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The methanogenic degradation of oil hydrocarbons can proceed through syntrophic partnerships of hydrocarbon-degrading bacteria and methanogenic archaea1-3. However, recent culture-independent studies have suggested that the archaeon 'Candidatus Methanoliparum' alone can combine the degradation of long-chain alkanes with methanogenesis4,5. Here we cultured Ca. Methanoliparum from a subsurface oil reservoir. Molecular analyses revealed that Ca. Methanoliparum contains and overexpresses genes encoding alkyl-coenzyme M reductases and methyl-coenzyme M reductases, the marker genes for archaeal multicarbon alkane and methane metabolism. Incubation experiments with different substrates and mass spectrometric detection of coenzyme-M-bound intermediates confirm that Ca. Methanoliparum thrives not only on a variety of long-chain alkanes, but also on n-alkylcyclohexanes and n-alkylbenzenes with long n-alkyl (C≥13) moieties. By contrast, short-chain alkanes (such as ethane to octane) or aromatics with short alkyl chains (C≤12) were not consumed. The wide distribution of Ca. Methanoliparum4-6 in oil-rich environments indicates that this alkylotrophic methanogen may have a crucial role in the transformation of hydrocarbons into methane.
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Euryarchaeota , Hidrocarburos , Metano , Alcanos/metabolismo , Biodegradación Ambiental , Euryarchaeota/enzimología , Euryarchaeota/genética , Hidrocarburos/metabolismo , Metano/metabolismo , Oxidorreductasas/metabolismo , FilogeniaRESUMEN
As a prototypical photocatalyst, TiO[Formula: see text] has been extensively studied. An interesting yet puzzling experimental fact was that P25-a mixture of anatase and rutile TiO[Formula: see text]-outperforms the individual phases; the origin of this mysterious fact, however, remains elusive. Employing rigorous first-principles calculations, here we uncover a metastable intermediate structure (MIS), which is formed due to confinement at the anatase/rutile interface. The MIS has a high conduction-band minimum level and thus substantially enhances the overpotential of the hydrogen evolution reaction. Also, the corresponding band alignment at the interface leads to efficient separation of electrons and holes. The interfacial confinement additionally creates a wide distribution of the band gap in the vicinity of the interface, which in turn improves optical absorption. These factors all contribute to the enhanced photocatalytic efficiency in P25. Our insights provide a rationale to the puzzling superior photocatalytic performance of P25 and enable a strategy to achieve highly efficient photocatalysis via interface engineering.
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Single-crystal semiconductor-based photocatalysts exposing unique crystallographic facets show promising applications in energy and environmental technologies; however, crystal facet engineering through solid-state synthesis for photocatalytic overall water splitting is still challenging. Herein, we develop a novel crystal facet engineering strategy through solid-state recrystallization to synthesize uniform SrTiO3 single crystals exposing tailored {111} facets. The presynthesized low-crystalline SrTiO3 precursors enable the formation of well-defined single crystals through kinetically improved crystal structure transformation during solid-state recrystallization process. By employing subtle Al3+ ions as surface morphology modulators, the crystal surface orientation can be precisely tuned to a controlled percentage of {111} facets. The photocatalytic overall water splitting activity increases with the exposure percentage of {111} facets. Owing to the outstanding crystallinity and favorable anisotropic surface structure, the SrTiO3 single crystals with 36.6% of {111} facets lead to a 3-fold enhancement of photocatalytic hydrogen evolution rates up to 1.55 mmol·h-1 in a stoichiometric ratio of 2:1 than thermodynamically stable SrTiO3 enclosed with isotropic {100} facets.
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Metal-organic frameworks (MOFs)-related Cu materials are promising candidates for promoting electrochemical CO2 reduction to produce valuable chemical feedstocks. However, many MOF materials inevitable undergo reconstruction under reduction conditions; therefore, exploiting the restructuring of MOF materials is of importance for the rational design of high-performance catalyst targeting multi-carbon products (C2). Herein, a facile solvent process is choosed to fabricate HKUST-1 with an anionic framework (a-HKUST-1) and utilize it as a pre-catalyst for alkaline CO2RR. The a-HKUST-1 catalyst can be electrochemically reduced into Cu with significant structural reconstruction under operating reaction conditions. The anionic HKUST-1 derived Cu catalyst (aHD-Cu) delivers a FEC2H4 of 56% and FEC2 of ≈80% at -150 mA cm-2 in alkaline electrolyte. The resulting aHD-Cu catalyst has a high electrochemically active surface area and low coordinated sites. In situ Raman spectroscopy indicates that the aHD-Cu surface displays higher coverage of *CO intermediates, which favors the production of hydrocarbons.
