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A copper–molybdenum–phosphate (CuMoP)‐modified screen‐printed carbon electrode (SPCE) was developed (mSPCE) via one‐step potentiostatic codeposition for the electrochemical detection of aspirin (acetylsalicylic acid, ASA). Microscopic and spectroscopic analyses confirmed a uniform, granular CuMoP film with mixed‐valence Cu + /Cu 2+ and Mo 6+ centers coordinated by phosphate groups, thereby enhancing electron–proton coupling. The sensor exhibited a well‐defined irreversible oxidation peak at 0.866 V (pH 3.0), showed highly sensitive detection for ASA, and followed a diffusion‐controlled two‐electron mechanism. Differential pulse voltammetry revealed an excellent linear response ( I = 0.036 + 0.012 C, R 2 = 0.9979) over 2.0–92.6 µM, with a limit of detection of 1.5 µM and a quantification limit of 5.0 µM. The mSPCE displayed high stability (RSD = 2.6%), reproducibility (RSD = 5.4%), and recovery of 91.21%–103.52% for pharmaceutical tablets. Outstanding selectivity against 100‐fold interfering species highlights the synergistic Cu–Mo–P redox network as an efficient, low‐cost, and portable platform for sensitive determination of ASA in real samples.

Multidrug‐resistant (MDR) Gram‐negative bacteria account for a majority of fatal infections, and development of new antibiotic principles and drugs is therefore of outstanding importance. Here, we report that five most clinically difficult‐to‐treat MDR Gram‐negative bacteria are highly sensitive to a synergistic combination of silver and ebselen. In contrast, silver has no synergistic toxicity with ebselen on mammalian cells. The silver and ebselen combination causes a rapid depletion of glutathione and inhibition of the thioredoxin system in bacteria. Silver ions were identified as strong inhibitors of Escherichia coli thioredoxin and thioredoxin reductase, which are required for ribonucleotide reductase and DNA synthesis and defense against oxidative stress. The bactericidal efficacy of silver and ebselen was further verified in the treatment of mild and acute MDR E. coli peritonitis in mice. These results demonstrate that thiol‐dependent redox systems in bacteria can be targeted in the design of new antibacterial drugs. The silver and ebselen combination offers a proof of concept in targeting essential bacterial systems and might be developed for novel efficient treatments against MDR Gram‐negative bacterial infections. Synopsis Silver acts synergistically with the selenazol drug ebselen to combat five clinically most difficult‐to‐treat multidrug‐resistant Gram‐negative bacteria, by targeting thiol‐dependent antioxidant systems. Five most clinically difficult‐to‐treat MDR Gram‐negative bacteria are highly sensitive to a synergistic combination of silver and ebselen. In contrast, silver has no synergistic toxicity with ebselen on mammalian cells. Silver and ebselen can directly inhibit E. coli thioredoxin reductase, and rapidly deplete GSH, which results in elevation of ROS production and stop in DNA synthesis to induce cell death. The bactericidal efficacy of silver and ebselen was further confirmed in the treatment of mild and acute MDR E. coli peritonitis in mice. The silver and ebselen combination offers a proof of concept in targeting essential bacterial systems to be developed for novel efficient treatments against MDR Gram‐negative bacterial infections. Graphical Abstract Silver acts synergistically with the selenazol drug ebselen to combat five clinically most difficult‐to‐treat multidrug‐resistant Gram‐negative bacteria, by targeting thiol‐dependent antioxidant systems.

