Reactive Production Research Articles

Oxidative degradation of sulfamethazine by manganese oxide supported biochar activated periodate: Effect and mechanism.

In this study, manganese oxide supported biochar (MBC) was used as a catalyst of periodate (PI) for the oxidative degradation of sulfonamide antibiotic sulfamethazine (SMZ). The degradation rate of 10 mg/L SMZ reached 99 % in 60 min in the MBC/PI system, and the optimal condition was pH 3.5, 0.12 g/L of MBC, and 0.17 mM of PI. Combined with quenching experiment and electron paramagnetic resonance (EPR) characterization, it was determined that the reactive oxygen species (ROS) participating in the reaction include iodate radical (IO3∙), singlet oxygen (1O2), and hydroxyl radical (∙OH). ROS, Mn(III) and electron transfer are three crucial SMZ removal mechanisms in MBC activated PI system, and the conversion process of reactive species was deduced. The manganese redox cycles, oxygen-containing functional groups on MBC surface, and BC-O-Mn(II) complex participated in reactive species production. The loading of manganese oxide increases the number of oxygen-containing functional group on the surface of BC, and BC-O-Mn(II) complex formation resulted in the higher catalytic activity compared with BC. Ten SMZ oxidative products and four transformation pathways was identified. This study provided an efficient and practical method to remove sulfonamide antibiotics and revealed its theoretical mechanism.

Rhaponticin Alleviates Collagen-induced Arthritis by Inhibiting NLRP3/GSDMD-mediated Neutrophil Extracellular Traps.

Neutrophil extracellular traps (NETs) play an important role in the inflammatory response and progressive joint destruction in rheumatoid arthritis (RA). Rhaponticin (Rha) is a stilbene glycoside compound with antioxidant and anti-inflammatory effects. This study aimed to investigate the therapeutic potential of Rha in RA, with a specific focus on its effects on NETs and on the underlying mechanisms of Rha. NETs formation induced by phorbol 12-myristate 13-acetate (PMA) and a collagen-induced arthritis (CIA) mouse model were implemented to evaluate the pharmacological effects of Rha in vitro and in vivo. The potential mechanism of Rha in improving RA was screened and verified using the SuperPred and DisGeNET databases. Disulfiram (a GSDMD inhibitor) and S100a8cre GSDMDfl/fl mice were used to confirm whether GSDMD is key to the role of Rha.The findings demonstrate that Rha significantly inhibited reactive oxygen species and NETs production in PMA-activated neutrophils. In vivo, Rha treatment significantly relieved joint symptoms in CIA mice and NETs production. Mechanistically, Rha reduced NETs production via inhibition of NLRP3/GSDMD activation. Neutrophil-specific GSDMD depletion eliminated the effects of Rha on NETs production in vitro. Disulfiram eliminated the effects of Rha on the inhibition of NETs production and alleviated joint inflammation in mice in vivo and in vitro. Overall, our results indicated that Rha exerts a protective effect against CIA by inhibiting NETs production through the NLRP3/GSDMD pathway. The results of this study provide new strategies for treating RA.

Unveiling the Phosphine-Mediated N-Transfer from Azide to Isocyanide en Route to Carbodiimides and 4-Imino-1,3,2-diazaphosphetidines.

Intramolecular reactions between isocyano and iminophosphorane functions yield species containing an embedded 1,3,2-diazaphosphetidine ring, as result of the [2 + 2] cycloaddition of the primary reactive product, the cyclic carbodiimide, with a second unit of reactant. DFT studies reveal a first rate-determining step entailing a [2 + 1] cycloaddition involving the isocyanide carbon atom and the P═N double bond, with the further intervention of a dipolar precursor of the intermediate carbodiimide. The 1,3,2-diazaphosphetidine ring of the final products is shown to be hydrolytically and thermally labile.

The Antioxidant and Anti-Inflammatory Activities of the Methanolic Extract, Fractions, and Isolated Compounds from Eriosema montanum Baker f. (Fabaceae).