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Copper is one of the predominant water pollutants. Excessive exposure to copper can cause harm to animal health, affecting the central nervous system and causing blood abnormalities. Cuproptosis is a novel form of cell death that differs from previous programmed cell death methods. However, the impact of copper on the intestines remains unclear. Therefore, we investigated the effects of different concentrations of copper exposure on the intestinal proteome of Takifugu rubripes (T. rubripes). Relevant biomarkers were used to detect cuproptosis. We revealed the crosstalk relationship between cuproptosis and self-rescue at different concentrations, and discussed the feasibility of using potential cuproptosis indicators as anti-infection factors. We observed intestinal damage in the three copper exposure groups, especially in T. rubripes treated with 100 and 500⯵g/L copper, with shedding and breakage of intestinal villus and fuzzy and loose structure of intestinal mucosa. The presence of copper stress not only causes cuproptosis but also oxidative damage caused by reactive oxygen species (ROS). The results of quantitative proteomics by TMT showed that compared to the 50 and 100⯵g/L copper exposure groups, the expression of glutaminase, pyruvate kinase, and skin mucus lectin in the 500⯵g/L group was significantly increased. The positive mediators COX5A and CTNNB1, as well as the negative mediators CD4 and FDXR, were found to be differentially expressed. Using the protein expression trends of cuproptosis indicator factors FDX1 and DLAT to indicate the concentration of copper ions in the environment. In addition, we found a new effect of promoting ferroptosis: providing additional copper ions can activate the phenomenon of ferroptosis. Our results expand our understanding of the potential health risks of copper in T. rubripes. At the same time, it is of great significance for the process of copper poisoning and the development of new environmental toxicology detection reagents.
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Cobre , Proteoma , Takifugu , Contaminantes Químicos del Agua , Animales , Cobre/toxicidad , Proteoma/efectos de los fármacos , Takifugu/metabolismo , Contaminantes Químicos del Agua/toxicidad , Estrés Oxidativo/efectos de los fármacos , Mucosa Intestinal/efectos de los fármacos , Mucosa Intestinal/metabolismo , Intestinos/efectos de los fármacos , Biomarcadores/metabolismo , Especies Reactivas de Oxígeno/metabolismoRESUMEN
Polysaccharide from Asarum sieboldii Miq (ASP) was extracted and five phosphorylation polysaccharides with different degree of substitution were obtained, namely ASPP1, ASPP2, ASPP3, ASPP4, and ASPP5 (ASPPs). The physical and chemical structure and biological activities were studied. The results suggested that the carbohydrate and protein content were reduced while uronic acid was increased after phosphorylation modification. The molecular weight of ASPPs was significantly lower than that of ASP. ASPPs were acidic heteropolysaccharides mainly composed of galacturonic acid, galactose, glucose, fructose, and arabinose. The UV-vis spectrum indicated that the polysaccharides did not contain nucleic acid or protein after modification. The Fourier transform infrared spectrum demonstrated that ASPPs contained characteristic absorption peaks of P=O and P-O-C near 1270 and 980â cm-1 . ASPPs presented a triple helix conformation, but it was not presented in ASP. The scanning electron microscopy analysis showed that the surface topography and particle structure of ASP were different after modification. Compared with ASP, ASPPs enhanced the activity to scavenge DPPH and ABTS free radicals and possessed more protective ability to DNA oxidation caused by OHâ , GSâ , and AAPH free radicals. These results suggest that chemical modification is beneficial for the exploitation and utilization of natural polysaccharides.
