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Electron transfer plays a crucial role in living systems, including the generation of reactive oxygen species (ROS). Oxygen acts as the terminal electron acceptor in the respiratory chains of aerobic organisms as well as in some photoinduced processes followed by the formation of ROS. This is why the participation of exogenous antioxidants in electron transfer processes in living systems is of particular interest. In the present study, using chemically induced dynamic nuclear polarization (CIDNP) and dissociative electron attachment (DEA) techniques, we have elucidated the affinity of solvated and free electrons to glycyrrhetinic acid (GA)—the aglicon of glycyrrhizin (the main active component of Licorice root). CIDNP is a powerful instrument to study the mechanisms of electron transfer reactions in solution, but the DEA technique shows its effectiveness in gas phase processes. For CIDNP experiments, the photoionization of the dianion of 5-sulfosalicylic acid (HSSA2−) was used as a model reaction of solvated electron generation. DEA experiments testify that GA molecules are even better electron acceptors than molecular oxygen, at least under gas-phase conditions. In addition, the effect of the solvent on the energetics of the reactants is discussed. [ABSTRACT FROM AUTHOR]

Despite the abundance of research investigating the efficacy of caffeine supplementation on exercise performance, the physiological and biochemical responses to caffeine supplementation during intermittent activities are less evident. This study investigated the acute effects of caffeine supplementation on measures of exercise performance, ratings of perceived exertion, and biomarkers of oxidative stress induced by an acute bout of sprint interval training. In a randomized crossover design, 12 healthy males (age: 26 ± 4 years, height: 177.5 ± 6 cm, body mass: 80.7 ± 7.6 kg) ingested 6 mg/kg of caffeine or placebo 60 min prior to performing sprint interval training (12 × 6 s "all-out sprints" interspersed by 60 s of rest). Performance scores and ratings of perceived exertion were assessed after every sprint. Blood samples were collected before supplementation, prior to and following each sprint, and 5 and 60 min after the last sprint. Caffeine had no effect on any performance measures, ratings of perceived exertion, or biomarkers of oxidative stress (p >.05). In conclusion, caffeine supplementation does not improve performance or decrease oxidative stress after an acute bout of sprint interval training. [ABSTRACT FROM AUTHOR]

In photodynamic therapy (PDT) treatment, heavy-atom-free photosensitizers (PSs) are a great source of singlet oxygen photosensitizer. Reactive oxygen species (ROS) are produced by an energy transfer from the lowest energy triplet excited state to the molecular oxygen of cancer cells. To clarify the photophysical characteristics in the excited states of a few experimentally identified thionated (>C=S) molecules and their oxygenated congeners (>C=O), a quantum chemical study is conducted. This study illustrates the properties of the excited states in oxygen congeners that render them unsuitable for PDT treatment. Concurrently, a hierarchy is presented based on the utility of the lowest-energy triplet excitons of thionated compounds. Their non-radiative decay rates are calculated for reverse-ISC and inter-system crossover (ISC) processes. In addition, the vibronic importance of C=O and C=S bonds is clarified by the computation of the Huang–Rhys factor, effective vibrational mode, and reorganization energy inside the Marcus–Levich–Jörtner system. ROS generation in thionated PSs exceeds their oxygen congeners as kf ≪ kISC, where radiative decay rate is designated as kf. As a result, the current work offers a calculated strategy for analyzing the effectiveness of thionated photosensitizers in PDT. [ABSTRACT FROM AUTHOR]

Purpose: We examined the effects of increasing hypoxia severity on oxygenation kinetics in the vastus lateralis muscle during repeated treadmill sprints, using statistical parametric mapping (SPM). Methods: Ten physically active males completed 8 sprints of 5 seconds each (recovery = 25 s) on a motorized sprint treadmill in normoxia (sea level; inspired oxygen fraction = 0.21), moderate hypoxia (inspired oxygen fraction = 0.17), and severe hypoxia (SH; inspired oxygen fraction = 0.13). Continuous assessment of tissue saturation index (TSI) in the vastus lateralis muscle was conducted using near-infrared spectroscopy. Subsequently, TSI data were averaged for the sprint–recovery cycle of all sprints and compared between conditions. Results: The SPM analysis revealed no discernible difference in TSI signal amplitude between conditions during the actual 5-second sprint phase. However, during the latter portion of the 25-second recovery phase, TSI values were lower in SH compared with both sea level (from 22 to 30 s; P =.003) and moderate hypoxia (from 16 to 30 s; P =.001). The mean distance covered at sea level (22.9 [1.0] m) was greater than for both moderate hypoxia (22.5 [1.2] m; P =.045) and SH (22.3 [1.4] m; P =.043). Conclusions: The application of SPM demonstrated that only SH reduced muscle oxygenation levels during the late portion of the passive (recovery) phase and not the active (sprint) phase during repeated treadmill sprints. These findings underscore the usefulness of SPM for assessing muscle oxygenation differences due to hypoxic exposure and the importance of the duration of the between-sprints recovery period. [ABSTRACT FROM AUTHOR]

Purpose: An inspiratory muscle warm-up (IMW) improves inspiratory muscle function, but the effects of high-intensity exercise are inconsistent. We aimed to determine the effects of high-intensity IMW on high-intensity exercise performance and muscle oxygenation. Methods: Ten healthy men (maximal oxygen uptake [ V ˙ O 2 max ] 52.2 [5.0] mL·kg–1·min–1) performed constant-load exercise to exhaustion on a cycle ergometer at V ˙ O 2 max under 2 IMW conditions: a placebo condition (PLA) and a high-intensity IMW condition (HIGH). The inspiratory loads were set at 15% and 80% of maximal inspiratory pressure, respectively. Maximal inspiratory pressure was measured before and after IMW. Oxyhemoglobin was measured in the vastus lateralis by near-infrared spectroscopy during exercise. Rating of perceived exertion (RPE) for a leg was measured after 1 and 2 minutes of exercise. Results: Exercise tolerance was significantly higher under HIGH than PLA (228 [49] s vs 218 [49] s, P =.003). Maximal inspiratory pressure was significantly increased by IMW under HIGH (from 125 [20] to 136 [25] cm H2O, P =.031). Oxyhemoglobin was significantly higher under HIGH than PLA at 80% of the total duration of exercise (P =.048). RPE for the leg was significantly lower under HIGH than PLA after 2 minutes of exercise (P =.019). Conclusions: Given that oxyhemoglobin is an index of local oxygen supply, the results of this study suggest that high-intensity IMW increases the oxygen supply to active limbs. It may also reflect a reduction in RPE in the leg. In addition, high-intensity IMW may improve exercise performance. [ABSTRACT FROM AUTHOR]

P/TGMS (Photo/thermo-sensitive genic male sterile) lines are crucial resources for two-line hybrid rice breeding. Previous studies revealed that slow development is a general mechanism for sterility-fertility conversion of P/TGMS in Arabidopsis. However, the difference in P/TGMS genes between rice and Arabidopsis suggests the presence of a distinct P/TGMS mechanism in rice. In this study, we isolated a novel P/TGMS line, ostms19, which shows sterility under high-temperature conditions and fertility under low-temperature conditions. OsTMS19 encodes a novel pentatricopeptide repeat (PPR) protein essential for pollen formation, in which a point mutation GTA(Val) to GCA(Ala) leads to ostms19 P/TGMS phenotype. It is highly expressed in the tapetum and localized to mitochondria. Under high temperature or long-day photoperiod conditions, excessive ROS accumulation in ostms19 anthers during pollen mitosis disrupts gene expression and intine formation, causing male sterility. Conversely, under low temperature or short-day photoperiod conditions, ROS can be effectively scavenged in anthers, resulting in fertility restoration. This indicates that ROS homeostasis is critical for fertility conversion. This relationship between ROS homeostasis and fertility conversion has also been observed in other tested rice P/TGMS lines. Therefore, we propose that ROS homeostasis is a general mechanism for the sterility-fertility conversion of rice P/TGMS lines.

