Oxidative Cyclization Research Articles

Transcriptional dynamic changes in energy metabolism, protein synthesis and cell cycle regulation reveal the biological adaptation mechanisms of juvenile Acrossocheilus wenchowensis under acute temperature changes

In recent years, frequent acute temperature changes have posed a serious threat to the physiology and survival of fish. This study utilized RNA-Seq technology to analyze the transcriptional dynamics in the muscle tissues of Acrossocheilus wenchowensis under various acute temperature conditions (16◦C, 20◦C, 24◦C, 28◦C and 32◦C). Through comprehensive analysis, we identified 11509 differentially expressed genes (DEGs), a gene set (profiles 19) that was significantly up-regulated with increasing temperature, and two weighted gene co-expression network analysis (WGCNA) modules that were significantly correlated with acute temperature changes. Furthermore, we identified 28 transcription factors that are pivotal in oxidative stress and energy metabolism under acute temperature changes. Our results showed that, compared to the control group (24°C), KEGG functional enrichment analysis revealed significant enrichment of DEGs in the cell cycle, DNA replication, and p53 signaling pathway, with an overall trend of suppressed expression. This indicates that maintaining cell stability and reducing cell damage is an effective adaptive mechanism for A. wenchowensis to cope with acute temperature changes. Through STEM analysis and the black WGCNA module associated with high-temperature stress, we identified significant up-regulation of pathways and hub genes related to energy metabolism including oxidative phosphorylation, TCA cycle, purine metabolism, and glutathione metabolism, as well as the central roles of signal transduction pathways such as MAPK signaling pathway and AMPK signaling pathway, which synergistically regulate energy production. Under acute low-temperature stress, the turquoise WGCNA module highlighted significant up-regulation of hub genes associated with Ribosomal and Spliceosomal pathways related to protein synthesis and processing, as well as activation of calcium signaling pathways, which plays an important role in maintaining cellular function during low-temperature adaptation. These findings provide a critical theoretical and molecular basis for the adaptation of eurythermal fish to rapid temperature changes.

Role of Prior Cyclic Oxidation on Tensile Deformation Behaviour of IN 713 C Alloy

Role of Prior Cyclic Oxidation on Tensile Deformation Behaviour of IN 713 C Alloy

Slurry sprayed glass-ceramic coating for boiler tubes and its high temperature performance

Industrial boilers operate in extreme environments and are prone to degradation caused by high temperature oxidation, corrosion, and erosion. Protective coatings provide boiler components with protection to prolong their operation lifetime. Thus, a glass-ceramic coating has been developed using a slurry spray technique on carbon steel AS/NZS 3678 substrates. Microstructure, mechanical characteristics, and high temperature performance of the coating were investigated. The coating composed of chemically inert oxide ceramics dispersed in a glassy silicate binder matrix. The adhesion strength of the coating was 10.79 ± 0.86 MPa. Coating mass loss after abrasion test was 0.013 % of the tested specimen. The coating withstood at least 75 air quenched thermal shock cycles from 800 °C to the room temperature without any visible spallation and cracks. The coating mostly remained undamaged after cyclic oxidation at 800 °C for 10 cycles. However, minor iron oxide formation was observed, specifically, in relatively thin sections of the coating. The oxidation resistance of the boiler steel has been improved with the developed coating. The linear oxidation rate constant of the boiler steel has been statistically reduced from 6.90 × 10−4 mg cm−2 s−1 to 1.95 × 10−4 mg cm−2 s−1 for coated steel (p = 0.007). The developed slurry spray glass-ceramic coating is a potential candidate for boiler environments.

Effect of reactive elements in MCrAlX bond coat for durability improvement of thermal barrier coatings

The effects of reactive elements (RE) in MCrAlX alloy (M: Metals, X: RE) as the bond coat for thermal barrier coatings durability were investigated by both experimental evaluation and density functional theory (DFT) calculations. Cyclic oxidation tests showed that the lifetime of the sample with Y, Hf, and Si as RE displayed approximately twice of the sample with Y only. Furthermore, the interface energies between oxide (α-Al2O3) and bond coat with various RE (Si, Sc, Ti, Y, Zr, Hf, La, and Ce) were calculated by DFT. DFT results indicate that Hf and Si doping effectively reduce the interface energy.

