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Electrooxidation of biomass-derived glycerol which is regarded as a main byproduct of industrial biodiesel production, is an innovative strategy to produce value-added chemicals, but currently showcases slow kinetics, limited Faraday efficiency, and unclear catalytic mechanism. Herein, we report high-efficiency electrooxidation of glycerol into formate via a Cu doped NiCo alloy catalyst supported on nickel foam (Cu-NiCo/NF) in a coupled system paired with nitrate reduction. The designed Cu-NiCo/NF delivers only 1.23 V vs. RHE at 10 mA cm-2, and a record Faraday efficiency of formate of 93.8%. The superior performance is ascribed to the rapid generation of NiIII-OOH and CoIII-OOH and favorable coupling of surface *O with reactive intermediates. Using Cu-NiCo/NF as a bifunctional catalyst, the coupled system synchronously produces NH3 and formate, showing 290 mV lower than the coupling of hydrogen evolution reaction, together with excellent long-term stability for up to 144 h. This work lays out new guidelines and reliable strategies from catalyst design to system coupling for biomass-derived electrochemical refinery.
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Using renewable electricity to convert CO2 into CO offers a sustainable route to produce a versatile intermediate to synthesize various chemicals and fuels. For economic CO2-to-CO conversion at scale, however, there exists a trade-off between selectivity and activity, necessitating the delicate design of efficient catalysts to hit the sweet spot. We demonstrate here that copper co-alloyed with isolated antimony and palladium atoms can efficiently activate and convert CO2 molecules into CO. This trimetallic single-atom alloy catalyst (Cu92Sb5Pd3) achieves an outstanding CO selectivity of 100% (±1.5%) at -402 mA cm-2 and a high activity up to -1 A cm-2 in a neutral electrolyte, surpassing numerous state-of-the-art noble metal catalysts. Moreover, it exhibits long-term stability over 528 h at -100 mA cm-2 with an FECO above 95%. Operando spectroscopy and theoretical simulation provide explicit evidence for the charge redistribution between Sb/Pd additions and Cu base, demonstrating that Sb and Pd single atoms synergistically shift the electronic structure of Cu for CO production and suppress hydrogen evolution. Additionally, the collaborative interactions enhance the overall stability of the catalyst. These results showcase that Sb/Pd-doped Cu can steadily carry out efficient CO2 electrolysis under mild conditions, challenging the monopoly of noble metals in large-scale CO2-to-CO conversion.
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It has been reported that it was selective to produce ammonia on metallic cobalt in the electrocatalytic nitric oxide reduction reaction (eNORR), where hexagonal close-packed (hcp) cobalt outperforms face-centered cubic (fcc) cobalt. However, hydroxylamine is more selectively produced on a cobalt single-atom catalyst (Co-SAC). Herein, we uncover the structural sensitivity over hcp-Co, fcc-Co, and Co-SAC in eNORR by employing a recently developed constant potential simulation method and microkinetic modeling. It was found that the superior activity for ammonia production on hcp-Co can be attributed to its facile electron and proton transfer and a stronger lateral suppression effect from NO* over fcc-Co. The exceptional hydroxylamine selectivity on Co-SAC is due to the modified electronic structure, namely, a positively charged active center. It was found that it is more favorable to produce NOH* over hcp-Co and fcc-Co, while HNO* is more preferable on Co-SAC, which are firmly correlated with the vertical and strong NO adsorption on the former and the moderate adsorption on the latter. In other words, a key factor for selectivity control is the first step of NO* protonation. Therefore, the local structure and electronic structure of the catalysts can be critical in regulating the activity and selectivity in eNORR.
