Probable Pathway Research Articles

Sonophotocatalytic degradation of rhodamine B dye using Zr doped ZnO nanoparticles: Kinetic study and toxicity assessment

This study investigates sonophotocatalysis for the oxidation of Rhodamine B (RhB) dye using Zr doped ZnO nanoparticles. The synthesized nanoparticles were characterized by scanning electron microscope, Fourier-transform infrared, X-ray diffraction, Brunauer Emmett-Teller, thermogravimetric analysis, and photoluminescence. The hybrid sonophotocatalysis system achieved 98.73 ± 1.25% degradation of RhB under the conditions: RhB dye concentration = 10 ppm, 4 wt% of Zr doped ZnO = 0.1 g, reaction temperature = 30 °C, time = 60 min, pH = 7. A kinetic model was developed to predict the efficiency of RhB degradation through intrinsic elementary chemical reactions. The high coefficient of determination (R2 = 0.96) indicates the model's prediction accuracy in describing the degradation kinetics of RhB within sonophotocatalysis system. The electrical energy per order (EEO) analysis demonstrated that US + UVC + 4 wt% of Zr doped ZnO significantly reduced EEO (1055 kWh m−3 order−1). The synergy index for this combination was approximately 1.60, demonstrating a significant synergistic effect. Density Functional Theory (DFT) studies were utilized to propose the most probable degradation pathway, identifying reactive sites and potential byproducts. The simulations revealed the central carbon atom (1C site) as highly susceptible to radical attacks, indicating potential decolorization pathways such as N-de-ethylation, chromophore cleavage, and ring opening. Toxicity assessments of both the parent dye and its intermediates were conducted using ECOSAR (Ecological Structure Activity Relationship) to evaluate their ecological impacts. The combination of experimental results and kinetic modeling and simulations offers a deep understanding of RhB degradation complexities, driving advancements in sustainable water treatment technologies.

A revision and addition to Zopheridae (Coleoptera: Tenebrionoidea) in Baltic amber: possible connections between modern Holarctic distributions and Eocene ‘amber forests’

One new extinct genus and six new extinct species of Zopheridae are described and illustrated from Eocene Baltic amber: Usechus andrushchenkoi Alekseev et Bukejs sp. nov., Coxelus carstengroehni Alekseev et Bukejs sp. nov., Paha vanivanitatum Alekseev et Bukejs sp. nov., Lasconotus tenebrisilvarum Alekseev et Bukejs sp. nov., Helioctamenus groehni Alekseev et Bukejs sp. nov., and Thanatoplagia tamutisi Alekseev et Bukejs gen. et sp. nov. These described taxa include the first fossil representatives of five extant genera and two extant tribes of the family Zopheridae. The assumed paleoecology of these taxa within the amber-producing forest paleohabitat, as well as zoogeography of new fossils are discussed. In addition, new fossil records of Xylolaemus legalovi Alekseev et Bukejs, 2016, X. richardklebsi Alekseev et Bukejs, 2016, Endophloeus gorskii Alekseev et Bukejs, 2016, Yantaroxenos colydioides Nabozhenko, Kirejtshuk et Merkl, 2016, and Zopheromimus auriborussiensis Alekseev et Nabozhenko, 2023 from Baltic amber are presented. A catalogue of Zopheridae described from Baltic amber (currently 19 species within 16 genera) is compiled herein, and an identification key for all taxa is provided. The zoogeographical affinities of the Baltic amber zopherid assemblage are assessed. The present-day disjunct distributions of the zopherid genera that have survived since the Eocene and are currently present in the Holarctic region probably resulted from a uniform fauna in the warm temperate regions of the Northern Hemisphere in the first half of the Paleogene. This uniform fauna was followed by independent reduction of distributions within four regions (West Palearctic, East Palearctic, West Nearctic, and East Nearctic). The ‘circum-Arctic quadrants’ schema is proposed for visualisation of this hypothesis. Additionally, a zonal middle to late Eocene ‘amberiferous ring’ is hypothesized as a probable migration pathway for several zopherids in this part of the Eocene. This ‘ring’ is a belt of amber-producing forests in the Northern Hemisphere, with the potential to preserve a wider distribution of taxa that relied on mixed conifer-fagacean forests similar to the Baltic amber forest flora and its faunal assemblage.

