Redox Environment Research Articles

Clinical markers of HIV predict redox-regulated neural and behavioral function in the sensorimotor system

Even in the modern era of combination antiretroviral therapy, aberrations in motor control remain a predominant symptom contributing to age-related functional dependencies (e.g., neurocognitive impairment) in people with HIV (PWH). While recent evidence implicates aberrant mitochondrial redox environments in the modulation of neural oscillatory activity serving motor control in PWH, the contribution of important clinical and demographic factors on this bioenergetic-neural-behavioral pathway is unknown. Herein, we evaluate the predictive capacity of clinical metrics pertinent to HIV (e.g., CD4 nadir, time with viremia) and age on mitochondrial redox-regulated sensorimotor brain-behavior dynamics in 69 virally-suppressed PWH. We used state-of-the-art systems biology and neuroscience approaches, including Seahorse analyzer of mitochondrial energetics, EPR spectroscopy of intracellular oxidant levels, antioxidant activity assays pertinent to superoxide and hydrogen peroxide (H2O2) redox environments, and magnetoencephalographic (MEG) imaging to quantify sensorimotor oscillatory dynamics. Our results demonstrate differential effects of redox systems on the neural dynamics serving motor function in PWH. In addition, measures of immune stability and duration of compromise due to HIV had dissociable effects on this pathway, above and beyond the effects of age alone. Moreover, peripheral measures of antioxidant activity (i.e., superoxide dismutase) fully mediated the relationship between immune stability and current behavioral performance, indicative of persistent oxidative environments serving motor control in the presence of virologic suppression. Taken together, our data suggest that disease-related factors, in particular, are stronger predictors of current redox, neural and behavioral profiles serving motor function, which may serve as effective targets for alleviating HIV-specific alterations in cognitive-motor function in the future.

Synergetic effects of conductive materials and bacterial population in inoculum on mixed-culture biohydrogen production

This study examined the effect of conductive materials (softwood pellet biochar pyrolyzed at 550 °C and 700 °C, powdered activated carbon and stainless-steel) on the two series of batch biohydrogen production inoculated with three types of heated-treated anaerobic digester sludge. Biochar pyrolyzed at 550 °C and stainless-steel exhibited the highest enhanced hydrogen yield up to 117 % in the first and second series of experiments, respectively. Importantly, the enhancement effect by the introduction of conductive materials was significantly affected by the microbial population in inoculum, particularly the relative abundance of electroactive H2-producing Clostridium sp. Metabolic flux analysis revealed that the enhanced H2 yield was concurrent with the decrease of lactate production and the increase of H2-producing acetogenesis. Conductive materials also improved electron transport system activity and NADH/NAD+ ratio, which are related with the metabolic activity. This study shows that introducing conductive material can control intracellular redox environment, thereby reinforcing the metabolic activity selectively.

Revisiting the applicability and constraints of molybdenum- and uranium-based paleo redox proxies: comparing two contrasting sill fjords

Abstract. Sedimentary molybdenum (Mo) and uranium (U) enrichments are often used as redox proxies to reconstruct bottom water redox changes. However, these redox proxies may not be equally reliable across a range of coastal settings due to varying depositional environments. Fjords vary greatly in their depositional conditions, due to their unique bathymetry and hydrography, and are highly vulnerable to anthropogenic and climatic pressures. Currently, it is unknown to what extent Mo and U sequestration is affected by variable depositional conditions in fjords. Here, we use pore water and sequential extraction data to investigate Mo and U enrichment pathways in sediments of two sill fjords on the Swedish west coast with contrasting depositional environments and bottom water redox conditions. Our data suggest that sedimentary authigenic Mo and U pools differ between the two fjords. At the (ir)regularly dysoxic (oxygen = 0.2–2 mL L−1) Gullmar Fjord, authigenic Mo largely binds to manganese (Mn) oxides and to a lesser extent to iron (Fe) oxides; Mo sulfides do not play a major role due to low sulfate reduction rates, which limits the rate of Mo burial. Authigenic U largely resides in carbonates. At the (ir)regularly euxinic (oxygen = 0 mL L−1; total hydrogen sulfide ≥ 0 mL L−1) Koljö Fjord, authigenic Mo is significantly higher due to binding with more refractory organic matter complexes and Mo-Fe-sulfide phases. Uranium is moderately enriched and largely bound to organic matter. We found no direct evidence for temporal changes in bottom water redox conditions reflected in Mo and U enrichments at either Gullmar Fjord or Koljö Fjord. While sulfidic bottom waters favor Mo sequestration at Koljö Fjord, enrichment maxima reflect a combination of depositional conditions rather than short-term low-oxygen events. Our data demonstrate that secondary pre- and post-depositional factors control Mo and U sequestration in fjords to such an extent that bottom water redox conditions are either not being systematically recorded or overprinted. This explains the large variability in trace metal enrichments observed in fjords and has implications for applying Mo and U as proxies for environmental redox reconstructions in such systems.