Magnetically Reusable Fe3O4‐CuO Nanoparticles as Catalyst for the Synthesis of Aryl‐Substituted Fluorescent Pyrazines for Fe Sensing and Ink Applications

AbstractThe synthesis of substituted pyrazines from readily available methyl aryl/heteroaryl ketones and 1,2‐diamines was achieved using highly stable and reusable ferrite‐stabilized copper nanoparticles (Fe3O4‐CuO) as a catalyst. The reaction proceeds through a cascade imine formation–oxidative cyclization method under an oxygen atmosphere. The nanocatalysts were readily recovered and reused up to three consecutive cycles without any significant decrease in particle size, catalytic activity and reaction yield, as evidenced by analytical techniques such as transmission electron microscopy (TEM) and powder X‐ray diffraction (PXRD). The synthesized pyrazines exhibited photophysical behaviour, displayed large Stokes shifts, and were explored as fluorescent probes for the sensitive as well as selective “turn‐off” detection of iron with a limit of detection of 0.63 μM. The sensing method is also useful for the quantification of iron in spiked water samples. Furthermore, the application of luminescent pyrazines as fluorescent ink was successfully demonstrated.

Thermodynamic properties of hercynite (FeAl2O4) for thermochemical water splitting applications: A first-principles approach

FeAl2O4 is considered as a potential material to produce solar thermochemical hydrogen. However, its temperature and pressure dependant thermodynamic properties have not yet been well explored. In this work, first-principles calculations have been applied to investigate the structural, mechanical, electronic and thermodynamic properties of FeAl2O4. The temperature and pressure-dependent thermal expansion coefficient and Grüneisen parameter have been calculated, leading to the calculation of molar heat capacity, cp = 5.50907 + 0.39378 T-202345.44153 T-2-94039T2 at 0 GPa. Change in Gibb's energy can be calculated at a given temperature and pressure during the reduction and oxidation cycle to computationally assess the suitability of FeAl2O4, as a catalyst for thermochemical water splitting. This approach may be further extended using suitable substitution and subsequent compositional variation of Fe and Al atoms, to explore more efficient catalyst.

Microstructure, high-temperature cyclic oxidation, and hot corrosion behaviors of Inconel 718 alloy produced by laser-induction hybrid cladding

The microstructure evolution, cyclic oxidation, and hot corrosion behavior of the unheated-treated (As-built) and solution + double aging (SDA)-treated Inconel 718 alloys fabricated through laser-induction hybrid cladding (LIHC) were investigated. It was found that the as-built Inconel 718 alloy exhibits a columnar dendritic with intergranular Laves phase. After SDA-treated, γ", γ′, δ and carbide phases precipitated, the Laves phase became fine and dispersed. After cyclic oxidation, the Cr2O3 scales were formed on both as-built and SDA-treated LIHC-produced Inconel 718 alloy, which could provide good cyclic oxidation resistance for the Inconel 718 alloy. However, the as-built and SDA-treated LIHC-produced Inconel 718 alloy suffered severe hot corrosion in 95 wt% Na2SO4 + 5 wt% NaCl mixed salt solution and many corrosion products were generated, including Cr2O3, NiCr2O4, NaNbO3, Na2CrO4, NiFe2O4, Fe3O4, and NiO. Nevertheless, the SDA-treated sample showed better cyclic oxidation and hot corrosion resistance than the as-built sample, owing to the more compact Cr2O3 scale.

Structure-Based Design of Ultrapotent Tricyclic Ligands for FK506-Binding Proteins.

Access to small, rigid, and sp3-rich molecules is a major limitation in the drug discovery for challenging protein targets. FK506-binding proteins hold high potential as drug targets or enablers of molecular glues but are fastidious in the chemotypes accepted as ligands. We here report an enantioselective synthesis of a highly rigidified pipecolate-mimicking tricyclic scaffold that precisely positions functional groups for interacting with FKBPs. This was enabled by a 14-step gram-scale synthesis featuring anodic oxidation, stereospecific vinylation, and N-acyl iminium cyclization. Structure-based optimization resulted in the discovery of FKBP inhibitors with picomolar biochemical and subnanomolar cellular activity that represent the most potent FKBP ligands known to date.

Investigation of High-Temperature Oxidation Behavior of Additive Manufactured CoCrMo Alloy for Mandrel Manufacturing.

The cyclic oxidation behavior of an additive manufactured CoCrMo alloy with 0.14 wt.% C was investigated at 914 °C for 32 cycles, each lasting 10 h, resulting in a total exposure time of 320 h. The oxidation rate was assessed for mass gain after finishing each 40 h oxidation cycle. It was experimentally determined that the oxidative process at 914 °C of this CoCrMo alloy follows a parabolic law, with the process being fast at the beginning and slowing down after the first 40 h. The microstructural analysis revealed that in the as-printed state, the phases developed were primarily the γ matrix and minor traces of ε phase. The oxidative process ensured an increase in the ε phase and precipitation of carbides which produced a 12% increase in the material's hardness after the first 40 h of exposure at 914 °C. The oxidation process led to the development of an oxide scale comprising a dense Cr2O3 layer and a porous layer of CoCr2O4 spinel, the latter spalling after the 240 h of exposure. Despite this spallation, the oxide scale continued to develop in the presence of O, Cr, and Co. The experimental analysis provided valuable insights regarding the material's behavior under prolonged exposure at high temperature in air, demonstrating its suitability as a candidate for additive manufactured mandrels used for bending metallic pipe fitting elbows.