Understanding the ignition and dynamic processes for the combustion of hydrate is crucial for efficient energy utilization. Through reactive force field molecular dynamics simulations, we studied the high-temperature decomposition and combustion processes of methane hydrates in a pure oxygen environment. We found that at an ignition temperature of 2800 K, hydrates decomposed from the interface to the interior, but the layer-by-layer manner was no longer strictly satisfied. At the beginning of combustion, water molecules reacted first to generate OH•, followed by methane oxidation. The combustion pathway of methane is C H 4 → CH 3 • → C H 3 O • → C H 2 O → H C • O → HCO O • → CO (C O 2 ). During the combustion process, a liquid water layer was formed between melted methane and oxygen, which hindered the reaction's progress. When there is no heat resistance, oxygen will transform into radicals such as OH• and O•, which have faster diffusion rates, allowing oxygen to conveniently cross the mass transfer barrier of the liquid water layer and participate in the combustion process. Increasing the amount of OH• may cause a surge in the reaction. On the other hand, when significant heat resistance exists, OH• is difficult to react with low-temperature hydrate components, but it can transform into O• to trigger the oxidation of methane. The H• generated has a sufficient lifetime to contact high-temperature oxygen molecules, converting oxygen into radicals that easily cross the water layer to achieve mass transfer. Therefore, finding ways to convert oxygen into various radicals is the key to solving the incomplete combustion of hydrates. Finally, the reaction pathways and microscopic reaction mechanisms of each species are proposed. [ABSTRACT FROM AUTHOR]

Photoredox properties of several earth-abundant light-harvesting transition metal complexes in combination with cobalt-based proton reduction catalysts have been investigated computationally to assess the fundamental viability of different photocatalytic systems of current experimental interest. Density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations using several GGA (BP86, BLYP), hybrid-GGA (B3LYP, B3LYP*), hybrid meta-GGA (M06, TPSSh), and range-separated hybrid (ωB97X, CAM-B3LYP) functionals were used to calculate relevant ground and excited state reduction potentials for photosensitizers, catalysts, and sacrificial electron donors. Linear energy correction factors for the DFT/TD-DFT results that provide the best agreement with available experimental reference results were determined in order to provide more accurate predictions. Among the selection of functionals, the B3LYP* and TPSSh sets of correction parameters were determined to give the best redox potentials and excited states energies, ΔEexc, with errors of ∼0.2 eV. Linear corrections for both reduction and oxidation processes significantly improve the predictions for all the redox pairs. In particular, for TPSSh and B3LYP*, the calculated errors decrease by more than 0.5 V against experimental values for catalyst reduction potentials, photosensitizer oxidation potentials, and electron donor oxidation potentials. Energy-corrected TPSSh results were finally used to predict the energetics of complete photocatalytic cycles for the light-driven activation of selected proton reduction cobalt catalysts. These predictions demonstrate the broader usefulness of the adopted approach to systematically predict full photocycle behavior for first-row transition metal photosensitizer–catalyst combinations more broadly. [ABSTRACT FROM AUTHOR]

The barrierless exothermic reactions between atomic oxygen and the cyano radical, O(3P) + CN(X2 Σ + ) → CO(X1Σ+) + N(2D)/N(4S), play a significant role in combustion, astrochemistry, and hypersonic environments. In this work, their dynamics and kinetics are investigated using both wave packet (WP) and quasi-classical trajectory (QCT) methods on recently developed potential energy surfaces of the 12A′, 12A,″ and 14A″ states. The product state distributions in the doublet pathway obtained with the WP method for a few partial waves show extensive internal excitation in the CO product. This observation, combined with highly oscillatory reaction probabilities, signals a complex-forming mechanism. The statistical nature of the reaction is confirmed by comparing the WP results with those from phase space theory. The calculated rate coefficients using the WP (with a J-shifting approximation) and QCT methods exhibit agreement with each other near room temperature, 1.77 × 10−10 and 1.31 × 10−10 cm3 molecule−1 s−1, but both are higher than the existing experimental results. The contribution of the quartet pathway is small at room temperature due to a small entrance channel bottleneck. The QCT rate coefficients are further compared with experimental results above 3000 K, and the agreement is excellent. [ABSTRACT FROM AUTHOR]

The production of e-cigarette aerosols through vaping processes is known to cause the formation of various free radicals and reactive oxygen species (ROS). Despite the well-known oxidative potential and cytotoxicity of fresh vaping emissions, the effects of chemical aging on exhaled vaping aerosols by indoor atmospheric oxidants are yet to be elucidated. Terpenes are commonly found in e-liquids as flavor additives. In the presence of indoor ozone (O3), e-cigarette aerosols that contain terpene flavorings can undergo chemical transformations, further producing ROS and reactive carbonyl species. Here, we simulated the aging process of the e-cigarette emissions in a 2 m3 FEP film chamber with 100 ppbv of O3 exposure for an hour. The aged vaping aerosols, along with fresh aerosols, were collected to detect the presence of ROS. The aged particles exhibited 2- to 11-fold greater oxidative potential, and further analysis showed that these particles formed a greater number of radicals in aqueous conditions. The aging process induced the formation of various alkyl hydroperoxides (ROOH), and through iodometric quantification, we saw that our aged vaping particles contained significantly greater amounts of these hydroperoxides than their fresh counterparts. Bronchial epithelial cells exposed to aged vaping aerosols exhibited an upregulation of the oxidative stress genes, HMOX-1 and GSTP1, indicating the potential for inhalation toxicity. This work highlights the indirect danger of vaping in environments with high ground-level O3, which can chemically transform e-cigarette aerosols into new particles that can induce greater oxidative damage than fresh e-cigarette aerosols. Given that the toxicological characteristics of e-cigarettes are mainly associated with the inhalation of fresh aerosols in current studies, our work may provide a perspective that characterizes vaping exposure under secondhand or thirdhand conditions as a significant health risk.

Copper plays critical roles as a metal active site cofactor and metalloallosteric signal for enzymes involved in cell proliferation and metabolism, making it an attractive target for cancer therapy. In this study, we investigated the efficacy of polydopamine nanoparticles (PDA NPs), classically applied for metal removal from water, as a therapeutic strategy for depleting intracellular labile copper pools in triple-negative breast cancer models through the metal-chelating groups present on the PDA surface. By using the activity-based sensing probe FCP-1, we could track the PDA-induced labile copper depletion while leaving total copper levels unchanged and link it to the selective MDA-MB-231 cell death. Further mechanistic investigations revealed that PDA NPs increased reactive oxygen species (ROS) levels, potentially through the inactivation of superoxide dismutase 1 (SOD1), a copper-dependent antioxidant enzyme. Additionally, PDA NPs were found to interact with the mitochondrial membrane, resulting in an increase in the mitochondrial membrane potential, which may contribute to enhanced ROS production. We employed an in vivo tumor model to validate the therapeutic efficacy of PDA NPs. Remarkably, in the absence of any additional treatment, the presence of PDA NPs alone led to a significant reduction in tumor volume by a factor of 1.66 after 22 days of tumor growth. Our findings highlight the potential of PDA NPs as a promising therapeutic approach for selectively targeting cancer by modulating copper levels and inducing oxidative stress, leading to tumor growth inhibition as shown in these triple-negative breast cancer models.

Maleic acid (MA) induces renal tubular cell dysfunction directed to acute kidney injury (AKI). AKI is an increasing global health burden due to its association with mortality and morbidity. However, targeted therapy for AKI is lacking. Previously, we determined mitochondrial-associated proteins are MA-induced AKI affinity proteins. We hypothesized that mitochondrial dysfunction in tubular epithelial cells plays a critical role in AKI. In vivo and in vitro systems have been used to test this hypothesis. For the in vivo model, C57BL/6 mice were intraperitoneally injected with 400 mg/kg body weight MA. For the in vitro model, HK-2 human proximal tubular epithelial cells were treated with 2 mM or 5 mM MA for 24 h. AKI can be induced by administration of MA. In the mice injected with MA, the levels of blood urea nitrogen (BUN) and creatinine in the sera were significantly increased (p

Osteosarcoma (OS) is the most common malignant bone tumor with a poor prognosis. Here, we show that the nuclear receptor RORγ may serve as a potential therapeutic target in OS. OS exhibits a hyperactivated oxidative phosphorylation (OXPHOS) program, which fuels the carbon source to promote tumor progression. We found that RORγ is overexpressed in OS tumors and is linked to hyperactivated OXPHOS. RORγ induces the expression of PGC-1β and physically interacts with it to activate the OXPHOS program by upregulating the expression of respiratory chain component genes. Inhibition of RORγ strongly inhibits OXPHOS activation, downregulates mitochondrial functions, and increases ROS production, which results in OS cell apoptosis and ferroptosis. RORγ inverse agonists strongly suppressed OS tumor growth and progression and sensitized OS tumors to chemotherapy. Taken together, our results indicate that RORγ is a critical regulator of the OXPHOS program in OS and provides an effective therapeutic strategy for this deadly disease.