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Antioxidantes , Asarum , Antioxidantes/farmacología , Antioxidantes/química , Fosforilación , Polisacáridos/farmacología , Polisacáridos/química , Radicales Libres , Espectroscopía Infrarroja por Transformada de FourierRESUMEN
Electrocatalytic carbon dioxide/carbon monoxide reduction reaction (CO(2)RR) has emerged as a prospective and appealing strategy to realize carbon neutrality for manufacturing sustainable chemical products. Developing highly active electrocatalysts and stable devices has been demonstrated as effective approach to enhance the conversion efficiency of CO(2)RR. In order to rationally design electrocatalysts and devices, a comprehensive understanding of the intrinsic structure evolution within catalysts and micro-environment change around electrode interface, particularly under operation conditions, is indispensable. Synchrotron radiation has been recognized as a versatile characterization platform, garnering widespread attention owing to its high brightness, elevated flux, excellent directivity, strong polarization and exceptional stability. This review systematically introduces the applications of synchrotron radiation technologies classified by radiation sources with varying wavelengths in CO(2)RR. By virtue of in situ/operando synchrotron radiationanalytical techniques, we also summarize relevant dynamic evolution processes from electronic structure, atomic configuration, molecular adsorption, crystal lattice and devices, spanning scales from the angstrom to the micrometer. The merits and limitations of diverse synchrotron characterization techniques are summarized, and their applicable scenarios in CO(2)RR are further presented. On the basis of the state-of-the-art fourth-generation synchrotron facilities, a perspective for further deeper understanding of the CO(2)RR process using synchrotron radiation analytical techniques is proposed.
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Polar materials with spontaneous polarization (Ps) have emerged as highly promising photocatalysts for efficient photocatalytic H2 evolution owing to the Ps-enhanced photogenerated carrier separation. However, traditional inorganic polar materials often suffer from limitations such as wide band gaps and poor carrier transport, which hinders their photocatalytic H2 evolution efficiency. Here, we rationally synthesized a series of isostructural two-dimensional (2D) aromatic Dion-Jacobson (DJ) perovskites, namely (2-(2-Aminoethyl)pyridinium)PbI4 (2-APDPI), (3-(2-Aminoethyl)pyridinium)PbI4 (3-APDPI), and (4-(2-Aminoethyl)pyridinium)PbI4 (4-APDPI), where 2-APDPI and 4-APDPI crystalize in polar space groups with piezoelectric constants (d33) of approximately 40â pm V-1 and 3-APDPI adopts a centrosymmetric structure. Strikingly, owing to the Ps-facilitated separation of photogenerated carriers, polar 2-APDPI and 4-APDPI exhibit a 3.9- and 2.8-fold increase, respectively, in photocatalytic H2 evolution compared to the centrosymmetric 3-APDPI. As a pioneering study, this work provides an efficient approach for exploring new polar photocatalysts and highlights their potential in promoting photocatalytic H2 evolution.
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Proton exchange membrane (PEM) electrolysis holds great promise for green hydrogen production, but suffering from high loading of platinum-group metals (PGM) for large-scale deployment. Anchoring PGM-based materials on supports can not only improve the atomic utilization of active sites but also enhance the intrinsic activity. However, in practical PEM electrolysis, it is still challenging to mediate hydrogen adsorption/desorption pathways with high coverage of hydrogen intermediates over catalyst surface. Here, operando generated stable palladium (Pd) hydride nanoclusters anchored on tungsten carbide (WCx) supports were constructed for hydrogen evolution in PEM electrolysis. Under PEM operando conditions, hydrogen intercalation induces formation of Pd hydrides (PdHx) featuring weakened hydrogen binding energy (HBE), thus triggering reverse hydrogen spillover from WCx (strong HBE) supports to PdHx sites, which have been evidenced by operando characterizations, electrochemical results and theoretical studies. This PdHx-WCx material can be directly utilized as cathode electrocatalysts in PEM electrolysis with ultralow Pd loading of 0.022â mg cm-2, delivering the current density of 1â A cm-2 at the cell voltage of ~1.66â V and continuously running for 200â hours without obvious degradation. This innovative strategy via tuning the operando characteristics to mediate reverse hydrogen spillover provide new insights for designing high-performance supported PGM-based electrocatalysts.
