmetrical thien-2-yl porphyrin dyads were synthesized by condensation of meso- and β-formyl derivatives of 5,10,15,20-tetrakis(3-methylthien-2-yl)porphyrinato nickel (II), Ni3MeThP with 5-(5-Aminothien-2-yl)-10,15,20-triphenylporphyrinato nickel(II), Ni5AThPP in the presence of lanthanum(III)triflate catalyst in toluene at 120 °C for 8 h. The structural, photophysical, and redox properties were investigated by 1H NMR, UV/Vis spectral, and electrochemical analysis. The near coplanarity of the linker thien-2-yl group with the central porphyrin π-system, which can influence the electron delocalization of these molecules, is explained using electronic spectroscopy and cyclic voltammetry. The stronger electronic interaction between the two porphyrin units and the increased nonplanarity of the macrocycle brought about by the β-meso imine bridging is indicated by the larger shift of redox potentials in the dyad-2 as compared to the dyad-1 system. The results of the present investigation reveal that the two distinct porphyrin units in dyads interact via their near planar thien-2-yl linker. [ABSTRACT FROM AUTHOR]

Abstract Reductive dissolution of barium (Ba) sulfate in wetland soils may increase Ba bioavailability in the environment, yet no information is available regarding Ba remediation using biochar. This study investigated the effectiveness of sugarcane (Saccharum officinarum) straw biochar pyrolyzed at 350 °C (BC350), 550 °C (BC550), and 750 °C (BC750) in inhibiting barite dissolution and, consequently, Ba availability in a soil artificially spiked with barite and flooded for 365 days. Increasing pyrolysis temperature alters the carbon structure, and increases dehydration and depolymerization, resulting in more stable biochar that releases less DOC (8.6-fold decrease from BC350 to BC750). Additionally, high-temperature biochar (BC750) had 1.7 times higher carbon (C) content, 2.4 times higher ash content, and a 13.1 times greater specific surface area (SSA) than low-temperature biochar (BC350). Amending soil with BC750 increased pH but did not promote reducing conditions, and thus did not promote barite dissolution. Conversely, greater DOC in low-temperature biochar, particularly BC350, favored reducing conditions and increased barite dissolution by 23%, with BC550 also showing an 18% increase. This enhancement led to a greater pool of Ba sorbed into more labile exchangeable sites. In summary, pyrolysis temperature affects biochar attributes, which in turn influences the soil geochemical environment and Ba speciation. Low-temperature biochar (BC350) shows potential as an amendment to increase the bioavailable Ba pool in assisted remediation programs, such as biochar-assisted phytoremediation. Graphical Abstract

The reducing capacity of humic acids (HA) was evaluated by the spectrophotometric method using Fe(III) complexes with organic and inorganic ligands as oxidizing agents, depending on the medium pH and reagent concentration. The maximum sensitivity of the method was observed at pH = 5 for Fe(III) complexes with α,α′-bipyridyl and o-phenanthroline, as well as at pH = 9 for potassium hexacyanoferrate(III). The obtained results were supported by computational modeling of the complexation and dissociation processes. The number of available surface functional groups was found to decrease with an increase in the HA concentration due to the molecular aggregation, thus resulting in a lower reducing capacity. The formal redox potential of HA, measured by redox titration, ranged from 530–to 535 mV.

Nonaqueous organic aluminum batteries are considered as promising high‐safety energy storage devices due to stable ionic liquid electrolytes and Al metals. However, the stability and capacity of organic positive electrodes are limited by their inherent high solubility and low active organic molecules. To address such issues, here porphyrin compounds with rigid molecular structures present stable and reversible capability in electrochemically storing AlCl2+. Comparison between the porphyrin molecules with electron‐donating groups (TPP‐EDG) and with electron‐withdrawing groups (TPP‐EWG) suggests that EDG is responsible for increasing both highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energy levels, resulting in decreased redox potentials. On the other hand, EWG is associated with decreasing both HOMO and LUMO energy levels, leading to promoted redox potentials. EDG and EWG play critical roles in regulating electron density of porphyrin π bond and electrochemical energy storage kinetics behavior. The competitive mechanism between electrochemical redox reaction and de/adsorption processes suggests that TPP‐OCH3 delivers the highest specific capacity ~171.8 mAh g−1, approaching a record in the organic Al batteries. [ABSTRACT FROM AUTHOR]

Nitroreductases (NRs) are NAD(P)H‐dependent flavoenzymes that reduce nitro aromatic compounds to their corresponding arylamines via the nitroso and hydroxylamine intermediates. Because of their broad substrate scope and versatility, NRs have found application in multiple fields such as biocatalysis, bioremediation, cell‐imaging and prodrug activation. However, only a limited number of members of the broad NR superfamily (> 24 000 sequences) have been experimentally characterized. Within this group of enzymes, only few are capable of amine synthesis, which is a fundamental chemical transformation for the pharmaceutical, agricultural, and textile industries. Herein, we provide a comprehensive description of a recently discovered NR from Bacillus tequilensis, named BtNR. This enzyme has previously been demonstrated to have the capability to fully convert nitro aromatic and heterocyclic compounds to their respective primary amines. In this study, we determined its biochemical, kinetic and structural properties, including its apparent melting temperature (Tm) of 59 °C, broad pH activity range (from pH 3 to 10) and a notably low redox potential (−236 ± 1 mV) in comparison to other well‐known NRs. We also determined its steady‐state and pre‐steady‐state kinetic parameters, which are consistent with other NRs. Additionally, we elucidated the crystal structure of BtNR, which resembles the well‐characterized Escherichia coli oxygen‐insensitive NAD(P)H nitroreductase (NfsB), and investigated the substrate binding in its active site through docking and molecular dynamics studies with four nitro aromatic substrates. Guided by these structural analyses, we probed the functional roles of active site residues by site‐directed mutagenesis. Our findings provide valuable insights into the biochemical and structural properties of BtNR, as well as its potential applications in biotechnology. [ABSTRACT FROM AUTHOR]

Peracetic acid (PAA) has a long history as an efficacious and eco‐friendly disinfectant. It was first synthesised in 1902, and since then a wide range of applications has been developed in various industries. Aquaculture is a more recent industry wherein the potential of PAA is significant. As the global demand for sustainable development increases, there has likewise been growing interest in using PAA in aquaculture as an alternative to less environmentally friendly practices. PAA has no carcinogenic risk to humans (unlike formalin), has negligible harmful by‐products (unlike chlorine‐based disinfectants) and with appropriate precautions, the risks of causing severe human health damage is easier to control than ozone. Fish show strong physiological recovery and adaptation to PAA, whereas susceptible life stages of pathogens are highly vulnerable, enabling a safe and efficacious disinfection of the entire culture water and not the flow‐restricted disinfection by such processes as ultraviolet radiation or ozone. The effective concentration of PAA against many fish pathogens is usually below 2 mg L−1, which is tolerable for most fish, and it has very low environmental risk due to rapid degradation. However, such degradation and the hydrodynamics in production‐scale aquaculture systems complicate the practical use of PAA. In this review, we summarise key results of safe concentrations of PAA and its effectiveness specifically for fish farmers. We also outline major difficulties and possible solutions for practical uses of PAA. We intend to bring global attention to this compound and inspire future possibilities for its sustainable use as a water disinfectant in aquaculture. [ABSTRACT FROM AUTHOR]