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A small fraction of NOx (<1%) always exists in CO2 feedstock (e.g. exhausted gas), which can significantly reduce the efficiency of CO2 electroreduction by â¼30%. Hence, electrochemical denitrification is the precondition of CO2 electroreduction. The pH effect is a key factor, and can be used to tune the selectivity between N2 and N2O production in electrochemical denitrification. However, there has been much controversy for many years about the origin of pH dependence in electrocatalysis. To this end, we present a new scheme to accurately model the pH dependence of the electrochemical mechanism. An extremely small pH variation from pH 12.7 to pH 14 can be accurately reproduced for N2O production. More importantly, the obviously different pH dependence of N2 production, compared to N2O, can be attributed to a cascade path. In other words, the N2 was produced from the secondary conversion of the as-produced N2O molecule (the major product), instead of the original reactant NO. This is further supported by more than 35 experiments over varying catalysts (Fe, Ni, Pd, Cu, Co, Pt and Ag), partial pressures (20%, 50% and 100%) and potentials (from -0.2 to 0.2 V vs. reversible hydrogen electrode). All in all, the insights herein overturn long-lasting views in the field of NO electroreduction and suggest that rational design should steer away from catalyst engineering toward reactor optimization.
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BACKGROUND: Renal fibrosis is considered an irreversible pathological process and the ultimate common pathway for the development of all types of chronic kidney diseases and renal failure. Diosmin is a natural flavonoid glycoside that has antioxidant, anti-inflammatory, and antifibrotic activities. However, whether Diosmin protects kidneys by inhibiting renal fibrosis is unknown. We aimed to investigate the role of Diosmin in renal interstitial fibrosis and to explore the underlying mechanisms. METHODS: The UUO mouse model was established and gavaged with Diosmin (50 mg/kg·d and 100 mg/kg·d) for 14 days. HE staining, Masson staining, immunohistochemistry, western blotting and PCR were used to assess renal tissue injury and fibrosis. Elisa kits were used to detect the expression levels of IL-1ß, IL-6, and TNF-α and the activity of SIRT3 in renal tissues. In addition, enrichment maps of RNA sequencing analyzed changes in signaling pathways. In vitro, human renal tubular epithelial cells (HK-2) were stimulated with TGF-ß1 and then treated with diosmin (75 µM). The protein and mRNA expression levels of SIRT3 were detected in the cells. In addition, 3-TYP (selective inhibitor of SIRT3) and SIRT3 small interfering RNA (siRNA) were used to reduce SIRT3 levels in HK-2. RESULTS: Diosmin attenuated UUO-induced renal fibrosis and TGF-ß1-induced HK-2 fibrosis. In addition, Diosmin reduced IL-1ß, IL-6, and TNF-α levels in kidney tissues and supernatants of HK-2 medium. Interestingly, Diosmin administration increased the enzymatic activity of SIRT3 in UUO kidneys. In addition, Diosmin significantly increased mRNA and protein expression of SIRT3 in vitro and in vivo. Inhibition of SIRT3 expression using 3-TYP or SIRT3 siRNA abolished the anti-inflammatory effects of diosmin in HK-2 cells. Enrichment map analysis by RNA sequencing indicates that the nuclear factor-kappa B (NF-κB) signaling pathway was inhibited in the Diosmin intervention group. Furthermore, we found that TGF-ß1 increased the nuclear expression of nuclear NF-κB p65 but had little significant effect on the total intracellular expression of NF-κB p65. Additionally, Diosmin reduced TGF-ß1-caused NF-κB p65 nuclear translocation. Knockdown of SIRT3 expression by SIRT3 siRNA increased the nuclear expression of NF-κB p65 and abolished the inhibition effect of Diosmin in NF-κB p65 expression. CONCLUSIONS: Diosmin reduces renal inflammation and fibrosis, which is contributed by inhibiting nuclear translocation of NF-κB P65 through activating SIRT3.
