Search

Shergottite meteorites, classified as depleted, intermediate, or enriched based on incompatible trace elements and specific radiogenic isotope compositions (Sr, Nd, and Hf isotope ratios), point to multiple Martian mantle source regions. The oxygen fugacity (f O 2) of these mantle regions, determined from early crystallizing minerals using the olivine-pyroxene-spinel oxybarometer, appears to correlate with incompatible trace element enrichment and isotope compositions. However, values derived from the vanadium-in-olivine oxybarometer challenge this correlation, hinting at potential biases in oxybarometry or complexities in the redox conditions of the Martian mantle. By analyzing the intermediate shergottite Northwest Africa (NWA) 11043 with various oxybarometers, this study deduced its origin from a reduced mantle source, with an average f O 2 value of −0.77 ± 0.35 relative to the iron-wüstite (IW) buffer. Notably, these values coincide with those of depleted shergottites, which represent the depleted Martian mantle region. This redox similarity between intermediate and depleted shergottites contrasts with earlier notions that postulated intermediate shergottites as a mix of depleted and enriched mantle derivatives. Moreover, intermediate shergottites such as NWA 11043, Elephant Moraine (EETA) 79001A, and Allan Hills (ALH) 77005 display 176Hf/177Hf values akin to those of depleted shergottites, suggesting that intermediate mantle components can be separated from the depleted mantle source at approximately 2.2 Ga based on model age calculations. Therefore, there presents a consistent redox state between mantle magma sources of both intermediate and depleted shergottites since the Hesperian period, while enriched shergottites lean toward more oxidized conditions past source formation. This study prompts a reassessment of conventional theories, emphasizing the nuanced redox evolution of the Martian mantle across distinct mantle source regions and underscoring the complexity of the redox evolution of the Martian mantle. The emergence of chemically diverse mantle reservoirs might predominantly arise from early magma ocean differentiation processes, albeit with inherent oxidation nuances. The differences in f O 2 observed between intermediate and depleted shergottites underscore the need for more in-depth studies to decipher Martian mantle differentiation and evolution. [ABSTRACT FROM AUTHOR]

Summary: Soil contamination with arsenic (As) can cause phytotoxicity and reduce crop yield. The mechanisms of As toxicity and tolerance are not fully understood.In this study, we used a forward genetics approach to isolate a rice mutant, ahs1, that exhibits hypersensitivity to both arsenate and arsenite. Through genomic resequencing and complementation tests, we identified OsLPD1 as the causal gene, which encodes a putative lipoamide dehydrogenase.OsLPD1 was expressed in the outer cell layer of roots, root meristem cells, and in the mesophyll and vascular tissues of leaves. Subcellular localization and immunoblot analysis demonstrated that OsLPD1 is localized in the stroma of plastids. In vitro assays showed that OsLPD1 exhibited lipoamide dehydrogenase (LPD) activity, which was strongly inhibited by arsenite, but not by arsenate. The ahs1 and OsLPD1 knockout mutants exhibited significantly reduced NADH/NAD+ and GSH/GSSG ratios, along with increased levels of reactive oxygen species and greater oxidative stress in the roots compared with wild‐type (WT) plants under As treatment. Additionally, loss‐of‐function of OsLPD1 also resulted in decreased fatty acid concentrations in rice grain.Taken together, our finding reveals that OsLPD1 plays an important role for maintaining redox homeostasis, conferring tolerance to arsenic stress, and regulating fatty acid biosynthesis in rice. [ABSTRACT FROM AUTHOR]

For many years, metal–flavonoid complexes have been widely studied as a part of drug discovery programs, but in the last decade their importance in materials science has increased significantly. A deeper understanding of the role of metal ions and flavonoids in constructing simple complexes and more advanced hybrid networks will facilitate the assembly of materials with tailored architecture and functionality. In this Review, we highlight the most essential data on metal–flavonoid systems, presenting a promising alternative in the design of hybrid inorganic–organic materials. We focus mainly on systems containing CuII/I and FeIII/II ions, which are necessary in natural and industrial catalysis. We discuss two kinds of interactions that typically ensure the formation of metal–flavonoid systems, namely coordination and redox reactions. Our intention is to cover the fundamentals of metal–flavonoid systems to show how this knowledge has been already transferred from small molecules to complex materials. [ABSTRACT FROM AUTHOR]

Oxidative stress is considered a contributor to declining muscle function and mobility during aging; however, the underlying molecular mechanisms remain poorly described. We hypothesized that greater levels of cysteine (Cys) oxidation on muscle proteins are associated with decreased measures of mobility. Herein, we applied a novel redox proteomics approach to measure reversible protein Cys oxidation in vastus lateralis muscle biopsies collected from 56 subjects in the Study of Muscle, Mobility and Aging (SOMMA), a community‐based cohort study of individuals aged 70 years and older. We tested whether levels of Cys oxidation on key muscle proteins involved in muscle structure and contraction were associated with muscle function (leg power and strength), walking speed, and fitness (VO2 peak on cardiopulmonary exercise testing) using linear regression models adjusted for age, sex, and body weight. Higher oxidation levels of select nebulin Cys sites were associated with lower VO2 peak, while greater oxidation of myomesin‐1, myomesin‐2, and nebulin Cys sites was associated with slower walking speed. Higher oxidation of Cys sites in key proteins such as myomesin‐2, alpha‐actinin‐2, and skeletal muscle alpha‐actin were associated with lower leg power and strength. We also observed an unexpected correlation (R = 0.48) between a higher oxidation level of eight Cys sites in alpha‐actinin‐3 and stronger leg power. Despite this observation, the results generally support the hypothesis that Cys oxidation of muscle proteins impairs muscle power and strength, walking speed, and cardiopulmonary fitness with aging. [ABSTRACT FROM AUTHOR]

Reactive oxygen species are known to have a harmful activity in living systems. It attracts the attention of researchers due to their capability of damaging crucial biomolecules such as nucleic acids, lipids, proteins, polyunsaturated fatty acids, and carbohydrates and which results many human ailments: atherosclerosis, cancer, diabetes, inflammation, cardiovascular diseases, and neurological disorders. Hence, the investigation of the already known compounds exhibiting antioxidant properties is still an important scientific challenge. So reaction with Co(II)-bound superoxo complex, [(NH3)5Co(O2)Co(NH3)5]5+ (MBSC) and Popofol (PPF), Ferulic Acid (FA) is chosen to study the antioxidant activity of PPF and FA. Redox properties of Popofol (PPF) and Ferulic Acid (FA) which are two phenolic antioxidants are studied through the reduction of Co(II)-bound superoxo complex, [(NH3)5Co(O2)Co(NH3)5]5+ (MBSC) in aqueous acidic media ([H+] = 0.02–0.70 M) under pseudo-first-order condition. For both the PPF and FA, the observed rate increase with the increase in [PPF] and [FA] and the decrease with media [H+] and ionic strength, I. The kinetic analysis reveals that the deprotonated conjugate bases from PPF and FA reduces MBSC with the diffusion-controlled rate of ~ 108 and ~ 1011 M−1 s−1. Since, the decrease in ko values with increase in V/V D2O were not significant, we can propose for a simple electron-transfer (ET) mechanism, rather than proton-coupled electron transfer (PCET) or hydrogen-atom transfer (HAT) mechanism for the reduction in bound superoxide by PPF and FA. The antioxidant property of propofol and ferulic acid has been evaluated by various methods but in our study, the novelty lies on the exploration of the real insight of their antioxidant property by studying the chemical mechanism of their redox properties with MBSC. [ABSTRACT FROM AUTHOR]

Encapsulins are protein nanocompartments that regulate cellular metabolism in several bacteria and archaea. Myxococcus xanthus encapsulins protect the bacterial cells against oxidative stress by sequestering cytosolic iron. These encapsulins are formed by the shell protein EncA and three cargo proteins: EncB, EncC, and EncD. EncB and EncC form rotationally symmetric decamers with ferroxidase centers (FOCs) that oxidize Fe+2 to Fe+3 for iron storage in mineral form. However, the structure and function of the third cargo protein, EncD, have yet to be determined. Here, we report the x-ray crystal structure of EncD in complex with flavin mononucleotide. EncD forms an α-helical hairpin arranged as an antiparallel dimer, but unlike other flavin-binding proteins, it has no ß-sheet, showing that EncD and its homologs represent a unique class of bacterial flavin-binding proteins. The cryo-EM structure of EncA-EncD encapsulins confirms that EncD binds to the interior of the EncA shell via its C-terminal targeting peptide. With only 100 amino acids, the EncD α-helical dimer forms the smallest flavin-binding domain observed to date. Unlike EncB and EncC, EncD lacks a FOC, and our biochemical results show that EncD instead is a NAD(P)H-dependent ferric reductase, indicating that the M. xanthus encapsulins act as an integrated system for iron homeostasis. Overall, this work contributes to our understanding of bacterial metabolism and could lead to the development of technologies for iron biomineralization and the production of iron-containing materials for the treatment of various diseases associated with oxidative stress. [ABSTRACT FROM AUTHOR]