Oxidative damage and cell cycle delay induced by vanadium(III) in human peripheral blood cells

Vanadium (V) is a metal that can enter the environment through natural routes or anthropogenic activity. In the atmosphere, V is present as V oxides, among which vanadium(III) oxide (V2O3) stands out. Cytogenetic studies have shown that V2O3 is genotoxic and cytostatic and induces DNA damage; however, the molecular mechanisms leading to these effects have not been fully explored. Therefore, we treated human peripheral blood lymphocytes in vitro, evaluated the effects of V2O3 on the phases of the cell cycle and the expression of molecules that control the cell cycle and examined DNA damage and the induction of oxidative stress. The results revealed that V2O3 did not affect cell viability at the different concentrations (2, 4, 8 or 16 μg/mL) or exposure times (24 h) used. However, V2O3 affected the percentage of G1- and S-phase cells in the cell cycle, decreased the expression of mRNAs encoding related proteins (cyclin D, cyclin E, CDK2 and CDK4) and increased the expression of γH2AX and the levels of reactive oxygen species. The ability of V2O3 to cause a cell cycle delay in G1-S phase may be associated with a decrease in the mRNA and protein expression of the cyclins/CDKs and with intracellular oxidative stress, which may cause DNA double-strand damage and H2AX phosphorylation.

Oxidative photochemical cyclisations to access spiroketals

The spiroketal moiety is an important substructure within many biological natural products. One method to access them is via the oxidative cyclisation of a pendant hydroxyl group on to a pre‐formed pyran. However applications of this methodology have been severely limited by requiring the use of toxic and powerful oxidants, such as lead (IV) tetraacetate or mercuric oxide. Herein we report a novel and high yielding photochemical route to prepare complex spiroketals using a photochemical oxidative approach with mild and non‐toxic reagents and demonstrate the methodology to the synthesis of a number of insect pheromones.

High temperature oxidation resistance and thermodynamic properties of (TaNbZr)N and (TaNbZr)C quaternary ceramic coating

A TaNbZr-based quaternary ceramic coating with a metallurgical transition layer on a titanium alloy surface has been produced. The quaternary ceramic coatings exhibit a face-centered cubic structure and distinct structural orientation. The introduction of carbon and nitrogen significantly improved high-temperature oxidation resistance compared to metallic coatings in cyclic oxidation tests. Specifically, the (TaNbZr)N coating provided effective thermal protection during 800 °C cyclic oxidation for 100 hours (10 cycles). The phase stability and evolution of quaternary ceramic coatings were clarified using in-situ XRD. Further, first-principles calculations elucidated the enhanced thermal stability and high-temperature performance of (TaNbZr)N and (TaNbZr)C coatings.

Cyclo‐Bis(Acyl)phosphine Oxides as Efficient Photoinitiators for Radical Polymerization

AbstractAcyclic acylphosphine oxides have been extensively utilized in industrial applications as typical photoinitiators (PIs). In this study, we demonstrate the efficiency of their cyclic analogues, cyclo‐bis(acyl)phosphine oxides (CBAPOs), as efficient PIs. We present the isolation and X‐ray crystallographic characterization of CBAPOs. These compounds exhibit a long maximum absorption wavelength ranging between 415 and 420 nm, extending well into the near 500 nm region. Radical trapping experiments suggest that CBAPOs undergo homolytic P−C(O) bond α‐cleavage. Steady‐state photolysis conducted with LED light at 390 nm, monitored by UV‐Vis spectroscopy, confirms the gradual decay of CBAPOs over time. Additionally, all CBAPOs are capable of initiating radical polymerization under irradiation at 365 nm. Notably, one of the CBAPOs (4a) demonstrates comparable photoinitiating efficiency to one of commercially available bis(acyl)phosphine oxides (Irgacure 819).