The addition of biochar inevitably modifies the acidity (pH), redox potential (Eh), and dissolved organic matter (DOM) level in the soil. These alterations also have coupled effects on the cycling of iron (Fe) and the composition of bacterial communities, thereby impacting the speciation and availability of arsenic (As) in the soil. This study explored the potential mechanisms through which biochar affects As in paddy soil during flooded cultivation with different pyrolysis temperature biochars (300 °C, 400 °C, and 500 °C) added. The results revealed that the TAs concentration increased in the initial 15 days of soil cultivation with SBC300 or SBC400 addition because increasing the concentration of DOM induced the mobility of As though the formation of As-DOM complexes. Meanwhile, biochar addition elevated the pH, decreased the Eh, and promoted the transformation of specific adsorbed As (A-As) and amorphous iron oxide-bound As (Amo-Fe-As) to supernatant As through enhancing the reductive dissolution of Fe(oxy)(hydr)oxides. Moreover, the biochar altered the relative abundance of As (V)-reducing bacteria (such as Firmicutes) and As (III)-oxidizing bacteria (such as Chloroflex), thereby affecting As speciation. However, these mechanistic effects varied depending on the pyrolysis temperature of the biochar. The microbial composition of SBC300 and SBC400 were similar, with both containing larger populations of Enterobacteriaceae (AsRB) and pseudomonas (FeRB) compared to CK and SBC500. It was proposed that lower pyrolysis temperatures (300 °C and 400 °C) are more favorable for the dissolution of Fe(oxy)(hydr)oxides and the reduction of As (V). However, the biochar from the higher pyrolysis temperature (500 °C) showed environmental impacts akin to the control group (CK). This study demonstrated potential mechanisms of biochar's effect on As and the role of pyrolysis temperature. [ABSTRACT FROM AUTHOR]

AbstractEne-reductase (ER) has been widely applied for asymmetrical synthesis of chiral intermediates due to its substrate promiscuity, photoexcited reactivity, and excellent property with producing two chiral centers at a time. Natural ERs often exhibit the same stereoselectivity, and they need to be engineered for opposite configuration of chiral compounds. The hydrogenation process toward activated alkenes by ERs is composed of reductive half reaction and oxidative half reaction, which are dependent upon two cofactors NAD(P)H and flavin mononucleotide. The catalytic activity of ERs will be affected by the size of the substrate, the activating strength of the electron-withdrawing groups, redox potential of cofactors, and the loop flexibility around catalytic cavity. Currently, protein engineering to ERs has been successfully employed to enhance various catalytic properties, including photoexcited asymmetric synthesis. This review summarizes the approaches to reverse the stereoselectivity and enhance catalytic activity of ERs and new applications of the engineered ERs in photobiocatalytic asymmetric synthesis, besides the discussion with the existing molecular mechanisms of mutants regarding the improved catalytic performance. [ABSTRACT FROM AUTHOR]

Potentially harmful element (PHE) bioavailability is important to environmental contamination and must be checked under several soil conditions. This study aimed to assess Fe, Mn, and PHE uptake by rice (Oryza sativa) grown on flooded and non-flooded Fe tailings collected from the Doce River basin after its collapse in Brazil. After 65 days of sowing, shoots and roots were harvested to determine PHE concentrations. The mean concentrations of Mn in shoots and Fe in the roots of rice grown on the flooded tailings were 2140 mg kg−1 and 15,219 mg kg−1, respectively. Mn was extensively translocated from roots to shoots (translocation factor (TF) = 2). Conversely, Fe accumulated in roots (TF = 0.015) and caused morphological damage to this rice organ. The application of macro and micronutrients lessened Fe toxicity in the roots of rice cultivated on the flooded tailings. The flooding of tailings influenced more Fe accumulation than Mn accumulation by rice plants. The PHE Ag, As, Cd, Ni, Hg, Pb, and Sb exhibited low total concentrations (maximum of 9 mg kg−1 for Ni and a minimum of 0.2 mg kg−1 for Cd, Hg, and Sb), and it was not observed an increase in their availability under tailings flooding conditions. [ABSTRACT FROM AUTHOR]

Porphyrins were identified some years ago as a promising, easily accessible, and tunable class of organic photoredox catalysts, but a systematic study on the effect of the electronic nature and of the position of the substituents on both the ground-state and the excited-state redox potentials of these compounds is still lacking. We prepared a set of known functionalized porphyrin derivatives containing different substituents either in one of the meso positions or at a β-pyrrole carbon, and we determined their ground- and (singlet) excited-state redox potentials. We found that while the estimated singlet excited-state energies are essentially unaffected by the introduction of substituents, the redox potentials (both in the ground- and in the singlet excited-state) depend on the electron-withdrawing or electron-donating nature of the substituents. Thus, the presence of groups with electron-withdrawing resonance effects results in an enhancement of the reduction facility of the photocatalyst, both in the ground and in the excited state. We next prepared a second set of four previously unknown meso-substituted porphyrins, having a benzoyl group at different positions. The reduction facility of the porphyrin increases with the proximity of the substituent to the porphine core, reaching a maximum when the benzoyl substituent is introduced at a meso position. [ABSTRACT FROM AUTHOR]

Main conclusion: Reactive nitrogen species mitigate the deteriorative effect of accelerated seed ageing by affecting the glutathione concentration and activities of GR and GPX-like. The treatment of apple (Malus domestica Borkh.) embryos isolated from accelerated aged seeds with nitric oxide-derived compounds increases their vigour and is linked to the alleviation of the negative effect of excessive oxidation processes. Reduced form of glutathione (GSH) is involved in the maintenance of redox potential. Glutathione peroxidase-like (GPX-like) uses GSH and converts it to oxidised form (GSSG), while glutathione reductase (GR) reduces GSSG into GSH. The aim of this work was to investigate the impact of the short-time NOx treatment of embryos isolated from apple seeds subjected to accelerated ageing on glutathione-related parameters. Apple seeds were subjected to accelerated ageing for 7, 14 or 21 days. Isolated embryos were shortly treated with NOx and cultured for 48 h. During ageing, in the axes of apple embryos, GSH and GSSG levels as well as half-cell reduction potential remained stable, while GR and GPX-like activities decreased. However, the positive effect of NOx in the vigour preservation of embryos isolated from prolonged aged seeds is linked to the increased total glutathione pool, and above all, higher GSH content. Moreover, NOx increased the level of transcripts encoding GPX-like and stimulated enzymatic activity. The obtained results indicate that high seed vigour related to the mode of action of NO and its derivatives is closely linked to the maintenance of higher GSH levels. [ABSTRACT FROM AUTHOR]