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Diosmina , Nefropatias , Sirtuína 3 , Humanos , Animais , Camundongos , NF-kappa B , Diosmina/farmacologia , Fator de Crescimento Transformador beta1 , Interleucina-6 , Fator de Necrose Tumoral alfa , Nefropatias/tratamento farmacológico , Inflamação/tratamento farmacológico , Anti-Inflamatórios/farmacologia , Fibrose , RNA Mensageiro , RNA Interferente PequenoRESUMO
Objective Our objective was to compare the long-term outcomes of endoscopic resection versus open surgery in combination with radiotherapy for locally advanced sinonasal malignancies (SNMs). Methods Data for continuous patients with sinonasal squamous cell carcinoma and adenocarcinoma who received surgery (endoscopic or open surgery) combined with radiotherapy in our center between January 1999 and December 2016 were retrospectively reviewed. A 1:1 matching with propensity scores was performed. Overall survival (OS), progression-free survival (PFS), and local recurrence rate (LRR) were evaluated. Results We identified 267 eligible patients, 90 of whom were included after matching: 45 patients in the endoscopy group and 45 in the open group. The median follow-up time was 87 months. In the endoscopic group, 84.4% of patients received intensity-modulated radiotherapy (IMRT), with a mean gross tumor volume (GTV) dose of 68.28 Gy; in the open surgery group, 64.4% of patients received IMRT, with a mean GTV dose of 64 Gy. The 5-year OS, PFS, and LRR were 69.9, 58.6, and 24.5% in the endoscopic group and 64.6, 54.4, and 31.8% in the open surgery group, respectively. Multivariable regression analysis revealed that the surgical approach was not associated with lower OS, PFS, or LRR. The overall postoperative complications were 13% in the endoscopic group, while 21.7% in the open group. Conclusion For patients with locally advanced SNMs, minimally invasive endoscopic resection, in combination with a higher radiation dose and new radiation techniques such as IMRT, yields survival outcomes similar to those of open surgery in combination with radiotherapy.
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Proton exchange membrane water electrolysis is a highly promising hydrogen production technique for sustainable energy supply, however, achieving a highly active and durable catalyst for acidic water oxidation still remains a formidable challenge. Herein, we propose a local microenvironment regulation strategy for precisely tuning In-RuO2 /graphene (In-RuO2 /G) catalyst with intrinsic electrochemical activity and stability to boost acidic water oxidation. The In-RuO2 /G displays robust acid oxygen evolution reaction performance with a mass activity of 671â A gcat -1 at 1.5â V, an overpotential of 187â mV at 10â mA cm-2 , and long-lasting stability of 350â h at 100â mA cm-2 , which arises from the asymmetric Ru-O-In local structure interactions. Further, it is unraveled theoretically that the asymmetric Ru-O-In structure breaks the thermodynamic activity limit of the traditional adsorption evolution mechanism which significantly weakens the formation energy barrier of OOH*, thus inducing a new rate-determining step of OH* absorption. Therefore, this strategy showcases the immense potential for constructing high-performance acidic catalysts for water electrolyzers.
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In contrast to numerous studies on oxygen species, the interaction of volatile organic compounds (VOCs) with oxides is also critical to the catalytic reaction but has hardly been considered. Herein, we develop a highly efficient Pt atom doped spinel CoMn2O4 (Pt-CoMn) for oxidation of toluene at low temperature, and the toluene conversion rate increased by 18.3 times (129.7 versus 7.1 × 10-11 mol/(m2·s)) at 160 °C compared to that of CoMn2O4. Detailed characterizations and density functional theory calculations reveal that the local electron environment of the Co sites is changed after Pt doping, and the formed electron-deficient Co sites in turn strengthen the interaction with toluene. Adsorbed toluene will react with lattice oxygen in Pt-CoMn and CoMn catalysts and convert into benzoate intermediates, and the consumption rate of benzoate is closely related to the activation of gaseous oxygen. Significantly, the abundant bulk defects of Pt-CoMn help to open the reaction channel in the CoMn spinel, which acts as an oxygen pump to promote the transformation of bulk lattice oxygen into surface lattice oxygen at lower temperatures, thus accelerating the conversion rate of benzoate intermediates into CO2 and enhancing low-temperature combustion of toluene. Pt-CoMn developed here emphasizes the regulation of VOCs adsorption strength and lattice oxygen transformation processes on CoMn2O4 by adjusting the local electron environment, which will provide new guidance for the design of efficient oxide catalysts for catalytic oxidation.
