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1.
J Colloid Interface Sci ; 678(Pt A): 63-76, 2025 Jan 15.
Artículo en Inglés | MEDLINE | ID: mdl-39180849

RESUMEN

Doping modification is a useful way to promote the catalytic activity of carbon nitride (CN). However, most doped CNs have lower structural symmetry and several edge defects, which hinder the transfer of charge carriers. This work reports a P-doped crystalline carbon nitride (crystalline PCN) for the efficient photoreduction of uranyl. The thermal polymerization and salt post-treatment convert the amorphous PCN into crystalline PCN. Compared to the pristine CN, the crystalline PCN has over 1620 % higher activity for uranyl (U(VI)) reduction, reaching a 97.8 % reduction rate in 60 min. Furthermore, the 2-PCN shows excellent stability and a U(VI) removal efficiency >85.7 % in the pH range of 5-8. Characterization analysis reveal that both the P doping and crystalline modulation do not obviously change their morphology, light absorption property and energy band structure, but markedly promote the delocalization of electrons around the doped P atoms, thereby severely inhibit direct electron-hole recombination. Thus, the more efficient separation of charge carriers generates more reactive specials to participate in the photocatalytic uranyl reduction reaction. This study demonstrates a dual-modification strategy for the rational synthesis of highly active metal-free CN-based photocatalysts for uranyl reduction.

2.
ACS Nano ; 18(41): 28433-28443, 2024 Oct 15.
Artículo en Inglés | MEDLINE | ID: mdl-39365637

RESUMEN

Manipulation of the spin state holds great promise to improve the electrochemical activity of transition metal-based catalysts. However, the underlying relationship between the nonplanar metal coordination environment and spin states remains to be explored. Herein, we report the precise regulation of nonplanar Fe atomic d-orbital energy level into an irregular tetrahedral crystal field configuration by introducing P atoms. With the increase of P coordination number, the spin magnetic moment decreases linearly from 3.8 µB to 0.2 µB, and the high spin content decreases linearly from 31% to 5%. Significantly, a volcanic curve between the spin states of Fe-based catalysts (Fe-NxPy) and oxygen reduction reaction (ORR) activity has been unequivocally established based on the thermodynamic results. Thus, the Fe-N3P1 catalyst with a 19% medium spin state experimentally exhibits the optimal reaction activity with a high half-wave potential of 0.92 V. These findings indicate that regulating electron spin moments through coordination engineering is a promising catalyst design strategy, providing important insights into spin catalysis.

3.
J Am Chem Soc ; 146(42): 29084-29093, 2024 Oct 23.
Artículo en Inglés | MEDLINE | ID: mdl-39394051

RESUMEN

Understanding the characteristics of interfacial hydroxyl (OH) at the solid/liquid electrochemical interface is crucial for deciphering synergistic catalysis. However, it remains challenging to elucidate the influences of spatial distance between interfacial OH and neighboring reactants on reaction kinetics at the atomic level. Herein, we visualize the distance-dependent synergistic interaction in heterogeneous dual-site catalysis by using ex-situ infrared nanospectroscopy and in situ infrared spectroscopy techniques. These spectroscopic techniques achieve direct identification of the spatial distribution of synergistic species and reveal that OH facilitates the reactant deprotonation process depending on site distances in dual-site catalysts. Via modulating Ir-Co pair distances, we find that the dynamic equilibrium between generation and consumption of OH accounts for high-efficiency synergism at the optimized distance of 7.9 Å. At farther or shorter distances, spatial inaccessibility and resistance of OH with intermediates lead to OH accumulation, thereby diminishing the synergistic effect. Hence, a volcano-shaped curve has been established between the spatial distance and mass activity using formic acid oxidation as the probe reaction. This notion could also be extended to oxophilic metals, like Ir-Ru pairs, where volcano curves and dynamic equilibrium further evidence the universal significance of spatial distances.

4.
Nanoscale ; 16(41): 19364-19373, 2024 Oct 24.
Artículo en Inglés | MEDLINE | ID: mdl-39330545

RESUMEN

The efficiency of the oxygen evolution reaction (OER) is severely limited by the sluggish proton-coupled electron transfer processes and inadequate long-term stability. Herein, we introduce a carboxylate group (TPA) to modify NiFe layered double hydroxide (NiFe LDH@TPA), resulting in notable improvements in both activity and stability. A combination of spectroscopic and theoretical investigations reveals the dual-functional role of incorporated TPA. It facilitates the deprotonation of OER intermediates while strengthening the Fe-O bond and acting as a molecular fence, ensuring superior OER kinetics and anti-dissolution properties. NiFe LDH@TPA delivers a low overpotential of 200 mV at 10 mA cm-2 and an impressive long-term stability of 500 h at 150 mA cm-2, significantly outperforming its unmodified counterpart. Furthermore, operating in an anion exchange membrane water electrolyzer, it affords prolonged stability at an industrial-scale current density of 1 A cm-2, sustaining performance for over 120 hours. This strategy offers a promising avenue for the development of durable and efficient OER catalysts.