Well Defined Phosphine Free Ni-Catalyzed Dehydrogenation of Secondary Alcohols for the Synthesis of Ketones and Ketazines.

In this work, we unveil a novel synthesis of bench stable Ni (II) complexes supported by tetradentate Schiff-base ligands and the complexes were devoid of any phosphine or phosphine-based ligand. These Ni-complexes were successfully applied for the dehydrogenation of secondary alcohols for ketone and ketazine syntheses. Secondary alcohols with different functional groups were well tolerated during catalytic cycle. Moreover, we successfully extended this protocol for the synthesis of biologically significant ketones and ketazines. On the basis of various control experiments, probable reaction pathway was proposed and an acceptorless alcohol dehydrogenation mechanism was suggested.

Bladder cancer associated with elevated heavy metals: Investigation of probable carcinogenic pathways through mitochondrial dysfunction, oxidative stress and mitogen-activated protein kinase

ObjectiveCarcinogenic mechanisms of heavy metals/ trace elements (HMTE) in bladder cancer (BC) are exactly unknown. Mitochondrial dysfunction (MD), oxidative stress (OS), and mitogen-activated protein kinases (MAPK) are probable carcinogenic mechanisms. The purpose is to investigate probable carcinogenic pathways of HMTE in BC using six MD genes, seven OS markers, and p38-MAPK. MethodsStudy included 125 BC/radical cystectomy (RC) patients between October 2020 and October 2022, and 72 controls. Exclusion criteria included previous neoplasm, chemo- or radiotherapy. Two samples (cancer/noncancer) were taken from RC specimens. Tissues/plasma/urine cadmium (Cd), lead (Pb), cobalt (Co), nickel (Ni), strontium (Sr), aluminium (Al), zinc (Zn), boron (B) were measured by ICP-OES. Tissue MD genes (mt-CO3, mt-CYB, mt-ATP 6, mt-ATP8, mt-CO1, mt-ND1), and serum OS markers (8-OHdG, MDA, 3-NT, AGEs, AOPP, ROS, SOD2), p38-MAPK were assessed by RT-PCR, and ELISA, respectively. ResultsBC and adjacent tissue showed higher (Al, Co, Pb, Ni, Zn, Cd,Sr), lower B concentrations, compared to controls. High tissue concentrations (Cd, Co, Pb, Ni, Sr) were associated with higher MD genes, OS, MAPK and lower SOD2 levels. The same differences were greater in 41 patients with concomitant elevation of two or more HMTE. Noninclusion of BC-related oncogenes (e.g. RAS) is a limitation. ConclusionsEvidence suggests that high BC tissue (Cd, Co, Pb, Ni, Si) concentrations are associated with over-expressed MD genes, OS, p38-MAPK and low SOD2. These findings provide important understanding keys of probable carcinogenic pathways in BC associated with HMTE. So, efforts should be performed to minimize and counteract exposure to toxic HMTE.

Dang-Gui-Bu-Xue decoction against diabetic nephropathy via modulating the carbonyl compounds metabolic profile and AGEs/RAGE pathway