Quantifying defects in carbon nanotubes undergoing prolonged electrochemical cycling with Raman phase map

Electrically conducting graphitic carbon materials are ubiquitous constituents of electrocatalysts and electrochemical energy storage materials. During electrolysis and electrochemical charge-discharge cycles, the carbon matrix is subjected to chemical stress due to drastic changes in the redox environment, the formation of reactive intermediate species and to steric strain caused by intercalation of counter ions. These factors trigger the formation of defects in the graphitic lattice, leading to scattering the charge carriers, thereby reducing the carrier mobility. It is of utmost importance to reliably monitor the graphitic lattice to maintain the integrity of the material and recognize the nature of defects. We have applied statistical Raman measurement technique in conjunction with Raman phase map and Raman ellipse to monitor and quantify the formation of point and line defects in functionalized carbon nanotubes. We also demonstrate how the Raman ellipse in combination with ID/ID′ is a new and powerful analytical tool which can serve to deduce the correct defect generation process in a graphitic lattice exposed to stress during electrochemical cycling. Thus, a deep mechanical insight by “simple” optical spectroscopy can be captured through our proposed Raman phase map analysis.

Paleo-marine redox environment fluctuation during the early Cambrian: Insight from iron isotope in the Tarim Basin, China

The Ediacaran to Cambrian period is generally considered to be the vital transition in the history of marine redox environment and life evolution on earth. The ocean oxygenation levels during this transition period are still debated. Since iron is widely involved in biogeochemical cycles and undergoes redox cycling both in the seawater and sediments, it has become a significant proxy to reconstruct paleo-marine environment. In order to constrain the paleo-marine redox state in the early Cambrian, the iron isotope composition of bulk rock (δ56FeT) is interpreted combining with iron-speciation, redox sensitive elements and pyrite sulfur isotope (δ34Spy) of Yuertusi Formation in Tarim Block. The δ56FeT values varies from −0.39 ‰ to 0.48 ‰, with an average of 0.07 ‰, mainly controlled by pyrite mineral facies in this study. Based on the mechanism of pyrite generation in different redox condition, it is proposed that the marine environment of the lower Cambrian in the Tarim basin is dominated by anoxic with intermittent euxinic state. The dynamic evolution of redox environment can be divided into three intervals. The gradual decrease of δ56Fe in Interval I indicates the paleo-marine environment changed from anoxic ferruginous to euxinic, and the paleo-marine sulfate reservoir decreased to a limited level, which might be attributed to abundant burial of organic matter and pyrite. For Interval II, δ56Fe values first increase to evident positive because of partial oxidization then decreased to that of seawater (about 0 ‰) due to complete oxidization. In Interval III, the continuous decrease of δ56Fe values infers a sustaining oxidization. In summary, the paleo-marine environment of the lower Cambrian Yuertusi Formation evolved from anoxic ferruginous to euxinic and then oxidized continuous. Iron isotope statistics from geological historical periods indicate that seawater was relatively oxidized after the NOE event but did not reach the oxidation levels of present-day seawater.