Coenzyme F430 is a nickel‐containing tetrapyrrole, serving as the prosthetic group of methyl‐coenzyme M reductase in methanogenic and methanotrophic archaea. During coenzyme F430 biosynthesis, the tetrapyrrole macrocycle is reduced by the nitrogenase‐like CfbC/D system consisting of the reductase component CfbC and the catalytic component CfbD. Both components are homodimeric proteins, each carrying a [4Fe‐4S] cluster. Here, the ligands of the [4Fe‐4S] clusters of CfbC2 and CfbD2 were identified revealing an all cysteine ligation of both clusters. Moreover, the midpoint potentials of the [4Fe‐4S] clusters were determined to be −256 mV for CfbC2 and −407 mV for CfbD2. These midpoint potentials indicate that the consecutive thermodynamically unfavorable 6 individual "up‐hill" electron transfers to the organic moiety of the Ni2+‐sirohydrochlorin a,c‐diamide substrate require an intricate interplay of ATP‐binding, hydrolysis, protein complex formation and release to drive product formation, which is a common theme in nitrogenase‐like systems. [ABSTRACT FROM AUTHOR]

Redox reactions control the environmental fate of selenium, an element of concern due to its small gap between beneficial and detrimental effects on human health and due to the longevity of the radionuclide 79Se produced in nuclear reactors. Fe-bearing clay minerals are major redox-active ingredients of Earth's critical zone and constitute an important component of the barrier in (radioactive and other) waste repositories. Here we systematically investigate selenite (Se(IV)O 3 2−) sorption and reduction by Fe-bearing clay minerals of the smectite group, using batch experiments and X-ray absorption fine structure (XAFS) spectroscopy to elucidate reaction mechanisms and kinetics up to 720 or 3600 h. We found a linear relationship between structural Fe(II) content and selenite reduction rate. Selenite reduction depends also on redox potential and pH, with pH 7 showing a slower reduction rate than at pH 5. Selenite first sorbs to clay edge sites by forming an inner-sphere sorption complex, before being reduced to Se(0). The first redox product was amorphous (red) Se(0), which gradually transformed into trigonal (grey) Se(0), indicative of a kinetically hindered conversion of an amorphous (or less crystalline) solid phase into the thermodynamically stable and more crystalline form of the solid. Despite an Fe2+ aq concentration of up to 6·10−4 M in the clay suspension, and their thermodynamic prediction for the clays at lower E h , we did not observe formation of iron selenides. These insights into the selenite reduction mechanisms by Fe-bearing clays provides valuable information for the development of effective approaches for selenite immobilization. [ABSTRACT FROM AUTHOR]

Chemical compounds belonging to the quinone class are known for their cyclic diketone structures. Anthraquinone derivatives have been used as sensing materials and dyes or pigments. The spectroscopic and voltammetric sensing capacity of 1-amino-4-hydroxy-9,10-anthraquinone was utilized to sense 2-bromobenzene-sulfonyl chloride, 4-nitrobenzene-sulfonyl chloride, benzoyl chloride, 2-chloro-benzoyl chloride and 4-bromo-benzoyl chloride. These substituted acyl chlorides and nitrobenzene sulfonyl chloride are important intermediates in various reactions, and the product formation is highly dependent on their concentration. Therefore, it is crucial to take special care as all these compounds are carcinogenic. All studies were carried out in ethanol solvent. Results showed that 1-AHAQ could be effectively used as a UV–visible sensor for sensing 2-bromo benzene sulfonyl chloride. 1-AHAQ demonstrates good results as a fluorescence sensor for sensing 4-bromobenzene-sulfonyl chloride and behaves as a good voltammetric sensor for sensing 4-nitrobenzene sulfonyl chloride. [ABSTRACT FROM AUTHOR]

An important contributing factor to the growth of aggressive and treatment-resistant tumors is tumor hypoxia. In this investigation, we created a unique tracer, 64Cu-biacetyl-bis(4-methyl-3-semicarbazone) Complex (64Cu-[APSC]2), for hypoxia imaging. Numerous spectral and electrochemical analyses were used to characterize the synthesized ligand and its metal complex. The coordination of the metal in the metal complex was also supported by DFT (B3LYP model) calculations. The radiochemical yields and purities of 64Cu-[APSC]2 were found to be quantitative, as determined by TLC and HPLC analyses.Stability studies in human plasma demonstrated that 64Cu-[APSC]2 remained steady for at least four hours while being incubated at 37 °C. MDA-MB-231 cell-line xenografts were placed in nude mice for biodistribution research. The results revealed significant accumulation of the tracer in tumors after 2 h post-injection, which correlated with the redox potential and reactive oxygen species. These findings suggest that 64Cu-[APSC]2 shows promising evidence as a theranostic radiopharmaceutical for hypoxic tumors.

The exploitation of high performance redox-active substances is critically important for the development of non-aqueous redox flow batteries. Herein, three tetrathiofulvalene (TTF) derivatives with different substitution groups, namely TTF diethyl ester (TTFDE), TTF tetramethyl ester (TTFTM), and TTF tetraethyl ester (TTFTE), are prepared and their energy storage properties are evaluated. It has been found that the redox potential and solubility of these TTF derivatives in conventional carbonate electrolytes increases with the number of ester groups. The battery with a catholyte of 0.2 mol L−1 of TTFTE delivers a specific capacity of more than 10 Ah L−1 at the current density of 0.5 C with two discharge voltage platforms locating at as high as 3.85 and 3.60 V vs. Li/Li+. Its capacity retention can be improved from 2.34 Ah L−1 to 3.60 Ah L−1 after 100 cycles by the use of an anion exchange membrane to block the crossover of TTF species. The excellent cycling stability of the TIF esters is supported by their well-delocalized electrons, as revealed by the density function theory calculations. Therefore, the introduction of more and larger electron-withdrawing groups is a promising strategy to simultaneously increase the redox-potential and solubility of redox-active materials for non-aqueous redox flow batteries.