Self-supported copper/copper oxide microspheres for efficient electrocatalytic removal of low-concentration nitrate from aqueous solutions

The electrochemical removal of nitrate (NO3−) from aqueous solutions is a promising strategy for wastewater treatment; however, highly active catalysts are required. In this study, self-supported Cu/copper oxide (CuO) microspheres (ms) on Ni foam (NF) (Cu/CuOms/NF) were fabricated for NO3− removal from water using an electrochemical method, achieving a transformation efficiency of up to 99.72 % and N2 selectivity of 97.97 %. Cu/CuOms/NF also exhibited excellent NO3− removal performance over a wide pH range, while maintaining extremely low levels of toxic ammonia residues. The Cu/CuOms/NF-driven NO3− removal rate remains as high as 95.45 % even after recycling for five times, demonstrating the remarkable electrochemical stability of the catalyst. The Cu/CuOms supported on NF provided active sites and accelerated the oxidation cycle involving Cl−, leading to the complete transformation of NO3− into harmless N2 gas. Therefore, this study not only achieved the environmentally friendly treatment of NO3− pollutants in wastewater but also provided a promising strategy for developing catalysts for electrochemical NO3− removal.

Towards detailed combustor wall kinetics: An experimental and kinetic modeling study of hydrogen oxidation on Inconel

Gas-phase hydrogen combustion is ubiquitous in industrial processes, and the associated surface kinetics on heat-resistant alloys plays a crucial role in designing efficient low-carbon technologies. We conducted new temperature programmed reduction experiments to determine the reducibility of materials following an oxidation cycle. These experiments were modeled using a thermoconsistent multi-site microkinetic model for H2 heterogeneous oxidation on Inconels, which was validated against literature experiments. This competitive adsorption model considers iron bulk content, hydrogen spillover and subsurface oxygen migration on hydrogen surface oxidation kinetics. New X-ray diffraction experiments confirmed the postulated crystallographic structures in the Inconel samples, suggesting their presence on the surface scale. The phenomenological model was coupled with several state-of-the-art gas-phase oxidation mechanisms to assess gas/surface reactions interaction as a function of material and temperature. The results reveal a complex interaction in which surface removes H radicals from the gas-phase, while the Bradford (H2+OH) reaction converts OH into H2O, promoting water adsorption on Inconel. This interaction was found to give rise to gas-phase thermokinetic oscillations. The model predicts a non-monotonous effect of reactor area-to-volume ratio on reactivity and emphasizes the impact of Inconel composition on product selectivity. Overall, the multi-site model provides new insight into the contrasting reactivities among active sites, bridging the gap between material science and heterogeneous combustion modeling.

Efficient synthesis and evaluation of therapeutic potential of fluorine containing 2-arylchromen-4-ones.

A large series of 2-arylchromen-4-ones containing from 1 to 3 fluorine atoms or a trifluoromethyl group in the structure was synthesized by condensation of fluorinated 2-hydroxyacetophenones with benzaldehydes in an alkaline medium and subsequent oxidative cyclization of the resulting 2'-hydroxychalcones by action of I2 in DMSO. The cytotoxicity of the obtained compounds was studied in glioblastoma cell line, SNB19, and in a monkey-derived normal kidney epithelium cell line, Vero. In addition, antiglycation activity of the obtained compounds was evaluated. The inhibitory activity of some fluorinated 2-arylchromen-4-ones against acetylcholinesterase, butyrylcholinesterase and carboxylesterase as well their primary antioxidant activity in ABTS and FRAP tests were investigated. Screening of the synthesized compounds for their inhibitory activity against influenza A virus A/Puerto Rico/8/34 (H1N1) in the MDCK cell culture revealed that fluorinated compounds 32, 31 and 39 showed manifest antiviral effects (with IS = 57, 38 and 25 correspondingly) that makes this series of new biologically attractive fluorinated heterocycles promising for further development and in-depth study.

Accumulation and growth toxicity mechanisms of fluxapyroxad revealed by physiological, hepatopancreas transcriptome, and gut microbiome analysis in Pacific white shrimp (Litopenaeus vannamei)

Fluxapyroxad (FX), a typical succinate dehydrogenase inhibitor fungicide, is causing increased global concerns due to its fungicide effects. However, the accumulation and grow toxicity of FX to Litopenaeus vannamei (L. vannamei) is poorly understand. Therefore, the accumulation pattern of FX in L. vannamei was investigated for the first time in environmental concentrations. FX accumulated rapidly in shrimp muscle. Meanwhile, growth inhibition was observed and the mechanism derived by primarily accelerated glycolipid metabolism and reduced glycolipid content. Moreover, exposure to environmental concentrations of FX induced significant growth inhibition and oxidative stress and inhibited oxidative phosphorylation and TCA cycle in L. vannamei. The endocytosis signaling pathway genes were activated, thereby driving growth toxicity. Oxidative phosphorylation and cytosolic gene expression were further rescued in elimination experiments, demonstrating the mechanism of growth toxicity by FX exposure. The results revealed that FX persistently altered the gut microbiome of L. vannamei using gut microbiome sequencing, particularly with increased Garcinia Purple Pseudoalteromonas luteoviolacea for organic pollutant degradation. This study provided new insights into the potential toxicity of FX to marine organisms, emphasizing the need for further investigation and potential regulatory considerations.