SUMMARY Redox changes of pyridine nucleotides in cellular compartments are highly dynamic and their equilibria are under the influence of various reducing and oxidizing reactions. To obtain spatiotemporal data on pyridine nucleotides in living plant cells, typical biochemical approaches require cell destruction. To date, genetically encoded fluorescent biosensors are considered to be the best option to bridge the existing technology gap, as they provide a fast, accurate, and real‐time readout. However, the existing pyridine nucleotides genetically encoded fluorescent biosensors are either sensitive to pH change or slow in dissociation rate. Herein, we employed the biosensors which generate readouts that are pH stable for in planta measurement of NADH/NAD+ ratio and NADPH level. We generated transgenic Arabidopsis lines that express these biosensors in plastid stroma and cytosol of whole plants and pollen tubes under the control of CaMV 35S and LAT52 promoters, respectively. These transgenic biosensor lines allow us to monitor real‐time dynamic changes in NADH/NAD+ ratio and NADPH level in the plastids and cytosol of various plant tissues, including pollen tubes, root hairs, and mesophyll cells, using a variety of fluorescent instruments. We anticipate that these valuable transgenic lines may allow improvements in plant redox biology studies. [ABSTRACT FROM AUTHOR]

Copper is a critical trace element in biological systems due the vast number of essential enzymes that require the metal as a cofactor, including cytochrome c oxidase, superoxide dismutase and dopamine‐β‐hydroxylase. Due its key role in oxidative metabolism, antioxidant defence and neurotransmitter synthesis, copper is particularly important for neuronal development and proper neuronal function. Moreover, increasing evidence suggests that copper also serves important functions in synaptic and network activity, the regulation of circadian rhythms, and arousal. However, it is important to note that because of copper's ability to redox cycle and generate reactive species, cellular levels of the metal must be tightly regulated to meet cellular needs while avoiding copper‐induced oxidative stress. Therefore, it is essential that the intricate system of copper transporters, exporters, copper chaperones and copper trafficking proteins function properly and in coordinate fashion. Indeed, disorders of copper metabolism such as Menkes disease and Wilson disease, as well as diseases linked to dysfunction of copper‐requiring enzymes, such as SOD1‐linked amyotrophic lateral sclerosis, demonstrate the dramatic neurological consequences of altered copper homeostasis. In this review, we explore the physiological importance of copper in the nervous system as well as pathologies related to improper copper handling. [ABSTRACT FROM AUTHOR]

Artificial organelles serve as functional counterparts to natural organelles, which are primarily employed to artificially replicate, restore, or enhance cellular functions. While most artificial organelles exhibit basic functions, we diverge from this norm by utilizing poly(ferrocenylmethylethylthiocarboxypropylsilane) microcapsules (PFC MCs) to construct multifunctional artificial organelles through water/oil interfacial self‐assembly. Within these PFC MCs, enzymatic cascades are induced through active molecular exchange across the membrane to mimic the functions of enzymes in mitochondria. We harness the inherent redox properties of the PFC polymer, which forms the membrane, to facilitate in‐situ redox reactions similar to those supported by the inner membrane of natural mitochondria. Subsequent studies have demonstrated the interaction between PFC MCs and living cell including extended lifespans within various cell types. We anticipate that functional PFC MCs have the potential to serve as innovative platforms for organelle mimics capable of executing specific cellular functions. [ABSTRACT FROM AUTHOR]

It has been observed by many authors that highly active electrocatalysts are frequently “disordered” or “amorphous” in nature. The correlation between this lack of order and functionality is highly debated, with researchers still questioning if this structural property is a simple coincidence of the material preparation method, or if this lack of order has an important functional role for these catalysts. Using metal oxides as an example, how amorphous and disordered metal oxides can react by fundamentally different pathways are explored from more ordered forms with very similar bonding and redox states. The distinction between amorphous, disordered, and crystalline materials is reviewed in different characterization methods and suggests how these material characteristics fundamentally change the reactivity of these materials beyond surface area effects. How disorder can change the underlying thermodynamic stability of a material is explored, which in turn impacts redox potential, proton‐transfer, and electron‐transfer properties. It is these fundamental properties that govern the electrocatalytic activity and microbial metabolism of these materials. It is further argued that understanding the amorphous and disordered state of materials may be key to understanding a range of catalytic reactions; from clean energy reactions to the biological systems that underpin life's existence. [ABSTRACT FROM AUTHOR]

Ascorbate peroxidase (APX) reduces H2O2 to H2O by utilizing ascorbate as a specific electron donor and constitutes the ascorbate–glutathione cycle in organelles of plants including chloroplasts, cytosol, mitochondria, and peroxisomes. It has been almost 40 years since APX was discovered as an important plant-specific H2O2-scavenging enzyme, during which time many research groups have conducted molecular physiological analyses. It is now clear that APX isoforms function not only just as antioxidant enzymes but also as important factors in intracellular redox regulation through the metabolism of reactive oxygen species. The function of APX isoforms is regulated at multiple steps, from the transcriptional level to post-translational modifications of enzymes, thereby allowing them to respond flexibly to ever-changing environmental factors and physiological phenomena such as cell growth and signal transduction. In this review, we summarize the physiological functions and regulation mechanisms of expression of each APX isoform. [ABSTRACT FROM AUTHOR]

The helical structure is a classical framework to design high-performance organic electro-optical materials. In this work, the structure-property's relationships of helical tetraspirobenzene (1) and its oxidation (12+) and reduction (12–) products are explored. The results show that the redox brings some distinctive changes in their geometric structure and electronic property, which regulate the first hyperpolarisability (βtot). Among these structures, the 12– has the largest βtot value of 4.2 × 104, which is greatly larger than 2.0 × 102 a.u. of. 12+. Therefore, the reduction effect is more obvious than the oxidation effect. Furthermore, the UV-Vis absorption spectrum also proves this phenomenon: the oxidation product has a new red-shifted absorption peak (571 nm) and the reduction product has two new red-shifted absorption peaks (577 and 797 nm). We hope the present work can provide theoretical guidance for the search for high-performance nonlinear optical materials by using the redox effect. [ABSTRACT FROM AUTHOR]

Cell proliferation depends on intracellular redox homeostasis to support anabolic metabolism and mitigate oxidative stress. Mammalian cells utilize a collection of electron-carrying molecules to coordinate a variety of redox reactions that occur in a temporally and spatially distinct manner. Cancer cells often display altered redox regulation as a result of oncogenic mutations, in order to meet their increased demand for electron acceptors, biosynthetic reducing equivalents, and antioxidant defense capability. The intracellular metabolic network comprises a variety of reduction–oxidation (redox) reactions that occur in a temporally and spatially distinct manner. In order to coordinate these redox processes, mammalian cells utilize a collection of electron-carrying molecules common to many redox reactions, including NAD, NADP, coenzyme Q (CoQ), and glutathione (GSH). This review considers the metabolic basis of redox regulation in the context of cell proliferation by analyzing how cells acquire and utilize electron carriers to maintain directional carbon flux, sustain reductive biosynthesis, and support antioxidant defense. Elucidating the redox requirement during cell proliferation can advance the understanding of human diseases such as cancer, and reveal effective therapeutic opportunities in the clinic. [ABSTRACT FROM AUTHOR]