UNLABELLED: Gonorrhea, caused by the bacterium Neisseria gonorrhoeae (Gc), is characterized by neutrophilic influx to infection sites. Gc has developed mechanisms to resist killing by neutrophils that include modifications to its surface lipooligosaccharide (LOS). One such LOS modification is sialylation: Gc sialylates its terminal LOS sugars with cytidine-5-monophosphate-N-acetylneuraminic acid, which is scavenged from the host using LOS sialyltransferase (Lst) since Gc cannot make its sialic acid. Sialylation enables sensitive strains of Gc to resist complement-mediated killing in a serum-dependent manner. However, little is known about the contribution of sialylation to complement-independent, direct Gc-neutrophil interactions. In the absence of complement, we found sialylated Gc expressing opacity-associated (Opa) proteins decreased the oxidative burst and granule exocytosis from primary human neutrophils. In addition, sialylated Opa+ Gc survived better than vehicle treated or Δlst Gc when challenged with neutrophils. However, Gc sialylation did not significantly affect Opa-dependent association with or internalization of Gc by neutrophils. Previous studies have implicated sialic acid-binding immunoglobulin-type lectins (Siglecs) in modulating neutrophil interactions with sialylated Gc. Blocking neutrophil Siglecs with antibodies that bind to their extracellular domains eliminated the ability of sialylated Opa+ Gc to suppress the oxidative burst and resist neutrophil killing. These findings highlight a new role for sialylation in Gc evasion of human innate immunity, with implications for the development of vaccines and therapeutics for gonorrhea. IMPORTANCE: Neisseria gonorrhoeae, the bacterium that causes gonorrhea, is an urgent global health concern due to increasing infection rates, widespread antibiotic resistance, and its ability to thwart protective immune responses. The mechanisms by which Gc subverts protective immune responses remain poorly characterized. One way N. gonorrhoeae evades human immunity is by adding sialic acid that is scavenged from the host onto its lipooligosaccharide, using the sialyltransferase Lst. Here, we found that sialylation enhances N. gonorrhoeae survival from neutrophil assault and inhibits neutrophil activation, independently of the complement system. Our results implicate bacterial binding of sialic acid-binding lectins (Siglecs) on the neutrophil surface, which dampens neutrophil antimicrobial responses. This work identifies a new role for sialylation in protecting N. gonorrhoeae from cellular innate immunity, which can be targeted to enhance the human immune response in gonorrhea.

Macrophage cholesterol homeostasis is crucial for health and disease and has been linked to the lipid-peroxidizing enzyme arachidonate 15-lipoxygenase type B (ALOX15B), albeit molecular mechanisms remain obscure. We performed global transcriptome and immunofluorescence analysis in ALOX15B-silenced primary human macrophages and observed a reduction of nuclear sterol regulatory element-binding protein (SREBP) 2, the master transcription factor of cellular cholesterol biosynthesis. Consequently, SREBP2-target gene expression was reduced as were the sterol biosynthetic intermediates desmosterol and lathosterol as well as 25- and 27-hydroxycholesterol. Mechanistically, suppression of ALOX15B reduced lipid peroxidation in primary human macrophages and thereby attenuated activation of mitogen-activated protein kinase ERK1/2, which lowered SREBP2 abundance and activity. Low nuclear SREBP2 rendered both, ALOX15B-silenced and ERK1/2-inhibited macrophages refractory to SREBP2 activation upon blocking the NPC intracellular cholesterol transporter 1. These studies suggest a regulatory mechanism controlling macrophage cholesterol homeostasis based on ALOX15B-mediated lipid peroxidation and concomitant ERK1/2 activation.

We report state-of-the-art first-principles molecular dynamics results on the heterogeneous chemical uptake of NO2, a major anthropogenic pollutant, on the dry and wet hydroxylated surface of α-quartz, which is a significant component of silica-based catalysts and atmospheric dust aerosols. Our investigation spotlights an unexpected chemical pathway by which NO2 (i) can be adsorbed as HONO by deprotonation of interfacial silanols (i.e., –Si–OH group) on silica, (ii) can be barrierless converted to nitric acid, and (iii) can finally dissociated to surface bounded NO and hydroxyl gas phase radicals. This chemical pathway does not invoke any previously experimentally postulated NO2 dimerization, dimerization that is less likely to occur at low NO2 concentrations. Moreover, water significantly catalyzes the HONO formation and the dissociation of nitric acid into surface-bounded NO and OH radicals, while visible light adsorption can further promote these chemical transformations. This work highlights how water-restricted solvation regimes on common mineral substrates are likely to be a source of reactive oxygen species, and it offers a theoretical framework for further and desirable experimental efforts, aiming to better constrain trace gases/mineral interactions at different relative humidity conditions. [ABSTRACT FROM AUTHOR]

We report the experimental measurements of the decay rate of polar cesium nD5/2 − 6S1/2 Rydberg-ground molecules with a large principal quantum number range of 35 ≤ n ≤ 40. Rydberg molecules are prepared employing the method of two-photon photoassociation and the molecular (atomic) ions, due to autoionization (blackbody photoionization), are detected with a microchannel plate detector. The decay rate Γ of the vibrational ground state of the deep and shadow bound molecules for triplet (TΣ) and mixed singlet-triplet (S,TΣ) are measured by fitting the molecular population with the exponential function. Comparing with the parent atom, the decay rate of the polar Rydberg-ground molecule shows an obvious increase with a magnitude of a few μs. The possible dissociation mechanism of polar Rydberg-ground molecules including a collisional decay, blackbody induced decay, and coupling of adjacent Rydberg states and tunneling decay are discussed in detail. The theoretical model is induced to simulate the measurements, showing agreement. [ABSTRACT FROM AUTHOR]

Resting metabolic rate (RMR) is an important component of total daily energy expenditure; however, it is currently not understood how it varies across a typical competitive match week in professional soccer players. For the first time, we aimed to assess RMR throughout an in-season competitive week in professional soccer players. Additionally, we aimed to assess energy and carbohydrate intake across the same week. Twenty-four professional soccer players from an English Premier League club (age: 18 ± 1.6 years) completed the study. RMR was assessed each morning of a typical competitive match week (match day [MD] −3, −2, −1, +1, +2, and + 3), and dietary intake (including MD) was assessed daily via the remote food photography method and 24-hr recall. Daily training load was quantified using Global Positioning System, daily muscle soreness ratings were recorded, and body composition was assessed via dual-energy X-ray absorptiometry. There was a significant (p =.0004) increase in mean RMR of ∼261 kcal/day on MD + 1, compared with MD − 1. Additionally, volume of oxygen consumed significantly increased at MD + 1 (p =.0002) versus MD − 1. There were no significant differences in daily energy or carbohydrate intake across the competitive week (p >.05), with inadequate carbohydrate intakes on MD − 1 (∼3.9 g/kg body mass), MD (∼4.2 g/kg body mass), and MD + 1 (∼3.6 g/kg body mass) in relation to current recommendations. We report, for the first time, that RMR is significantly increased following a competitive match in professional soccer players. In addition, we confirm previous findings to reinforce that players exhibit inadequate nutrition periodization practices, which may impair physical performance and recovery. [ABSTRACT FROM AUTHOR]

The changes in the properties of three biological events that occur with cerebral aging are discussed. These adverse changes already begin to develop early in mid-life and gradually become more pronounced with senescence. Essentially, they are reflections of the progressive decline in effectiveness of key processes, resulting in the deviation of essential biochemical trajectories to ineffective and ultimately harmful variants of these programs. The emphasis of this review is the major role played by the mitochondria in the transition of these three important processes toward more deleterious variants as brain aging proceeds. The immune system: the shift away from an efficient immune response to a more unfocused, continuing inflammatory condition. Such a state is both ineffective and harmful. Reactive oxygen species are important intracellular signaling systems. Additionally, microglial phagocytic activity utilizing short lived reactive oxygen species contribute to the removal of aberrant or dead cells and bacteria. These processes are transformed into an excessive, untargeted, and persistent generation of pro-oxidant free radicals (oxidative stress). The normal efficient neural transmission is modified to a state of undirected, chronic low-level excitatory activity. Each of these changes is characterized by the occurrence of continuous activity that is inefficient and diffused. The signal/noise ratio of several critical biological events is thus reduced as beneficial responses are gradually replaced by their impaired and deleterious variants.