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Elétrons , Oxigênio , Adsorção , Óxidos , Tolueno , Benzoatos , CatáliseRESUMO
Background: Intrahepatic cholestasis of pregnancy (ICP) is likely to lead to unfavorable consequences. Total bile acid (TBA) is thought to be the sole ICP indicator available as of now, but it comes with some kind of restrictions in terms of sensitivity and specificity. We were endeavoring to find potential diagnostic biomarkers for ICP in this investigation. Methods: This case-control study with a prospective nature included 40 females in the stage of pregnancy who were diagnosed with ICP. It also included another 20 females who were also pregnant but with sound physical condition(control). Placental and plasma samples were collected from all females that were in the stage of pregnancy, except for 20 ICP patients, in which only plasma was collected. We used four-dimensional data-independent acquisition followed by enzyme-linked immunosorbent assay and immunohistochemistry to identify and validate plasma and placental profiles in ICP patients and controls. Bioinformatics was adopted in an effort to demonstrate the relevant biological processes and signalling pathways. Correlation analysis was used to analyse the consistency of tissue and plasma protein expression and the correlation between sequencing and experimental results. Results: The expression levels of nectin-1 (NECTIN1), Kunitz-type protease inhibitor 1 (SPINT1), and inter-alpha-trypsin inhibitor heavy chain H3 (ITIH3) were remarkably higher in ICP patients than in controls. However, heparin cofactor 2 (SERPIND1) expression levels in female participants in the stage of pregnancy who were diagnosed with ICP were remarkably lower than those pregnant females with good physical fitness. In addition to the negative correlation between SERPIND1 and TBA, NECTIN1, SPINT1, and ITIH3 expression positively correlated with TBA. Area under the receiver operating characteristic curve (AUC) values of 0.7925, 0.8313, 0.8163, and 0.9025, respectively, were used to assess the diagnostic accuracies of NECTIN1, SPINT1, ITIH3, and SERPIND1. AUC (0.9438) was considerably greater when NECTIN1, SPINT1, and SERPIND1 were integrated, according to binary logistic regression. The AUC of the ROC curve for various combinations of SERPIND1 and other indicators was higher than itself, thus providing a more reliable ICP diagnosis. Furthermore, according to the bioinformatics analysis, the NECTIN1, SPINT1, ITIH3, and SERPIND1 were identified as secreted proteins because they were localized in the extracellular region. Conclusions: This research discovered new non-invasive ICP indicators. On top of this, it sheds new light on the crucial diagnostic function of secreted proteins in ICP.
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Full understanding to the origin of the catalytic performance of a supported nanocatalyst from the points of view of both the active component and support is significant for the achievement of high performance. Herein, based on a model electrocatalyst of single-iridium-atom-doped iron (Fe)-based layered double hydroxides (LDH) for oxygen evolution reaction (OER), we reveal the first completed origin of the catalytic performance of such supported nanocatalysts. Specially, besides the activity enhancement of Ir sites by LDH support, the stability of surface Fe sites is enhanced by doped Ir sites: DFT calculation shows that the Ir sites can reduce the activity and enhance the stability of the nearby Fe sites; while further finite element simulations indicate, the stability enhancement of distant Fe sites could be attributed to the much low concentration of OER reactant (hydroxyl ions, OH- ) around them induced by the much fast consumption of OH- on highly active Ir sites. These new findings about the interaction between the main active components and supports are applicable in principle to other heterogeneous nanocatalysts and provide a completed understanding to the catalytic performance of heterogeneous nanocatalysts.
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OBJECTIVE: To analyze the failure patterns in patients with different histological subtypes of sinonasal malignancies (SNMs). STUDY DESIGN: Retrospectively gathered data. SETTING: Academic university hospital. METHODS: Patients with SNMs treated at a tertiary referral center between January 1999 and January 2019 were included. We assessed the failure patterns within different histological subtypes. RESULTS: The study included 897 patients. The median follow-up time was 100 months. Adenoid cystic carcinoma (ACC) had a moderate risk of developing local recurrence (LR) and distant metastasis (DM). Compared with ACC, squamous cell carcinoma (SCC), adenocarcinoma (AC), soft tissue sarcoma (STS), and mucosal melanoma (MM) were classified as a high LR risk group. For DM, neuroendocrine carcinoma (NEC), STS, and MM were in the high-risk group. CONCLUSIONS: ACC had intermediate local and distant failure risks, while SCC, AC, STS, and MM were at high LR risks. NEC, STS, and MM were at high DM risk.