The key role of manganese (Mn) in the biogeochemical cycle of trace elements has been of great interest in recent years. Nevertheless, the redox properties of aqueous Mn(III) have been studied to a lesser extent. Mn(III) is not stable in solution by itself. However, when complexed with inorganic ligands, it has shown potential to oxidize and reduce trace elements. In the present study, we are exploring the redox characteristics of the complex Mn(III)-Pyrophosphate (Mn(III)-PP). This complex is stable over a wide range of pH values but requires the ratio of Mn:PP to be less than 1:6. Specifically, the redox reaction of chromium (Cr(III)) and Mn(III)-PP is investigated. A solid, Cr(OH) 3 , is used as a source of Cr(III). For this reaction, environmentally relevant parameters, such as pH, ionic strength, ratio Mn(III)/Cr(III), and excess of ligand, were assessed. Results showed that Mn(III) can effectively oxidize Cr(III) to Cr(VI), taking about 15 days for the reaction to complete. This reaction occurs only under acidic conditions (pH 4), and with a low excess of Pyrophosphate. The initial Mn(III) concentration decreases as the Cr(VI) is produced, and Cr(VI) can be adsorbed back into the Cr(OH) 3 surface, limiting the mobility of this toxic species. Despite this adsorption, significant amounts of Cr(VI) are release in the aqueous phase. This study shows the importance of a mobile species (Mn-PP complex) in the oxidation of Cr(III) and the release of Cr(VI) to the environment. [ABSTRACT FROM AUTHOR]

Radical‐polar crossover reactions were studied for the intramolecular cyclopropanation of active methylene derivatives. In the presence of FeCl3 as a stoichiometric oxidant and K2HPO4 as a base, the dehydrogenative cyclopropanation of active methylenes proceeded through the FeCl3‐promoted oxidative radical cyclization followed by the ionic cyclization to give the bicyclic cyclopropanes. The use of α‐chloro‐active methylenes leads the subcatalytic cyclopropanation involving two redox pathways. In the presence of K2HPO4, the redox cyclopropanation proceeded by using FeCl2 (20 mol%) in combination with ligand (20 mol%). [ABSTRACT FROM AUTHOR]

As a critical radioactive anionic contaminant, traditional adsorbents primarily remove iodate (IO3−) through ion exchange or hard acid‐hard base interactions, but suffer from limited affinity and capacity. Herein, employing the synergistic effect of ion exchange and redox, we successfully synthesized a redox‐active cationic polymer network (SCU‐CPN‐6, [C9H10O2N5 ⋅ Cl]n) by merging guanidino groups with ion‐exchange capability and phenolic groups with redox ability via a Schiff base reaction. SCU‐CPN‐6 exhibits a groundbreaking adsorption capacity of 896 mg/g for IO3−. The inferior adsorption capacities of polymeric networks containing only redox (~0 mg/g) or ion exchange (232 mg/g) fragments underscore the synergistic “1+1>2” effect of the two mechanisms. Besides, SCU‐CPN‐6 shows excellent uptake selectivity for IO3− in the presence of high concentrations of SO42−, Cl−, and NO3−. Meanwhile, a high distribution coefficient indicates its exemplary deep‐removal performance for low IO3− concentration. The synergic strategy not only presents a breakthrough solution for the efficient removal of IO3− but also establishes a promising avenue for the design of advanced adsorbents for diverse applications. [ABSTRACT FROM AUTHOR]

Recently, thermodynamic modeling has demonstrated that reduction of nonstoichiometric oxides in a counterflow gas current with a single inlet and exit must result in an equilibrium temperature gradient that deviates from the typically assumed isothermal operation at every single point but one, under assumed mass balance constraints. This necessity for a temperature gradient results in real processes that are near isothermal to deviate from the ideal reversible process, except for the single point where the Gibbs free energy change is zero. In this paper, new configurations with additional inlets and exits that can better approximate reversible and isothermal countercurrent flow reactors are considered and thermodynamically modeled. We show that it is possible to decrease irreversibilities while operating under the same maximum temperature, gas flowrates and initial nonstoichiometry simply by employing two or more exits and/or inlets. Under the most optimal conditions where the normalized irreversibilities are lowest, utilizing either an extra exit or extra inlet and exit show improved results in terms of minimizing the Gibbs free energy and lowering the needed separation work for the gases. Generally, as more irreversibilities are generated within the reactor, the more significant the usage of extra inlets/exits becomes. • Development of thermodynamic models for two new thermal reduction reactor configurations. • Gibbs free energy and separation work are examined to compare the different reactors. • Parametric study based on operating temperature, initial oxidized nonstoichiometry, and inlet sweep gas purity. • Both new reactor designs demonstrate a decrease in irreversibilities compared to the conventional design. [Display omitted] [ABSTRACT FROM AUTHOR]

Cu‐thiosemicarbazones have been intensively investigated for their application in cancer therapy or as antimicrobials. Copper(II)‐di‐2‐pyridylketone‐4,4‐dimethyl‐thiosemicarbazone (CuII‐Dp44mT) showed anticancer activity in the submicromolar concentration range in cell culture. The interaction of CuII‐Dp44mT with thiols leading to their depletion or inhibition was proposed to be involved in this activity. Indeed, CuII‐Dp44mT can catalyze the oxidation of thiols although with slow kinetics. The present work aims to obtain insights into the catalytic activity and selectivity of CuII‐Dp44mT toward the oxidation of different biologically relevant thiols. Reduced glutathione (GSH), L‐cysteine (Cys), N‐acetylcysteine (NAC), D‐penicillamine (D‐Pen), and the two model proteins glutaredoxin (Grx) and thioredoxin (Trx) were investigated. CuII‐Dp44mT catalyzed the oxidation of these thiols with different kinetics, with rates in the following order D‐Pen>Cys≫NAC>GSH and Trx>Grx. CuII‐Dp44mT was more efficient than CuII chloride for the oxidation of NAC and GSH, but not D‐Pen and Cys. In mixtures of biologically relevant concentrations of GSH and either Cys, Trx, or Grx, the oxidation kinetics and spectral properties were similar to that of GSH alone, indicating that the interaction of these thiols with CuII‐Dp44mT is dominated by GSH. Hence GSH could protect other thiols against potential deleterious oxidation by CuII‐Dp44mT. [ABSTRACT FROM AUTHOR]

A divergent synthetic approach to access highly substituted indole scaffolds is illustrated. By virtue of a tunable electrochemical strategy, distinct control over the C‐3 substitution pattern was achieved by employing two analogous 2‐styrylaniline precursors. The chemoselectivity is governed by the fine‐tuning of the acidity of the amide proton, relying on the appropriate selection of N‐protecting groups, and assisted by the reactivity of the electrogenerated intermediates. Detailed mechanistic investigations based on cyclic voltametric experiments and computational studies revealed the crucial role of water additive, which assists the proton‐coupled electron transfer event for highly acidic amide precursors, followed by an energetically favorable intramolecular C−N coupling, causing exclusive fabrication of the C‐3 unsubstituted indoles. Alternatively, the implementation of an electrogenerated cationic olefin activator delivers the C‐3 substituted indoles through the preferential nucleophilic nature of the N‐acyl amides. This electrochemical approach of judicious selection of N‐protecting groups to regulate pKa/E° provides an expansion in the domain of switchable generation of heterocyclic derivatives in a sustainable fashion, with high regio‐ and chemoselectivity. [ABSTRACT FROM AUTHOR]

In addition to its primary oxygen-atom-transfer function, cysteamine dioxygenase (ADO) exhibits a relatively understudied anaerobic disproportionation reaction (ADO-Fe(III)-SR → ADO-Fe(II) + ½ RSSR) with its native substrates. Inspired by ADO disproportionation reactivity, we employ [Fe(tacn)Cl3] (tacn = 1,4,7-triazacyclononane) as a precursor for generating Fe(III)–thiolate model complexes in buffered aqueous media. A series of Fe(III)–thiolate model complexes are generated in situ using aqueous [Fe(tacn)Cl3] and thiol-containing ligands cysteamine, penicillamine, mercaptopropionate, cysteine, cysteine methyl ester, N-acetylcysteine, and N-acetylcysteine methyl ester. We observe trends in UV–Vis and electron paramagnetic resonance (EPR) spectra, disproportionation rate constants, and cathodic peak potentials as a function of thiol ligand. These trends will be useful in rationalizing substrate-dependent Fe(III)–thiolate disproportionation reactions in metalloenzymes. [ABSTRACT FROM AUTHOR]

This study explored the potential of Andrographis paniculata in regulating redox imbalance using planaria as a model organism. Decapitated planaria were regenerated in water, A. paniculata extract, hydrogen peroxide, and a combination of hydrogen peroxide and A. paniculata. The growth was 26% higher, locomotion 15% higher, and protein 35% higher in A. paniculata group. The stressed group had 33% higher growth, 17% higher locomotion, and 36% higher protein when treated with A. paniculata. In conclusion, A. paniculata accelerated the regeneration and minimized the stress induced by hydrogen peroxide and hence can be a promising option for the prevention of neurodegenerative diseases. [ABSTRACT FROM AUTHOR]