Functional validation of Lobularia maritima thioredoxin-h2 protein for its ability to combat bacterial and fungal infections

Thioredoxins (Trxs) belong to a family of multifunctional redox proteins that is critical for maintaining and regulating the cellular redox environment during plant cell growth. Also, they are important for the development of plant's response to biotic and abiotic stress; however, the specific biological functions of h-type thioredoxins (Trxhs) in plants have not been fully elucidated. Herein, we investigated the role of LmTrxh2, a specific member of the Trxh family, in response to various biotic stress simulants, including mechanical wounding, exposure to jasmonic acid (JA), picolinic acid (PA), salicylic acid (SA), ethephon (ETP), and hydrogen peroxide (H2O2). We observed that LmTrxh2 transcripts were significantly upregulated upon exposure to these stress simulants. The characterization of enzymatic activity revealed that the recombinant LmTrxh2 protein functions as a disulfide reductase. While the role of Trx proteins in redox regulation is well known, their involvement in antimicrobial activity is still unexplored. Therefore, we assessed the antimicrobial effect of LmTrxh2 towards various microorganisms and observed a concentration-dependent inhibition of microbial growth. The minimum inhibitory and minimum bactericidal concentrations and the diameters of the inhibition zones were 40–1250 μg/mL, 40–1250 μg/mL, and 12.5–32.5 mm, respectively. In addition, we used previously developed LmTrxh2-transgenic tobacco lines and found that they showed enhanced resistance to fungal infections triggered by Fusarium graminearum and Aspergillus niger. This resistance was associated with an upregulation of known defense-related genes. Overall, our findings suggest that LmTrxh2 is responsive to multiple biotic stress simulants and plays a critical role in the basal resistance of plants to pathogen infections. These results highlight the potential of LmTrxh2 in the development of strategies to protect crops from various stress factors and emphasize its importance in the adaptation of plants to different stress conditions.

Analyzing Electrochemical Sensing Fundamentals for Health Applications

AbstractHumans continuously interact with physical, chemical, and biological environments that influence their health, safety, and quality of life. Sensing devices, such as electrochemical sensors that translate environmental qualities into electrical signals, are crucial for detecting biomarker concentrations in various biofluids. However, the understanding of electrochemical sensing is often incomplete, necessitating further study of chemical reactions and sensor‐electrode interactions for healthcare applications. This review analyzes crucial topics in chemical reactions in electrochemical sensing environments. First, the dynamics of chemical energy, the roles of acidic and alkaline fluids, chemical reaction tendencies, thermodynamic equilibria, Gibbs free energy, water dissociation, and the pH scale are discussed. Sensor materials or biomarkers undergo oxidation and reduction reactions in electrochemical sensing. Oxygen‐derived radicals and nonradical reactive species significantly influence biochemical reactions, cellular responses, and clinical outcomes. Then, the review delves into the impact of oxidation reduction reactions on human pathophysiology, redox reactions in hemoglobin, redox environments in human serum albumin and cells/tissues, and thermodynamics of biological redox reactions. Finally, recent advances in electrochemical techniques are presented and research challenges and future perspectives in electrochemical sensing for health applications are addressed.

Nitrogen isotopic compositions of organic-rich shales (∼560 Ma) in the Chengkou region, South China: Implications for a stable and relatively large nitrate reservoir of the late Ediacaran ocean