Background: Inflammation is a natural body's defense mechanism against harmful stimuli such as pathogens, chemicals, or irradiation. But when the inflammatory response becomes permanent, it can lead to serious health problems. In the present study, the antioxidant and anti-inflammatory potentials of the Eriosema montanum methanolic extract (EMME), as well as its isolated fractions (FA-FJ) and compounds (1-7), were evaluated by using in vitro and cellular models. Methods: The total phenolic and flavonoid contents were determined using, respectively, Folin-Ciocalteu and aluminum chloride colorimetric methods, while 2,2'-azinobis-(3-ethylbenzothiazoline-6-sulfonic acid (ABTS), 2,2'-diphenyl-1-picrylhy-drazyl (DPPH), and ferric ion reducing antioxidant power (FRAP) were used to determine the antioxidant activity. Thin Layer Chromatography (TLC) and column chromatography (CC) were used to isolate and purify the compounds and their elucidation using their NMR spectroscopic data. Results:EMME had moderate antioxidant and anti-inflammatory activities, while fraction FF showed much higher efficacy with IC50 values of 34.64, 30.60, 16.43, and 77.29 μg/mL against DPPH, ABTS, NO, and 15-LOX inhibitory activities, respectively. The EMME fraction was found to be very rich in flavonoids and phenolic compounds, with 82.11 mgQE/g and 86.77 mgGAE/g of dry extract, respectively. Its LC-MS profiling allowed us to identify genistin (5) as the most concentrated constituent in this plant species, which was further isolated together with six other known compounds, namely, n-hexadecane (1), heptacosanoic acid (2), tricosan-1-ol (3), lupinalbin A (4), d-pinitol (6), and stigmasterol glucoside (7). Given these compounds, genistin (5) showed moderate activity against reactive oxygen species (ROS) and NO production in LPS-stimulated RAW264.7 cells compared to EMME, which suggested a synergy of (5) with other compounds. To the best of our knowledge, compounds (1), (2), and (3) were isolated for the first time from this plant species.

Antifungal activity of dimethyl trisulfide and potential biocontrol against Alternaria alternata on postharvest Lycium barbarum

Abstract Lycium barbarum, is a medicine-food homology plant, so sustainable control of the postharvest Goji berry black mold caused by Alternaria alternata is particularly critical. In this paper, the impact of dimethyl trisulfide (DMTS) on A. alternata was studied, as well as the effects of DMTS on hypha ultrastructure, membrane permeability, reactive oxygen production, and essential enzymes of the cellular defense system. DMTS was shown to significantly inhibit the spore germination and hyphal growth of A. alternata in a concentration-dependent manner. The results of scanning electron microscopy (SEM) and transmission electron microscopy (TEM) showed that A. alternata cells were separated between cytoplasm and cell wall, organelles such as mitochondria were vacuolate or even disappeared, and the cytoplasm was fused. PI staining, conductivity measurements, and intracellular nucleic acid and protein content measurements showed that the permeability of the cell membrane changed after DTMS treatment, leading to the leakage of intracellular nucleic acid and protein. DMTS could also cause the accumulation of hydrogen peroxide (H2O2) and malondialdehyde (MDA), thus causing membrane oxidative damage. Through directly destroying the fungal cell and indirectly inducing membrane damage, DMTS can control the postharvest Goji berry black mold, and is a potential application prospect in the control of postharvest diseases.

Anthocyanin stability and antioxidant capacity of Clitoria ternatea incorporated jelly

Antioxidants from natural sources from Clitoria ternatea (butterfly blue pea flower) have recently received great attention as an increase in oxidative stress disease is concerning. One of the most useful bioactive compounds from C. ternatea extract is anthocyanin, which is generally unstable due to various factors. Therefore, the extraction process needs to be optimized with a condition that favours the stability of anthocyanin. The effect of sugar as a preservative on the anthocyanin stability and antioxidant capacity of C. ternatea has been studied on anthocyanin-rich jelly formulated in two different conditions using dried butterfly blue pea flowers. The extract (E), jelly with sugar (JWS), and jelly without sugar (JWOS) were analyzed for their anthocyanin stability and antioxidant capacity for 11 weeks at two storage temperatures (25°C and 4°C). Total anthocyanin content was determined by the pH differential method, while antioxidant capacity was determined by a common 2,2-diphenyl-1-picrylhydrazyl (DPPH) assay. After two weeks of storage, the total anthocyanin content in the extract and jelly samples decreased over time, with no major difference between the samples in temperature and the presence of sugar. However, the extract alone possessed a higher and better stability of anthocyanin content (56.27 µg/ mL to 7.19 µg/mL) after 14 days of storage at both temperatures (25°C and 4°C) compared to the processed food. It might be due to the processing effect on jelly samples during the analysis that might influence the final anthocyanin content (TAC). On the other hand, jelly incorporated with anthocyanin gives a significantly higher and more stable free radical scavenging activity than the extract, with no remarkable difference between jelly with sugar and without sugar at a different temperature. In addition, anthocyanin pigments from extract and jelly samples steadily degrade during storage at 25°C after 35 days of storage, which dramatically impacts colour quality and may also affect its nutritional properties. In conclusion, their food preparation (in extract or processed form) and storage temperature highly affected anthocyanin stability and its antioxidant capacity. 1. Introduction The current lifestyle of commonly consuming processed foods, lack of exercise, and exposure to a wide range of toxins may lead to a condition defined as oxidative stress. It is marked by an imbalance in the formation and buildup of reactive oxygen species (ROS) in cells and tissues, with the biological system's inability to detoxify these reactive products that worsen the situation (Sharifi-Rad et al., 2020). From another point of view, modernization also brings a new chapter to technological and scientific innovation, which help