In steatotic liver diseases (SLDs), including metabolic dysfunction-associated SLD and alcohol-associated liver disease, the excessive hepatic metabolism of lipids and alcohol leads to an increase in hepatic mitochondrial reductive stress, which in turn contributes to the development of SLD. Recent genetic studies conducted on both humans and mice have provided further evidence highlighting the key role played by hepatic mitochondrial reductive stress in the pathogenesis of SLD. Several pharmaceutical agents currently in development for the treatment of SLD, such as peroxisome proliferator-activated receptor gamma (PPAR-γ) agonists, thyroid hormone receptor agonists, acetyl-CoA carboxylase (ACC) inhibitors, and mitochondrial uncouplers, share an under-recognized common characteristic in that they decrease hepatic mitochondrial reductive stress. A more comprehensive understanding of hepatic mitochondrial reductive stress could help elucidate disease pathogenesis and facilitate the identification of new therapeutic approaches. Steatotic liver diseases (SLDs) affect one-third of the population, but the pathogenesis underlying these diseases is not well understood, limiting the available treatments. A common factor in SLDs is increased hepatic mitochondrial reductive stress, which occurs as a result of excessive lipid and alcohol metabolism. Recent research has also shown that genetic risk factors contribute to this stress. This review aims to explore how these risk factors increase hepatic mitochondrial reductive stress and how it disrupts hepatic metabolism, leading to SLDs. Additionally, the review will discuss the latest clinical studies on pharmaceutical treatments for SLDs, specifically peroxisome proliferator-activated receptor gamma (PPAR-γ) agonists, thyroid hormone receptor (THR) agonists, acetyl-CoA carboxylase (ACC) inhibitors, and mitochondrial uncouplers. These treatments have a common effect of decreasing hepatic mitochondrial reductive stress, which has been largely overlooked. [ABSTRACT FROM AUTHOR]

2,6-Diaryl-4H-tetrahydro-thiopyran-4-ones and corresponding sulfoxide and sulfone derivatives were designed to lower the major toxicity of their parent anti-kinetoplatidal diarylideneacetones through a prodrug effect. Novel diastereoselective methodologies were developed and generalized from diarylideneacetones and 2,6-diaryl-4H-tetrahydro-thiopyran-4-ones to allow the introduction of a wide substitution profile and to prepare the related S-oxides. The in vitro biological activity and selectivity of diarylideneacetones, 2,6-diaryl-4H-tetrahydro-thiopyran-4-ones, and their S-sulfoxide and sulfone metabolites were evaluated against Trypanosoma brucei brucei, Trypanosoma cruzi, and various Leishmania species in comparison with their cytotoxicity against human fibroblasts hMRC-5. The data revealed that the sulfides, sulfoxides, and sulfones, in which the Michael acceptor sites are temporarily masked, are less toxic against mammal cells while the anti-trypanosomal potency was maintained against T. b. brucei, T. cruzi, L. infantum, and L. donovani, thus confirming the validity of the prodrug strategy. The mechanism of action is proposed to be due to the involvement of diarylideneacetones in cascades of redox reactions involving the trypanothione system. After Michael addition of the dithiol to the double bonds, resulting in an elongated polymer, the latter—upon S-oxidation, followed by syn-eliminations—fragments, under continuous release of reactive oxygen species and sulfenic/sulfonic species, causing the death of the trypanosomal parasites in the micromolar or submicromolar range with high selectivity indexes. [ABSTRACT FROM AUTHOR]

In this work, reactions between 6,7-dichloropyrido[1,2-a]benzimidazole-8,9-diones with different benzohydrazides were studied. Nucleophilic substitution at C(6) was followed by isomerization and led to α-hydroxy-p-quinone imine derivatives. Synthesized compounds represent a combination of several structural motifs: a benzimidazole core fused with α-hydroxy-p-quinone imine, which contains a benzamide fragment. X-ray crystallography analysis revealed the formation of dimers linked through OH···O interactions and stabilization of the imine form by strong intramolecular NH···N hydrogen bonds. The protonation/deprotonation processes were investigated in a solution using UV–Vis spectroscopy and a 1H NMR titration experiment. Additionally, the electrochemical properties of 6,7-dichloropyrido[1,2-a]benzimidazole-8,9-dione and its α-hydroxy-p-quinone imine derivative as cathode materials were investigated in acidic and neutral environments using cyclic voltammetry measurements. Cathode material based on 6,7-dichloropyrido[1,2-a]benzimidazole-8,9-dione could act as a potentially effective active electrode in aqueous electrolyte batteries; however, further optimization is required. [ABSTRACT FROM AUTHOR]

Levels and chemical species of reactive oxygen/nitrogen species (ROS/RNS) determine oxidative eustress and distress. Abundance of uptake pathways and high oxygen consumption for ATP-dependent transport makes the renal proximal tubule particularly susceptible to cadmium (Cd2+)-induced oxidative stress by targeting ROS/RNS generation or antioxidant defence mechanisms, such as superoxide dismutase (SOD) or H2O2-metabolizing catalase (CAT). Though ROS/RNS are well-evidenced, the role of distinct ROS profiles in Cd2+ concentration-dependent toxicity is not clear. In renal cells, Cd2+ (10–50 µM) oxidized dihydrorhodamine 123, reaching a maximum at 2–3 h. Increases (up to fourfold) in lipid peroxidation by TBARS assay and H2O2 by Amplex Red were evident within 30 min. ROS and loss in cell viability by MTT assay with 50 µM Cd2+ could not be fully reversed by SOD mimetics Tempol and MnTBAP nor by SOD1 overexpression, whereas CAT expression and α-tocopherol were effective. SOD and CAT activities were attenuated below controls only with >6 h 50 µM Cd2+, yet augmented by up to 1.5- and 1.2-fold, respectively, by 10 µM Cd2+. Moreover, 10 µM, but not 25–50 µM Cd2+, caused 1.7-fold increase in superoxide anion (O2•−), detected by dihydroethidium, paralled by loss in cell viability, that was abolished by Tempol, MnTBAP, α-tocopherol and SOD1 or CAT overexpression. H2O2-generating NADPH oxidase 4 (NOX4) was attenuated by ~50% with 10 µM Cd2+ at 3 h compared to upregulation by 50 µM Cd2+ (~1.4-fold, 30 min), which was sustained for 24 h. In summary, O2•− predominates with low–moderate Cd2+, driving an adaptive response, whereas oxidative stress by elevated H2O2 at high Cd2+ triggers cell death signaling pathways. Highlights Different levels of reactive oxygen species are generated, depending on cadmium concentration. Superoxide anion predominates and H2O2 is suppressed with low cadmium representing oxidative eustress. High cadmium fosters H2O2 by inhibiting catalase and increasing NOX4 leading to oxidative distress. Superoxide dismutase mimetics and overexpression were less effective with high versus low cadmium. Oxidative stress profile could dictate downstream signalling pathways. [ABSTRACT FROM AUTHOR]