Photodynamic therapy (PDT) is a promising cancer treatment but has limitations due to its dependence on oxygen and high-power-density photoexcitation. Here, we report polymer-based organic photosensitizers (PSs) through rational PS skeleton design and precise side-chain engineering to generate •O2- and •OH under oxygen-free conditions using ultralow-power 808 nm photoexcitation for tumor-specific photodynamic ablation. The designed organic PS skeletons can generate electron-hole pairs to sensitize H2O into •O2- and •OH under oxygen-free conditions with 808 nm photoexcitation, achieving NIR-photoexcited and oxygen-independent •O2- and •OH production. Further, compared with commonly used alkyl side chains, glycol oligomer as the PS side chain mitigates electron-hole recombination and offers more H2O molecules around the electron-hole pairs generated from the hydrophobic PS skeletons, which can yield 4-fold stronger •O2- and •OH production, thus allowing an ultralow-power photoexcitation to yield high PDT effect. Finally, the feasibility of developing activatable PSs for tumor-specific photodynamic therapy in female mice is further demonstrated under 808 nm irradiation with an ultralow-power of 15 mW cm-2. The study not only provides further insights into the PDT mechanism but also offers a general design guideline to develop an oxygen-independent organic PS using ultralow-power NIR photoexcitation for tumor-specific PDT.

Hepatic inflammation is commonly identified in Wilson disease (WD), a genetic disease of hepatic and brain copper accumulation. Copper accumulation is associated with increased oxidative stress and reactive oxygen species generation which may result in non-enzymatic oxidation of membrane-bound polyunsaturated fatty acids (PUFA). PUFA can be oxidized enzymatically via lipoxygenases (LOX), cyclooxygenases (COX), and cytochrome P450 monooxygenases (CYP). Products of PUFA oxidation are collectively known as oxylipins (OXL) and are bioactive lipids that modulate hepatic inflammation. We examined hepatic OXL profiles at early stages of WD in two mouse models, the toxic milk mouse from The Jackson Laboratory (tx-j) and the Atp7b knockout on a C57Bl/6 background (Atp7b-/-B6). Targeted lipidomic analysis performed by ultra-high-performance liquid chromatography-electrospray ionization-tandem mass spectrometry showed that in both tx-j and Atp7b-/-B6 mice, hepatic OXL profiles were altered with higher thromboxane and prostaglandins levels. The levels of oxidative stress marker, 9-HETE were increased more markedly in tx-j mice. However, both genotypes showed upregulated transcript levels of many genes related to oxidative stress and inflammation. Both genotypes showed higher prostaglandins, thromboxin along with higher PUFA-derived alcohols, diols, and ketones with altered epoxides; the expression of Alox5 was upregulated and many CYP-related genes were dysregulated. Pathway analyses show dysregulation in arachidonic acid and linoleic acid metabolism characterizes mice with WD. Our findings indicate alterations in hepatic PUFA metabolism in early-stage WD and suggest the upregulation of both, non-enzymatic ROS-dependent and enzymatic PUFA oxidation, which could have implications for hepatic manifestations in WD and represent potential targets for future therapies.

The development of new antibiotics has stalled, and novel strategies are needed as we enter the age of antibiotic resistance. Certain naturally occurring clays have been shown to be effective in killing antibiotic resistant bacteria. However, these natural clays are too variable to be used in clinical settings. Our study shows that synthetic antibacterial minerals exhibit potent antibacterial activity against topical MRSA infections and increase the rate of wound closure relative to controls. The antibacterial minerals maintain a redox cycle between Fe2+/Fe3+ and the surfaces of pyrite minerals, which act as a semiconductor and produce reactive oxygen species (ROS), while smectite minerals act as a cation exchange reservoir. Acidic conditions are maintained throughout the application of the hydrated minerals and can mitigate the alkaline pH conditions observed in chronic non-healing wounds. These results provide evidence for the strategy of iron overload to combat antibiotic resistant infections through the maintained release of Fe2+ and generation of ROS via distinct geochemical reactions that can break the chronic wound damage cycle.

Respiratory chain dysfunction can decrease ATP and increase reactive oxygen species (ROS) levels. Despite the importance of these metabolic parameters to a wide range of cellular functions and disease, we lack an integrated understanding of how they are differentially regulated. To address this question, we adapted a CRISPRi- and FACS-based platform to compare the effects of respiratory gene knockdown on ROS to their effects on ATP. Focusing on genes whose knockdown is known to decrease mitochondria-derived ATP, we showed that knockdown of genes in specific respiratory chain complexes (I, III, and CoQ10 biosynthesis) increased ROS, whereas knockdown of other low ATP hits either had no impact (mitochondrial ribosomal proteins) or actually decreased ROS (complex IV). Moreover, although shifting metabolic conditions profoundly altered mitochondria-derived ATP levels, it had little impact on mitochondrial or cytosolic ROS. In addition, knockdown of a subset of complex I subunits-including NDUFA8, NDUFB4, and NDUFS8-decreased complex I activity, mitochondria-derived ATP, and supercomplex level, but knockdown of these genes had differential effects on ROS. Conversely, we found an essential role for ether lipids in the dynamic regulation of mitochondrial ROS levels independent of ATP. Thus, our results identify specific metabolic regulators of cellular ATP and ROS balance that may help dissect the roles of these processes in disease and identify therapeutic strategies to independently target energy failure and oxidative stress.

Carbon-based functional nanocomposites have emerged as potent antimicrobial agents and can be exploited as a viable option to overcome antibiotic resistance of bacterial strains. In the present study, graphitic carbon nitride nanosheets are prepared by controlled calcination of urea. Spectroscopic measurements show that the nanosheets consist of abundant carbonyl groups and exhibit apparent photocatalytic activity under UV photoirradiation towards the selective production of singlet oxygen. Therefore, the nanosheets can effectively damage the bacterial cell membranes and inhibit the growth of bacterial cells, such as Gram-negative Escherichia coli, as confirmed in photodynamic, fluorescence microscopy, and scanning electron microscopy measurements. The results from this research highlight the unique potential of carbon nitride derivatives as potent antimicrobial agents.

Cornified envelopes (CEs) of human epidermis ordinarily consist of transglutaminase-mediated cross-linked proteins and are essential for skin barrier function. However, in addition to enzyme-mediated isopeptide bonding, protein cross-linking could also arise from oxidative damage. Our group recently demonstrated abnormal incorporation of cellular proteins into CEs by pro-oxidants in woodsmoke. In this study, we focused on 2,3-dimethoxy-1,4-naphthoquinone (DMNQ), mesquite liquid smoke (MLS), and 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD), to further understand the mechanisms through which environmental pro-oxidants induce CE formation and alter the CE proteome. CEs induced by the ionophore X537A were used for comparison. Similar to X537A, DMNQ- and MLS-induced CE formation was associated with membrane permeabilization. However, since DMNQ is non-adduct forming, its CEs were similar in protein profile to those from X537A. By contrast, MLS, rich in reactive carbonyls that can form protein adducts, caused a dramatic change in the CE proteome. TCDD-CEs were found to contain many CE precursors, such as small proline-rich proteins and late cornified envelope proteins, encoded by the epidermal differentiation complex. Since expression of these proteins is mediated by the aryl hydrocarbon receptor (AhR), and its well-known downstream protein, CYP1A1, was exclusively present in the TCDD group, we suggest that TCDD alters the CE proteome through persistent AhR activation. This study demonstrates the potential of environmental pro-oxidants to alter the epidermal CE proteome and indicates that the cellular redox state has an important role in CE formation.