Impact of sub-basalt thrust systems on the Faroe continental shelf for the late Paleoproterozoic–Cenozoic tectonic evolution of the margin.

Background The Faroe margin in the northeastern Atlantic is segmented by margin-orthogonal, WNW–ESE-striking lineaments extending several hundred kilometers out to the continent–ocean transition. Despite several earlier studies speculating that these features are the product of reactivation of pre-Cenozoic basement-seated structures at depth, the thick Cenozoic volcano-sedimentary sequences deposited along the margin mask the underburden, thus rendering the identification and interpretation of such structures and resolving the pre-Cenozoic history of the area challenging. The present study documents for the first time the existence of margin-orthogonal basement-seated thrust systems and describes their detailed geometry, kinematics, and tectonic evolution. Methods We interpreted basement-seated tectonic structures on seismic reflection data from TGS on the Faroe Platform and the Wyville–Thomson and Munkagrunnur ridges using the newly established seismic facies of major thrust systems. Results The data show that the Wyville–Thomson Ridge, Munkagrunnur Ridge, and Faroe Platform are cored by WNW–ESE-striking thrust systems hundreds of kilometers long and 30–50 km wide, showing dominantly top-SSW kinematics. The thrusts were reworked into NE–SW-striking folds during the Caledonian Orogeny and controlled the formation of Caledonian thrusts, which in turn controlled the formation of post-Caledonian faults. The pre-Caledonian nature of the WNW–ESE-striking thrusts and their geometry and kinematics suggest a relationship with late Paleoproterozoic Laxfordian shear zones onshore northern Scotland and the continuation of the coeval Nagssugtoqidian Orogen in southeastern Greenland, the Ammassalik Belt. The thrust systems also align with the Tornquist Zone in eastern Europe and the North Sea, thus suggesting either that they controlled the formation of the Tornquist Zone or a possibly much longer (Paleoproterozoic?) tectonic history for the Tornquist Zone. Conclusions The Faroe Island margin is crosscut by late Paleoproterozoic Laxfordian–Nagssugtoqidian thrust systems, which controlled further tectonic development of the margin.

Liang-Ge-San Decoction Ameliorates Acute Respiratory Distress Syndrome via Suppressing p38MAPK-NF-κ B Signaling Pathway.

To explore the potential effects and mechanisms of Liang-Ge-San (LGS) for the treatment of acute respiratory distress syndrome (ARDS) through network pharmacology analysis and to verify LGS activity through biological experiments. The key ingredients of LGS and related targets were obtained from the Traditional Chinese Medicine Systems Pharmacology Database and Analysis Platform. ARDS-related targets were selected from GeneCards and DisGeNET databases. Gene Ontology and Kyoto Encyclopedia of Genes and Genomes enrichment analyses were performed using the Metascape Database. Molecular docking analysis was used to confirm the binding affinity of the core compounds with key therapeutic targets. Finally, the effects of LGS on key signaling pathways and biological processes were determined by in vitro and in vivo experiments. A total of LGS-related targets and 496 ARDS-related targets were obtained from the databases. Network pharmacological analysis suggested that LGS could treat ARDS based on the following information: LGS ingredients luteolin, wogonin, and baicalein may be potential candidate agents. Mitogen-activated protein kinase 14 (MAPK14), recombinant V-Rel reticuloendotheliosis viral oncogene homolog A (RELA), and tumor necrosis factor alpha (TNF-α) may be potential therapeutic targets. Reactive oxygen species metabolic process and the apoptotic signaling pathway were the main biological processes. The p38MAPK/NF-κ B signaling pathway might be the key signaling pathway activated by LGS against ARDS. Moreover, molecular docking demonstrated that luteolin, wogonin, and baicalein had a good binding affinity with MAPK14, RELA, and TNF α. In vitro experiments, LGS inhibited the expression and entry of p38 and p65 into the nucleation in human bronchial epithelial cells (HBE) cells induced by LPS, inhibited the inflammatory response and oxidative stress response, and inhibited HBE cell apoptosis (P<0.05 or P<0.01). In vivo experiments, LGS improved lung injury caused by ligation and puncture, reduced inflammatory responses, and inhibited the activation of p38MAPK and p65 (P<0.05 or P<0.01). LGS could reduce reactive oxygen species and inflammatory cytokine production by inhibiting p38MAPK/NF-κ B signaling pathway, thus reducing apoptosis and attenuating ARDS.