BackgroundDang-Gui-Bu-Xue decoction (DBD) is a traditional Chinese medicine prescription clinically employed for diabetic nephropathy (DN). However, the components and pharmacological mechanisms of DBD against DN remain incompletely understood. PurposeTo clarify the beneficial effect of DBD on DN and to explore its nephroprotective effect's probable mechanism and the main components. MethodsA diabetic mice model was established by feeding a high-fat diet (HFD) and intraperitoneal injections of streptozotocin (STZ, 40 mg‧kg-1). Subsequently, the mice were maintained on a HFD and administered with DBD. The benefits of DBD against DN were comprehensively assessed by monitoring energy and water intake, blood glucose and lipids, renal functions and pathological status. The UPLC-MS/MS was measured to detect chemical constituents in DBD and absorbed components in DBD-treated plasma under physiological and pathological states. Network pharmacology was employed to forecast the probable pathways of DBD intervention in DN, with subsequent validation of these predictions through testing biochemical parameters, anti-glycation and ELISA assays, immunofluorescence, immunohistochemistry, and western blotting. Then, a chemical derivatization method paired with UPLC-MS/MS analysis was performed to detect the carbonyl compounds in renal tissue. Finally, the main components of DBD against DN were screened by anti-glycation and MTT assays. ResultsDBD regulated energy and water intakes, glucose and lipid metabolism disorders, renal dysfunction, glomerular filtration rate, renal interstitial glycogen accumulation and fibrosis in HFD/STZ-induced DN mice. A total of 129 distinct chemical constituents in DBD were characterized, of which 28 were detected in the DBD-treated plasma under a pathological state. The network pharmacological results suggested AGEs/RAGE and its downstream pathway may be a potential pathway for DBD intervention in DN. Further experiments confirmed that DBD reduced renal oxidative stress by modulating the AGEs/RAGE pathway. Moreover, 21 differential carbonyl compounds were detected between normal and DN mice, and DBD significantly modulated 16. Ultimately, seven components were screened out in DBD, which may be the main components of DBD regulating carbonyl compounds metabolic profile and AGEs/RAGE pathway. ConclusionOur findings suggested for the first time that DBD could regulate the carbonyl compounds metabolic profile and AGEs/RAGE signaling pathway to ameliorate DN.

Nonclassical C86 and C88 Chlorofullerenes via Complex Chlorination-Promoted Skeletal Transformations of IPR Isomers of C88 and C96.

Upon high-temperature (340-360 °C) chlorination with VCl4, an isolated-pentagon-rule (IPR) C2-C88(33) fullerene is just chlorinated to C88(33)Cl22 and C88(33)Cl28, but a VCl4/SbCl5 mixture promotes a five-step cage transformation to nonclassical C86(NC2)Cl30 with two heptagons and five pairs of fused pentagons. Another chlorination-promoted seven-step transformation of an IPR fullerene removes as many as four C2 fragments from C96 to give a nonclassical C88(NC1)Cl30 with cage heptagon and six fused pairs of pentagons. We discuss the driving forces behind the observed transformations and probable detailed pathways thereof.

Study of Fe3O4 and Cu2+ doped modified Fe3O4 nano catalyst for photocatalytic degradation of methylene blue and eriochrome black-T dyes: Synthesis, characterization, and antimicrobial assessment

This study presents the synthesis and characterization of undoped Fe3O4 and 3% Cu-doped Fe3O4 nanoparticles via a cost-effective and environmentally friendly co-precipitation method. A comprehensive suite of nanomaterial characterization techniques, including energy dispersive spectroscopy (EDS), scanning electron microscopy (SEM), X-ray diffraction (XRD), high-resolution transmission electron microscopy (HR-TEM), and X-ray photoelectron spectroscopy (XPS), was employed to confirm the elemental composition, structural parameters, and chemical states of the prepared materials. Additionally, fragmentation analysis using LC–MS illustrated the structural stability and breakdown of the nanoparticles under specific conditions. Both the materials were characterized by vibrating sample magnetometer (VSM), Brunauer-Emmett-Teller (BET) for investigating the magnetic, and surface characteristics respectively. Furthermore, the synthesized nanoparticles were evaluated for their photocatalytic degradation efficiency towards methylene blue and eriochrome black T dyes. A systematic investigation of various parameters, including the pH of the dye solution, dye concentration over time, catalyst dose, dye concentration versus degradation, catalyst reusability, and kinetic study, was conducted to understand the factors influencing the photocatalytic activity of both undoped and Cu-doped Fe3O4 nanoparticles. The LC-MS analysis predicted the probable degradation pathways of MB and EBT dyes. This work provides insights into the sustainable synthesis, comprehensive characterization, and practical application of Fe3O4-based nanoparticles for water treatment applications, highlighting their potential as efficient and environmentally benign Photocatalyst for wastewater remediation. An investigation was conducted to investigate the antimicrobial properties of both undoped and doped nanoparticles. The minimum inhibitory concentration (MIC) of the synthesized nanoparticles were determined against the bacterial strains E. coli, P. aeruginosa, S. aureus, and S. pyogenes, as well as the fungal strains C. albicans, A. niger, and A. clavatus.