Surface property modification of catalyst support is a straightforward approach to optimize the performance of supported noble metal catalysts. In particular, oxygen vacancies and hydroxyl groups play significant roles in promoting noble metal dispersion on catalysts as well as catalytic stability. In this study, we developed a nanoflower-like TiO2-supported Pd catalyst that has a higher concentration of oxygen vacancies and surface hydroxyl groups compared to that of commercial anatase and P25 support. Notably, due to the distinctive structure of the nanoflower-like TiO2, our catalyst exhibited improved dispersion and stabilization of Pd species and the formation of abundant reactive oxygen species, thereby facilitating the activation of CO and O2 molecules. As a result, the catalyst showed remarkable efficiency in catalyzing the low-temperature CO oxidation reaction with a complete CO conversion at 80 °C and stability for over 100 h. [ABSTRACT FROM AUTHOR]

Atmospheric pressure plasmas generated from a helium gas with admixtures of water vapor have numerous applications in biomedicine. It is important that the chemistry of such plasmas can be tightly controlled so that they may be tailored for their intended use. In this study, computational modeling is used to vary the pulse repetition frequency of a nanosecond-pulsed, pin-to-pin He + 0.25% H 2 O discharge in the range of 1–100 kHz to determine the influence of the pulse repetition frequency on the resulting densities of reactive oxygen species and the rates of dominant reaction pathways involving them. The plasma is simulated using the 0D plasma-chemical kinetics model GlobalKin. The pulse shape is kept constant. The afterglow duration is, therefore, dependent on the repetition frequency. Analysis of the bulk plasma chemistry after the plasma has reached equilibrium shows that the peak electron density is only weakly dependent on the pulse repetition frequency. Increasing the pulse repetition frequency is shown to increase the density of H, O, and OH radicals, while the relationship between the repetition frequency and the densities of species with longer lifetimes, namely, H 2 O 2 and O 3 , is found to be more complex. These are formed throughout the afterglow, and their density depends on the availability of reactant species, the afterglow duration, and the background gas temperature. This work concludes that the pulse repetition frequency is not a simple control parameter, especially for species that are predominantly produced in the afterglow. Detailed modeling is required for accurate control of species densities using the pulse repetition frequency. [ABSTRACT FROM AUTHOR]

In this work, we test a recently developed method to enhance classical auxiliary-field quantum Monte Carlo (AFQMC) calculations with quantum computers against examples from chemistry and material science, representative of classes of industry-relevant systems. As molecular test cases, we calculate the energy curve of H4 and the relative energies of ozone and singlet molecular oxygen with respect to triplet molecular oxygen, which is industrially relevant in organic oxidation reactions. We find that trial wave functions beyond single Slater determinants improve the performance of AFQMC and allow it to generate energies close to chemical accuracy compared to full configuration interaction or experimental results. In the field of material science, we study the electronic structure properties of cuprates through the quasi-1D Fermi–Hubbard model derived from CuBr2, where we find that trial wave functions with both significantly larger fidelities and lower energies over a mean-field solution do not necessarily lead to AFQMC results closer to the exact ground state energy. [ABSTRACT FROM AUTHOR]

The majority of previously reported cathodic electrochemiluminescence (ECL) systems often required very negative potential to be carried out, which has greatly limited their applications in the sensing field. Screening high-performance cathodic ECL systems with low triggering potential is a promising way to broaden their applications. In this work, rhenium disulfide nanosheets (ReS2 NS) have been revealed as an efficient co-promoter to realize low-triggering-potential cathodic luminol ECL. One strong cathodic ECL signal appeared at a potential of −0.3 V and one anodic ECL peak was obtained at −0.15 V under the reverse potential scan, which were caused by electrogenerated reactive oxygen species (ROS) from hydrogen peroxide. The generation of strong luminol ECL at low potential was the result of the electrocatalytic effect of ReS2 NS on the reduction of H2O2. The scavenging effect of uric acid (UA) on the ROS could significantly inhibit the cathodic ECL. As a result, an ECL sensor was proposed, which showed outstanding performance for the detection of UA in the range of 10 nM to 0.1 mM with a low detection limit of 1.53 nM. Moreover, the ECL sensor was successfully applied in the sensitive detection of UA in real samples. This work provides a new avenue to establish a low-potential cathodic ECL system, which will sufficiently expand the potential application of cathodic ECL in the sensing field. [ABSTRACT FROM AUTHOR]

Ferroptosis is a way of cell death mainly due to the imbalance between the production and degradation of lipid reactive oxygen species, which is closely associated with various diseases. Endogenous hypochlorous acid (HOCl) mainly produced in mitochondria is regarded as an important signal molecule of ferroptosis. Therefore, monitoring the fluctuation of endogenous HOCl is beneficial to better understand and treat ferroptosis-related diseases. Inspired by the promising aggregation-induced emission (AIE) properties of tetraphenylethene (TPE), herein, we rationally constructed a novel AIE-based fluorescent probe, namely QTrPEP, for HOCl with nice mitochondria-targeting ability and high sensitivity and selectivity. Probe QTrPEP consisted of phenylborate ester and the AIE fluorophore of quinoline-conjugated triphenylethylene (QTrPE). HOCl can brighten the strong fluorescence through a specific HOCl-triggered cleavage of the phenylborate ester bond and release of QTrPE, which has been demonstrated by MS, HPLC, and DLS experiments. In addition, combining QTrPE-doped test strips with a smartphone-based measurement demonstrated the excellent performance of the probe to sense HOCl. The obtained favorable optical properties and negligible cytotoxicity allowed the use of this probe for tracking of HOCl in three different cells. In particular, this work represents the first AIE-based mitochondria-targeting fluorescent probe for monitoring the fluctuation of HOCl in ferroptosis. [ABSTRACT FROM AUTHOR]

Reactive oxygen species (ROS) including the superoxide anion (O2•−) are typically studied in cell cultures using fluorescent dyes, which provide only discrete single-point measurements. These methods lack the capabilities for assessing O2•− kinetics and release in a quantitative manner over long monitoring times. Herein, we present the fabrication and application of an electrochemical biosensor that enables real-time continuous monitoring of O2•− release in cell cultures for extended periods (> 8 h) using an O2•− specific microelectrode. To achieve the sensitivity and selectivity requirements for cellular sensing, we developed a biohybrid system consisting of superoxide dismutase (SOD) and Ti3C2Tx MXenes, deposited on a gold microwire electrode (AuME) as O2•− specific materials with catalytic amplification through the synergistic action of the enzyme and the biomimetic MXenes-based structure. The biosensor demonstrated a sensitivity of 18.35 nA/μM with a linear range from 147 to 930 nM in a cell culture medium. To demonstrate its robustness and practicality, we applied the biosensor to monitor O2•− levels in human leukemia monocytic THP-1 cells upon stimulation with lipopolysaccharide (LPS). Using this strategy, we successfully monitored LPS-induced O2•− in THP-1 cells, as well as the quenching effect induced by the ROS scavenger N-acetyl-l-cysteine (NAC). The biosensor is generally useful for exploring the role of oxidative stress and longitudinally monitoring O2•− release in cell cultures, enabling studies of biochemical processes and associated oxidative stress mechanisms in cellular and other biological environments. [ABSTRACT FROM AUTHOR]

BACKGROUND: Most of the formulas for the clinical treatment of premature ovarian insufficiency have evolved from the basic formula of Liuwei Dihuang Pills, and have achieved good therapeutic efficacy. Currently, most of the experimental studies on Liuwei Dihuang Pills focus on morphological observations and physiological and biochemical detection of in vivo animal models, while fewer studies on molecular mechanisms have been reported. OBJECTIVE: To explore the molecular mechanism of Liuwei Dihuang Pills in the treatment of premature ovarian insufficiency based on the receptor gamma coactivator-1 alpha/mitochondrial transcription factor A/reactive oxygen species pathway. METHODS: Premature ovarian insufficiency model was established in mice by intraperitoneal injection of cyclophosphamide 120 mg/kg combined with busulfan 12 mg/kg, and then Liuwei Dihuang Pill suspension was used to intervene in premature ovarian insufficiency mice. After 12 weeks of intervention, the levels of follicle-stimulating hormone, luteinizing hormone, estradiol, anti-Mullerian hormone, 8-hydroxydeoxyguanosine, total antioxidant capacity and reactive oxygen species in serum of mice were detected by ELISA method. The morphological changes in mouse ovaries were observed by hematoxylin-eosin staining. The ultrastructure of mouse follicular granulosa cells and the apoptosis of granulosa cell mitochondria were observed by transmission electron microscopy. The expression levels of receptor gamma coactivator-1 alpha and mitochondrial transcription factor A in mouse ovarian granulosa cells were detected by immunohistochemistry. RESULTS AND CONCLUSION: Compared with the model group, serum levels of follicle-stimulating hormone, luteinizing hormone, reactive oxygen species, and 8-hydroxydeoxyguanosine were decreased in the experimental group (P < 0.05), and the levels of estradiol, anti-Mullerian hormone, and total antioxidant capacity were increased (P < 0.05). Hematoxylin-eosin staining showed that in the model group, there were more atretic follicles and corpus luteum forms, some secondary follicles, and interstitial fibrosis and hyperplasia; in the experimental group, a large number of atretic follicles, few corpus luteum forms, primordial follicles were observed at the edges but there were few secondary follicles and no mature follicles. Transmission electron microscopy showed that the organelles in ovarian granulosa cells of mice in the experimental groups were relatively intact. Immunohistochemical results showed that compared with the model group, the expression level of receptor gamma coactivator-1 alpha in the ovarian tissue of mice increased slightly in the experimental group at the 4th week, and there was no significant change at the 8th and 12th weeks. The expression level of mitochondrial transcription factor A in the ovarian tissues of mice in the experimental group was transiently increased at the 4th week, and then slightly decreased, which were all significantly different from those of the model group. To conclude, Liuwei Dihuang Pills inhibit ovarian granulosa cell apoptosis in mice with premature ovarian insufficiency to a certain extent through the receptor gamma coactivator-1 alpha/mitochondrial transcription factor A/reactive oxygen species signaling pathway, thereby improving the endocrine function of the ovary, enhancing the antioxidant capacity, and attenuating the degree of oxidative stress damage. [ABSTRACT FROM AUTHOR]