Simple Summary: This clinical study explored the use of the positron emission tomography radiotracer, [18F]FSPG, for cancer imaging. [18F]FSPG measures a process involved in antioxidant production, which is important for cancer prognosis. We compared the distribution of this imaging agent in subjects with head and neck squamous cell cancer (HNSCC) and non-small-cell lung cancer (NSCLC). Results showed similar distribution in healthy organs but varied uptake in tumors, both between subjects and across different lesions. Although [18F]FSPG PET/CT offers insights into individual tumor behavior, its diagnostic potential is limited due to this variability in tumor uptake. Variability in [18F]FSPG retention, however, may provide crucial information about how tumors respond to therapy and mechanisms of treatment resistance. Background: (4S)-4-(3-[18F]fluoropropyl)-L-glutamic acid ([18F]FSPG) positron emission tomography/computed tomography (PET/CT) provides a readout of system xc− transport activity and has been used for cancer detection in clinical studies of different cancer types. As system xc− provides the rate-limiting precursor for glutathione biosynthesis, an abundant antioxidant, [18F]FSPG imaging may additionally provide important prognostic information. Here, we performed an analysis of [18F]FSPG radiotracer distribution between primary tumors, metastases, and normal organs from cancer patients. We further assessed the heterogeneity of [18F]FSPG retention between cancer types, and between and within individuals. Methods: This retrospective analysis of prospectively collected data compared [18F]FSPG PET/CT in subjects with head and neck squamous cell cancer (HNSCC, n = 5) and non-small-cell lung cancer (NSCLC, n = 10), scanned at different institutions. Using semi-automated regions of interest drawn around tumors and metastases, the maximum standardized uptake value (SUVmax), SUVmean, SUV standard deviation and SUVpeak were measured. [18F]FSPG time–activity curves (TACs) for normal organs, primary tumors and metastases were subsequently compared to 18F-2-fluoro-2-deoxy-D-glucose ([18F]FDG) PET/CT at 60 min post injection (p.i.). Results: The mean administered activity of [18F]FSPG was 309.3 ± 9.1 MBq in subjects with NSCLC and 285.1 ± 11.3 MBq in those with HNSCC. The biodistribution of [18F]FSPG in both cohorts showed similar TACs in healthy organs from cancer patients. There was no statistically significant overall difference in the average SUVmax of tumor lesions at 60 min p.i. for NSCLC (8.1 ± 7.1) compared to HNSCC (6.0 ± 4.1; p = 0.29) for [18F]FSPG. However, there was heterogeneous retention between and within cancer types; the SUVmax at 60 min p.i. ranged from 1.4 to 23.7 in NSCLC and 3.1–12.1 in HNSCC. Conclusion: [18F]FSPG PET/CT imaging from both NSCLC and HNSCC cohorts showed the same normal-tissue biodistribution, but marked tumor heterogeneity across subjects and between lesions. Despite rapid elimination through the urinary tract and low normal-background tissue retention, the diagnostic potential of [18F]FSPG was limited by variability in tumor retention. As [18F]FSPG retention is mediated by the tumor's antioxidant capacity and response to oxidative stress, this heterogeneity may provide important insights into an individual tumor's response or resistance to therapy. [ABSTRACT FROM AUTHOR]

Ancient manganese (Mn) deposits are primarily characterized by the presence of Mn(II) carbonates that likely formed by the diagenetic reduction of precursor Mn(IV) oxides. As such, Precambrian sedimentary Mn deposits have been used as a line of evidence for the evolution of oxygen in Earth's surface environments. However, recent studies have shown that these Mn(II)-carbonates have the ability to directly accumulate within anoxic water columns, where free oxygen does not play a role in their formation. This alternative pathway casts uncertainty on the robustness of using ancient Mn deposits to constrain the redox fabric of the past marine water columns. Here, we investigate the Wafangzi Mn and Fe ore deposit from the 1.45 billion-year-old Tieling Formation, North China. The deposit contains Mn(II,III) mineral phases (hausmannite, braunite) as inclusions, or unreacted residues, trapped within Mn(II) carbonate (Ca-rhodochrosite). Some nodules and oolites of Mn(II) and Fe(II)-carbonate phases are also present and display a banded structure with concentric rings. Mn(III) oxide (manganite) is present in a paragenetic assemblage along with hematite and replacement textures with braunite. The negative carbon isotope composition (δ13C, –7‰ to –4‰) from Mn(II) carbonate samples in the Wafangzi Mn deposit which are distinct from that of contemporaneous seawater (~0‰), along with petrographic and speciation analyses, collectively suggest that the Mn(II,III)- and Fe(II)-bearing mineral phases formed through the diagenetic reduction of primary Mn(IV)/Fe(III) minerals coupled to the oxidation of organic matter. Therefore, the Wafangzi Mn deposit suggests the presence of sufficiently oxygenated marine waters, overlying anoxic ferruginous deeper waters with a transitional manganous water layer that could have driven the redox cycling of Mn, Fe, and C. Given the contemporaneous economic Mn deposits in the 1.45 Ga Ullawarra Formation in Western Australia, our findings imply the existence of a transient, and perhaps widespread, pulsed oxygenation event in the mid-Proterozoic oceans. [ABSTRACT FROM AUTHOR]

Reactive oxygen species (ROS) are highly reactive and their accumulation causes oxidative damage to cells. Cells maintain survival upon mild oxidative stress with anti-oxidative systems, such as the kelch-like ECH-associated protein 1 (Keap1)-nuclear factor erythroid 2-related factor 2 (Nrf2) system. On the other hand, upon severe oxidative stress, cells undergo regulated cell death, including apoptosis, for eliminating damaged cells. To execute efficient cell death, cells need to turn off the anti-oxidant systems, while triggering cell death. However, it remains unknown how cells orchestrate these two conflicting systems under excessive oxidative stress. Herein, we show that when cells are exposed to excessive oxidative damage, an E3 ubiquitin ligase Roquin-2 (also known as RC3H2) plays a key role in switching cell fate from survival to death by terminating activation of transforming growth factor-β-activated kinase 1 (TAK1), a positive regulator for Nrf2 activation. Roquin-2 interacted with TAK1 via four cysteine residues in TAK1 (C96, C302, C486, and C500) that are susceptible to oxidative stress and participate in oligomer formation via disulfide bonds, promoting K48-linked polyubiquitination and degradation of TAK1. Nrf2 was inactivated upon lethal oxidative stress in wild-type mouse embryonic fibroblast (MEF) cells, whereas it sustained activation and conferred resistance to Roquin-2 deficient cells, which was reversed by pharmacological or genetic inhibition of TAK1. These data demonstrate that in response to excessive ROS exposure, Roquin-2 promotes ubiquitination and degradation of TAK1 to suppress Nrf2 activation, and thereby contributes to an efficient cell death, providing insight into the pathogenesis of oxidative stress-related diseases, including cancer. [Display omitted] • TAK1 binds to Roquin-2 via four oxidation-sensitive cysteine residues in TAK1. • Ubiquitination of TAK1 by Roquin-2 facilitates its proteasomal degradation. • Roquin-2 sensitizes cells to oxidative stress by suppressing the TAK1-Nrf2 axis. • Roquin-2 is required for efficient cell death upon lethal oxidative stress. [ABSTRACT FROM AUTHOR]

Sulfur (S) is a central element in global biogeochemical cycling and Earth's redox evolution. Minerals that contain S are an important record of local environmental conditions at the time of their formation based on chemical speciation and redox. However, the oxidation state of S for hundreds of different S-containing minerals and thousands of S-containing mineral localities is unknown, largely sulfides and sulfosalts, and the redox state alone does not fully capture mineral chemistry diversity, thus limiting understanding of S redox evolution. Here, we use mineral chemistry network analysis and the weighted Mineral Element Electronegativity Coefficient of Variation (wMEE CV) metric to investigate the element interactions and localities of S-containing minerals from the Mineral Evolution Database (MED) to infer the redox state of S in minerals where the redox state is unknown (SU). Louvain community detection of the S mineral chemistry redox network reveals that there are three main network communities that are separated by redox state. The S6+ community includes minerals that contain the S6+ redox state and a small number of S4+ and S2+ minerals, the S2− community includes S2−-containing minerals, and the SU community includes minerals in which the redox state of S is unknown. The wMEE CV values of the SU community closely overlap with the wMEE CV values of the S2− community, and do not overlap with the wMEE CV values of the S6+ community, indicating the SU community minerals contain predominately reduced S. Assuming that SU community minerals contain reduced S, as supported by their network chemical associations and wMEE CV values, then reduced S-containing minerals make up approximately 81 % of S-containing mineral localities in the S mineral chemistry network, even though the majority of all mineral localities (S-containing and non-S-containing) are oxygen (O)-containing minerals. Additionally, reduced S-containing minerals make up the majority (∼75 %) of all non-O containing mineral localities in the MED, representing the importance of reduced S as an electron source and substrate in the evolution of microbial metabolic networks. The range wMEE CV values of S6+ community minerals expands through time due primarily to formation of chemically diverse sulfate minerals, coinciding with crustal oxidation from the late Proterozoic to Phanerozoic and the expansion of the marine sulfate reservoir. The intersection of shared constituent elements among reduced and oxidized S in the mineral chemistry network represents redox convergence of weathered S in the geosphere that was crucial in the formation of natural resource deposits and the evolution of biogeochemical cycles. [ABSTRACT FROM AUTHOR]