Synergistic adsorption-photocatalytic remediation of methylene blue dye from textile industry wastewater over NiFe LDH supported on tyre-ash derived activated carbon

The photocatalytic performance of the multilayered NiFe LDH/Activated Carbon was evaluated for the degradation of methylene blue (MB) in industrial textile wastewater, considering prior adsorption on the photocatalyst surface. The XRD, XPS, BET, TEM and FE-SEM results confirmed that the highly exposed mesoporous layers, carbon backbone, and interlayer anions serve as active sites responsible for the adsorption of MB dye due to the expected electrostatic interactions. Electrochemical methods such as CV, LSV and EIS revealed the improved conductivity and supported the interactions observed. Encouraged by these interactions, the irradiation of visible light enabled the degradation of methylene blue, and the degradation products were monitored using UPLC chromatograms and MS spectra. The removal efficiencies of the MB dye were found to be 17.5 %, 51.2 %, 67.1 %, 84.8 %, and 94.2 % due to photolysis, adsorption, and degradation on AC, NiFe LDH nanosheets, and NiFe LDH/AC nanocomposite, respectively. The results of the UPLC chromatograms and MS spectra suggested that MB was mineralized into simpler fragments after 30 min of visible light irradiation. Scavenging studies were examined using a series of scavenging agents. However, the maximum photodegradation was attained in the absence of the scavengers. The reusability studies showed that the MB photodegradation efficiency declined by 20.8 %, possibly due to the loss of the catalyst during the washing step. Nonetheless, the NiFe LDH/AC structure remained intact, suggesting the strong stability of the photocatalyst. The plausible degradation mechanism and probable degradation pathway of MB were outlined and supported by the chromatographs and MS results. The overall results suggest that photocatalysis of cationic dyes such as MB on NiFe LDH/AC should be encouraged to work towards sustainable solutions for textile water treatment.

Mapping the intricacies of GLI1 in hedgehog signaling: A combined bioinformatics and clinical analysis in Head & Neck cancer in Western India

BackgroundActivation of various cancer stem cell pathways are thought to be responsible for treatment failure and loco-regional recurrence in Head and Neck cancer. Hedgehog signaling, a major cancer stem signaling pathway plays a major role in relapse of disease. GLI1, a transcription activator, plays an important role in canonical/non-canonical activation of Hedgehog signaling. MethodsData for H&N cancer patients were collected from The Cancer Genome Atlas- H&N Cancer (TCGA-HNSC). GLI1 co-expressed genes in TCGA-HNSC were then identified using cBioPortal and subjected to KEGG pathway analysis by DAVID tool. Network Analyzer and GeneMania plugins from CytoScape were used to identify hub genes and predict a probable pathway from the identified hub genes respectively. To confirm the hypothesis, real-time gene expression was carried out in 75 patients of head and neck cancer. ResultsSignificantly higher GLI1 expression was observed in tumor tissues of H&N cancer and it also showed worst overall survival. Using cBioPortal tool, 2345 genes were identified that were significantly co-expressed with GLI1. From which, 15 hub genes were identified through the Network Analyzer plugin in CytoScape. A probable pathway prediction based on hub genes showed the interconnected molecular mechanism and its role in non-canonical activation of Hedgehog pathway by altering the GLI1 activity. The expressions of SHH, GLI1 and AKT1 were significant with each other and were found to be significantly associated with Age, Lymph-Node status and Keratin. ConclusionThe study emphasizes the critical role of the Hh pathway's activation modes in H&N cancer, particularly highlighting the non-canonical activation through GLI1 and AKT1. The identification of SHH, GLI1 and AKT1 as potential diagnostic biomarkers and their association with clinic-pathological parameters underscores their relevance in prognostication and treatment planning. Hh pathway activation through GLI1 and its cross-talk with various pathways opens up the possibility of newer treatment strategies and developing a panel of therapeutic targets in H&N cancer patients.

Emerging biological functions of Twist1 in cell differentiation.