BACKGROUND: Studies have shown that hesperetin exerts protective effects on chondrocytes through a variety of mechanisms or signaling pathways, but the protective mechanisms have not been fully elucidated. OBJECTIVE: To investigate the effect of hesperetin on lipopolysaccharide-induced inflammatory degeneration of chondrocytes. METHODS: Knee joint chondrocytes from suckling Sprague-Dawley rats were isolated and cultured in vitro, and identified by Safranine O staining. The cytotoxicity of hesperetin on chondrocytes was determined by the MTT assay to ensure the optimal concentration of hesperetin. Chondrocytes were randomly divided into three groups, including the control group, model group, and experimental group. The cellular model of osteoarthritis was established in the latter two groups by simulating chondrocytes with lipopolysaccharide. Chondrocytes in the experimental group was then intervened with hesperetin for 24 hours. Calcein-AM/EthD-I staining was used to detect cell viability. Immunohistochemical staining was performed to determine the expression of type II collagen in chondrocytes. Intracellular reactive oxygen species level was detected by a reactive oxygen species detection kit. Total glutathione level was detected by ELISA. Real-time fluorescent PCR was employed to detect the expression of interleukin 1β, interleukin 6, tumor necrosis factor α and type II collagen. RESULTS AND CONCLUSION: Safranine O staining results showed that the cells extracted were chondrocytes. Cytotoxicity test results showed 0.5 μmol/L hesperetin had the most significant effect on chondrocyte vitality. Compared with the control group, the model group showed a decrease in chondrocyte proliferation ability, an increase in reactive oxygen species levels, a decrease in total glutathione levels, an increase in type II collagen degradation, an increase in the levels of interleukin 1β, interleukin 6, and tumor necrosis factor α, and a decrease in the expression of type II collagen (P < 0.05). Compared with the model group, in the experimental group, the proliferation ability of chondrocytes increased, reactive oxygen species levels decreased, total glutathione levels increased, and type II collagen degradation decreased, levels of interleukin 1β, interleukin 6, and tumor necrosis factor α downregulated, and the expression of type II collagen upregulated (P < 0.05). To conclude, hesperetin has a protective effect on lipopolysaccharide-induced inflammatory degeneration of osteoarthritic chondrocytes, and the mechanism may be associated with inhibition of reactive oxygen species-mediated oxidative stress. [ABSTRACT FROM AUTHOR]

Summary: Chloroplasts play a crucial role in plant defense against pathogens, making them primary targets for pathogen effectors that suppress host immunity. This study characterizes the Plasmopara viticola CRN‐like effector, PvCRN20, which interacts with DEG5 in the cytoplasm but not with its interacting protein, DEG8, which is located in the chloroplast.By transiently overexpressing in tobacco leaves, we show that PvCRN20 could inhibit INF1‐ and Bax‐triggered cell death. Constitutive expression of PvCRN20 suppresses the accumulation of reactive oxygen species (ROS) and promotes pathogen colonization. PvCRN20 reduces DEG5 entry into chloroplasts, thereby disrupting DEG5 and DEG8 interactions in chloroplasts.Overexpression of VvDEG5 and VvDEG8 induces ROS accumulation and enhances grapevine resistance to P. viticola, whereas knockout of VvDEG8 represses ROS production and promotes P. viticola colonization. Consistently, ectopic expression of VvDEG5 and VvDEG8 in tobacco promotes chloroplast‐derived ROS accumulation, whereas co‐expression of PvCRN20 counteracted this promotion by VvDEG5. Therefore, DEG5 is essential for the virulence function of PvCRN20. Although PvCRN20 is located in both the nucleus and cytoplasm, only cytoplasmic PvCRN20 suppresses plant immunity and promotes pathogen infection.Our results reveal that PvCRN20 dampens plant defenses by repressing the chloroplast import of DEG5, thus reducing host ROS accumulation and facilitating pathogen colonization. [ABSTRACT FROM AUTHOR]

Summary: Coral thermal bleaching resilience can be improved by enhancing photosymbiont thermal tolerance via experimental evolution. While successful for some strains, selection under stable temperatures was ineffective at increasing the thermal threshold of an already thermo‐tolerant photosymbiont (Durusdinium trenchii). Corals from environments with fluctuating temperatures tend to have comparatively high heat tolerance. Therefore, we investigated whether exposure to temperature oscillations can raise the upper thermal limit of D. trenchii.We exposed a D. trenchii strain to stable and fluctuating temperature profiles, which varied in oscillation frequency. After 2.1 yr (54–73 generations), we characterised the adaptive responses under the various experimental evolution treatments by constructing thermal performance curves of growth from 21 to 31°C for the heat‐evolved and wild‐type lineages. Additionally, the accumulation of extracellular reactive oxygen species, photophysiology, photosynthesis and respiration rates were assessed under increasing temperatures.Of the fluctuating temperature profiles investigated, selection under the most frequent oscillations (diurnal) induced the greatest widening of D. trenchii's thermal niche. Continuous selection under elevated temperatures induced the only increase in thermal optimum and a degree of generalism.Our findings demonstrate how differing levels of thermal homogeneity during selection drive unique adaptive responses to heat in a coral photosymbiont. [ABSTRACT FROM AUTHOR]

Comprehensive Summary: Redox nanozymes offer an appealing reactive oxygen species (ROS)‐based antibacterial strategy via disrupting intracellular homeostasis, however, they still face many obstacles such as low enzymic activity and irreversible loss of catalytic active center. Meanwhile, the antioxidant glutathione (GSH) overexpressed in infected sites would limit the therapy efficiency. Herein, we develop a multifunctional nanozyme based on copper(I) (Cu+) ion doped MoO3–x (Cu+‐MoO3–x) by a simple yet efficient oxygen vacancy‐reduced strategy without any pretreatment or additional agents. The resultant Cu+‐MoO3–x hybrid possesses enhanced peroxidase‐like (POD‐like) activity, rapid GSH‐depleting function and biodegradable ability. It can achieve highly efficient elimination of Pseudomonas aeruginosa (P. aeruginosa) via disrupting cellular redox balance. More intriguingly, GSH‐depleting redox reaction between Cu+‐MoO3–x and GSH could translate Mo6+ into Mo5+, thereby leading to partial recovery of POD‐like activity of Cu+‐MoO3–x hybrid for continuous ∙OH generation. In vitro and in vivo experiments demonstrated that Cu+‐MoO3–x hybrid had stronger antibacterial property compared to MoO3–x by rapid GSH consumption and plentiful ∙OH generation without providing extra H2O2, as well as neglective toxicity to healthy organs. In view of its remarkable enzymic activity and good biosafety, the developed Cu+‐MoO3–x redox nanozyme can be used as a promising antimicrobial for P. aeruginosa infection. [ABSTRACT FROM AUTHOR]