The late Ediacaran period is a critical transitional period in Earth's history, marked by the evolution of the Ediacara biota (∼574 to 538.8 Ma). The marine redox state and nutrient level, having a close relationship with bioevolution, can be reflected by sedimentary nitrogen isotopes (δ15N). Doushantuo Formation Member IV, a widespread organic-rich interval during this critical period of South China, may provide important clues for nitrogen (N) cycling. However, high-resolution δ15N research on Member IV is still lacking. In this study, a drill core from the Chengkou sub-basin, with the well-developed Doushantuo Member IV, was carefully studied base on its N isotopic composition. The implications for the N cycling characteristics are discussed using a combination of proxies for bottom water redox conditions and basin openness. The total nitrogen (TN) concentrations (up to 0.79 wt%) of these organic-rich samples are substantially higher than those of other counterpart profiles. The TOC content shows a positive linear relationship with TN concentration, and a significant positive TN-intercept (∼0.21 wt%) represents the addition of inorganic N produced by the remineralization of sinking organic N. The high TN concentrations may also be due to the flourishing and enhanced burial of primary producers. The δ15N value in the Doushantuo Member IV progressively decreases from ∼8.2‰ to ∼3.2‰ (from bottom to top), a result of the changes in basin openness and the enhancement of N2-fixation. Compilation shows the δ15N and δ13Corg values are approximately covariant, and both have significant temporal and spatial variations at this member of South China, indicating a strong heterogeneity in the water column redox environments and changes in the type of primary producers. A mode δ15N value of 4‰ indicates a stable and relatively large nitrate reservoir in the late Ediacaran ocean.

Erosion and deposition regulate soil carbon by mediating Fe-Carbon fixation mode in a typical catchment in the black soil region of Northeastern China

Soil carbon is critical to soil quality and the global carbon cycle, while Fe is highly sensitive to redox processes and can affect soil carbon stocks by sequestrating and releasing carbon. Soil erosion and deposition can cause the spatial heterogeneity of soil properties along landscapes and alter the redox environment, thus further influence carbon fixation by Fe in situ. Carbon, especially Fe-oxide-bound carbon (OC-Fe) were poorly studied in different erosion intensities. Here, we investigated OC-Fe, soil organic carbon (SOC), and inorganic carbon (SIC) contents at erosion and deposition sites in a typical catchment of Northeast China, and evaluated the responses of oxygen diffusion state (DCo), Fe oxides (Fep, Fed) and valence state of Fe (Fe(II), Fe(III)) to erosion and deposition. We have also quantified factors affecting Fe and carbon to elucidate the drivers of Fe-mediated carbon stock variations induced by erosion. Results showed that with a higher erosion intensity, a greater redistribution was emerged on OC-Fe and SIC in the 0–10 cm soil layer of study catchment. Compared to deposition sites, OC-Fe and SIC increase by 63.32 % and 11.41 times at erosion sites, respectively. However, SOC increased 18.56 % at deposition sites. In the 10–20 cm soil layer, where erosion forces were more pronounced, the binding mode of Fe oxides to carbon changed from co-precipitation to adsorption. The presence of Fe(II) promoted OC-Fe formation. Structural equation modelling（SEM）constructed by the varied particle composition with erosion and deposition explained 79 % of the variation in carbon stock in 0–20 cm soil layer. This study concluded that subsoil carbon stocks (>10 cm) are mainly affected by the application rate of exogenous carbon and variations of its mineral content. Erosion-induced variations of carbon sequestration patterns have continuous effects on farmland carbon turnover capacity.

Modulation of Kynurenic Acid Production by N-acetylcysteine Prevents Cognitive Impairment in Adulthood Induced by Lead Exposure during Lactation in Mice.

Lead (Pb2+) exposure during early life induces cognitive impairment, which was recently associated with an increase in brain kynurenic acid (KYNA), an antagonist of NMDA and alpha-7 nicotinic receptors. It has been described that N-acetylcysteine (NAC) favors an antioxidant environment and inhibits kynurenine aminotransferase II activity (KAT II, the main enzyme of KYNA production), leading to brain KYNA levels decrease and cognitive improvement. This study aimed to investigate whether the NAC modulation of the brain KYNA levels in mice ameliorated Pb2+-induced cognitive impairment. The dams were divided into four groups: Control, Pb2+, NAC, and Pb2++NAC, which were given drinking water or 500 ppm lead acetate in the drinking water ad libitum, from 0 to 23 postnatal days (PNDs). The NAC and Pb2++NAC groups were simultaneously fed NAC (350 mg/day) in their chow from 0 to 23 PNDs. At PND 60, the effect of the treatment with Pb2+ and in combination with NAC on learning and memory performance was evaluated. Immediately after behavioral evaluation, brain tissues were collected to assess the redox environment; KYNA and glutamate levels; and KAT II activity. The NAC treatment prevented the long-term memory deficit exhibited in the Pb2+ group. As expected, Pb2+ group showed redox environment alterations, fluctuations in glutamate levels, and an increase in KYNA levels, which were partially avoided by NAC co-administration. These results confirmed that the excessive KYNA levels induced by Pb2+ were involved in the onset of cognitive impairment and could be successfully prevented by NAC treatment. NAC could be a tool for testing in scenarios in which KYNA levels are associated with the induction of cognitive impairment.