High‐valent Fe(IV)=O intermediates of metalloenzymes have inspired numerous efforts to generate synthetic analogs to mimic and understand their substrate oxidation reactivities. However, high‐valent M(IV) complexes of late transition metals are rare. We have recently reported a novel Co(IV)−dinitrate complex (1‐NO3) that activates sp3 C−H bonds up to 87 kcal/mol. In this work, we have shown that the nitrate ligands in 1‐NO3 can be replaced by azide, a more basic coordinating base, resulting in the formation of a more potent Co(IV)−diazide species (1‐N3) that reacts with substrates (hydrocarbons and phenols) at faster rate constants and activates stronger C−H bonds than the parent complex 1‐NO3. We have characterized 1‐N3 employing a combination of spectroscopic and computational approaches. Our results clearly show that the coordination of azide leads to the modulation of the Co(IV) electronic structure and the Co(IV/III) redox potential. Together with the higher basicity of azide, these thermodynamic parameters contribute to the higher driving forces of 1‐N3 than 1‐NO3 for C−H bond activation. Our discoveries are thus insightful for designing more reactive bio‐inspired high‐valent late transition metal complexes for activating inert aliphatic hydrocarbons. [ABSTRACT FROM AUTHOR]

In wine technology, the on-line measurement of redox potential is a fast, accurate, and reliable measurement that provides insight into the metabolism of Saccharomyces cerevisiae, its microbial activity, and the oxidation and reduction state of wine, as well as insight into its quality and stability. The significance of the redox potential measurement and control in wine technology as well as the maintenance and regulation of fermentation redox potential using temperature and carbon dioxide fluxes are discussed. Redox potential levels from Eh 100 to 180 mV are typical for non-oxidized wine that is bottling-ready, while levels of Eh 270 to 460 mV represent oxidized wines with typical failures. The relevance of redox potential measurement during the 2-year maturation of Blau Fränkisch wine in 225 L oak barrels at six levels at a temperature 15 °C is presented. The measurement of the redox potential, expressing heterogeneity in redox layers during wine maturation in oak barrels, is represented in various oxido-reductive fermentation zones. On the contrary, the end of the maturation process is indicated by the homogeneity of redox zones, where the matured wine shows no differences in redox measurement on all levels. Using redox potential as a key scale-up criteria ensures comparable and reproducible amounts of the final product even in geometrically non-similar fermenter systems. [ABSTRACT FROM AUTHOR]

In the present study, we have investigated factors affecting the accuracy of computational chemistry calculation of redox potentials, namely the gas‐phase ionization energy (IE) and electron affinity (EA), and the continuum solvation effect. In general, double‐hybrid density functional theory methods yield IEs and EAs that are on average within ~0.1 eV of our high‐level W3X‐L benchmark, with the best performing method being DSD‐BLYP/ma‐def2‐QZVPP. For lower‐cost methods, the average errors are ~0.2–0.3 eV, with ωB97X‐3c being the most accurate (~0.15 eV). For the solvation component, essentially all methods have an average error of ~0.3 eV, which shows the limitation of the continuum solvation model. Curiously, the directly calculated redox potentials show errors of ~0.3 eV for all methods. These errors are notably smaller than what can be expected from error propagation with the two components (IE and EA, and solvation effect). Such a discrepancy can be attributed to the cancellation of errors, with the lowest‐cost GFN2‐xTB method benefiting the most, and the most accurate ωB97X‐3c method benefiting the least. For organometallic species, the redox potentials show large deviations exceeding ~0.5 eV even for DSD‐BLYP. The large errors are attributed to those for the gas‐phase IEs and EAs, which represents a major barrier to the accurate calculation of redox potentials for such systems. [ABSTRACT FROM AUTHOR]

In this study, Fe3O4/Ag magnetite-silver (MSx) nanocomposites were investigated as catalysts for advanced oxidation processes by coupling the plasmonic effect of silver nanoparticles and the ferromagnetism of iron oxide species. A surfactant-free co-precipitation synthesis method yielded pure Fe3O4 magnetite and four types of MSx nanocomposites. Their characterisation included structural, compositional, morphological and optical analyses, revealing Fe3O4 magnetite and Ag silver phases with particle sizes ranging from 15 to 40 nm, increasing with the silver content. The heterostructures with silver reduced magnetite particle aggregation, as confirmed by dynamic light scattering. The UV–Vis spectra showed that the Fe:Ag ratio strongly influenced the absorbance, with a strong absorption band around 400 nm due to the silver phase. The oxidation kinetics of organic pollutants, monitored by in situ luminescence measurements using rhodamine B as a model system, demonstrated the higher performance of the developed catalysts with increasing Ag content. The specific surface area measurements highlighted the importance of active sites in the synergistic catalytic activity of Fe3O4/Ag nanocomposites in the photo-Fenton reaction. Finally, the straightforward fabrication of diverse Fe3O4/Ag heterostructures combining magnetism and plasmonic effects opens up promising possibilities for heterogeneous catalysis and environmental remediation. [ABSTRACT FROM AUTHOR]

The redox properties of Feaq2+ -iron oxide heterogeneous systems play an important role in the environmental behaviors of heavy metal and organic pollutants. However, the determination of Eh for heterogeneous systems is still challenging due to the redox equilibration between the electrode and suspension is sluggish. In this study, goethite was chosen as the representative of iron oxide in the aquifer. Both mediated and nonmediated potential methods were conducted to obtain the Eh of Feaq2+ -goethite heterogeneous system through the optimizing of measurement conditions. Moreover, the effect of the working electrode surface state, the kind of mediators, and the equilibrium time on the Eh measurement were investigated. The results indicated that the working electrode surface state, the suitable mediators, and the establishment of equilibrium were crucial for obtaining accurate Eh. Compared with the non-mediated potentiometric method, the mediated method can shorten the determination time, but the appropriate mediator must be chosen. In non-mediated potentiometric method, the equilibrium between the working electrode and goethite must be established. The standard redox potential (Eh0 ) of goethite with different particle sizes was obtained, which demonstrated the practicability of this method. The results provide the method for the Eh measurement of mineral heterogeneous systems, and also provide theoretical support for predicting the pollutant abiotic attenuation rate induced by Feaq2+ -iron oxide heterogeneous systems. [ABSTRACT FROM AUTHOR]

This article presents the results of cyanide leaching of gold-containing concentrate using the trichlorocyanuric acid (TCCA) oxidizer. Gold-containing concentrate was obtained from a gold tailings sample from a gold recovery factory (GRF) in one of the deposits of Kazakhstan that have not previously been studied for concentrability. According to X-ray phase analysis and energy dispersive spectrometry (DSM) data, the main compounds in the tailings sample under study are pyrite FeS2, quartz SiO2, calcite CaCO3, albite NaAlSi3O8, muscovite KAl2Si3AlO10(OH)8, dolomite CaMg(CO3)2, and oxidized iron compounds. Microscopic studies of the concentrate have established the presence of ultrafine gold with sizes from Au 0.9 to 10.2 μm in pyrite. Obtaining the gold-containing concentrate with a gold content of 15.95 g/t is possible according to the enrichment scheme, which includes centrifugal separation, classification according to the fineness class −0.05 mm, additional grinding of hydrocyclone sands to a fineness of 90.0–95.0% of the class finer than 0.050 mm, and control centrifugal separation. Since pyrite in technogenic raw materials is the main gold-containing mineral, this paper presents studies on the oxidizability of pyrite with the TCCA oxidizer. The results of studies on the oxidation of pyrite using the TCCA oxidizer show the products of its hydrolysis oxidize pyrite with the formation of various iron compounds on its surface. Pretreatment of gold-containing concentrate with oxidizer TCCA for 3 h before the cyanidation process (20 h) allows for an increase in the recovery of gold in the solution by 5.8%. [ABSTRACT FROM AUTHOR]