Hypothiocyanous acid (HOSCN) is an endogenous oxidant produced by peroxidase oxidation of thiocyanate (SCN−), an ubiquitous sulfur-containing pseudohalide synthesized from cyanide. HOSCN serves as a potent microbicidal agent against pathogenic bacteria, viruses, and fungi, functioning through thiol-targeting mechanisms, independent of currently approved antimicrobials. Additionally, SCN− reacts with hypochlorous acid (HOCl), a highly reactive oxidant produced by myeloperoxidase (MPO) at sites of inflammation, also producing HOSCN. This imparts both antioxidant and antimicrobial potential to SCN−. In this review, we discuss roles of HOSCN/SCN− in immunity and potential therapeutic implications for combating infections. [Display omitted] • Hypothiocyanous acid (HOSCN) is an endogenous oxidant that demonstrates antimicrobial activities against viruses, bacteria and fungi. • Multiple preclinical studies reported benefits of promoting HOSCN formation in vivo to treat pulmonary infections. • HOSCN is better tolerated by mammalian cells than other chordata peroxidase-derived oxidants, such as hypochlorous acid. • Some bacterial strains are resistant to HOSCN, primarily via similar oxidoreductase mechanisms to those reported in mammalian cells. • HOSCN/SCN- treatment holds promise for viral, bacterial, and fungal infections, but potential toxicity and HOSCN resistance must be considered. [ABSTRACT FROM AUTHOR]

Glutamate is the main excitatory neurotransmitter in the brain and plays a leading role in degenerative diseases, such as motor neuron diseases. Riluzole is a glutamate regulator and a therapeutic drug for motor neuron diseases. In this work, the interaction between glutamate and riluzole was studied using cyclic voltammetry and square-wave voltammetry at a glassy carbon electrode (GCE). It was shown that glutamate underwent a two-electron transfer reaction on the GCE surface, and the electrochemical detection limits of glutamate and riluzole were 483 μmol/L and 11.47 μmol/L, respectively. The results confirm that riluzole can promote the redox reaction of glutamate. This work highlights the significance of electrochemical technology in the sensing detection of the interaction between glutamate and related psychotropic drugs. [ABSTRACT FROM AUTHOR]

Caveolae are small flask-shaped invaginations of the surface membrane which are proposed to recruit and co-localize signaling molecules. The distinctive caveolar shape is achieved by the oligomeric structural protein caveolin, of which three isoforms exist. Aside from the finding that caveolin-3 is specifically expressed in muscle, functional differences between the caveolin isoforms have not been rigorously investigated. Caveolin-3 is relatively cysteine-rich compared to caveolins 1 and 2, so we investigated its cysteine post-translational modifications. We find that caveolin-3 is palmitoylated at 6 cysteines and becomes glutathiolated following redox stress. We map the caveolin-3 palmitoylation sites to a cluster of cysteines in its C terminal membrane domain, and the glutathiolation site to an N terminal cysteine close to the region of caveolin-3 proposed to engage in protein interactions. Glutathiolation abolishes caveolin-3 interaction with heterotrimeric G protein alpha subunits. Our results indicate that a caveolin-3 oligomer contains up to 66 palmitates, compared to up to 33 for caveolin-1. The additional palmitoylation sites in caveolin-3 therefore provide a mechanistic basis by which caveolae in smooth and striated muscle can possess unique phospholipid and protein cargoes. These unique adaptations of the muscle-specific caveolin isoform have important implications for caveolar assembly and signaling. [ABSTRACT FROM AUTHOR]

Metallosupramolecular polymers (MSPs) have reversible electrochromic (EC) characteristics. Transition metal ions and ditopic organic ligands are complexed 1:1 to form MSPs, but the complexation conditions depend on the metal species ions. Herein, a microwave‐assisted (MWA) quick synthesis of a Ru(II)‐based MSP (polyRu–MWA) as a novel preparation method for MSPs is reported. PolyRu–MWA is synthesized under microwave irritation for 60 min using 770 W and 2.45 GHz frequency, whereas a conventionally synthesized Ru(II)‐based MSP (polyRu–CS) is obtained using oil‐bath at 160 °C for 24 h. PolyRu–MWA is found to show much better EC properties than polyRu–CS. A film of polyRu–MWA prepared on an indium tin oxide glass exhibits higher optical contrast (transmittance change, ΔT: 81.39%) than polyRu–CS (67.73%). Coloration efficiency(CE, η) of polyRu–MWA (425.7 cm2 C−1) is also higher than that of polyRu–CS (318.3 cm2 C−1). Interestingly, the charge and discharge current ratio for bleaching and coloring in polyRu–MWA is ≈1.7 times higher than that for polyRu–CS, probably because of the high molecular weight polymer formation in polyRu–MWA. A polyRu–MWA film also displays a longer EC optical memory than polyRu–CS. [ABSTRACT FROM AUTHOR]

The interactions between transition metals and sulfur have long been studied for potential applications in catalysis and energy storage and due to the relevance of these motifs in biological and geological systems. Complexes with sulfur-containing ligands can undergo redox transformations centered on sulfur as well as at the metal. Sulfur also readily catenates with other sulfur centers to form polysulfur motifs. Here, the synthesis and structures of notable examples of metal complexes with sulfur-containing ligands (sulfido, polysulfido, and polysulfanido) are described. Aspects of sulfur-centered redox, including spectroscopic and structural considerations, and future research opportunities are highlighted. [ABSTRACT FROM AUTHOR]

Objective The objective of this study was to assess oxidative stress in small for gestational age (SGA) newborns and their mothers by evaluating intra- and extracellular thiol homeostasis and the quantification of major oxidants and antioxidants. Methods A total of 75 mothers and their 75 newborns (43 SGA) were enrolled in this study. Thiol-disulfide homeostasis, serum myeloperoxidase, catalase, total oxidant, and antioxidant status were analyzed. Additionally, erythrocytic glutathione (GSH) homeostasis was measured. Results Although native and total thiol levels were decreased, disulfide levels were increased in SGA groups. Additionally, myeloperoxidase activity and total oxidant status levels were significantly elevated whereas total antioxidant status levels and enzymatic antioxidant systems were diminished in SGA groups. Similarly, intra-erythrocytic GSH homeostasis was shifted in favor of oxidants in SGA groups. Conclusion Our results demonstrate that insufficient antioxidant systems in mothers and a robust source of oxidative stress in SGA might contribute to the pathophysiology of SGA births. [ABSTRACT FROM AUTHOR]

This article discusses the progress made in the enantioselective total synthesis of γ-rubromycin, a Streptomyces antibiotic. The researchers previously reported a successful photoirradiation method using a chiral, non-racemic 1,2-naphthoquinone to produce an enantioenriched spiroacetal. However, in their latest study, they found that the viability of the photochemical reaction depended on the chromophore structure of the quinones. They also observed that the color of the quinones correlated with their reactivity, with yellow or orange quinones being reactive and red or dark red-purple quinones being unreactive. Further studies are being conducted to gain insights into the photoreaction viability and guide substrate design for the synthesis of γ-rubromycin. [Extracted from the article]

Moisture‐enabled electricity generation (MEG) is a prominent renewable energy harvesting technology in hydrovoltaic power generation, boasting the broadest energy harvesting spectrum. However, practical application faces limitations due to irreversible performance degradation caused by structural changes and moisture‐generated carrier (MGC) losses in Moisture‐enabled electricity (ME) materials, rendering them non‐renewable. This study introduces a rechargeable moisture‐enabled electricity cell (rMEC) based on dual ME functional layers and active metal electrodes. The rMEC demonstrates outstanding power generation performance, with a single cell providing an output voltage of 1.08 V and a power density of 5.83 µW cm−2 through redox assistance. Moreover, it can be recharged when MGCs are lost, utilizing the reversibility of the redox reaction (moisture of H2O2 solution) for self‐repair. Notebly, the rMEC maintains stable operation for over 2080 h and undergoes 100 charging/working cycles, marking the longest span life record in MEG research history. When exposed to industrial wastewater/gases with oxidation characteristics, the rMEC not only completes charging but also facilitates the reuse of toxic waste resources. The environmentally friendly rMEC, with its long cycle life, significantly overcomes the limitations of non‐renewable ME materials, serving as a paradigm for promoting iterative upgrades in MEG technology. [ABSTRACT FROM AUTHOR]