Twist1 is required for embryonic development and expresses after birth in mesenchymal stem cells derived from mesoderm, where it governs mesenchymal cell development. As a well-known regulator of epithelial-mesenchymal transition or embryonic organogenesis, Twist1 is important in a variety of developmental systems, including mesoderm formation, neurogenesis, myogenesis, cranial neural crest cell migration, and differentiation. In this review, we first highlight the physiological significance of Twist1 in cell differentiation, including osteogenic, chondrogenic, and myogenic differentiation, and then detail its probable molecular processes and signaling pathways. On this premise, we summarize the significance of Twist1 in distinct developmental disorders and diseases to provide a reference for studies on cell differentiation/development-related diseases.

Intercalation of novel Ocimum Sanctum leaves derived carbon dots between g-C3N4/CoFe2O4 Z-scheme heterojunction system for boosting the radicals’ generation in photo-Fenton degradation and synchronized electrochemical sensing of sulfamethoxazole antibiotic

Deeming about incessant consumption and disposal of pharmaceutical antibiotics in natural water bodies, this study demonstrates the synthesis of a novel Tulsi leaves (Ocimum Sanctum) derived carbon dots modified Z-scheme g-C3N4/CoFe2O4 heterojunction system. Characterization techniques namely XRD, FT-IR, XPS, FE-SEM, HR-TEM and EDX supported composite formation. Fabricated catalysts presented excellent photocatalytic performance towards removal of sulfamethoxazole (SMX). UV–vis DRS, PL and EIS findings suggested the augmented visible light absorption capability, suppression of electron-hole pairs recombination and effective separation of charge carriers which were accountable for degradation process. Probable mechanistic pathway for SMX removal was photo-Fenton assisted with Z-scheme separated electron-hole pairs via activation of H2O2, where hydroxyl radicals (•OH) were main reactive species. Additionally, the prepared material was employed as electrochemical sensor for individual as well as simultaneous detection of SMX and trimethoprim with quite impressive detection limits of 0.042 µM and 0.047 µM, respectively.

Decomposition of tetracycline with peroxymonosulfate activated by an ordered hierarchical pores Fe-N/C catalyst rich in FeNx sites: Insights into singlet oxygen mechanism

FeNx sites show significant superiority in the degradation of antibiotic contaminants, but there are difficulties in successfully constructing highly dispersed FeNx sites. In this work, Fe-N/C catalysts doped with hierarchical ordered pores structure and FeNx active sites were prepared by metal node exchange strategy. Among them, Fe-N/C-2 had more excite species for peroxymonosulfate (PMS) owing to the synergy between Fe and N coordination, which achieved 89.36 % tetracycline (TC) removal rate within 20 min, and its reaction kinetic (k = 0.245 min−1) is 7.66 times more than original PMS system. Moreover, the material exhibited excellent activation performance in a variety of complex water environments, such as the coexistence of multiple anions, strong acids and alkalis (pH = 2.90 ∼ 10.73), and natural organic matter interference. Chemical bond detection confirmed the successful formation of FeNx sites, free radical trapping experiments showed that FeNx was the main catalytic site, and 1O2 was the main active component. Furthermore, the reaction principle of the FeNx site catalyzing the production of 1O2 from PMS was revealed in detail through mechanism exploration. Next, the probable pathways of TC decomposition were elaborated in terms of the intermediates identified by Liquid Chromatograph Mass Spectrometer (LC-MS). This study emphasized the significant potential of synthesizing Fe-N/C catalysts with activated FeNx sites, elucidated mechanism of FeNx in PMS activation, and confirmed its feasibility in TC degradation.