Background and Purpose: Fibromyalgia is a complex clinical disorder with an unknown aetiology, characterized by generalized pain and co‐morbid symptoms such as anxiety and depression. An imbalance of oxidants and antioxidants is proposed to play a pivotal role in the pathogenesis of fibromyalgia symptoms. However, the precise mechanisms by which oxidative stress contributes to fibromyalgia‐induced pain remain unclear. The transient receptor potential ankyrin 1 (TRPA1) channel, known as both a pain sensor and an oxidative stress sensor, has been implicated in various painful conditions. Experimental Approach: The feed‐forward mechanism that implicates reactive oxygen species (ROS) driven by TRPA1 was investigated in a reserpine‐induced fibromyalgia model in C57BL/6J mice employing pharmacological interventions and genetic approaches. Key Results: Reserpine‐treated mice developed pain‐like behaviours (mechanical/cold hypersensitivity) and early anxiety‐depressive‐like disorders, accompanied by increased levels of oxidative stress markers in the sciatic nerve tissues. These effects were not observed upon pharmacological blockade or global genetic deletion of the TRPA1 channel and macrophage depletion. Furthermore, we demonstrated that selective silencing of TRPA1 in Schwann cells reduced reserpine‐induced neuroinflammation (NADPH oxidase 1‐dependent ROS generation and macrophage increase in the sciatic nerve) and attenuated fibromyalgia‐like behaviours. Conclusion and Implications: Activated Schwann cells expressing TRPA1 promote an intracellular pathway culminating in the release of ROS and recruitment of macrophages in the mouse sciatic nerve. These cellular and molecular events sustain mechanical and cold hypersensitivity in the reserpine‐evoked fibromyalgia model. Targeting TRPA1 channels on Schwann cells could offer a novel therapeutic approach for managing fibromyalgia‐related behaviours. [ABSTRACT FROM AUTHOR]

Dielectric barrier discharge (DBD) plasma regulates the levels of reactive oxygen species (ROS), which are critical for sperm quality. MicroRNAs (miRNAs) are non-coding single-stranded RNA molecules encoded by endogenous genes, which regulate post-transcriptional gene expression in animals. At present, it is unknown whether DBD plasma can regulate sperm ROS levels through miRNAs. To further understand the regulatory mechanism of DBD plasma on sperm ROS levels, miRNAs in fresh boar spermatozoa were detected using Illumina deep sequencing technology. We found that 25 known miRNAs and 50 novel miRNAs were significantly upregulated, and 14 known miRNAs and 74 novel miRNAs were significantly downregulated in DBD plasma-treated spermatozoa. Gene Ontology (GO) and Kyoto Encyclopedia of Genes and Genomes (KEGG) analysis showed that target genes of differentially expressed miRNAs were involved in many activities and pathways associated with antioxidants. We verified that DBD plasma significantly increased boar sperm quality and reduced ROS levels. These results suggest that DBD plasma can improve sperm quality by regulating ROS levels via miRNAs. Our findings provide a potential strategy to improve sperm quality through miRNA-targeted regulation of ROS, which helps to increase male reproduction and protect cryopreserved semen in clinical practice. • DBD plasma improves boar sperm quality by regulating ROS levels. • DBD plasma affects sperm ROS levels via differentially expressed miRNAs. • DBD plasma regulates sperm ROS levels via miRNA-targeted antioxidant enzyme genes. • DBD plasma regulates sperm ROS levels via miRNAs targeting the KEAP1/NRF2 pathway. [ABSTRACT FROM AUTHOR]

Objectives of the present study were to investigate the characteristics including glucose-6-phosphate dehydrogenase activity, as determined by Brilliant Cresyl Blue (BCB) staining, of suboptimal porcine oocytes and to enhance the meiotic competence of those through pre-culture with cumulus cell masses (CCMs). Percentage of oocyte-cumulus complexes (OCCs) derived from small follicles (SF; <3 mm in diameter) containing the oocytes that were assessed as BCB-negative (BCB-) was significantly higher than those derived from medium follicles (MF; 3–6 mm in diameter). Degrees of dead cumulus cells were significantly higher in OCCs containing BCB- oocytes, regardless of the origin of OCCs (MF vs. SF), than those containing BCB-positive (BCB+) ones. Exposing OCCs containing BCB+ oocytes to the apoptosis inducer, carbonyl cyanide m-chlorophenylhydrazone, for 20 h significantly induced the transition to BCB- and meiotic progression of exposed OCCs were significantly reduced in both SF and MF derived ones. Transit of BCB- oocytes to BCB+ was induced when OCCs were pre-cultured with CCMs of MF derived OCCs containing BCB+ oocytes for 20 h before IVM. This pre-culture also significantly increased the meiotic competence of BCB- oocytes, particularly in SF derived ones. However, reactive oxygen species levels were significantly higher in BCB+ oocytes as compared with BCB- ones, regardless of pre-culture with CCMs, whereas no significant differences were found in the ATP contents among the treatment groups. In conclusion, the BCB result of oocytes could be regulated by the healthy status and content of surrounding cumulus cells and the meiotic competence of suboptimal BCB- porcine oocytes is improved by pre-culture with healthy CCMs. • BCB assessment is effective to select SF-derived porcine oocytes with relatively high meiotic competence in vitro. • The incidence of BCB- oocytes increases when apoptosis of the oocyte-cumulus complexes is induced by CCCP. • Preculture of SF-derived BCB- oocytes results in the conversion of those to BCB+ and enhances their meiotic competence. [ABSTRACT FROM AUTHOR]

[Display omitted] Exploring highly efficient ultrasound-triggered catalysts is pivotal for various areas. Herein, we presented that Ba2+ doped brookite TiO 2 nanorod (TiO 2 : Ba) with polarization-induced charge separation is a candidate. The replacement of Ba2+ for Ti4+ not only induced significant lattice distortion to induce polarization but also created oxygen vacancy defects for facilitating the charge separation, leading to high-efficiency reactive oxygen species (ROS) evolution in the piezo-catalytic processes. Furthermore, the piezocatalytic ability to degrade dye wastewater demonstrates a rate constant of 0.172 min-1 and achieves a 100 % antibacterial rate at a low dose for eliminating E. coli. This study advances that doping can induce piezoelectricity and reveals that lattice distortion-induced polarization and vacancy defects engineering can improve ROS production, which might impact applications such as water disinfection and sonodynamic therapy. [ABSTRACT FROM AUTHOR]

[Display omitted] The clinical translation of photosensitizers based on ruthenium(II) polypyridyl complexes (RPCs) in photodynamic therapy of cancer faces several challenges. To address these limitations, we conducted an investigation to assess the potential of a cubosome formulation stabilized in water against coalescence utilizing a polyphosphoester analog of Pluronic F127 as a stabilizer and loaded with newly synthesized RPC-based photosensitizer [Ru(dppn) 2 (bpy-morph)](PF 6) 2 (bpy-morph = 2,2′-bipyridine-4,4′-diylbis(morpholinomethanone)), PS-Ru. The photophysical characterization of PS-Ru revealed its robust capacity to induce the formation of singlet oxygen (1O 2). Furthermore, the physicochemical analysis of the PS-Ru-loaded cubosomes dispersion demonstrated that the encapsulation of the photosensitizer within the nanoparticles did not disrupt the three-dimensional arrangement of the lipid bilayer. The biological tests showed that PS-Ru-loaded cubosomes exhibited significant phototoxic activity when exposed to the light source, in stark contrast to empty cubosomes and to the same formulation without irradiation. This promising outcome suggests the potential of the formulation in overcoming the drawbacks associated with the clinical use of RPCs in photodynamic therapy for anticancer treatments. [ABSTRACT FROM AUTHOR]

[Display omitted] Nanomedicines that combine reactive oxygen species (ROS)-responsive polyprodrug and photodynamic therapy have shown great potential for improving treatment efficacy. However, the consumption of ROS by overexpressed glutathione in tumor cells is a major obstacle for achieving effective ROS amplification and prodrug activation. Herein, we report a polyprodrug-based nanoparticle that can realize ROS amplification and cascaded drug release. The nanoparticle can respond to the high level of hydrogen peroxide in tumor microenvironment, achieving self-destruction and release of quinone methide. The quinone methide depletes intracellular glutathione and thus decreases the antioxidant capacity of cancer cells. Under laser irradiation, a large amount of ROS will be generated to induce cell damage and prodrug activation. Therefore, the glutathione-depleting polyprodrug nanoparticles can efficiently inhibit tumor growth by enhanced photodynamic therapy and cascaded locoregional chemotherapy. [ABSTRACT FROM AUTHOR]