PTM-Psi: A python package to facilitate the computational investigation of post-translational modification on protein structures and their impacts on dynamics and functions.

Post-translational modification (PTM) of a protein occurs after it has been synthesized from its genetic template, and involves chemical modifications of the protein's specific amino acid residues. Despite of the central role played by PTM in regulating molecular interactions, particularly those driven by reversible redox reactions, it remains challenging to interpret PTMs in terms of protein dynamics and function because there are numerous combinatorially enormous means for modifying amino acids in response to changes in the protein environment. In this study, we provide a workflow that allows users to interpret how perturbations caused by PTMs affect a protein's properties, dynamics, and interactions with its binding partners based on inferred or experimentally determined protein structure. This Python-based workflow, called PTM-Psi, integrates several established open-source software packages, thereby enabling the user to infer protein structure from sequence, develop force fields for non-standard amino acids using quantum mechanics, calculate free energy perturbations through molecular dynamics simulations, and score the bound complexes via docking algorithms. Using the S-nitrosylation of several cysteines on the GAP2 protein as an example, we demonstrated the utility of PTM-Psi for interpreting sequence-structure-function relationships derived from thiol redox proteomics data. We demonstrate that the S-nitrosylated cysteine that is exposed to the solvent indirectly affects the catalytic reaction of another buried cysteine over a distance in GAP2 protein through the movement of the two ligands. Our workflow tracks the PTMs on residues that are responsive to changes in the redox environment and lays the foundation for the automation of molecular and systems biology modeling.

Pancreatic Antioxidative Defense and Heat Shock Proteins Prevent Islet of Langerhans Cell Death After Chronic Oral Exposure to Cadmium LOAEL Dose.

Cadmium, a hazardous environmental contaminant, is associated with metabolic disease development. The dose with the lowest observable adverse effect level (LOAEL) has not been studied, focusing on its effect on the pancreas. We aimed to evaluate the pancreatic redox balance and heat shock protein (HSP) expression in islets of Langerhans of male Wistar rats chronically exposed to Cd LOAEL doses, linked to their survival. Male Wistar rats were separated into control and cadmium groups (drinking water with 32.5 ppm CdCl2). At 2, 3, and 4 months, glucose, insulin, and cadmium were measured in serum; cadmium and insulin were quantified in isolated islets of Langerhans; and redox balance was analyzed in the pancreas. Immunoreactivity analysis of p-HSF1, HSP70, HSP90, caspase 3 and 9, and cell survival was performed. The results showed that cadmium exposure causes a serum increase and accumulation of the metal in the pancreas and islets of Langerhans, hyperglycemia, and hyperinsulinemia, associated with high insulin production. Cd-exposed groups presented high levels of reactive oxygen species and lipid peroxidation. An augment in MT and GSH concentrations with the increased enzymatic activity of the glutathione system, catalase, and superoxide dismutase maintained a favorable redox environment. Additionally, islets of Langerhans showed a high immunoreactivity of HSPs and minimal immunoreactivity to caspase associated with a high survival rate of Langerhans islet cells. In conclusion, antioxidative and HSP pancreatic defense avoids cell death associated with Cd accumulation in chronic conditions; however, this could provoke oversynthesis and insulin release, which is a sign of insulin resistance.