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Carcinoma Adenoide Cístico , Carcinoma de Células Escamosas , Melanoma , Humanos , Estudos Retrospectivos , Carcinoma Adenoide Cístico/patologia , Carcinoma Adenoide Cístico/secundário , Carcinoma Adenoide Cístico/terapia , Carcinoma de Células Escamosas/patologia , Recidiva Local de Neoplasia/patologiaRESUMO
Molybdenum supported on zeolites has been extensively studied as a catalyst for methane dehydroaromatization. Despite significant progress, the actual intermediates and particularly the first C-C bond formation have not yet been elucidated. Herein we report evolution of methyl radicals during non-oxidative methane activation over molybdenum single sites, which leads selectively to value-added chemicals. Operando X-ray absorption spectroscopy and online synchrotron vacuum ultraviolet photoionization mass spectroscopy in combination with electron microscopy and density functional theory calculations reveal the essential role of molybdenum single sites in the generation of methyl radicals and that the formation rate of methyl radicals is linearly correlated with the number of molybdenum single sites. Methyl radicals transform to ethane in the gas phase, which readily dehydrogenates to ethylene in the absence of zeolites. This is essentially similar to the reaction pathway over the previously reported SiO2 lattice-confined single site iron catalyst. However, the availability of a zeolite, either in a physical mixture or as a support, directs the subsequent reaction pathway towards aromatization within the zeolite confined pores, resulting in benzene as the dominant hydrocarbon product. The findings reveal that methyl radical chemistry could be a general feature for metal single site catalysis regardless of the support (either zeolites MCM-22 and ZSM-5 or SiO2) whereas the reaction over aggregated molybdenum carbide nanoparticles likely facilitates carbon deposition through surface C-C coupling. These findings allow furthering the fundamental insights into non-oxidative methane conversion to value-added chemicals.
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Electrohydrodynamic jet (E-Jet) printing technology provides unmatched advantages in the fabrication of patterned micro/nanostructures. However, the rapid jets generated during printing can lead to localized droplet accumulation on complex structures due to the relatively slow motion control achieved with motorized translation stages, resulting in distorted patterns. To address this challenge, we introduce two jet-deflecting electrodes orthogonally placed on each other, which can rapidly change the electric field in the vicinity of the jet and thus flexibly adjust the flight trajectory of the fast jet to avoid the region where droplets have been deposited. In this way, the jet droplets are precisely controlled to generate high-fidelity microstructures with arbitrary predefined patterns on the stationary substrate. The maximum deflection distance of the jet droplets reaches several hundred microns. Furthermore, the positioning error of the printed structure is less than 3%. Moreover, we successfully obtained a diverse range of complex patterns by combining this technique with stage motion. This innovative printing technology not only enables the fabrication of complex patterned structures with high fidelity but also opens up exciting possibilities for new applications that require complete control of fast droplet positioning.
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EZH2 is a member of PcG and can induce the occurrence of cancer when it is highly expressed. As an EZH2 inhibitor, Tazemetostat (EPZ6438) can inhibit the methylation catalytic activity of EZH2. However, many studies have shown that inhibition of EZH2 alone does not efficiently block tumor development. Therefore, in this study, proteolytic targeting chimera technology was employed to enhance the antiproliferative potency of EPZ6438 by degrading the oncogenic activity of EZH2. Several PROTACs have been synthesized by combining EPZ6438 with four E3 ligase ligands based on VHL, CRBN, MDM2, and cIAP E3 ligase systems. In our study, compound E-3P-MDM2 is the most active PROTAC molecule. It degraded EZH2 of the SU-DHL-6 cells in a concentration and dose-dependent manner and also degraded both EED and SUZ12 protein without affecting their mRNA levels, then significantly inhibited the expression of H3K27me3. The in vitro antiproliferative activity of E-3P-MDM2 was much stronger than that of EPZ6438.