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In the context of oxygen evolution reaction (OER), the construction of high-valent transition metal sites to trigger the lattice oxygen oxidation mechanism is considered crucial for overcoming the performance limitations of traditional adsorbate evolution mechanism. However, the dynamic evolution of lattice oxygen during the reaction poses significant challenges for the stability of high-valent metal sites, particularly in high-current-density water-splitting systems. Here, we have successfully constructed Co-O-Fe catalytic active motifs in cobalt-iron Prussian blue analogs (CoFe-PBA) through oxygen plasma bombardment, effectively activating lattice oxygen reactivity while sustaining robust stability. Our spectroscopic and theoretical studies reveal that the Co-O-Fe bridged motifs enable a unique double-exchange interaction between Co and Fe atoms, promoting the formation of high-valent Co species as OER active centers while maintaining Fe in a low-valent state, preventing its dissolution. The resultant catalyst (CoFe-PBA-30) requires an overpotential of only 276 mV to achieve 1000 mA cm-2. Furthermore, the assembled alkaline exchange membrane electrolyzer using CoFe-PBA-30 as anode material achieves a high current density of 1 A cm-2 at 1.76 V and continuously operates for 250 hours with negligible degradation. This work provides significant insights for activating lattice oxygen redox without compromising structure stability in practical water electrolyzers.
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Electrochemical CO2 -to-CO conversion offers an attractive and efficient route to recycle CO2 greenhouse gas. Molecular catalysts, like CoPc, are proved to be possible replacement for precious metal-based catalysts. These molecules, a combination of metal center and organic ligand molecule, may evolve into single atom structure for enhanced performance; besides, the manipulation of molecules' behavior also plays an important role in mechanism research. Here, in this work, the structure evolution of CoPc molecules is investigated via electrochemical-induced activation process. After numbers of cyclic voltammetry scanning, CoPc molecular crystals become cracked and crumbled, meanwhile the released CoPc molecules migrate to the conductive substrate. Atomic-scale HAADF-STEM proves the migration of CoPc molecules, which is the main reason for the enhancement in CO2 -to-CO performance. The as-activated CoPc exhibits a maximum FECO of 99% in an H-type cell and affords a long-term durability at 100 mA cm-2 for 29.3 h in a membrane electrode assembly reactor. Density-functional theory (DFT) calculation also demonstrates a favorable CO2 activation energy with such an activated CoPc structure. This work provides a different perspective for understanding molecular catalysts as well as a reliable and universal method for practical utilization.
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Background: Although machine learning (ML)-based prediction of coronary artery disease (CAD) has gained increasing attention, assessment of the severity of suspected CAD in symptomatic patients remains challenging. Methods: The training set for this study consisted of 284 retrospective participants, while the test set included 116 prospectively enrolled participants from whom we collected 53 baseline variables and coronary angiography results. The data was pre-processed with outlier processing and One-Hot coding. In the first stage, we constructed a ML model that used baseline information to predict the presence of CAD with a dichotomous model. In the second stage, baseline information was used to construct ML regression models for predicting the severity of CAD. The non-CAD population was included, and two different scores were used as output variables. Finally, statistical analysis and SHAP plot visualization methods were employed to explore the relationship between baseline information and CAD. Results: The study included 269 CAD patients and 131 healthy controls. The eXtreme Gradient Boosting (XGBoost) model exhibited the best performance amongst the different models for predicting CAD, with an area under the receiver operating characteristic curve of 0.728 (95% CI 0.623-0.824). The main correlates were left ventricular ejection fraction, homocysteine, and hemoglobin (p < 0.001). The XGBoost model performed best for predicting the SYNTAX score, with the main correlates being brain natriuretic peptide (BNP), left ventricular ejection fraction, and glycated hemoglobin (p < 0.001). The main relevant features in the model predictive for the GENSINI score were BNP, high density lipoprotein, and homocysteine (p < 0.001). Conclusions: This data-driven approach provides a foundation for the risk stratification and severity assessment of CAD. Clinical Trial Registration: The study was registered in www.clinicaltrials.gov protocol registration system (number NCT05018715).
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Designing highly excellent and stable catalysts for alkaline oxygen evolution reaction (OER) is gradually pivotal for clean energy development. In this work, a heterogeneous Fe-doped Ni(OH)2 (Ni/Fe-0.1) was developed via simple one-step electrodeposition onto nickel mesh. The heterogeneous interface structure generates sufficient active sites, significantly improving OER performance with an overpotential of 174â mV at 10â mA cm-2 (η10 ), while Tafel slope is only 43.0â mV dec-1 . In particular, Ni/Fe-0.1 is still able to operate stably at a current density of 1â A cm-2 for 100â h without obvious potential decay. The oxidation of Ni2+ to Ni3+ was detected by X-ray photoelectron spectroscopy, proving that the heterogeneous catalyst could stabilize the high-valence state of nickel as active sites to its superior OER performance. This work provides a convenient synthetic strategy for forming heterogeneous catalysts toward efficient water electrolysis.