The purpose of this study was to investigate the antimicrobial activity of citrate-stabilized sols of cerium oxide nanoparticles at different concentrations via different microbiological methods and to compare the effect with the peroxidase activity of nanoceria for the subsequent development of a regeneration-stimulating medical and/or veterinary wound-healing product providing new types of antimicrobial action. The object of this study was cerium oxide nanoparticles synthesized from aqueous solutions of cerium (III) nitrate hexahydrate and citric acid (the size of the nanoparticles was 3–5 nm, and their aggregates were 60–130 nm). Nanoceria oxide sols with a wide range of concentrations (10−1–10−6 M) as well as powder (the dry substance) were used. Both bacterial and fungal strains (Bacillus subtilis, Bacillus cereus, Staphylococcus aureus, Pseudomonas aeruginosa, Escherichia coli, Proteus vulgaris, Candida albicans, Aspergillus brasielensis) were used for the microbiological studies. The antimicrobial activity of nanoceria was investigated across a wide range of concentrations using three methods sequentially; the antimicrobial activity was studied by examining diffusion into agar, the serial dilution method was used to detect the minimum inhibitory and bactericidal concentrations, and, finally, gas chromatography with mass-selective detection was performed to study the inhibition of E. coli's growth. To study the redox activity of different concentrations of nanocerium, we studied the intensity of chemiluminescence in the oxidation reaction of luminol in the presence of hydrogen peroxide. As a result of this study's use of the agar diffusion and serial dilution methods followed by sowing, no significant evidence of antimicrobial activity was found. At the same time, in the current study of antimicrobial activity against E. coli strains using gas chromatography with mass spectrometry, the ability of nanoceria to significantly inhibit the growth and reproduction of microorganisms after 24 h and, in particular, after 48 h of incubation at a wide range of concentrations, 10−2–10−5 M (48–95% reduction in the number of microbes with a significant dose-dependent effect) was determined as the optimum concentration. A reliable redox activity of nanoceria coated with citrate was established, increasing in proportion to the concentration, confirming the oxidative mechanism of the action of nanoceria. Thus, nanoceria have a dose-dependent bacteriostatic effect, which is most pronounced at concentrations of 10−2–10−3 M. Unlike the effects of classical antiseptics, the effect was manifested from 2 days and increased during the observation. To study the antimicrobial activity of nanomaterials, it is advisable not to use classical qualitative and semi-quantitative methods; rather, the employment of more accurate quantitative methods is advised, in particular, gas chromatography–mass spectrometry, during several days of incubation. [ABSTRACT FROM AUTHOR]

This study explored the mechanism of antimony (Sb) isotopic fractionation during chemical weathering and soil biogeochemical processes, which have important implications for Sb isotopic composition in the hydrosphere. We analyzed the major and trace element contents and Sb isotopic composition along an 8 m deep basalt weathering profile in the Huguangyan area of Guangdong Province, southern China. Mineral adsorption experiments were conducted to determine the mechanism of Sb isotopic fractionation in the weathering profile. The following minerals, α-FeOOH, γ-Fe 2 O 3 , β-MnO 2 , γ-Al 2 O 3 , montmorillonite-K10, and kaolinite-1A, preferentially adsorbed light Sb isotopes, and increased pH may lead to a lighter isotopic composition of adsorbed Sb. The positive values of τ Sb TiO 2 in the upper profile reflect exogenous Sb inputs, such as rainfall and litterfall. Accordingly, Sb isotopic fractionation is controlled by Sb adsorption onto organic matter and Fe (hydr)oxides in surface soil. At a depth of 1.8 m, Sb and other redox-sensitive elements, such as Fe, Mn, Ce, Co, Cr, and Mo, were distinctly enriched. Changes in the redox conditions result in strong Sb isotopic fractionation. In the middle layer (2–4 m), the combined effects of changes in organic matter content, soil pH, and weathering intensity explains the enrichment of light Sb isotopes. The bottom layer of the profile did not receive exogenous Sb and exhibited an Sb isotopic fractionation pattern similar to that of the basaltic bedrock. In the bottom layer, secondary Fe (hydr)oxides (e.g., goethite and hematite) preferentially adsorb the light Sb isotope (121Sb), whereas the heavy Sb isotope (123Sb) is released into the aquatic environment during intensive chemical weathering. [ABSTRACT FROM AUTHOR]

Mass-independent isotopic anomalies in meteorites are probes to the dynamics and evolution of the protoplanetary disc and the reservoirs from which planetary bodies accreted. Variable Cr nucleosynthetic compositions between meteorite groups are observed but the cause is not well understood. Investigations on presolar carriers in unequilibrated chondrites are thus required to establish these relationships. For that purpose, we analysed the Cr isotope compositions of leachates (stepwise dissolution solutions) of one ordinary chondrite and two enstatite chondrites of EL and EH subgroups previously measured for Nd and Sm isotopes. The leachates of the ordinary chondrite display large variations of their Cr isotope compositions, whereas the leachates of the enstatite chondrites show very limited variations of their nucleosynthetic compositions, confirming other studies. The Cr isotope compositions of leachates of unequilibrated chondrites are significantly modified by thermal processing and aqueous alteration under various conditions. The leachates of the enstatite chondrites are relatively homogeneous for Cr isotope composition, suggesting that presolar carriers of Cr are not stable under very reduced conditions and are likely oxidised phases. After careful examination of the role of parent body processing, we conclude that there is one predominant presolar carrier enriched in 54Cr that produced most of the nucleosynthetic variations observed in leachates. This carrier is likely depleted in the carbonaceous reservoir relative to the non-carbonaceous reservoir. The drastically different isotope compositions of Cr and heavy refractory lithophile elements such as Nd of leachates of chondrites reflect relative preservation biases of their respective presolar carriers, namely a still poorly characterised presolar oxide and silicon carbide (SiC), respectively. [ABSTRACT FROM AUTHOR]

The combination of the ferrocene moiety with gold(I) catalysis remains a relatively unexplored field. In this article, we delve into the synthesis, characterization, and potential catalytic activity of four complexes utilizing both monodentate and bidentate ferrocenyl diphenylphosphane ligands (ppf and dppf), coordinated with two gold(I) metal centers, linked by either chloride or pentafluorophenylthiolate bridging ligands. This leads to the formation of cationic "self‐activated" precatalysts capable of initiating the catalytic cycle without the need for external additives. The catalytic activity of these complexes was assessed through a model reaction in gold(I) catalysis, specifically the cyclization of a N‐propargylbenzamide to produce an oxazole. In addition, we studied and compared the influence exerted by both the phosphane and the bridging ligand on the performance of these catalysts. [ABSTRACT FROM AUTHOR]

The precise synthesis of chiral small molecules is a core research area in chemical science. Deracemization, an appealing technology that converts racemate to its single enantiomer with the same constitution in theoretical 100 % yield, appears as a straightforward and efficient strategy in asymmetric synthesis. A cascading redox sequence was the most employed approach to drive deracemization through destroy and recreate the stereocenter in a given molecule. This review mainly focuses on the progress of redox deracemization driven by respective biocatalysis and chemo–catalysis. In particular, each section will be subdivided according to the action modes, the respective substrate classes and perspectives on future development. [ABSTRACT FROM AUTHOR]

Mongolian willow (Salix linearistipularis) is a naturally occurring woody dioecious plant in the saline soils of north-eastern China, which has a high tolerance to alkaline salts. Although transcriptomics studies have identified a large number of salinity-responsive genes, the mechanism of salt tolerance in Mongolian willow is not clear. Here, we found that in response to Na2CO3 stress, Mongolian willow regulates osmotic homeostasis by accumulating proline and soluble sugars and scavenges reactive oxygen species (ROS) by antioxidant enzymes and non-enzymatic antioxidants. Our quantitative proteomics study identified 154 salt-sensitive proteins mainly involved in maintaining the stability of the photosynthetic system and ROS homeostasis to cope with Na2CO3 stress. Among them, Na2CO3-induced rubredoxin (RUB) was predicted to be associated with 122 proteins for the modulation of these processes. The chloroplast-localized S. linearistipularis rubredoxin (SlRUB) was highly expressed in leaves and was significantly induced under Na2CO3 stress. Phenotypic analysis of overexpression, mutation and complementation materials of RUB in Arabidopsis suggests that SlRUB is critical for the regulation of photosynthesis, ROS scavenging and other metabolisms in the seedlings of Mongolian willow to cope with Na2CO3 stress. This provides more clues to better understand the alkali-responsive mechanism and RUB functions in the woody Mongolian willow. [ABSTRACT FROM AUTHOR]

The strong development of mankind is inseparable from the proper use of drugs, and the electroanalytical research of drugs occupies an important position in the field of analytical chemistry. This review mainly elaborates the research progress of drugs electroanalysis based on direct electrochemical redox on various electrodes for the recent decade from 2011 to 2021. At first, we summarize some frequently used electrochemical data processing and electrochemical mechanism research derivation methods in the literature. Then, according to the drug therapeutic and application/usage purposes, the research progress of drugs electrochemical analysis is classified and discussed, where we focus on drugs electrochemical reaction mechanism. At the same time, the comparisons of electrochemical sensing performance of the drugs on various electrodes from recent studies are listed, so that readers can more intuitively compare and understand the electroanalytical sensing performance of each modified electrode for each of the drug. Finally, this review discusses the shortcomings and prospects of the drugs electroanalysis based on direct electrochemical redox research. [ABSTRACT FROM AUTHOR]