Background/Aim: Intrauterine insemination (IUI) is the most common assisted-reproduction treatment. However, it has lower success rate in comparison to other treatments. Therefore, determining factors that contribute to IUI success is of particular interest and this was the purpose of this prospective study. Patients and Methods: In this study, only homologous inseminations with fresh semen samples were included. All women received mild ovarian stimulation with clomiphene citrate and gonadotropins. Before IUI, basic semen analysis, evaluation of DNA fragmentation index (DFI), as well as measurement of sperm redox potential, were performed on each semen sample. Semen was processed with density-gradient centrifugation and 500 µl of processed sperm was used for insemination. Results: In 200 cycles, there were 36 pregnancies, six of them ectopic. Cycles with ongoing pregnancies were characterized by younger male and female age and higher number of follicles. Multivariate logistic regression analysis showed that only female age was significantly associated with ongoing pregnancy. DFI was positively correlated with male age and negatively correlated with sperm concentration and progressive motility. Semen redox potential showed a strong negative correlation with sperm concentration and positive correlation with DFI. [ABSTRACT FROM AUTHOR]

E. coli nitroreductase A (NfsA) is a candidate for gene-directed prodrug cancer therapy using bioreductively activated nitroaromatic compounds (ArNO2). In this work, we determined the standard redox potential of FMN of NfsA to be −215 ± 5 mV at pH 7.0. FMN semiquinone was not formed during 5-deazaflavin-sensitized NfsA photoreduction. This determines the two-electron character of the reduction of ArNO2 and quinones (Q). In parallel, we characterized the oxidant specificity of NfsA with an emphasis on its structure. Except for negative outliers nitracrine and SN-36506, the reactivity of ArNO2 increases with their electron affinity (single-electron reduction potential, E17) and is unaffected by their lipophilicity and Van der Waals volume up to 386 Å. The reactivity of quinoidal oxidants is not clearly dependent on E17, but 2-hydroxy-1,4-naphthoquinones were identified as positive outliers and a number of compounds with diverse structures as negative outliers. 2-Hydroxy-1,4-naphthoquinones are characterized by the most positive reaction activation entropy and the negative outlier tetramethyl-1,4-benzoquinone by the most negative. Computer modelling data showed that the formation of H bonds with Arg15, Arg133, and Ser40, plays a major role in the binding of oxidants to reduced NfsA, while the role of the π–π interaction of their aromatic structures is less significant. Typically, the calculated hydride-transfer distances during ArNO2 reduction are smallwer than for Q. This explains the lower reactivity of quinones. Another factor that slows down the reduction is the presence of positively charged aliphatic substituents. [ABSTRACT FROM AUTHOR]

The aim of this study was to evaluate the effect of hop extracts on changes in the primary and secondary fat oxidation products, physicochemical properties, and microbiological quality of pâté-type offal sausages obtained through the partial replacement of animal fat with vegetable fat. This study demonstrated that the extraction efficiency varied among hop cone varieties, with the highest efficiency observed for the Lubelski variety and the lowest for the Magnum variety. The phenolic compound content was higher in the Magnum cones (2.74 ± 0.11 mg/g dry matter) compared to the Lubelska cones (2.27 ± 0.05 mg/g of product). Additionally, the DPPH radical scavenging activity was greater in the extract from the Magnum cones (4.21 ± 0.09 mg TE/g d.w.) than in the extract from the Lublelski cones (3.87 ± 0.05 mg TE/ g d.w.). Similarly, the extracts from the Lubelski cones exhibited a higher antiradical activity against the ABTS radical compared to the extract from Magnum cones. Throughout storage, a significant increase in the pH value was observed in the control sample and in the samples with a 20% replacement of animal fat with rapeseed oil and Magnum hop extract. However, the addition of Lubelski hop extract resulted in a decrease in the pH value during the 15-day storage period. The samples with a 20% replacement of animal fat with rapeseed oil and 0.1% Lubelski hop extract showed the least changes in water activity during storage. The samples with a 20% replacement of animal fat with rapeseed oil and the addition of 0.2% Lubelski hop extract had the lowest peroxide value and TBARS index throughout the storage period. The addition of hop extract inhibited the growth of the total number of microorganisms in the tested sausages. In the samples with a 20% replacement of animal fat with rapeseed oil, the content of aerobic microorganisms, compared to the control sample, was statistically significantly lower. [ABSTRACT FROM AUTHOR]

Avenanthramides (AVs) are the phytochemicals found in cereals exclusively in oats. These are widely known natural substances that have antioxidant properties. The free radical deactivation potential of the eight AVs against five reactive species has been studied in physiological pH. At physiological pH, the radical quenching processes were studied using the sequential proton loss followed by electron transfer (SPLET) from the phenolic hydroxyl groups. Using density functional theory (DFT) computations, theoretical studies have been carried out in the gas phase and aqueous solution at M06-2X/6-31 + G (d,p) level of theory. The free radical scavenging ability of the studied AVs was analyzed by using conceptual density functional theory-based parameters and electrostatic potential analysis. By examining the hydrogen atom and electron affinities of each reactive species, the relative destructive potential of each has been compared. The electron transfer capabilities between the studied compound and reactive species were identified by utilizing the ionization energy and electron affinity plots. Additionally, by calculating the redox potentials and equilibrium constants for the entire process in the aqueous solution, the viability of scavenging the free radical species by selected AVs (both in neutral and mono-deprotonated) has been investigated. From the analysis, the neutral as well as the mono-deprotonated form of AVs are found to scavenge •OH and •OOH, and •NO2 radicals effectively, while they are inefficacious toward the O2•‾ and •NO radicals. [ABSTRACT FROM AUTHOR]

Employing the formalism of the joint density functional theory (JDFT) in the grand canonical ensemble, this paper studies the electronic structure and relative reactivity of an hydroxyl radical adsorbed on the surface of three different metal oxides that share the rutile-type structure and the (110) crystal plane; these materials are electrodes used in electrochemical advanced oxidation processes which consist in the generation of hydroxyl radicals, highly reactive species, that are able to oxidize organic compounds to CO 2 , making these anodes efficient for wastewater treatment. By analyzing the changes in the average number of electrons as a function of the applied chemical potential at fixed external potential, we studied two reactivity indices from conceptual density functional theory: global and local softness, to help us understand the differences between these materials, additionally we propose a new scheme to approximate the redox properties of clean surfaces or surfaces in contact with different adsorbed molecules so that these values can be arranged in a relative potential scale which would allow direct comparison with experimental results. [ABSTRACT FROM AUTHOR]