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To simultaneously improve the hole extraction ability of the BiVO4 photoanode and accelerate the surface reaction kinetics, herein, a carbon nanolayer conformally coated Fe2 O3 (C-Fe2 O3 ) as oxygen evolution catalyst (OEC) is loaded on the H2 plasma treated nanoporous BiVO4 (BVO(H2 )) surface by a hydrothermal reaction. It is found that the H2 plasma induced vacancies in BVO remarkably increases the conductivity, and the C-Fe2 O3 enables hole extraction from the bulk to the surface as well as efficient hole injection to the electrolyte. As a result, the C-Fe2 O3 /BVO(H2 ) photoanode achieves a photocurrent density of 4.4â mA/cm2 at 1.23â V vs. reversible hydrogen electrode (RHE) and an ABPE value of 1.5 % at 0.68â V vs. RHE, which are 4.8-fold and 13-fold higher than that of BVO photoanode, respectively.
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Electrocatalytic water splitting is one of the most commercially valuable pathways of hydrogen production especially combined with renewable electricity; however, efficient and durable electrocatalysts are urgently needed to reduce electric energy consumption. Here, we reported a Ru and Fe co-doped Mo2 C on nitrogen doped carbon via a controllable two-step method, which can be used for efficient and enduring hydrogen evolution reaction. At 10, 100 and 200â mA cm-2 in acidic electrolyte, the resultant Ru-Fe/Mo2 C@NC delivered low overpotentials of 31, 78 and 103â mV, respectively, which are comparable to that of the commercial Pt/C (20â wt %). At an applied current density of 100â mA cm-2 , stable hydrogen production was conducted for 120â h without obvious degradation. In alkaline media, Ru-Fe/Mo2 C@NC can also deliver a current density of 100â mA cm-2 for more than 100â h. Furthermore, the Ru-Fe/Mo2 C@NC electrocatalyst was used as cathode in an anion exchange membrane water electrolyzer under industrial environments for robust hydrogen production. The characterization and electrochemical results prove the synergism effects between Ru, Fe dopants and Mo2 C for promoting hydrogen evolution activity. This work would pave a new avenue to fabricate low-cost, high-performance hydrogen evolution electrocatalysts for industrial water electrolyzers.
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The discovery of high-performance catalysts for the electrochemical CO2 reduction reaction (CO2 RR) has faced an enormous challenge for years. The lack of cognition about the surface active structures or centers of catalysts in complex conditions limits the development of advanced catalysts for CO2 RR. Recently, the positive valent metal sites (PVMS) are demonstrated as a kind of potential active sites, which can facilitate carbon dioxide (CO2 ) activation and conversation but are always unstable under reduction potentials. Many advanced technologies in theory and experiment have been utilized to understand and develop excellent catalysts with PVMS for CO2 RR. Here, we present an introduction of some typical catalysts with PVMS in CO2 RR and give some understanding of the activity and stability for these related catalysts.
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Aeromonas salmonicida (A. salmonicida) is a pathogenic bacterium that causes serious problems in the global Atlantic salmon aquaculture industry. In this study, we comprehensively analyzed the profiles of lncRNAs, miRNAs and mRNAs in gills of Atlantic salmon at high-dose A. salmonicida infection (3.06 × 108 CFU/mL), low-dose A. salmonicida infection (3.06 × 105 CFU/mL), and a PBS (100 µL) control. We identified 65 differentially expressed lncRNAs, 41 miRNAs, and 512 mRNAs between the control group and infection groups. Functional analysis showed that these genes were significantly enriched in the p53 signaling pathway, Wnt signaling pathway, mTOR signaling pathway, JAK-STAT signaling pathway, and Toll-like receptor signaling pathway. In addition, we predicted key genes in immune-related pathways and constructed a lncRNA-miRNA-mRNA network based on whole transcriptomic analysis. We further predicted three lncRNA-miRNA-mRNA axes as potential novel biomarkers in regulating the immune response of Atlantic salmon against A. salmonicida infection.