Comparison of the Proteome of Huh7 Cells Transfected with Hepatitis B Virus Subgenotype A1, with or without G1862T.

HBeAg is a non-structural, secreted protein of hepatitis B virus (HBV). Its p25 precursor is post-translationally modified in the endoplasmic reticulum. The G1862T precore mutation leads to the accumulation of P25 in the endoplasmic reticulum and activation of unfolded protein response. Using mass spectrometry, comparative proteome profiling of Huh-7 cells transfected with wildtype (WT) or G1862T revealed significantly differentially expressed proteins resulting in 12 dysregulated pathways unique to WT-transfected cells and 7 shared between cells transfected with either WT or G1862T. Except for the p38 MAPK signalling pathway, WT showed a higher number of DEPs than G1862T-transfected cells in all remaining six shared pathways. Two signalling pathways: oxidative stress and cell cycle signalling were differentially expressed only in cells transfected with G1862T. Fifteen pathways were dysregulated in G1862T-transfected cells compared to WT. The 15 dysregulated pathways were involved in the following processes: MAPK signalling, DNA synthesis and methylation, and extracellular matrix organization. Moreover, proteins involved in DNA synthesis signalling (replication protein A (RPA) and DNA primase (PRIM2)) were significantly upregulated in G1862T compared to WT. This upregulation was confirmed by mRNA quantification of both genes and immunofluorescent confocal microscopy for RPA only. The dysregulation of the pathways involved in these processes may lead to immune evasion, persistence, and uncontrolled proliferation, which are hallmarks of cancer.

The Chemistry of Angucyclines.

Angucyclines and angucyclinones represent a class of natural compounds that belong to the group of aromatic polyketides. They exhibit a wide array of biological properties, such as antimicrobial, antiviral, and cytotoxic. Their considerable therapeutic potential and diverse scaffolds have attracted many synthetic chemists to devise novel strategies to construct their intricate molecular architecture. Over 300 class members have been isolated from natural sources, mainly from bacterial strains of Streptomyces species. This review highlights recent advancements in their synthesis, such as oxidative cyclization, photooxidation, and metal-catalyzed [4+2]-cycloaddition, which has facilitated the efficient and practical total syntheses of various angucycline and angucyclinone natural products.

Epithelial Membrane Protein 2 (EMP2) Blockade Attenuates Pathological Neovascularization in Murine Oxygen-Induced Retinopathy.

Retinopathy of prematurity (ROP) results from postnatal hyperoxia exposure in premature infants and is characterized by aberrant neovascularization of retinal blood vessels. Epithelial membrane protein-2 (EMP2) regulates hypoxia-inducible factor (HIF)-induced vascular endothelial growth factor (VEGF) production in the ARPE-19 cell line and genetic knock-out of Emp2 in a murine oxygen-induced retinopathy (OIR) model attenuates neovascularization. We hypothesize that EMP2 blockade via intravitreal injection protects against neovascularization. Ex vivo choroid sprouting assay was performed, comparing media and human IgG controls versus anti-EMP2 antibody (Ab) treatment. In vivo, eyes from wild-type (WT) mice exposed to hyperoxia from postnatal (P) days 7 to 12 were treated with P12 intravitreal injections of control IgG or anti-EMP2 Abs. Neovascularization was assessed at P17 by flat mount imaging. Local and systemic effects of anti-EMP2 Ab treatment were assessed. Choroid sprouts treated with 30µg/mL of anti-EMP2 Ab demonstrated a 48% reduction in vessel growth compared to control IgG-treated sprouts. Compared to IgG-treated controls, WT OIR mice treated with 4µg/g of intravitreal anti-EMP2 Ab demonstrated a 42% reduction in neovascularization. They demonstrated down-regulation of retinal gene expression in pathways related to vasculature development and up-regulation in genes related to fatty acid oxidation and tricarboxylic acid cycle respiratory electron transport, compared to controls. Anti-EMP2 Ab-treated OIR mice did not exhibit gross retinal histologic abnormalities, vision transduction abnormalities, or weight loss. Our results suggest that EMP2 blockade could be a local and specific treatment modality for retinal neovascularization in oxygen-induced retinopathies, without systemic adverse effects.