Aquaculture pond is a dynamic ecosystem with continuously changing physical, chemical, and biological elements. Environmental issues often create significant hindrances to long-term development of aquaculture industries in developing countries. Lack of knowledge on scientific aquaculture farm management has resulted in excessive usage of antibiotics and other chemicals leading to significant impacts to the surrounding ecosystem. While focussing on sustainable aquaculture, pond bottom sediment quality is an important aspect in aquaculture; but it receives far less attention than water quality. Usually, deterioration of accumulated organic matter in bottom sediment increases oxygen demand and influences redox potential. This creates anoxic conditions in the sediments and at the sediment-water interface, and releases ammonia, hydrogen sulfide, nitrogenous compounds and other toxic gases, leading to massive losses in aquaculture production. This could therefore reduce production capacity and be less profitable to farmers, discouraging them from entering to aquaculture sectors, especially the younger generation. An eco-friendly, convenient and low-cost aquaculture waste management strategies need to be adopted to mitigate these issues and make the system productive and profitable. This review critically evaluates the importance, feasibility and bioremediation potential of Immobilized microbial consortia (IMC) in general and specifically addresses Bacillus MCCB 101 for detritus or organic matter degradation, nitrifying bacterial consortia (NBC) for nitrification and photosynthetic sulfur bacteria (PSB), Rhodospeudomonas julia MCCB 147, for hydrogen sulfide mitigation from aquaculture ponds towards converting to a long-term sustainable production system.

Abstract Carbon monoxide (CO) is a primary air pollutant and a poisonous species for human beings, animals, and some catalytic reactions. Meanwhile, CO is also a versatile feedstock in the chemical industry to produce high‐value chemicals and clean fuels, which has stimulated extensive research interests in exploiting efficient CO conversion processes. Redox potential is a key thermodynamic quantity in these processes whereas only standard reduction potentials at 25°C and 1 atm are currently available. Herein, it is the first time to report the effects of temperature (0–1000°C), pressure (1–100 atm), and adsorption on the redox potentials of 18 CO conversion reactions to form carbon dioxide, methane, straight‐chain alkanes (ethane, propane, and butane), light olefins (ethylene, propylene, and butylene), benzene, alcohols, aldehydes, acids, and dimethyl ether, based on theoretical calculations. It was noticed that gas‐phase, aqueous‐phase, and adsorption‐state redox potentials decrease with increasing temperature at an increased rate while they show different responses to pressure change. Namely, gas‐phase and most aqueous‐phase redox potentials increase with pressure at a gradually declined rate, while adsorption‐state redox potentials are not influenced by pressure. Most importantly, the significant differences up to 2.06 V under varied conditions highlight the necessity of applying operando redox potentials for CO conversion reactions.

In coordination chemistry, 2,2′:6′,2″-terpyridine is a versatile and extensively studied tridentate ligand. Terpyridine forms stable complexes with a variety of metal ions through coordination sites provided by the three nitrogen atoms in its pyridine rings. This paper presents an electrochemical study on various bis(terpyridine)osmium(II) complexes, addressing the absence of a systematic investigation into their redox behavior. Additionally, a computational chemistry analysis was conducted on these complexes, as well as on eight previously studied osmium(II)-bipyridine and -phenanthroline complexes, to expand both the experimental and theoretical understanding. The experimental redox potentials, Hammett constants, and DFT-calculated energies show linear correlations due to the electron-donating or electron-withdrawing nature of the substituents, as described by the Hammett constants. These substituent effects cause shifts to lower or higher redox potentials, respectively.

The presence of fermentative hotspots in municipal waste dumps has been reported for several decades, but no study has focused on their size and shape. The uncontrolled landfill of Soub Sekt, covering an area of about 8 hectares in the Tadla plain in Morocco, is the source of a permanent pollution plume in the groundwater, detected by self-potential (SP) measurements. The study aims to detect and characterize these hotspots as well as the leachates that form within them. These hotspots are typically circular and smaller than 3 m in size, and they are concentrated within recent waste deposits. Intense electron transfer activities, particularly during redox reactions leading to metal solubilization, result in very low SP values (down to −60 mV), facilitating their detection. Several successive field campaigns suggest that they are active for 2–3 weeks. Due to the low permeability of the soils, highly mineralized leachates (average Electrical Conductivity 45 mS cm−1) rich in organic ions accumulate on the soil surface at the base of the waste windrows. There, they evolve by concentration due to evaporation and oxidation due to slow diffusion of atmospheric O2. Despite the small size of the hotspots generating the leachates, the accumulation of leachates in ponds and the low soil permeability limits the percolation rate, resulting in moderate but permanent groundwater pollution. [ABSTRACT FROM AUTHOR]

The assessment of mineral surface hydrophobicity at the industrial scale is a challenge. In some industrial situations, such information is indirectly obtained from other proxy variables. A well-known example of this is observed in the Cu-Mo selective flotation operation, where sodium hydrosulphide is used to change the redox potential and, controlling this value, determine when Cu-sulphide floatability is inhibited. Preliminary experiments indicate that this reagent may also promote the formation of solid precipitates, reducing its impact on the redox potential. This study aims at designing a simple strategy at the laboratory scale to report and quantify NaSH losses due to parallel, irreversible, and/or fast reactions, such as precipitation. Experiments carried out using process water coming from a Cu-Mo selective flotation plant in Chile show that departing from different pH conditions and the addition of hydrosulphide ions effectively triggers the precipitation of specific metal ions, decreasing its availability to reduce the redox potential of the aqueous solution. For this specific case scenario and water quality, around 5% of the NaSH dosed precipitated. An SEM-EDX analysis of the produced solid phase shows that it is composed of mainly iron sulphide and hydroxide, along with other metal hydroxides. More importantly, it was found that dosing the reagent at the same concentration, but in the form of small increments, allows reaching the redox potential more efficiently, reducing to some extent the precipitate production and the unnecessary NaSH consumption in up to 30% of the NaSH dosed. Preliminary 1-D modelling of the process, based on mass transport coupled with reaction mechanisms, provided a first indication of the best dosing conditions for this reagent. The latter is expected to contribute to the development of better and improved reagent dosage technologies in froth flotation environments. [ABSTRACT FROM AUTHOR]

In this work, we demonstrate a novel design that integrates a modified Nernst equation and readings from a microbial fuel cell (MFC)‐based device, facilitating real‐time monitoring of microbial growth. The MFC‐based device is comprised of an H‐shaped double‐chamber MFC, specifically designed to incorporate an oxidation–reduction potential (ORP) sensor, allowing for simultaneous measurements of both parameters. The Nernst equation was adjusted to assimilate readings from both the ORP sensor and the MFC device, ultimately deriving a unitless curve that represents the online dynamics of microbial growth. This curve exhibits two distinct peaks: the first peak indicates the initiation of the exponential phase, while the second peak signals its termination. The proposed design can be seamlessly integrated into fermentation processes to continually monitor progress, boost productivity, develop tailored control strategies that meet specific objectives, and so on. [ABSTRACT FROM AUTHOR]