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Aeromonas salmonicida , MicroARNs , ARN Largo no Codificante , Salmo salar , Aeromonas salmonicida/genética , Aeromonas salmonicida/metabolismo , Animales , MicroARNs/genética , ARN Largo no Codificante/genética , ARN Mensajero/genética , ARN Mensajero/metabolismo , Salmo salar/genética , Salmo salar/metabolismoRESUMEN
The imbalance of redox homeostasis is a major characteristic of aging and contributes to the pathogenesis of various aging-related diseases. As a regulatory hub of redox homeostasis, nuclear factor erythroid 2-related factor 2 (NRF2) can attenuate oxidative stress by activating the transcription of many antioxidant enzymes. China is the birthplace of traditional Chinese medicine (TCM) which has been wildly used as medicine for thousands of years. Recently, TCM as anti-aging medicine has attracted enormous attention. Focusing on the NRF2 signaling pathway, this paper summarizes the correlation between various anti-aging TCM and the NRF2 signaling, and discusses the common key mechanisms by which TCM slows the aging process by targeting the NRF2 signaling network.
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Medicina Tradicional China , Factor 2 Relacionado con NF-E2 , Factor 2 Relacionado con NF-E2/metabolismo , Estrés Oxidativo , Transducción de SeñalRESUMEN
OBJECTIVE: To explore the potential action mechanisms of Xiaoluowan (II) (XLW-II) in the treatment of epididymitis through a network pharmacology approach. METHODS: We searched various databases for relevant targets associated with epididymitis and XLW-II and obtained the common targets of epididymitis and XLW-II on the Venny platform. We acquired the protein-protein interactions (PPI) using the STRING data and had them visualized with the Cytoscape software. After topological analysis, we retrieved the key targets, followed by gene ontology (GO) and KEGG pathway enrichment analyses using the DAVID database. RESULTS: A total of 2 38 drug targets, 2 150 disease targets and 85 common targets were identified. The core targets for the treatment of epididymitis with XLW-II identified by PPI network analysis included TNF, IL6, IL1B, MMP9, AKT1, PTGS2 and TP53. GO function analysis revealed the involvement of the common targets in such biological processes as response to hypoxia, regulation of apoptotic processes, inflammatory response, and positive regulation of the MAPK cascade. KEGG pathway analysis suggested that the signaling pathways such as the cancer pathway, PI3K-Akt pathway, protein glycosylation pathway in cancer, Ras pathway and chemokine pathway might be related to the action mechanisms of XLW-II in the treatment of epididymitis. CONCLUSION: The potential targets and signaling pathways of Xiaoluowan (II) in the treatment of epididymitis were identified on the basis of network pharmacology, which has provided a novel insight into its action mechanisms and offered a new direction for further relevant studies.
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Medicamentos Herbarios Chinos , Epididimitis , Neoplasias , Masculino , Humanos , Epididimitis/tratamiento farmacológico , Farmacología en Red , Fosfatidilinositol 3-QuinasasRESUMEN
OBJECTIVE: To explore the potential mechanism of action of levocarnitine in the treatment of epididymitis based on network pharmacology and experimental research. METHODS: The target proteins related to epididymitis and levocarnitine were retrieved through multiple databases, and the common targets were obtained using Venny software. The protein-protein interactions were obtained using the STRING database. Cytoscape software was used for visualization, and key targets were selected after topological analysis. GO and KEGG pathway enrichment analysis was performed using the DAVID database. Molecular docking was performed using Autodock Vina. RESULTS: A total of 130 drug targets and 2 151 disease targets were obtained, with 47 common targets. Protein-protein interaction network analysis identified core targets of levocarnitine in the treatment of epididymitis, including AKT1, HSP90AA1, ALB, CASP3, GSK3B, and GSR. KEGG pathway analysis suggested that metabolic pathways, lipid metabolism and atherosclerosis, cancer pathways, fluid shear stress and atherosclerosis, measles, chemical carcinogens-reactive oxygen species, purine metabolism, PI3K-Akt, and other signaling pathways may be associated with the mechanism of levocarnitine in the treatment of epididymitis. CONCLUSION: This study revealed through network pharmacology that levocarnitine may act on multiple signaling pathways by targeting AKT1, HSP90AA1, ALB, CASP3, GSK3B, GSR, etc., thereby potentially exerting therapeutic effects on epididymitis.