Cytotoxic Effects of ZnO and Ag Nanoparticles Synthesized in Microalgae Extracts on PC12 Cells.

The green synthesis of silver (Ag) and zinc oxide (ZnO) nanoparticles (NPs), as well as Ag/Ag2O/ZnO nanocomposites (NCs), using polar and apolar extracts of Chlorella vulgaris, offers a sustainable method for producing nanomaterials with tunable properties. The impact of the synthesis environment and the nanomaterials' characteristics on cytotoxicity was evaluated by examining reactive species production and their effects on mitochondrial bioenergetic functions. Cytotoxicity assays on PC12 cells, a cell line originated from a rat pheochromocytoma, an adrenal medulla tumor, demonstrated that Ag/Ag2O NPs synthesized with apolar (Ag/Ag2O NPs A) and polar (Ag/Ag2O NPs P) extracts exhibited significant cytotoxic effects, primarily driven by Ag+ ion release and the disruption of mitochondrial function. However, it is more likely the organic content, rather than size, influenced anticancer activity, as commercial Ag NPs, despite smaller crystallite sizes, exhibit less effective activity. ZnO NPs P showed increased reactive oxygen species (ROS) generation, correlated with higher cytotoxicity, while ZnO NPs A produced lower ROS levels, resulting in diminished cytotoxic effects. A comparative analysis revealed significant differences in LD50 values and toxicity profiles. Differentiated PC12 cells showed higher resistance to ZnO, while AgNPs and Ag/Ag2O-based materials had similar effects on both cell types. This study emphasizes the crucial role of the synthesis environment and bioactive compounds from C. vulgaris in modulating nanoparticle surface chemistry, ROS generation, and cytotoxicity. The results provide valuable insights for designing safer and more effective nanomaterials for biomedical applications, especially for targeting tumor-like cells, by exploring the relationships between nanoparticle size, polarity, capping agents, and nanocomposite structures.

Metformin Modulates Cell Oxidative Stress to Mitigate Corticosteroid-Induced Suppression of Osteogenesis in a 3D Model.

Corticosteroids provide well-established therapeutic benefits; however, they are also accompanied by adverse effects on bone. Metformin is a widely used medication for managing type 2 diabetes mellitus. Recent studies have highlighted additional therapeutic benefits of metformin, particularly concerning bone health and oxidative stress. This research investigates the effects of prednisolone on cellular metabolic functions and bone formation using a 3D in vitro model. Then, we demonstrate the potential therapeutic effects of metformin on oxidative stress and the formation of calcified matrix due to corticosteroids. Human mesenchymal stem cells (MSCs) and macrophages were cultured in a 3D GelMA scaffold and stimulated with prednisolone, with and without metformin. The adverse effects of prednisolone and metformin's therapeutic effect(s) were assessed by analyzing cell viability, osteogenesis markers, bone mineralization, and inflammatory markers. Oxidative stress was measured by evaluating reactive oxygen species (ROS) levels and ATP production. Prednisolone exhibited cytotoxic effects, reducing the viability of MSCs and macrophages. Lower osteogenesis potential was also detected in the MSC group. Metformin positively affected cell functions, including enhanced osteoblast activity and increased bone mineralization. Furthermore, metformin effectively reduced oxidative stress, as evidenced by decreased ROS levels and increased ATP production. These findings indicate that metformin protects against oxidative damage, thus supporting osteogenesis. Metformin exhibits promising therapeutic potential beyond its role in diabetes management. The capacity to alleviate oxidative stress highlights the potential of metformin in supporting bone formation in inflammatory environments.