The tendency of the periplasmic redox proteins in acidophiles to have more positive redox potentials (Em) than their homologous counterparts in neutrophiles suggests an adaptation to acidic pH at protein level, since thermodynamics of electron transfer processes are also affected by acidic pH. Since this conclusion is mainly based on the electrochemical characterization of redox proteins from extreme acidophiles of the genus Acidithiobacillus, we aimed to characterize three recombinant redox proteins of the more moderate acidophile Ferrovum sp. PN-J47-F6. We applied protein film voltammetry and linear sweep voltammetry coupled to UV/Vis spectroscopy to characterize the redox behavior of HiPIP-41, CytC-18, and CytC-78, respectively. The Em-values of HiPIP-41 (571 ± 16 mV), CytC-18 (276 ± 8 mV, 416 ± 2 mV), and CytC-78 (308 ± 7 mV, 399 ± 7 mV) were indeed more positive than those of homologous redox proteins in neutrophiles. Moreover, our findings suggest that the adaptation of redox proteins with respect to their Em occurs more gradually in response to the pH, since there are also differences between moderate and more extreme acidophiles. In order to address structure function correlations in these redox proteins with respect to structural features affecting the Em, we conducted a comparative structural analysis of the Ferrovum-derived redox proteins and homologs of Acidithiobacillus spp. and neutrophilic proteobacteria. Hydrophobic contacts in the redox cofactor binding pockets resulting in a low solvent accessibility appear to be the major factor contributing to the more positive Em-values in acidophilederived redox proteins. While additional cysteines in HiPIPs of acidophiles might increase the effective shielding of the [4Fe-4S]-cofactor, the tight shielding of the heme centers in acidophile-derived cytochromes is achieved by a drastic increase in hydrophobic contacts (A.f. Cyc41), and by a larger fraction of aromatic residues in the binding pockets (CytC-18, CytC-78). [ABSTRACT FROM AUTHOR]

Galvanic interactions present alternative strategies to achieve a more efficient Cu dissolution from CuFeS2. The present work studied the interaction between chalcopyrite–magnetite (CuFeS2-Fe3O4) in acidified ferric sulphate Fe2(SO4)3-H2SO4 at a solution pH of 1.8 and a temperature of 25 or 50 °C. The addition of Fe3O4 to CuFeS2 forms a galvanic couple, which positively impacts the dissolution of Cu. The results showed that the presence of Fe3O4 led to high and fast Cu dissolution rates and decreased significantly the activation energy, from 83 to 57 kJ/mol. In addition to that, the solid residues revealed that CuFeS2 dissolution produced intermediate Cu-S-rich phases: CuS, Cu2S and Cu5FeS4, which appeared to envelop CuFeS2, had no observable intermediate phase while in the presence of Fe3O4. The results showed that 94% of Cu could be recovered after 5 h of leaching at 50 °C at a Fe3O4/CuFeS2 ratio of 4:1 and a 460 mV Ag/AgCl solution potential. The findings of this study present an option for efficient Cu dissolution from CuFeS2 in ferric sulphate at atmospheric pressure. [ABSTRACT FROM AUTHOR]

Carbon monoxide (CO) is a primary air pollutant and a poisonous species for human beings, animals, and some catalytic reactions. Meanwhile, CO is also a versatile feedstock in the chemical industry to produce high‐value chemicals and clean fuels, which has stimulated extensive research interests in exploiting efficient CO conversion processes. Redox potential is a key thermodynamic quantity in these processes whereas only standard reduction potentials at 25°C and 1 atm are currently available. Herein, it is the first time to report the effects of temperature (0–1000°C), pressure (1–100 atm), and adsorption on the redox potentials of 18 CO conversion reactions to form carbon dioxide, methane, straight‐chain alkanes (ethane, propane, and butane), light olefins (ethylene, propylene, and butylene), benzene, alcohols, aldehydes, acids, and dimethyl ether, based on theoretical calculations. It was noticed that gas‐phase, aqueous‐phase, and adsorption‐state redox potentials decrease with increasing temperature at an increased rate while they show different responses to pressure change. Namely, gas‐phase and most aqueous‐phase redox potentials increase with pressure at a gradually declined rate, while adsorption‐state redox potentials are not influenced by pressure. Most importantly, the significant differences up to 2.06 V under varied conditions highlight the necessity of applying operando redox potentials for CO conversion reactions. [ABSTRACT FROM AUTHOR]

A study is performed of the maximum saturation of humic acids with Fe(III) ions when obtaining a complex humic sorbent. The complex sorbent HAmodFe retains 16.5 mmol/g of the functional groups of humic acids out of a total of 25 mmol/g that can participate in exchange reactions with metal ions. The maximum adsorption of Cd(II) by the sorbent is observed after 5 h of sorbate–sorbent contact and is 76 ± 2 mg/g. Extending the period of contact to 24 h results in the desorption of Cd(II) and the sorption exchange capacity of the sorbent drops to 55 ± 2 mg/g. The maximum adsorption of Cr(VI) is observed after 250 h of sorbate–sorbent contact. Having Cd(II) in the solution does not affect the sorption of Cr(VI) by the complex sorbent, which is 61 ± 1 mg/g. The rate of the adsorption of the considered metal ions is described by an equation of the pseudo-second order and is accompanied by mixed processes of diffusion. The redox potential of the falls 77 mV in the sorbent + Cr(VI) system and 38 mV in the sorbent + Cr(V) + Cd(II) system with a 250 h period of contact. [ABSTRACT FROM AUTHOR]

The reasonability of using the redox potential to characterize the state of a certain water system was substantiated. Peat fulvic acids characteristic for the natural water of the Dnipro River were selected as a target compound for study before and after the adsorption processes. Fruitstone-derived activated carbon (FDAC), FDAC oxidized by hydrogen peroxide (FADC-O), and FDAC modified with iron oxides (FDAC-Fe) were used as adsorbents. All the systems with both distilled and tap water were shown to have an oxidative character for the period of study, especially after sodium azide and hydrogen peroxide were added. The introduction of fulvic acids into the system neutralized this effect due to their interaction. The redox potential was proposed to use for simplified measurement as an indicator of pollution in water of different types. [ABSTRACT FROM AUTHOR]