Synergistic performance and mechanisms of plasma and peracetic acid for antibiotic degradation in water

Antibiotic pollution has become one of the most challenging environmental issues in aquatic ecosystems, with adverse effects on human health. It is imperative to develop efficient technologies to degrade antibiotics in water to ensure environmental safety. In this study, a novel, efficient, and environmentally friendly method combining peracetic acid with dielectric barrier discharge (PAA/DBD) was developed to degrade sulfamethoxazole (SMX) in wastewater. The combination of PAA and DBD had significant synergistic effects on SMX decomposition with a synergistic factor of 3.67. The incorporation of PAA into the DBD system obviously reduced energy consumption with a 191 % increase in energy yield. The synergistic effects of PAA/DBD can be attributed to the PAA-activating factors generated by DBD (including O3, ultraviolet (UV), H2O2, and heat) and the enhanced effects of H2O2 and CH3COOH (released by PAA) on DBD. This symbiotic relationship between PAA and DBD enhanced the production of various reactive species (including •OH, 1O2, •O2−, ONOO−, and •CH3). The contributions of these reactive species to SMX removal followed the sequence of •O2− > ONOO− >1O2 > •CH3 > •OH. Increasing the PAA dosage and/or DBD discharge power enhanced the efficiencies of the reactive species. Commonly existing anions and cations in wastewater influence the SMX removal efficiency in various ways. Based on the 12 detected intermediates, probable degradation pathways for SMX were proposed. The ecotoxicity assessments of SMX and its intermediates indicated that PAA/DBD treatment minimized the negative effects of SMX on the environment. These observations demonstrated the versatility of PAA/DBD in providing a green, efficient, and innovative approach for removing antibiotics from the water environment.

Phosphorylation reaction mechanism of 5,7-Dichloro-4,6-DinitroBenzofuroxane

The molecular mechanism of the phosphorylation reaction of 5,7-Dichloro-4,6-DinitroBenzofuroxane (DCDNBFX) by tertiary phosphines is clarified by means of a state-of-the-art computational investigation. The reaction with trimethylphosphine is used as a study case. The possible electrophilic attack sites are analysed and the most probable pathway is established. Structural, electrostatic, electronic and topological properties of the product are presented along with the analysis of the vibrational spectra. The results are corroborated by experimental evidences from the literature.

Identification, characterization, and in silico ADMET prediction of nirmatrelvir and its degradation products using HPLC-PDA and LC-QTOF-MS/MS.

Nirmatrelvir is a protease inhibitor that is essential for virus replication. Nirmatrelvir is indicated for the management of mild to severe cases of COVID-19 in individuals who are 12 years of age or older. Forced degradation studies of nirmatrelvir were carried out on the drug substance in solid and solution forms, subjecting it to various stress conditions according to International Conference on Harmonisation (ICH) Q1A(R2) and Q1B guidelines. The analytical method was validated as per the ICH Q2(R1) guidelines. The drug substance (nirmatrelvir) was subjected to hydrolysis (acidic, alkaline, and neutral), thermal, photolytic, and oxidative stress conditions. Five degradation products (DPs) of nirmatrelvir formed under hydrolytic (acidic and alkaline) and oxidative (2,2-azobisisobutyronitrile) stress conditions. These degradation products were identified and separated using reverse-phase HPLC on a phenomenex kinetex C8 column (250 mm ×4.6mm ×5μm) with gradient elution. The mobile phase consisted of 0.1% formic acid and acetonitrile, and detection was carried out at a wavelength of 210 nm. Nirmatrelvir and its five DPs were efficiently separated using reverse phase-HPLC. These five DPs were identified and characterized using LC-electrospray ionization (ESI)-Q-TOF-coupled mass spectrometry analysis in the ESI-positive ionization mode. The formation mechanisms of the DPs and the most probable mass fragmentation pathways for both nirmatrelvir and its DPs were elucidated. The developed method demonstrated selectivity, accuracy, linearity, and reproducibility, making it appropriate for quality control of nirmatrelvir and future research studies. Additionally, the physicochemical and Absorption, Distribution, Metabolism, Excretion, and Toxicity (ADMET) properties of nirmatrelvir and its DPs were predicted using ADMET predictor software. The toxicity profile revealed that DP2 and DP3 have teratogenic effects while DP1 and DP3 caused phospholipidosis.

Elucidating the Synergistic Promotional Mechanism of Water and Oxygen in the Aerobic C-C Homocoupling Reaction Catalyzed by Visible-Light-Derived Core-Shell Pd@A-CQDs Nanostructures.