Ferroptosis: A novel cell death modality as a synergistic therapeutic strategy with photodynamic therapy.

Although there has been significant progress in current comprehensive anticancer treatments centered on surgery, postoperative recurrence and tumor metastasis still significantly affect both prognosis and quality of life of the patient. Hence, the development of precisely targeted tumor therapies and exploration of immunotherapy represent additional strategies for tumor treatment. Photodynamic therapy (PDT) is a relatively safe treatment modality that not only induces multiple modes of tumor cell death but also mediates the secondary immunological responses against tumor resistance and metastasis. Ferroptosis, an iron-dependent type of programmed cell death characterized by accumulation of reactive oxygen species and lipid peroxidation products to lethal levels, has emerged as an attractive target trigger for tumor therapies. Recent research has revealed a close association between PDT and ferroptosis, suggesting that combining ferroptosis inducers with PDT could strengthen their synergistic anti-tumor efficiency. Here in this review, we discuss the rationale for combining PDT with ferroptosis inducers and highlight the progress of single-molecule photosensitizers to induce ferroptosis, as well as the applications of photosensitizers combined with other therapeutic drugs for collaborative therapy. Furthermore, given the current research dilemma, we propose potential therapeutic strategies to advance the combined usage of PDT and ferroptosis inducers, providing the basis and guidelines for prospective clinical translation and research directionality with regard to PDT.

Saccharomyces cerevisiae inactivation during water disinfection by underwater plasma bubbles: Preferential reactive species production and subcellular mechanisms.

The escalating challenges posed by water resource contamination, especially exacerbated by health concerns associated with microbial fungi threats, necessitate advanced disinfection technologies. Within this context, non-thermal plasma generated within bubble column reactors emerges as a promising antifungal strategy. The effects of direct plasma bubbles within different discharge modes and thus-produced plasma activated water (PAW) on the inactivation of Saccharomyces cerevisiae are investigated. Results show that plasma bubbles generated by dielectric barrier discharge (DBD) mode can effectively inactivate yeast cells (∼4.44 logs reduction) within 1 min, outperforming the spark discharge (SD). In this case, SD can cause a significant portion of cell necrosis, possibly due to the high electric field at the bubble interface. In PAW, DBD and SD produce different dominant long-lived oxygen and nitrogen species, while the crucial short-lived species in yeast apoptosis are both attributed to the singlet oxygen (1O2) as confirmed by scavenger tests. The detection of intracellular reactive oxygen species and antioxidant enzymes further illustrates the role of PAW in triggering apoptosis. Overall, this study demonstrates the discharge mode-dependent modulation of reactive species chemistry in plasma-liquid interactions and provides new insights into the subcellular mechanism of plasma-enabled yeast inactivation for water resource decontamination.

Improvement of antioxidant capability by dietary N-acetyl cysteine supplementation alleviates bone loss induced by chronic heat stress in finisher broilers

BackgroundHeat stress (HS) incidence is associated with the accumulation of reactive substances, which might be associated with bone loss. N-Acetylcysteine (NAC) exhibits strong antioxidants due to its sulfhydryl group and being as the precursor for endogenous glutathione synthesis. Therefore, interplay between oxidative stress and bone turnover of broilers and the effects of dietary NAC inclusion on antioxidant capability and “gut-bone” axis were evaluated during chronic HS.ResultsImplementing cyclic chronic HS (34 °C for 7 h/d) evoked reactive oxygen species excessive production and oxidant stress, which was accompanied by compromised tibia mass. The RNA-seq of proximal tibia also revealed the enrichment of oxidation–reduction process and inflammatory outbursts during HS. Although no notable alterations in the growth performance and cecal microbiota were found, the diet contained 2 g/kg NAC enhanced the antioxidant capability of heat-stressed broiler chickens by upregulating the expression of Nrf2 in the ileum, tibia, and bone marrow. Simultaneously, NAC tended to hinder NF-κB pathway activation and decreased the mRNA levels of the proinflammatory cytokines in both the ileum and bone marrow. As a result, NAC suppressed osteoclastogenesis and osteoclast activity, thereby increasing osteocyte-related gene expression. Furthermore, the inclusion of NAC tended to increase the ash content and density of the whole tibia, as well as improve cortical thickness and bone volume of the diaphysis.ConclusionsThese findings HS-mediated outburst of oxidant stress accelerates bone resorption and negatively regulates the bone quality of tibia, which is inhibited by NAC in broilers.Graphical abstract

Effect of Low-Frequency, Low-Energy Pulsed Electromagnetic Fields in Neuronal and Microglial Cells Injured with Amyloid-Beta.