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Linfoma , Neoplasias , Humanos , Quimera de Direcionamento de Proteólise , Linfoma/metabolismo , Neoplasias/metabolismo , Núcleo Celular/metabolismo , Ubiquitina-Proteína Ligases/metabolismo , Proteólise , Proteína Potenciadora do Homólogo 2 de Zeste/metabolismoRESUMO
Objective: To investigate the effect of cardiac valve calcification (CVC) on the prognosis of patients with chronic kidney disease (CKD). Methods: A total of 343 CKD patients were retrospectively analyzed, and divided into two groups according to the presence or absence of cardiac valve calcification. All patients were followed until death, loss to follow-up, or the end point of the study (December 2021). Results: The incidence of CVC among the 343 CKD patients was 29.7%, including 21 cases of mitral valve calcification, 63 cases of aortic valve calcification, and 18 cases of mitral valve combined with aortic valve calcification. The incidence of CVC in CKD stages 1-2 was 0.3%, 5.2% in CKD stages 3-4, and 24.2% in CKD stage 5 (P < 0.05). Advanced age, higher serum albumin, higher cystatin C and lower uric acid levels were all associated with a higher risk of CVC. After six years of follow-up, 77 patients (22.4%) died. The causes of death were cardiovascular and cerebrovascular diseases in 36 cases (46.7%), infection in 29 cases (37.7%), gastrointestinal bleeding in nine cases (11.7%), and "other" in the remaining three cases (3.9%). A Kaplan Meier survival analysis showed that the overall survival rate of patients with CVC was lower than that of patients without CVC. Conclusion: The incidence of CVC, mainly aortic calcification, is high in patients with CKD. Advanced age, higher serum albumin and higher cystatin C levels were associated with a higher risk of CVC. Hyperuricemia was associated with a lower risk of CVC. The overall survival rate of patients with CVC was lower than that of patients without CVC.
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Doenças das Valvas Cardíacas , Insuficiência Renal Crônica , Humanos , Estudos Retrospectivos , Cistatina C , Diálise Renal , Doenças das Valvas Cardíacas/epidemiologia , Insuficiência Renal Crônica/epidemiologia , Valva Aórtica/diagnóstico por imagemRESUMO
Electrochemical CO2 conversion to methane, powered by intermittent renewable electricity, provides an entrancing opportunity to both store renewable electric energy and utilize emitted CO2. Copper-based single atom catalysts are promising candidates to restrain C-C coupling, suggesting feasibility in further protonation of CO* to CHO* for methane production. In theoretical studies herein, we find that introducing boron atoms into the first coordination layer of Cu-N4 motif facilitates the binding of CO* and CHO* intermediates, which favors the generation of methane. Accordingly, we employ a co-doping strategy to fabricate B-doped Cu-Nx atomic configuration (Cu-NxBy), where Cu-N2B2 is resolved to be the dominant site. Compared with Cu-N4 motifs, as-synthesized B-doped Cu-Nx structure exhibits a superior performance towards methane production, showing a peak methane Faradaic efficiency of 73% at -1.46 V vs. RHE and a maximum methane partial current density of -462 mA cm-2 at -1.94 V vs. RHE. Extensional calculations utilizing two-dimensional reaction phase diagram analysis together with barrier calculation help to gain more insights into the reaction mechanism of Cu-N2B2 coordination structure.
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Dióxido de Carbono , Cobre , Boro , Eletricidade , MetanoRESUMO
Ammonia is important for modern agriculture and food production as it is a major source of fertilizer. Electrochemical ammonia synthesis (EAS) with sustainable energy generated electricity and decentralized reactors has been considered as environmentally friendly process. Several nitrogen sources have been considered and intensively studied in experiments and computations. Recently, it has been proposed and demonstrated that nitrogen oxides (NOx ) electroreduction for selective ammonia production is feasible. Fundamental insights on experimental observation are necessary for more rational design of catalysts and reactors in the future. In this concept, we review the theoretical and computational insights of electrochemical nitrogen oxides reduction, particularly, the activity trend over diverse transition metal catalysts and products selectivity at varying potentials. Finally, we address the opportunities and challenges in the reverse artificial nitrogen cycle, as well as fundamental issues in electrochemical reaction modelling.