Rational design and precise synthesis of biogenic noble-metal-based catalysts possessing distinctive structure and composition play a crucial role in the chemical industry, enabling sustainable construction of an inclusive range of chemical resources. In this study, we have effectively fabricated Pd@A-CQDs through a straightforward one-pot aqueous protocol assisted by visible light employing renewable biomass-derived amine-rich carbon quantum dots (A-CQDs). The remarkable visible light harnessing capability (bandgap, ca. 2.81 eV), high density (35.7 × 1018 cm-3), and long lifetime (25 ps) of photocharge carriers and amine-rich surface in A-CQDs make them ideal candidates as both reducing and stabilizing agents, thereby facilitating the in situ construction of metallic Pd(0) nanoparticles. Comprehensive physicochemical characterizations have provided compelling evidence for the spherical morphology of Pd@A-CQDs core-shell nanostructures, with ultrathin A-CQDs shells of ca. 1.9 nm and an average diameter of 14 ± 1 nm. The effectiveness of the synthesized Pd@A-CQDs catalysts was assessed in the ligand- and base-free homocoupling reaction of arylboronic acids in water at ambient temperature. The catalytic tests demonstrated the selective production of the homocoupled compound over protodeboronation products with excellent yield and high catalyst recyclability under ambient conditions. The protocol employed exhibited a high TOF (1.05 × 10-2 mol g-1 min-1) and a low E-factor, with a remarkably low palladium loading. XPS analysis confirmed the retention of the metallic nature of the palladium core within the catalysts during the reaction. The catalytic function of the palladium core in conjunction with the A-CQDs shell, along with the promotional effects provided by water and oxygen for the formation of nucleophilic tetravalent boron, was conclusively recognized by 11B NMR and O2-TPD measurements. The obtained experimental results deliver valuable insights into the probable reaction pathway for the homocoupling reaction catalyzed by the Pd@A-CQDs catalysts. Through a comprehensive and sustainable evaluation, the current methodology exhibits superior performance compared to previously documented techniques in relation to estimated circularity and adherence to good manufacturing practices (GMP).

Thiuram Disulfide Mediated Copper-Catalyzed C–S Cross-Coupling: Synthesis of S-Thiocarbamate Compounds

AbstractThiuram disulfides undergo a Cu(I)-catalyzed C–S cross-coupling with aryl iodides through Cu(OAc)2·H2O-assisted desulfurization to produce the S-thiocarbamate ester compounds efficiently. Various aryl iodides containing diverse substituents underwent a smooth reaction with a series of cyclic and acyclic secondary amine-based thiuram disulfides under an open-air atmosphere. A probable mechanistic pathway has been suggested based on control experiments and reports from the literature.

Phillyrin: A potential therapeutic agent for osteoarthritis via modulation of NF-κB and Nrf2 signaling pathways

Osteoarthritis (OA) is the predominant cause of disability among elderly people worldwide and is characterized by cartilage degeneration and excessive bone formation. Phillyrin, derived from forsythia, is a key extract renowned for its pronounced antibacterial and anti-inflammatory effects. Forsythia, deeply integrated into traditional Oriental medicine, has historically been utilized for its various pharmacological effects, including antibacterial, anti-inflammatory, and hepato-protective properties. Nevertheless, the anti-inflammatory impact of phillyrin on the progression of osteoarthritis remains enigmatic. The objective of this research was to assess the anti-inflammatory and anti-aging properties of phillyrin in mouse chondrocytes induced by IL-1β, as well as to elucidate the fundamental mechanisms underlying the phenomenon at play. Additionally, the investigation extends to observing the impact of phillyrin by establishing a murine osteoarthritic model. The ultimate goal was to identify phillyrin as a potential antiosteoarthritic agent. This investigation employs a multifaceted approach. Initially, key action targets of phillyrin, along with its probable action pathways, were identified by molecular docking and network pharmacological techniques. These findings were subsequently confirmed through both in vivo and in vitro studies. Network pharmacological analysis revealed NFE2L2 (NRF2), NFKB1, TLR4, and SERPING1 as pivotal candidate targets for the treatment of osteoarthritis with phillyrin. Molecular docking revealed hydrogen bond interactions between phillyrin and Arg415, Arg483, Ser508, and Asn387 on the Nrf2 receptor, while electrostatic interactions occurred with residues Arg415 and Arg380. Experiments conducted in vitro indicated that phillyrin preconditioning hindered the IL-1β-induced expression of proinflammatory factors which included TNF-α, COX-2, IL-6, and iNOS. Furthermore, phillyrin counteracts the IL-1β-induced degradation of aggrecan and collagen II within the extracellular matrix (ECM). This protective action is caused by the inhibition of the NF-κB pathway by phillyrin. Additionally, the mitigation of chondrocyte aging by phillyrin was observed. Our investigation revealed that phillyrin mitigates inflammation and counteracts cartilage degeneration in osteoarthritis (OA) patients by suppressing inflammation in chondrocytes and impeding aging through suppression of the NF-κB pathway.