Alzheimer's disease (AD) is a neurodegenerative pathology covering about 70% of all cases of dementia. It is associated with neuroinflammation and neuronal cell death, which are involved in disease progression. There is a lack of effective therapies, and halting this process represents a therapeutic challenge. Data in the literature suggest several neuroprotective effects of low-frequency, low-energy pulsed electromagnetic fields (PEMFs) on biological systems, and clinical studies report that PEMF stimulation is safe and well tolerated. The aim of this work is to investigate the effects of PEMF exposure on oxidative stress and cell death in in vitro-injured cellular models of neurons and microglia. SH-SY5Y cells were stimulated by hydrogen peroxide (H2O2) or amyloid-β (Aβ) peptide, and N9 microglial cells were activated with lipopolysaccharide (LPS) or Aβ peptide. Reactive oxygen production, mitochondrial integrity, and cell death modulation were investigated through 2',7'-dichlorodihydrofluorescein diacetate (H2DCFDA) and 5,5',6,6'-tetrachloro-1,1',3,3'-tetraethylbenzimidazolocarbo-cyanine iodide (JC-1) biochemical assays, fluorescence, and MTS experiments. Cells were exposed to PEMFs producing a pulsed signal with the following parameters: pulse duration of 1.3 ms and frequency of 75 Hz. The outcomes demonstrated that PEMFs defended SH-SY5Y cells against Aβ peptide- or H2O2-induced oxidative stress, mitochondrial damage, and cell death. Furthermore, in microglia activated by LPS or Aβ peptide, they reverted the reduction in mitochondrial potential, oxidative damage, and cell death. Overall, these findings imply that PEMFs influence the redox state of the cells by significantly boosting antioxidant levels in both injured microglia and neuronal in vitro cells mimicking in vitro AD.

Systematic, computational discovery of multicomponent and one-pot reactions

Discovery of new types of reactions is essential to organic chemistry because it expands the scope of accessible molecular scaffolds and can enable more economical syntheses of existing structures. In this context, the so-called multicomponent reactions, MCRs, are of particular interest because they can build complex scaffolds from multiple starting materials in just one step, without purification of intermediates. However, for over a century of active research, MCRs have been discovered rather than designed, and their number remains limited to only several hundred. This work demonstrates that computers taught the essential knowledge of reaction mechanisms and rules of physical-organic chemistry can design – completely autonomously and in large numbers – mechanistically distinct MCRs. Moreover, when supplemented by models to approximate kinetic rates, the algorithm can predict reaction yields and identify reactions that have potential for organocatalysis. These predictions are validated by experiments spanning different modes of reactivity and diverse product scaffolds.

Inhalable nanocatalytic therapeutics for viral pneumonia.

Pneumonia is a ubiquitous disease caused by viral and bacterial infections, characterized by high levels of reactive oxygen species in inflamed areas. Therapeutic strategies targeting reactive oxygen species levels in pneumonia have limited success due to the intricate nature of lung tissues and lung inflammatory responses. Here we describe an inhalable, non-invasive therapeutic platform composed of engineered cerium-based tannic acid nanozymes bound to a self-assembling peptide. In vitro and in vivo studies show that the nanozyme is internalized mostly by activated macrophages and epithelial cells in the inflamed sites. In the oxidative environments of a mouse model of viral pneumonia, nanozyme aggregates into catalytically active structures that reduce reactive oxygen species levels and inflammatory cytokine production and promote macrophage polarization to the prohealing (M2) phenotype. Moreover, the nanozyme attenuates bacterial inflammation and reduces tissue damage in a mouse viral pneumonia model with secondary bacterial infection. Overall, this nanozyme platform is a promising strategy for treating pneumonia and its associated conditions.