Adsorbents based on single-bilayer graphene oxide sheet (hereafter termed “graphene oxide”) are widely used in contaminated environments cleanup which may easily open the avenues for their entry to different environmental compartments, exposure to organisms and their subsequent transfer to human/animal food chain. Considering a common food crop—faba bean ( Vicia faba L.) germinating seedlings as a model plant system, this study assesses the V. faba -tolerance to different concentrations (0, 100, 200, 400, 800, and 1600 mg L −1 ) of graphene oxide (0.5–5 μm) and evaluates glutathione (γ-glutamyl-cysteinyl-glycine) redox system significance in this context. The results showed significantly increased V. faba sensitivity under three graphene oxide concentrations (in order of impact: 1,600 > 200 > 100 mg graphene oxide L −1 ), which was accompanied by decreased glutathione redox (reduced glutathione-to-oxidized glutathione) ratio, reduced glutathione pool, as well as significant and equally elevated activities of glutathione-regenerating (glutathione reductase) and glutathione-metabolizing (glutathione peroxidase; glutathione sulfo-transferase) enzymes. Contrarily, the two graphene oxide concentrations (in order of impact: 800 > 400 graphene oxide mg L −1 ) yielded promising results; where, significant improvements in V. faba health status (measured as increased graphene oxide tolerance) were clearly perceptible with increased ratio of the reduced glutathione-to-oxidized glutathione, reduced glutathione pool and glutathione reductase activity but decreased activities of glutathione-metabolizing enzymes. It is inferred that V. faba seedlings-sensitivity and/or tolerance to graphene oxide concentrations depends on both the cellular redox state (reduced glutathione-to-oxidized glutathione ratio) and the reduced glutathione pool which in turn are controlled by a finely tuned modulation of the coordination between glutathione-regenerating and glutathione-metabolizing enzymes.

Oxidative stress and decline in cellular redox regulation have been hypothesized to play a key role in cardiovascular aging; however, data on antioxidant and redox regulating systems in the aging heart are controversial. The aim of the present study was to examine the effect of aging on critical antioxidant enzymes and two major redox-regulatory systems glutathione (GSH) and thioredoxin (Trx) system in hearts from adult (6-month-old), old (15-month-old), and senescent (26-month-old) rats. Aging was associated with a non-uniform array of changes, including decline in contents of reduced GSH and total mercaptans in the senescent heart. The activities of Mn-superoxide dismutase (SOD2), glutathione peroxidase (GPx), glutathione reductase (GR), and thioredoxin reductase (TrxR) exhibited an age-related decline, whereas catalase was unchanged and Cu,Zn-superoxide dismutase (SOD1) displayed only slight decrease in old heart and was unchanged in the senescent heart. GR, Trx, and peroxiredoxin levels were significantly reduced in old and/or senescent hearts, indicating a diminished expression of these proteins. In contrast, SOD2 level was unchanged in the old heart and was slightly elevated in the senescent heart. Decline in GPx activity was accompanied by a loss of GPx level only in old rats, the level in senescent heart was unchanged. These results indicate age-related posttranslational protein modification of SOD2 and GPx. In summary, our data suggest that changes are more pronounced in senescent than in old rat hearts and support the view that aging is associated with disturbed redox balance that could alter cellular signaling and regulation.

Ammonia is one of the most common aquatic pollutants. To analyze the effect of ammonia exposure on the glutathione redox system, we investigated the levels of hydrogen peroxide (H 2 O 2 ) and glutathione, and transcription and activities of glutathione-related enzymes in liver and gills of FFRC strain common carp ( Cyprinus carpio L.) exposed to 0, 10, 20, and 30 mg/L of ammonia. The results showed that H 2 O 2 content reached a maximum level at 48 h of exposure in the liver of fish. In gills, H 2 O 2 increased rapidly at 6 h and reached to maximum levels at 24 h of exposure, indicating that gills experienced oxidative stress earlier than the liver of fish exposed to ammonia. Reduced glutathione (GSH) content and reduced glutathione/oxidized glutathione (GSH/GSSG) ratio increased significantly within 24 h of exposure. Meanwhile, the transcription and activities of glutathione S-transferase (GST) and glutathione reductase (GR) increased significantly in the liver, and glutathione peroxidase (GSH-Px) and GST increased in the gills of fish exposed to ammonia. Malondialdehyde (MDA) content kept at a low level after exposure to low concentration of ammonia, but increased significantly after exposure to 30 mg/L ammonia for 48 h along with a decrease in GSH content and GSH/GSSG ratio. These data showed that the glutathione redox system played an important role in protection against ammonia-induced oxidative stress in the liver and gills of FFRC strain common carp, though the defense capacity was not able to completely prevent oxidative damage occurring after exposure to higher concentration of ammonia. This research systematically studied the response of the glutathione redox system to ammonia stress and would provide novel information for a better understanding of the adaptive mechanisms of fish to environmental stress.