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AIM: To investigate the contribution of GAS5 in the pathogenesis of SLE. BACKGROUND: Systemic Lupus Erythematosus (SLE) is characterized by aberrant activity of the immune system, leading to variable clinical symptoms. The etiology of SLE is multifactor, and growing evidence has shown that long noncoding RNAs (lncRNAs) are related to human SLE. Recently, lncRNA growth arrest-specific transcript 5 (GAS5) has been reported to be associated with SLE. However, the mechanism between GAS5 and SLE is still unknown. OBJECTIVE: Find the specific mechanism of action of lncRNA GAS5 in SLE. METHODS: Collecting samples of the SLE patients, Cell culture and treatment, Plasmid construction, and transfection, Quantitative real-time PCR analysis, Enzyme-linked immunosorbent assay (ELISA), Cell viability analysis, Cell apoptosis analysis, Western blot. RESULTS: In this research, we investigated the contribution of GAS5 in the pathogenesis of SLE. We confirmed that, compared to healthy people, the expression of GAS5 was significantly decreased in peripheral monocytes of SLE patients. Subsequently, we found that GAS5 can inhibit the proliferation and promote the apoptosis of monocytes by over-expressing or knocking down the expression of GAS5. Additionally, the expression of GAS5 was suppressed by LPS. Silencing GAS5 significantly increased the expression of a group of chemokines and cytokines, including IL-1ß, IL-6, and THFα, which were induced by LPS. Furthermore, it was identified the involvement of GAS5 in the TLR4-mediated inflammatory process was through affecting the activation of the MAPK signaling pathway. CONCLUSION: In general, the decreased GAS5 expression may be a potential contributor to the elevated production of a great number of cytokines and chemokines in SLE patients. And our research suggests that GAS5 contributes a regulatory role in the pathogenesis of SLE, and may provide a potential target for therapeutic intervention.
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Lúpus Eritematoso Sistêmico , RNA Longo não Codificante , Humanos , Citocinas , Lipopolissacarídeos , Lúpus Eritematoso Sistêmico/genética , RNA Longo não Codificante/genética , Transdução de SinaisRESUMO
Breaking the trade-off between activity and selectivity has been a long-standing challenge in the field of catalysis. We demonstrate the importance of disentangling the target reaction from the secondary reactions for the case of direct syngas conversion to light olefins by incorporating germanium-substituted AlPO-18 within the framework of the metal oxide-zeolite (OXZEO) catalyst concept. The attenuated strength of the catalytically active Brønsted acid sites allows enhancing the targeted carbon-carbon coupling of ketene intermediates to form olefins by increasing the active site density while inhibiting secondary reactions that consume the olefins. Thus, a light-olefins selectivity of 83% among hydrocarbons and carbon monoxide conversion of 85% were obtained simultaneously, leading to an unprecedented light-olefins yield of 48% versus current reported light-olefins yields of ≤27%.
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The oxide-zeolite (OXZEO) catalyst design concept has been demonstrated in an increasing number of studies as an alternative avenue for direct syngas conversion to light olefins. We report that face-centered cubic (FCC) MnGaOx -Spinel gives 40 % CO conversion, 81 % light olefins selectivity, and a 0.17â g gcat -1 h-1 space-time yield of light olefins in combination with SAPO-18. In comparison, solid solution MnGaOx (characterized by Mn-doped hexagonal close-packed (HCP) Ga2 O3 ) with a similar chemical composition gives a much inferior activity, i.e., the specific surface activity is one order of magnitude lower than the spinel oxide. Photoluminescence (PL), in situ Fourier-transform infrared (FT-IR), and density functional theory (DFT) calculations indicate that the superior activity of MnGaOx -Spinel can be attributed to its higher reducibility (higher concentration of oxygen vacancies) and the presence of coordinatively unsaturated Ga3+ sites, which facilitates the dissociation of the C-O bond via a more efficient ketene-acetate pathway to light olefins.