MLIP-DFT Combined High-Throughput Screening of Alkaline Stable Lithium Conductors

Solid-state Li-air batteries can prevent the parasitic reaction between the highly reactive discharge product Li2O2 and the organic electrolytes, which is a common challenge for the conventional dry Li-O2 battery. Using humidified air can further improve the battery performance by converting the discharge product to LiOH –– a less reactive and more reversible product. To achieve such solid-state humidified Li-air batteries, it is highly desirable to design Li ion conductors that can withstand humid and highly alkaline environment established by the highly saturated LiOH solution on the material surface.In this work, we combine the pre-trained universal machine learning interatomic potential (MLIP) –– Crystal Hamiltonian Graph neural Network (CHGNet) –– and the density functional theory (DFT) calculations to conduct a large-scale hierarchical high-throughput computational screening of Li conductors. Our screening strategy is to choose a known Li superionic conductor framework and to optimize the compositions by examining the material stabilities targeting for the real battery operating conditions. We developed specific design criteria to achieve better stability in alkaline environments.CHGNet structural relaxations are performed in the first screening stage to evaluate the energy of several hundred thousand different compositions. These candidate compositions are screened based on the various stability criteria. The structures of candidates passed the CHGNet screening (stage-1 candidates) are further relaxed with DFT to obtain energies with higher accuracy. The candidates are re-evaluated with stricter stability conditions, leading to the identification of lithium conductors characterized by both high synthesizability and robust stability against the operating conditions of humidified Li-air battery (stage-2 candidates). Our screening campaign demonstrates that owing to the recent development of universal MLIP with near-quantum accuracy, it is now possible to conduct computational evaluation of compositions with orders of magnitude larger chemical space than what conventional ab-initio high-throughput screening was capable of. Our final candidates not only include some of the known lithium superionic conductors, but also the new compositions with high alkaline stability, indicating the effectiveness of using MLIP for pre-screening purposes. Our strategy can be easily transferred to different material frameworks or other materials applications. We anticipate that with a continuous improvement of MLIPs, the scalability of in-silico material design can be significantly enhanced.

Monitoring the Species Formed at High Cathode Potentials at Ni-Rich Cathodes in Lithium-Ion Batteries Using a Novel Dual Working Electrode

The pursuit to optimize cathode active materials (CAMs) stands as a paramount endeavor within academia and industry to push for higher energy densities in lithium-ion batteries (LiBs). Predominately, aims have focused on the increase of the Nickel content of CAMs to achieve Ni-rich (> 80%) layered transition metal oxides such as NCAs (LiNixCoyAlzO2, where x+y+z=1), owing to their higher achievable capacity at given cut-off voltages. With the increase in Ni-content, however, the structural stability of these CAMs is significantly decreased at high upper cut-off potentials, resulting in capacity fading.[1] The reduced structural stability is accompanied by the release of reactive oxygen species, occurring at ~80% delithiation.[2,3] The released oxygen can trigger a cascade of follow-up reactions, such as the chemical oxidation of electrolyte solvents, conduction salt decomposition, and transition metal (TM) dissolution.[4,5] Charging to even higher voltages (> 4.7 V vs. Li+/Li at 25°C) induces the so called electrochemical oxidation of the electrolyte, which as a result of its reactive reaction products, can induce further CAM degradation.[6-8] These reactions significantly impede the lifetime of batteries, and hence require in depth understanding of their underlying mechanisms to establish improved cell chemistries which enable high voltage operation of cells. On-line electrochemical mass spectrometry (OEMS) for the detection of gas evolution, or synchrotron operando X-ray absorption spectroscopy (XAS) for the detection of TM-dissolution delivered valuable insights in the mechanistic understanding.[9] However, as these methods are very time and cost-intensive, a simplified cell design based on a dual working electrode setup was developed by our group, which enables the investigation of parasitic reactions without the use of complex auxiliary devices. In its first proof-of-concept application, it enabled the quantification of oxygen release via the measurement of reductive currents at an sense carbon electrode.[9] In the present study, we apply a three-electrode setup for the qualitative analysis of parasitic species formed when Ni-rich cathodes are charged to high cell voltages in LiBs. As in our previous study, the working electrode (WE) is based on LiNi0.80Co0.15Al0.05O2 (NCA; BASF TODA Battery Materials LLC, Japan) and the sense electrode (SE) is a carbon black based electrode (Vulcan-type carbon, XC-72, Tanaka, Japan), both coated on a stainless-steel mesh. As counter electrode (CE), a lithium iron phosphate (LFP) based electrode, delithiated to a degree of 90% and capacitively oversized was used, providing a constant CE potential (at ~3.43 V vs. Li+/Li). This setup allows us to cycle the NCA WE within a desired potential window, while holding the carbon SE at a constant voltage against the LFP CE. Hence, the SE can be used to reduce the species formed at the NCA WE, with the reduction current being a measure of their quantity. The experiments were conducted in a LP47 electrolyte (1 M LiPF6 in EC:DEC (3:7)).We apply the developed cell setup to study the formation of O2, H2O, H+, HF, and dissolved transition metal species (TMz+) while the NCA WE is charged to 5.0 V vs. Li+/Li via an intermittent CV charging protocol at temperatures of 10, 25, and 45°C by holding the sense electrode at potentials where the parasitic reactions of interest can be probed. The hereby derived reductive currents are compared to temperature dependent gassing traces determined via OEMS, as well as the TM dissolution behavior measured via operando XAS.