Redox-responsive biodegradable dendronized polymers: A side-chain modulation based fabrication of drug delivery vehicles

Among various nanomedicine platforms, stimuli-responsive biodegradable polymeric micelles offer a viable approach to address challenges in cancer therapy. Herein, we report the fabrication of redox-responsive micellar aggregates based on an amphiphilic dendron-polymer conjugate. In particular, acid-degradable hydrophobic polyester dendrons are attached as side chain moieties through a disulfide linkage on a hydrophilic copolymer. Polymers containing three generations of dendrons are synthesized using the thiol-disulfide exchange reaction and utilized to obtain micellar aggregates. The stability of the obtained aggregates, drug loading, and release characteristics in neutral, acidic, and redox environments were investigated. It was established that micelles are efficiently internalized by cells, and the highest level of cytotoxicity was observed for MDA-MB-231 breast cancer carcinoma cells under a reducing environment.

Breaking Barriers to High-Practical Li-S Batteries with Isotropic Binary Sulfiphilic Electrocatalyst: Creating a Virtuous Cycle for Favorable Polysulfides Redox Environments.

Investigations into lithium-sulfur batteries (LSBs) has focused primarily on the initial conversion of lithium polysulfides (LiPSs) to Li2 S2 . However, the subsequent solid-solid reaction from Li2 S2 to Li2 S and the Li2 S decomposition process should be equally prioritized. Creating a virtuous cycle by balancing all three chemical reaction processes is crucial for realizing practical LSBs. Herein, amorphous Ni3 B in synergy with carbon nanotubes (aNi3 B@CNTs) is proposed to implement the consecutive catalysis of S8(solid) → LiPSs(liquid) → Li2 S(solid) →LiPSs(liquid) . Systematic theoretical simulations and experimental analyses reveal that aNi3 B@CNTs with an isotropic structure and abundant active sites can ensure rapid LiPSs adsorption-catalysis as well as uniform Li2 S precipitation. The uniform Li2 S deposition in synergy with catalysis of aNi3 B enables instant/complete oxidation of Li2 S to LiPSs. The produced LiPSs are again rapidly and uniformly adsorbed for the next sulfur evolution process, thus creating a virtuous cycle for sulfur species conversion. Accordingly, the aNi3 B@CNTs-based cell presents remarkable rate capability, long-term cycle life, and superior cyclic stability, even under high sulfur loading and extreme temperature environments. This study proposes the significance of creating a virtuous cycle for sulfur species conversion to realize practical LSBs.

High-Affinity Fluorogenic Substrate for Tissue Transglutaminase Reveals Enzymatic Hysteresis.

Transglutaminases (TGases) are a family of calcium-dependent enzymes primarily known for their ability to cross-link proteins. Transglutaminase 2 (TG2) is one isozyme in this family whose role is multifaceted. TG2 can act not only as a typical transamidase through its catalytic core but also as a G-protein via its GTP binding site. These two discrete activities are tightly regulated by both environmental stimuli and redox reactions. Ubiquitously expressed in humans, TG2 has been implicated in numerous disease pathologies that require extensive investigation. The catalytic activity of TG2 can be monitored through various mechanisms, including hydrolysis, transamidation, or cleavage of isopeptide bonds. Activity assays are required to monitor the activity of this isozyme not only for studying its transamidation reaction but also for validation of therapeutics designed to abolish this activity. Herein, we present the design, synthesis, and evaluation of a new TG2 activity substrate based on a previously optimized inhibitor scaffold. The substrate APH7 exhibits excellent affinity, selectivity, and reactivity with TG2 (KM = 3.0 μM). Furthermore, its application also allowed the discovery of unique hysteresis at play within the catalytic activity and inhibition reactivity of TG2.

BOLA3 and NFU1 link mitoribosome iron-sulfur cluster assembly to multiple mitochondrial dysfunctions syndrome.