Simple Summary: This study confirms the potential of methylene blue (MB) in treatment strategies for ovarian cancer. Ovarian cancer cells taken from patients were inserted into mice, and their growth was followed together with mouse health. Our findings revealed MB's ability to impede ovarian cancer progression, especially against tumors showing resistance to conventional chemotherapies. By investigating the effects of MB on cancer cell behavior and metabolism, this research revealed novel therapeutic targets for affecting tumor growth. These insights suggest that MB could be a valuable complementary therapeutic to existing treatments or an alternative for patients facing limited options. This research thus opens new avenues for developing targeted therapies that can remotely control cancer cell development. Ovarian cancer remains a significant challenge, especially in platinum-resistant cases where treatment options are limited. In this study, we investigated the potential of methylene blue (MB) as a metabolic therapy and complementary treatment approach for ovarian cancer. Our findings demonstrated a significant in vivo reduction in the proliferation of TOV112D-based ovarian-cell-line xenografts. In this preclinical study, which used a carboplatin-resistant ovarian cancer tumor model implanted into mice, MB-mediated metabolic therapy exhibited superior tumor slowdown compared to carboplatin treatment alone. This indicates, for the first time, MB's potential as an alternative or adjuvant treatment, especially for resistant cases. Our in vitro study on TOV112D and ARPE-19 sheds light on the impact of such an MB-based metabolic therapy on mitochondrial energetics (respiration and membrane potential). MB showed a modulatory role in the oxygen consumption rate and the mitochondrial membrane potential. These results revealed, for the first time, that MB specifically targets TOV112D mitochondria and probably induces cell apoptosis. The differential response of normal (ARPE-19) and cancer (TOV112D) cells to the MB treatment suggests potential alterations in cancer cell mitochondria, opening avenues for therapeutic approaches that target the mitochondria. Overall, our findings suggest the efficacy of MB as a possible treatment for ovarian cancer and provide valuable insights into the mechanisms underlying the efficacy of methylene blue metabolic therapy in ovarian cancer treatment. [ABSTRACT FROM AUTHOR]

Flooding and drainage cycles affect the biological and chemical characteristics of the soil in paddy fields and play an important role in cadmium (Cd) availability. In this study, the effect of biochar (B), hematite (H), and their simultaneous application (HB) on pH, Eh, and calcium chloride extractable Cd was investigated in a Cd-contaminated soil during a flooding and drainage period. Also, the Cd fractionation at the end of the incubation period was studied. The pH value increased during the flooding period and decreased with the beginning of the drainage period. The Eh value decreased from the beginning of the flooding and showed an increasing trend during the drainage period. Calcium chloride extractable Cd decreased during the flooding period, while at the beginning of the drainage increased with a slight slope and followed a decreasing trend up to the end of the drainage period. Cd concentration reduced at the end of the flooding period in the B, H and HB treatments compared to the control by 16.8%, 20.5%, and 25.7%, respectively. Also, the reduction in Cd concentration compared to the control treatment at the end of the drainage period was 18.2, 23.1 and 28.2% respectively. HB treatment reduced the Cd availability by reducing the soluble and exchangeable fractions and increasing organic, iron, and manganese oxides fractions. The results indicated that the application of amendments can reduce Cd availability in paddy fields and its uptake by the rice plant. [ABSTRACT FROM AUTHOR]

The objective of this work is to review the main hydrogeological characteristics and to understand the hydrochemical dynamics of the denitrification process in the gravel aquifer located in the low plain of the Seybouse watershed. The methodology implemented consisted in the identification of physico-chemical indicators characterizing the denitrification phenomenon: groundwater contents in NO , SO , FeO2, and hydrogeological conditions represented by the captivity of the aquifer and the reducing environment, associated with the presence of a support rich in sulfur and denitrifying bacteria. The chemical monitoring carried out on the fourteen drillings along a South-North profile, in the direction of the underground flow, separates globally two different zones, which are positioned from the upstream to the downstream of the gravel aquifer. The first one corresponds to the oxidizing environment, located mainly in the southern part or the deep aquifer and in direct contact with the surface aquifer. [ABSTRACT FROM AUTHOR]

Biological filtration is a complex process consisting of two consecutive stages. The nutrient transport stage, which is influenced by various fluid mechanical and surface-physical factors, represents a precondition for the biochemical process taking place within the biofilm. Biological water filtration is based on the catalyzed decomposition of contaminant molecules with the help of enzymes. This article, in addition to describing the conditions and mode of action typical within this second stage, also aims to explore the practical implications of the established results, including the controllability of biological reactors. [ABSTRACT FROM AUTHOR]

This study demonstrates the potential application of a portable 3D‐printed sensor to monitor microbial growth during soil bioremediation. Bacillus subtilis, a commonly found soil microorganism, is used to evaluate its growth characteristics. The integration of real‐time oxidation–reduction potential (ORP) reading and voltage output allows for a better illustration of microbial growth, with a focus on the mid‐exponential growth phase. This new technology can potentially increase the efficiency of soil bioremediation techniques by providing a better understanding of the microbial interactions and growth patterns involved. [ABSTRACT FROM AUTHOR]

The redox potential plays a critical role in sustaining the stability of gut microbiota. This study measured the fecal redox potential in healthy and diarrheal pigs using direct and dilution methods and investigated their correlation with microbiota. The results showed that the fluctuations in the redox potential of healthy pig feces were consistent using two different methods and the two methods are equivalent based on an equivalence test. The redox potential was positively correlated with the number of fungi and negatively related to the total bacteria. The relative or absolute abundances of many bacteria at the phyla and genus levels were associated with redox potential. In diarrheal pigs, the potentiometric trends of the two methods demonstrated an opposing pattern and the correlation with total bacteria was reversed. Precipitously elevated redox potential was detected post-diarrhea using dilution methods. The absolute abundance of Escherichia-Shigella and Fuurnierella was positively correlated with redox potential, while both relative and absolute abundances of Limosilactobacillus were positively correlated. These results suggest that both methods are suitable for detecting gut redox potential in healthy pigs, while the dilution method is more suitable for diarrheal pigs. The findings on the correlation of Limosilactobacillus, Prevotella, and Escherichia-Shigella with redox potential offer novel insights for targeted modulation of intestinal health. [ABSTRACT FROM AUTHOR]

ABSTRACT: Yogurt is made by fermenting milk with 2 lactic acid bacteria, Lactobacillus delbrueckii ssp. bulgaricus and Streptococcus thermophilus. To comprehensively understand the protocooperation mechanism between S. thermophilus and L. bulgaricus in yogurt fermentation, we examined 24 combinations of cocultures comprising 7 fast- or slow-acidifying S. thermophilus strains with 6 fast- or slow-acidifying L. bulgaricus strains. Furthermore, 3 NADH oxidase (Nox)-deficient mutants (Δnox) and one pyruvate formate-lyase deficient mutant (ΔpflB) of S. thermophilus were used to evaluate the factor that determines the acidification rate of S. thermophilus. The results revealed that the acidification rate of S. thermophilus monoculture determined the yogurt fermentation rates, despite the coexistence of L. bulgaricus, whose acidification rate was either fast or slow. Significant correlation was found between the acidification rate of S. thermophilus monoculture and the amount of formate production. Result using ΔpflB showed that the formate was indispensable for the acidification of S. thermophilus. Moreover, results of the Δnox experiments revealed that formate production required Nox activity, which not only regulated dissolved oxygen, but also the redox potential. The Nox provided the large decrease in redox potential required by pyruvate formate-lyase to produce formate. A highly significant correlation was found between formate accumulation and Nox activity in S. thermophilus. In conclusion, the formate production ability provided by the action of Nox activity determines the acidification rate of S. thermophilus, and consequently, regulates yogurt coculture fermentation.