Electrochemically Assisted Cobalt/MXene Membrane for Effective Water Treatment: Synchronously Improving Catalytic Performance and Anti-Interference Ability.

Catalytic membrane technology for water treatment is often constrained by a trade-off between permeability and catalytic efficiency as well as interference from coexisting anions and organic matter in natural water matrices. Herein, a novel cobalt-loaded MXene (Co/MXene) 2D membrane with good hydrophilicity, electrical conductivity, and PMS activation function is constructed. The negative voltage is exerted on the membrane to significantly enhance its PMS activation efficiency and anti-interference capacity toward effective water treatment. Under -2 V, the optimal Co/MXene catalytic membrane displays 100% rhodamine b (RhB) removal within a residence time of only 1.1 s, whose RhB degradation kinetic constant (k of 6.85 s-1) is 17.6 times higher than that of the Co/MXene catalytic membrane alone and is also greatly superior to other advanced catalysts and catalytic membranes. Meanwhile, the catalytic membrane displays obvious anti-interference ability in the presence of various coexisting substances of the water matrix and performs well in treating the secondary effluent of coking wastewater. The radical-dominated (SO4•- and •OH) mechanism accompanied by the nonradical species (1O2 and Co(VI)═O) is revealed in the system, and the reactive species production is obviously enhanced under negative voltage. Experimental results and theoretical calculations jointly confirm the key role of electrochemical assistance in enhancing membrane performance, which not only facilitates cycling of Co3+/Co2+ for enhanced PMS activation via improving PMS adsorption and promoting charge transfer from Co to PMS but also hinders interference from coexisting substances in water via electrostatic repulsion.

Chemiluminescence-based evaluation of styrene block copolymers’ recyclability

The study presents the chemiluminescence based (CL) evaluation of the recyclability of linear styrene block copolymers. This analysis can provide insight into the material’s degradation state and predict its suitability for further recycling cycles, helping to avoid unnecessary energy consumption during processing.The thermal stability of four similar copolymer structures − styrene-isoprene-styrene (SIS), styrene-butadiene-styrene (SBS) copolymers with different styrene/butadiene ratios, and styrene-ethylene-butadiene-styrene (SEBS) − was studied using isothermal and non-isothermal chemiluminescence (CL). The activation energies for oxidative degradation were calculated based on oxidation induction times indicated by the CL intensities evolution. The results, which highlight the influence of molecular structure on stability under aging conditions, as presented by the calculated for the activation energy (kJ mol−1), show the following sequence: SBS (styrene 30%) (117 kJ mol−1) ≈ SIS 120 (kJ mol−1) < SBS (styrene 40%) (176 kJ mol−1) < SEBS (180 kJ mol−1). The CL data were correlated with infrared (IR) spectroscopy and differential scanning calorimetry (DSC) data, providing a comprehensive understanding of the thermal stability and degradation mechanisms during recycling proces. The sequence of the composing units determines the degradation process, with weaker points predominantly attacked in the linear moieties of isoprene, butadiene, and vinyl segments. The experimental data indicate that SIS and SBS (30% styrene) copolymers degrade the fastest likely due to the rapid accumulation of hydroperoxide radicals. The SEBS copolymer also experiences significant degradation, but this occurs at higher temperatures (above 220 ⁰C) and progresses more gradually once it begins. In contrast, the SBS copolymer with 40% styrene content degrades more slowly and exhibits minimal mass loss, primarily due to the formation of less reactive keto degradation products.