The human mitochondrial ribosome contains three [2Fe-2S] clusters whose assembly pathway, role, and implications for mitochondrial and metabolic diseases are unknown. Here, structure-function correlation studies show that the clusters play a structural role during mitoribosome assembly. To uncover the assembly pathway, we have examined the effect of silencing the expression of Fe-S cluster biosynthetic and delivery factors on mitoribosome stability. We find that the mitoribosome receives its [2Fe-2S] clusters from the GLRX5-BOLA3 node. Additionally, the assembly of the small subunit depends on the mitoribosome biogenesis factor METTL17, recently reported containing a [4Fe-4S] cluster, which we propose is inserted via the ISCA1-NFU1 node. Consistently, fibroblasts from subjects suffering from 'multiple mitochondrial dysfunction' syndrome due to mutations in BOLA3 or NFU1 display previously unrecognized attenuation of mitochondrial protein synthesis that contributes to their cellular and pathophysiological phenotypes. Finally, we report that, in addition to their structural role, one of the mitoribosomal [2Fe-2S] clusters and the [4Fe-4S] cluster in mitoribosome assembly factor METTL17 sense changes in the redox environment, thus providing a way to regulate organellar protein synthesis accordingly.

Flexible catabolism of monoaromatic hydrocarbons by anaerobic microbiota adapting to oxygen exposure

Microbe-mediated anaerobic degradation is a practical method for remediation of the hazardous monoaromatic hydrocarbons (BTEX, including benzene, toluene, ethylbenzene and xylenes) under electron-deficient contaminated sites. However, how do the anaerobic functional microbes adapt to oxygen exposure and flexibly catabolize BTEX remain poorly understood. We investigated the switches of substrate spectrum and bacterial community upon oxygen perturbation in a nitrate-amended anaerobic toluene-degrading microbiota which was dominated by Aromatoleum species. DNA-stable isotope probing demonstrated that Aromatoleum species was involved in anaerobic mineralization of toluene. Metagenome-assembled genome of Aromatoleum species harbored both the nirBD-type genes for nitrate reduction to ammonium coupled with toluene oxidation and the additional meta-cleavage pathway for aerobic benzene catabolism. Once the anaerobic microbiota was fully exposed to oxygen and benzene, 1.05 ± 0.06% of Diaphorobacter species rapidly replaced Aromatoleum species and flourished to 96.72 ± 0.01%. Diaphorobacter sp. ZM was isolated, which was not only able to utilize benzene as the sole carbon source for aerobic growth and but also innovatively reduce nitrate to ammonium with citrate/lactate/glucose as the carbon source under anaerobic conditions. This study expands our understanding of the adaptive mechanism of microbiota for environmental redox disturbance and provides theoretical guidance for the bioremediation of BTEX-contaminated sites.

Melatonin targets ferroptosis through bimodal alteration of redox environment and cellular pathways in NAFLD model.

Ferroptosis is a non-conventional cellular death caused by lipid peroxide induced iron deposition. Intracellular lipid accumulation followed by generation of lipid peroxides is an Hallmark of Non Alcoholic Fatty Liver Disease (NAFLD). Melatonin (MLT) is an important pineal hormone with tremendous antioxidant and anti-inflammatory properties. Various studies targeted ferroptosis in different diseases using melatonin. However, none of them focused the intrinsic mechanism of MLT's action to counteract ferroptosis in NAFLD. Hence, the present study investigated the role of MLT in improvement of NAFLD induced ferroptosis. &#160;HepG2 cells were treated with Free Fatty Acids (FFAs) to induce in vitro NAFLD state and C57BL/6 mice were fed with HFD followed by MLT administration 1.</p> &#160;The results indicated that MLT administration caused the recovery from both FFA and HFD induced ferroptotic state via increasing GSH and SOD level, decreasing lipid ROS and MDA (Malondialdehyde) level, increasing Nrf2 and HO-1 level to defend cells against an oxidative environment. MLT also altered the expression of two key proteins GPX4 and SLC7A11 back to their normal levels, which would otherwise cause ferroptosis. MLT also protected against histopathological damage of both liver tissue and HepG2 cells as depicted by Oil Red O, HE staining and immunofluorescence microscopy. MLT also had control over pAMPKα as well as PPARγ and PPARα responsible for lipid homeostasis and lipogenesis.</p> &#160;In brief, MLT exerted its multifaceted effect in FFA and HFD induced NAFLD by retrieving cellular oxidative environment, reducing lipogenesis and lipid peroxidation and modulating Nrf2/HO-1 and GPX4/SLC7A11 axis to combat ferroptosis.</p>.