Regulation of the p53/SLC7A11/GPX4 Pathway by Gentamicin Induces Ferroptosis in HEI-OC1 Cells.

Gentamicin is a commonly used aminoglycoside antibiotic, with ototoxicity as a significant side effect. Ferroptosis, an iron-dependent form of cell death, has been implicated in a variety of disorders. Whether ferroptosis impacts gentamicin ototoxicity is not yet known. The current work used an in-vitro model to examine the influence of gentamicin-induced ferroptosis on cochlear hair cell damage and probable molecular biological pathways. House Ear Institute-Organ of Corti 1 (HEI-OC1) cells were treated with different concentrations of gentamicin for 24 hours, with or without ferrostatin-1 pretreatment, to observe gentamicin-induced ferroptosis. The role of p53/solute carrier family 7 member 11 (SLC7A11)/glutathione peroxidase 4 (GPX4) signaling in gentamicin-induced ferroptosis was explored by pretreating cells with the p53 inhibitor pifithrin-α (PFT-α). We investigated the effect of gentamicin on cells by assessing cell viability. Cellular proteins were isolated and Western blots were performed to detect changes in the expression of p53, SLC7A11, and GPX4. Fluorescence staining was used to assess levels of reactive oxygen species. An enzymatic detection kit was used to detect glutathione, Fe, and malondialdehyde markers. Gentamicin reduced cell viability, glutathione content, and SLC7A11 and GPX4 protein levels, and increased levels of p53 protein, reactive oxygen species, malondialdehyde, and Fe. These effects were largely blocked by pretreatment with ferrostatin-1. Pretreatment with the p53 inhibitor PFT-α prevented the gentamicin-induced reduction in SLC7A11 and GPX4, which alleviated several features of ferroptosis including glutathione depletion, iron overload, and lipid peroxidation build-up. Gentamicin induces ferroptosis in the HEI-OC1 cell line, and the mechanism may be related to the p53/SLC7A11/GPX4 signaling pathway.

Two invasive bark beetles Phloeosinus armatus Reitter and Xylosandrus compactus (Eichhoff) (Coleoptera, Curculionidae: Scolytinae) newly recorded in Russia

AbstractIn 2023, two bark beetle species were recorded in Russia for the first time based on findings in Sochi: the cypress bark beetle, Phloeosinus armatus, on Mediterranean cypress (Cupressus sempervirens) and the black twig borer, Xylosandrus compactus, on southern magnolia (Magnolia grandiflora), noble laurel (Laurus nobilis), and cherry laurel (Prunus laurocerasus). P. armatus is a Mediterranean pest attacking exclusively Cupressaceae. In Sochi, it was recorded on cypress trees in several locations, including on plants for planting imported from Italy. X. compactus is a highly polyphagous pest from East Asia. In Sochi, it has established populations in ornamental planted areas. The paper provides species descriptions with identification keys. One specimen of X. compactus from Sochi was DNA‐barcoded and compared with 31 specimens deposited in the BOLD and GenBank under the name of X. compactus. High genetic variability (>7%) was detected highlighting the difficulty of identifying ‘true’ X. compactus using DNA data. Genetically, the specimen of X. compactus from Sochi was identical to those from Italy, Spain and France. An accidental introduction with ornamental plants for planting from Italy is considered the most probable pathway of invasion of both bark beetle species into the Russian Black Sea coast of the Caucasus.