The method of electrochemical reduction utilizes electrons as agent to achieve the reduction of indigo, vat dyes and pollution emissions, as well as the recycling of electrolyte. In this study, Ca2+-Fe3+-triethanolamine (TEA) redox system was used as the mediator to achieve the indirect electrochemical reduction of indigo. The optimization of parameter was analyzed by reduction efficiency (RE) and current efficiency (CE). The result showed that indigo could be reduced by electrochemical method and the best optimization recipe was 20 g/L NaOH + 5 g/L Fe2(SO4)3 + 30 g/L TEA + 5 g/L Calcium gluconate + 3 g/L indigo in 1 A·dm-2 current density at 50°C. This work suggested that Ca2+-Fe3+-TEA redox system in reduction of indigo was an effective way with higher CE (75.9 %).

Background: Many bacteria are capable of reducing selenium oxyanions, primarily selenite (SeO32-), in most cases forming selenium(0) nanostructures. The mechanisms of these transformations may vary for different bacterial species and have so far not yet been clarified in detail. Bacteria of the genus Azospirillum, including ubiquitous phytostimulating rhizobacteria, are widely studied and have potential for agricultural biotechnology and bioremediation of excessively seleniferous soils, as they are able to reduce selenite ions. Methods: Cultures of A.brasilense Sp7 and its derivatives (mutant strains) were grown on the modified liquid malate salt medium in the presence or absence of selenite. The following methods were used: spectrophotometric monitoring of bacterial growth; inhibition of glutathione (GSH) synthesis in bacteria by L-buthionine-sulfoximine (BSO); optical selenite and nitrite reduction assays; transmission electron microscopy of cells grown with and without BSO and/or selenite. Results: In a set of separate comparative studies of nitrite and selenite reduction by the wild-type strain A.brasilense Sp7 and its three specially selected derivatives (mutant strains) with different rates of nitrite reduction, a direct correlation was found between their nitrite and selenite reduction rates for all the strains used in the study. Moreover, for BSO it has been shown that its presence does not block selenite reduction in A.brasilense Sp7. Conclusions: Evidence has been presented for the first time for bacteria of the genus Azospirillum that the denitrification pathway known to be inherent in these bacteria, including nitrite reductase, is likely to be involved in selenite reduction. The results using BSO also imply that detoxification of selenite through the GSH redox system (which is commonly considered as the primary mechanism of selenite reduction in many bacteria) does not play a significant role in A.brasilense. The acquired knowledge on the mechanisms underlying biogenic transformations of inorganic selenium in A.brasilense is a step forward both in understanding the biogeochemical selenium cycle and to a variety of potential nano- and biotechnological applications.

This study, based on a greenhouse pot culture experiment conducted with 15-day-old rapeseed (Brassica campestris L. cv. Pusa Gold; family Brassicaceae) and moong bean (Vigna radiata L. Wilczek cv. Pusa Ratna; family Fabaceae) plants treated with cadmium (Cd) concentrations (0, 50, and 100 mg kg−1 soil), investigates their potential for Cd accumulation and tolerance, and dissects the underlying basic physiological/biochemical mechanisms. In both species, plant dry mass decreased, while Cd concentration of both root and shoot increased with increase in soil Cd. Roots harbored a higher amount of Cd (vs. shoot) in B. campestris, while the reverse applied to V. radiata. By comparison, root Cd concentration was higher in B. campestris than in V. radiata. The high Cd concentrations in B. campestris roots and V. radiata shoots led to significant elevation in oxidative indices, as measured in terms of electrolyte leakage, H2O2 content, and lipid peroxidation. Both plants displayed differential adaptation strategies to counteract the Cd burden-caused anomalies in their roots and shoots. In B. campestris, increasing Cd burden led to a significantly decreased reduced glutathione (GSH) content but a significant increase in activities of GSH reductase (GR), GSH peroxidase (GPX), and GSH sulfotransferase (GST). However, in V. radiata, increasing Cd burden caused significant increase in GSH content and GR activity, but a significant decline in activities of GPX and GST. Cross talks on Cd burden of tissues and the adapted Cd tolerance strategies against Cd burden-accrued toxicity indicated that B. campestris and V. radiata are good Cd stabilizer and Cd extractor, respectively, wherein a fine tuning among the major components (GR, GPX, GST, GSH) of the GSH redox system helped the plants to counteract differentially the Cd loadinduced anomalies in tissues. On the whole, the physiological/biochemical characterization of the B. campestris and V. radiata responses to varying Cd concentrations can be of great help in elaborating the innovative plant-based remediation technologies for metal/metalloidcontaminated sites.