Spatial lithological heterogeneity of the deep-sea sediments and its controlling factors in the northern West Caroline Basin, tropical West Pacific

Uncovering the spatial distribution of deep-sea sediment lithologies is crucial for the research on earth system science and the exploration of critical mineral resources. The conventional global deep-sea sediment lithology distribution maps showed that the lithologies were relatively uniform in the global major ocean basins. Furthermore, it was deemed that the deep-sea sediment lithologies were related to the productivity of surface seawater. However, later studies have illustrated that the distribution of deep-sea sediment lithologies exhibited greater variability and heterogeneity than conventional maps and that water depth played a more important role in controlling deep-sea sediment lithologies than productivity. In addition, few studies have focused on the relationship between the heterogeneous deep-sea sediment lithologies and the diverse seafloor topography in the West Pacific. In this study, we provide a high-resolution spatial distribution map of deep-sea sediment lithologies by systematic descriptions of 112 surface samples in the northern West Caroline Basin, tropical West Pacific, with a large range of water depth and a diverse seafloor topography to verify the previous prediction of sediment lithology distribution. Subsequently, based on the results of the determinations of carbonate and biogenic silica contents, the sediment redox-potential tests, and the calculations of multiple variables, we carried out quantitative studies and correlation analyses for these variables to reveal the relative contribution of different factors to the lithological heterogeneity in the northern West Caroline Basin. Our results show that the actual deep-sea sediments have greater heterogeneity in terms of lithological classes and distribution patterns than the earlier predicted lithology maps. Furthermore, our analyses reveal that water depth and seafloor topography are the more important controlling factors on the deep-sea sediment lithology to some extent than productivity and that water depth and topography may exert different effects on the different sediment components. For the calcareous component, water depth is the main controlling factor due to the increased solubility of carbonate with water depth. Carbonate materials can dilute other components in the waters above the carbonate compensation depth, which is around 4500 m below the sea surface in the study area. Meanwhile, the siliceous component may be enriched in the unique negative seafloor topography of the trench and trough with the specific lateral transport mechanism and the redox environment. These findings imply a more complicated actual deep-sea sediment lithology distribution than previously thought given that various water depths and diverse topography in the global oceans, which are significant for understanding deep-sea sedimentary processes and improving the models for predicting global sediment lithology in the deep sea.

Dissolved carbon in biochar: Exploring its chemistry, iron complexing capability, toxicity in natural redox environment

Dissolved black carbon (DBC) plays a crucial role in the migration and bioavailability of iron in water. However, the properties of DBC releasing under diverse pyrolysis conditions and dissolving processes have not been systematically studied. Here, the compositions of DBC released from biochar through redox processes dominated by bacteria and light were thoroughly studied. It was found that the DBC released from straw biochar possess more oxygen-containing functional groups and aromatic substances. The content of phenolic and carboxylic groups in DBC was increased under influence of microorganisms and light, respectively. The concentration of phenolic hydroxyl groups increased from 10.0∼57.5 mmol/gC to 6.6 ∼65.2 mmol/gC, and the concentration of carboxyl groups increased from 49.7∼97.5 mmol/gC to 62.1 ∼113.3 mmol/gC. Then the impacts of DBC on pyrite dissolution and microalgae growth were also investigated. The complexing Fe3+ was proved to play a predominant role in the dissolution of ferrous mineral in DBC solution. Due to complexing between iron ion and DBC, the amount of dissolved Fe in aquatic water may rise as a result of elevated number of aromatic components with oxygen containing groups and low molecular weight generated under light conditions. Fe-DBC complexations in solution significantly promoted microalga growth, which might be attributed to the stimulating effect of dissolved Fe on the chlorophyll synthesis. The results of study will deepen our understanding of the behavior and ultimate destiny of DBC released into an iron-rich environment under redox conditions.