[Display omitted] Carbon dots (CDs) are carbon nano materials (CNMs) that find use across several biological applications because of their water solubility, biocompatible nature, eco-friendliness, and ease of synthesis. Additionally, their physiochemical properties can be chemically tuned for further optimization towards specific applications. Here, we investigate the efficacy of C70-derived Graphene Acid Quantum Dots (GAQDs) in mitigating the transformation of soluble, monomeric Hen Egg-White Lysozyme (HEWL) to mature fibrils during its amyloidogenic trajectory. Our findings reveal that GAQDs exhibit dose-dependent inhibition of HEWL fibril formation (up to 70 % at 5 mg/mL) without affecting mitochondrial membrane potential or inducing apoptosis at the same density. Furthermore, GAQDs scavenged reactive oxygen species (ROS); achieving a 50 % reduction in ROS levels at a mere 100 µg/mL when exposed to a standard free radical generator. GAQDs were not only found to be biocompatible with a human neuroblastoma-derived SHSY-5Y cell line but also rescued the cells from rotenone-induced apoptosis. The GAQD-tolerance of SHSY-5Y cells coupled with their ability to restitute cells from rotenone-dependent apoptosis, when taken in conjunction with the biocompatibility data, indicate that GAQDs possess neuroprotective potential. The data position this class of CNMs as promising candidates for resolving aberrant cellular outputs that associate with the advent and progress of multifactorial neurodegenerative disorders including Parkinson's (PD) and Alzheimer's diseases (AD) wherein environmental causes are implicated (95 % etiology). The data suggest that GAQDs are a multifunctional carbon-based sustainable nano-platform at the intersection of nanotechnology and neuroprotection for advancing green chemistry-derived, sustainable healthcare solutions. [ABSTRACT FROM AUTHOR]

[Display omitted] Ce-based three-dimensional (3D) mesoporous microspheres with Mn homogeneous incorporation were synthesized. The CeMn-0.4, characterized by a Ce/Mn molar ratio of 6:4, demonstrated exceptional catalytic activity and stability. The formation of CeMn solid solution strengthened the Ce-Mn interaction, yielding higher concentrations of Ce3+ and Mn4+. Mn4+ initiated toluene preliminary activation owing to its robust oxidative properties, while Ce3+ contributed to oxygen vacancy generation, enhancing the activation of gaseous oxygen and lattice oxygen mobility. Integrating experiments and Density Functional Theory (DFT) calculations elucidated the oxygen reaction mechanisms. A portion of oxygen was converted into surface reactive oxygen species (O ads) that directly oxidized toluene. Additionally, the presence of oxygen vacancies promoted the participation of oxygen in toluene oxidation by converting it into lattice oxygen, which was crucial for the deep oxidation of toluene. Diffuse Reflectance Fourier Transform Infrared Spectroscopy (DRIFTS) indicated the accumulation of benzene-ring intermediates on the catalyst surface hindered continuous toluene oxidation. Thus, the abundant oxygen vacancies in CeMn-0.4 played a pivotal role in sustaining the oxidation process by bolstering the activation of gaseous oxygen and the mobility of lattice oxygen. [ABSTRACT FROM AUTHOR]

[Display omitted] Whilst the development of advanced organic dots with aggregation-induced emission characteristics (AIE-dots) is being intensively studied, their clinical translation in efficient biotherapeutic devices has yet to be tackled. This study explores the synergistic interplay of oligo(styryl)benzenes (OSBs), potent fluorogens with an increased emission in the aggregate state, and Indocyanine green (ICG) as dual Near Infrared (NIR)-visible fluorescent nanovesicles with efficient reactive oxygen species (ROS) generation capacity for cancer treatment using photodynamic therapy (PDT). The co-loading of OSBs and ICG in different nanovesicles has been thoroughly investigated. The nanovesicles' physicochemical properties were manipulated via molecular engineering by modifying the structural properties of the lipid bilayer and the number of oligo(ethyleneoxide) chains in the OSB structure. Diffusion Ordered Spectroscopy (DOSY) NMR and spectrofluorometric studies revealed key differences in the structure of the vesicles and the arrangement of the OSB and ICG in the bilayer. The in vitro assessment of these OSB-ICG nanovesicles revealed that the formulations can increase the temperature and generate ROS after photoirradiation, showing for the first time their potential as dual photothermal/photodynamic (PTT/PDT) agents in the treatment of prostate cancer. Our study provides an exciting opportunity to extend the range of applications of OSB derivates to potentiate the toxicity of phototherapy in prostate and other types of cancer. [ABSTRACT FROM AUTHOR]

[Display omitted] • Control of ROS types and ratios based on catalyst structure and component modulation. • Selective degradation of pollutants according to the ratio of different ROSs in the system. • Abundant large pores and open channels are created by confined expansion pore-making strategy. • Possible degradation pathways were proposed by DFT calculations and LC-MS. Selective removal of target organic pollutants in complex water quality of municipal sewage is extremely important for the deep treatment of water quality. Here, energetic MOF and Fe-MOF are doped in electrostatic spinning process to adjust the structure and composition of the catalysts, active oxygen species (ROSs), realizing the selective removal of organic pollutants. Non-azo and azo pollutants are selected as target pollutants. Catalysts PCFe-8 with Fe nanoclusters, EPCFe-8 with Fe-N x , and EPC-8 without Fe doping are used to activate peroxymonosulfate (PMS) for degrading pollutants. The results show that the PCFe-8/PMS system can produce the most SO 4 − and exhibit superior removal of azo pollutants, whereas the degradation behavior of non-azo pollutants is more inclined to occur in the EPCFe-8/PMS system and the EPC-8/PMS system. This work provides a reference for elucidating the relationship between catalyst structure and components, types of ROSs, and selective degradation of pollutants. [ABSTRACT FROM AUTHOR]

The agricultural growth of the nation resulted in the elevated amount of agricultural toxic contaminants in water. It is a promising technique for the degradation of agricultural pollutants. Photocatalysis is termed the utilization of light energy as an inexhaustible and green energy source for degrading organic pollutants through reactive oxygen species generation. The agricultural pollutants mainly comprise pesticides, herbicides, and certain veterinary contaminants. This paper aims to discuss the prevalence of various photocatalytic agents in the degradation process of agricultural pollutants in water. Considering this, the present review has attempted to look back at the existing research based on applying chemical agents as photocatalysts to treat contaminated water systems. Literature that falls within the period from 2018 to 2023 is chosen, and the effects of various photocatalytic agents on agricultural pollutants have been explored. The categorization of the existing literature is highly relevant for future research that aims to recognize the role of photocatalytic agents and their contribution toward the purification of water systems and the eradication of agricultural pollutants. It also highlights the challenges and benefits of incorporating photocatalytic agents for the degradation process of agricultural pollutants. [ABSTRACT FROM AUTHOR]

Enzyme-mimicking nanomaterials (nanozymes) with antioxidant activity are at the forefront of research efforts towards biomedical and industrial applications. The selection of enzymatically active substances and their incorporation into novel inorganic nanozyme structures is critically important for this field of research. To this end, the fabrication of composites can be desirable as these can either exhibit multiple enzyme-like activities in a single material or show increased activity compared to the nanozyme components. Conversely, by modifying the structure of a nanomaterial, enzyme-like activities can be induced in formerly inert particles. We identify herein the three main routes of composite nanozyme synthesis, namely, surface functionalization of a particle with another compound, heteroaggregation of individual nanozymes, and modification of the bulk nanozyme structure to achieve optimal antioxidant activity. We discuss in particular the different inorganic support materials used in the synthesis of nanozyme architectures and the advantages brought forth by the use of composites. [ABSTRACT FROM AUTHOR]

Novel porphyrin(2.1.2.1) Pd(II) complexes with various aromatic π rings (benzo, naphthalene and thiophene) embedded between dipyrrin units have been synthesized. Their molecular structures and optical and electronic properties were confirmed and fully investigated. These Pd(II) complexes showed moderate to good capacity of singlet oxygen generation under light irradiation. [ABSTRACT FROM AUTHOR]

Singlet oxygen production and its reactivity have significant implications in fields ranging from polymer science to photodynamic therapy. Extensive research has focused on the development of organic-based materials and heavy metal complexes, including Ru(II), Rh(III), Ir(III) and Pt(II). However, metal complexes containing Au(I) have been scarcely explored and warrant further investigation. This review provides a comprehensive analysis of reported compounds, classified based on the ligands coordinated to the gold(I) centre. Additionally, future directions in photosensitizer development and singlet oxygen applications are discussed. [ABSTRACT FROM AUTHOR]