Theory suggests that many chemical reactions (not simply, as is often thought, redox reactions) might be catalysed by an applied electric field; experimental evidence for this is now provided from single-molecule studies of the formation of carbon–carbon bonds in a Diels–Alder reaction. Electrically driven catalysis of a redox reaction Theory suggests that many chemical reactions — not simply, as is often thought, redox reactions — might be catalysed by an applied electrical field. Experimental evidence for this is now provided from single-molecule studies of the formation of carbon–carbon bonds in a Diels–Alder reaction. In a series of scanning tunnelling microscopy break-junction experiments, the authors observe a fivefold increase in the frequency of single-molecule junction formation when the electrical field is present and aligned in the direction to favour electron flow from the dienophile to the diene. The demonstration that it is possible to manipulate chemical reactions with electric fields offers proof-of-principle for a novel approach to heterogeneous catalysis. It is often thought that the ability to control reaction rates with an applied electrical potential gradient is unique to redox systems. However, recent theoretical studies suggest that oriented electric fields could affect the outcomes of a range of chemical reactions, regardless of whether a redox system is involved 1 , 2 , 3 , 4 . This possibility arises because many formally covalent species can be stabilized via minor charge-separated resonance contributors. When an applied electric field is aligned in such a way as to electrostatically stabilize one of these minor forms, the degree of resonance increases, resulting in the overall stabilization of the molecule or transition state. This means that it should be possible to manipulate the kinetics and thermodynamics of non-redox processes using an external electric field, as long as the orientation of the approaching reactants with respect to the field stimulus can be controlled. Here, we provide experimental evidence that the formation of carbon–carbon bonds is accelerated by an electric field. We have designed a surface model system to probe the Diels–Alder reaction, and coupled it with a scanning tunnelling microscopy break-junction approach 5 , 6 , 7 . This technique, performed at the single-molecule level, is perfectly suited to deliver an electric-field stimulus across approaching reactants. We find a fivefold increase in the frequency of formation of single-molecule junctions, resulting from the reaction that occurs when the electric field is present and aligned so as to favour electron flow from the dienophile to the diene. Our results are qualitatively consistent with those predicted by quantum-chemical calculations in a theoretical model of this system, and herald a new approach to chemical catalysis.

Abstract Efficient saccharification of lignocellulosic biomass requires concerted development of a pretreatment method, an enzyme cocktail and an enzymatic process, all of which are adapted to the feedstock. Recent years have shown great progress in most aspects of the overall process. In particular, increased insights into the contributions of a wide variety of cellulolytic and hemicellulolytic enzymes have improved the enzymatic processing step and brought down costs. Here, we review major pretreatment technologies and different enzyme process setups and present an in-depth discussion of the various enzyme types that are currently in use. We pay ample attention to the role of the recently discovered lytic polysaccharide monooxygenases (LPMOs), which have led to renewed interest in the role of redox enzyme systems in lignocellulose processing. Better understanding of the interplay between the various enzyme types, as they may occur in a commercial enzyme cocktail, is likely key to further process improvements.