The low‐density lipoprotein (LDL) receptor‐related protein (LRP)1 participates in the metabolism of apolipoprotein (apo) E‐containing lipoproteins (apoE‐LP). We investigated the effects of modifications of cysteine (Cys)‐thiol of apoE on LRP1‐mediated metabolism. Among the three isoforms, apoE2‐LP exhibited the lowest affinity for LRP1 but was significantly catabolized, whereas apoE4‐LP was sufficiently bound to LRP1 but showed the lowest catabolic capability. The reduction enhanced the binding and suppressed the catabolism of apoE3‐LP, but had no effect on apoE2‐LP. The formation of disulfide‐linked complexes with apoAII suppressed binding, but enhanced the catabolism of apoE2‐LP. Redox modifications of apoE‐Cys‐thiol may modulate the LRP1‐mediated metabolism of apoE2‐ or apoE3‐LP, but not apoE4‐LP. The failure of this function may be involved in the pathophysiology of dyslipidemia. [ABSTRACT FROM AUTHOR]

The established strategy unveils a metal and mediator‐free electrochemical [3+2] cycloaddition approach among α‐amino carbonyls and tosylmethyl isocyanide (TosMIC) fabricating substituted imidazole scaffolds. Implementation of electro‐redox conditions on this cycloaddition approach eliminates the essential requirement of transition metal catalysts and chemical oxidants. A wide variety of different functionalities are well tolerated under this reaction condition, contributing to the substrate scope and applicability. Several control experiments and cyclic voltammetry studies suggest an electro‐oxidation triggered successive C−C and C−N bond formations followed by rapid aromatization for constructing the five‐membered core structure. [ABSTRACT FROM AUTHOR]

The Cryogenian period of the Neoproterozoic was marked by two Snowball Earth glaciations that bookended a non-glacial interval that lasted roughly 10 million years. The break-up of Rodinia in the early Neoproterozoic gave rise to numerous rift basins whose time-varying redox dynamics, linked to marine productivity and biogeochemical cycling, were likely controlled by varying degrees of basin restriction in response to sea-level change. Those drivers were associated with both global glaciations (Sturtian deglaciation and the possibly early onset of the Marinoan) and local tectonics (regional basin uplift/subsidence). To explore these relationships, we focus on the Datangpo Formation, an exceptional shale sequence deposited in a marginal rift basin in South China. The Datangpo succession comprises lower organic-rich black shales and upper organic-lean gray shales/siltstones. As elucidated by our integrated data, the former were deposited in H 2 S-rich, deep-water settings underlying highly productive surface waters. We attribute this productivity to elevated nutrient supplies replenished from the open ocean following a sea-level rise, as augmented by high terrestrial input of phosphate in the wake of the Sturtian deglaciation. By contrast, the gray shales/siltstones were associated with relatively shallow deposition in an oxic/suboxic water column with suppressed primary production. The major driver of this dramatic shift in water chemistry may lie with a greater extent of basin isolation and the corresponding reduction in nutrient fluxes from the global ocean due to a significant sea-level fall—possibly linked to regional basin uplift. At this time, the basin experienced an elevated influx of detrital clays and organic material, perhaps triggered by lower sea level. Surprisingly, we found that euxinic conditions prevailed in the water column for a substantial period following the onset of more isolated conditions. This relationship can be attributed to redox-dependent phosphorus cycling. Specifically, H 2 S-replete conditions facilitated regeneration of bioavailable phosphorus, initiating a positive feedback that allowed the persistence of anoxic waters. This study advances our understanding of nutrient cycling and biogeochemical evolution during the Cryogenian under the influence of large-scale sea-level fluctuations and associated time-varying connectivity to the open ocean that must have been common in many basins at this time. Furthermore, our study sheds novel light on the iron proxy and early sulfur cycling. Almost all of the terrestrial silicate-bound iron was likely converted into highly reactive phases due to strong chemical weathering, while sulfur data revealed isotopic stratification in the wake of Sturtian deglaciation, with important messages for interpretations of analogous data in the aftermath of other climate upheavals in Earth history. [ABSTRACT FROM AUTHOR]

The extensively evaluated and consistent thermodynamic database, the Molten Salt Thermal Properties Database—Thermochemical (MSTDB-TC), was used along with additional thermodynamic values from other sources as examples of ways to examine molten salt reactor (MSR) fuel behavior. Relative stability with respect to halide potential and temperature for likely fuel and fission product components were mapped in Ellingham diagrams for the chloride and fluoride systems. The Ellingham diagrams provide a rich, visual means for identifying halide-forming components in proposed fuel/solvent salt systems. Thermochemical models and values from MSTDB-TC and ancillary sources were used in global equilibrium calculations to provide compositions for a close analysis of the behavior of a possible Molten Chloride Salt Fast Reactor and a Molten Salt Reactor Experiment-type system at high burnup (100 GWd/t). The results illustrated the oxidative nature of burnup in MSRs and provided information about redox behavior and possible control. [ABSTRACT FROM AUTHOR]

Three examples of dibenzi heteroheptaphyrin(2.0.1.1.1.1.0)s were synthesized by condensing bis(phenylene ethene) based hexapyrrane with appropriate diol, 2,5‐bis(α‐hydroxy‐α‐arylmethyl) thiophene or selenophene in CH2Cl2 under BF3 ⋅ OEt2 catalyzed inert atmosphere conditions followed by DDQ oxidation in open air. HR‐MS analyses confirmed the identities of dibenzi heteroheptaphyrins. The DFT optimized structures revealed that dibenzi heteroheptaphyrins were highly distorted nonplanar macrocycles with two thiophene rings preferred to be in an inverted conformation. 1D & 2D NMR helped in deducing the molecular structures of dibenzi heteroheptaphyrins and supported their nonaromatic nature. The theoretical NMR calculations were carried which matched closely with the experimental NMR data. NMR studies also revealed that the π‐delocaliztion was significantly altered in dibenzi heteroheptaphyrins compared to previously reported dibenzi hexaphyrins. The dibenzi heptaphyrins showed one sharp absorption band in 400–500 nm region and a broad band in the region of 600–800 nm which were bathochromically shifted in their diprotonated derivatives. The theoretical absorption calculations corroborate the slight hypsochromic shift of the broad absorption band in the lower energy region of dibenzi heptaphyrins compared to dibenzi hexaphyrins. The electrochemical studies revealed that the dibenzi heptaphyrins were easier to reduce but difficult to oxidize compared to dibenzi hexaphyrins. [ABSTRACT FROM AUTHOR]

Chemical looping represents a promising technology with various applications ranging from clean power production to alternative syngas production. In this work, two oxygen carriers with different Ni loadings (4.3% wt. and 12% wt.) and similar Fe loadings (9.9% wt. and 8.5% wt.) are synthesized through a co-precipitation/impregnation route and tested in two thermogravimetric analyzers. Firstly, the effect of temperature (700–900 °C) on the oxygen transport capacity and reduction conversion of both materials is assessed at ambient pressure (0.5 nl/min with 20% H 2 /N 2). The influence of material loading is also studied, and it is shown that higher Ni loadings provide a significant improvement in material activity. A complete reduction conversion is achieved at 900 °C and ambient pressure. At high pressure (10–20 bar), tests are carried out in a temperature range of 700–850 °C. The effect of flow rate (2 nl/min to 6 nl/min with 50% H 2 /N 2) is first assessed to prevent external mass transfer limitations. Higher total pressures have a negative effect on reduction kinetics, while higher Ni loadings demonstrate increased final reduction conversion also at high pressure, reaching about 75% conversion after 20 min. The long-term cyclability of the material is also investigated both at low (100 cycles) and high pressure (80 cycles) conditions and a conversion gain is observed throughout the cycles in both cases. No changes in the material microstructure are observed after 80 high-pressure cycles. • Chemical looping cycles were carried out at ambient and high-pressure conditions. • Full reduction conversion was achieved at 900 °C after 200 s of testing for a nickel ferrite with 12% wt Ni and 8.5% wt Fe. • Total pressure showed a negative effect on reaction kinetics. • No significant changes in the microstructure of the material were observed. [ABSTRACT FROM AUTHOR]