5.
Natl Sci Rev ; 11(10): nwae252, 2024 Oct.
Artículo en Inglés | MEDLINE | ID: mdl-39301064

RESUMEN

While atomically precise metal nanoclusters (NCs) with unique structures and reactivity are very promising in catalysis, the spatial resistance caused by the surface ligands and structural instability poses significant challenges. In this work, Au25(Cys)18 NCs are encapsulated in multivariate metal-organic frameworks (MOFs) to afford Au25@M-MOF-74 (M = Zn, Ni, Co, Mg). By the MOF confinement, the Au25 NCs showcase highly enhanced activity and stability in the intramolecular cascade reaction of 2-nitrobenzonitrile. Notably, the interaction between the metal nodes in M-MOF-74 and Au25(Cys)18 is able to suppress the free vibration of the surface ligands on the Au25 NCs and thereby improve the accessibility of Au sites; meanwhile, the stronger interactions lead to higher electron density and core expansion within Au25(Cys)18. As a result, the activity exhibits the trend of Au25@Ni-MOF-74 > Au25@Co-MOF-74 > Au25@Zn-MOF-74 > Au25@Mg-MOF-74, highlighting the crucial roles of microenvironment modulation around the Au25 NCs by interaction between the surface ligands and MOF hosts.

6.
Artículo en Inglés | MEDLINE | ID: mdl-39244957

RESUMEN

BACKGROUND: The Atractylodes chinensis (DC.) Koidz (A. chinensis) Chinese herb possesses numerous therapeutic properties and is extensively utilized in the pharmaceutical industry. Its quality is closely associated with the harvest periods. However, the optimal quality and harvest periods of A. chinensis remain elusive. METHODS: The bioactive compounds of perennial A. chinensis were detected by ultra-high-performance liquid chromatography coupled with quadrupole Orbitrap mass spectrometry (UHPLC-Q-Orbitrap/MS) metabolomics, and differentially abundant compounds were selected by multivariate statistical analysis. Then, variations in the content of differential compounds in samples harvested at different periods were analyzed, while correlation analysis was carried out on the differential compounds to determine the suitable harvest period for distinct components. RESULTS: A total of 61 bioactive compounds were detected in all samples, grouped into 9 known classes. The results revealed that the chemical compositions of A. chinensis at different harvest periods were significantly different. The volatile oil content in the four-year-old and five-year-old samples was relatively high, at 31.92 mg/g and 32.42 mg/g, respectively. There were also significant differences in the content of the six active ingredients, for example, the five-year-old sample had the highest content of atractylodin (4.38 mg/g). Indeed, the harvest period was correlated with the abundance of most bioactive compounds. Specifically, quinquennial samples were significantly negatively correlated with the abundance of organic acids and aliphatics while moderately positively correlated with the abundance of other classes of bioactive compounds. CONCLUSIONS: According to the results, the ideal harvest time for atractylenolide Ⅲ was 3 years. Regarding organic acids, the optimal harvest time was around 2-3 years. Taken together, these results offer valuable insights to producers for optimizing the harvest period for A. chinensis.


Asunto(s)
Atractylodes , Atractylodes/química , Cromatografía Líquida de Alta Presión/métodos , Análisis Multivariante , Sesquiterpenos/análisis , Lactonas/análisis , Medicamentos Herbarios Chinos/química , Medicamentos Herbarios Chinos/análisis , Aceites Volátiles/análisis , Aceites Volátiles/química , Espectrometría de Masas/métodos , Metabolómica/métodos
7.
Nat Commun ; 15(1): 6972, 2024 Aug 14.
Artículo en Inglés | MEDLINE | ID: mdl-39143059

RESUMEN

Cations such as K+ play a key part in the CO2 electroreduction reaction, but their role in the reaction mechanism is still in debate. Here, we use a highly symmetric Ni-N4 structure to selectively probe the mechanistic influence of K+ and identify its interaction with chemisorbed CO2-. Our electrochemical kinetics study finds a shift in the rate-determining step in the presence of K+. Spectral evidence of chemisorbed CO2- from in-situ X-ray absorption spectroscopy and in-situ Raman spectroscopy pinpoints the origin of this rate-determining step shift. Grand canonical potential kinetics simulations - consistent with experimental results - further complement these findings. We thereby identify a long proposed non-covalent interaction between K+ and chemisorbed CO2-. This interaction stabilizes chemisorbed CO2- and thus switches the rate-determining step from concerted proton electron transfer to independent proton transfer. Consequently, this rate-determining step shift lowers the reaction barrier by eliminating the contribution of the electron transfer step. This K+-determined reaction pathway enables a lower energy barrier for CO2 electroreduction reaction than the competing hydrogen evolution reaction, leading to an exclusive selectivity for CO2 electroreduction reaction.

8.
Cell Signal ; 121: 111287, 2024 Sep.
Artículo en Inglés | MEDLINE | ID: mdl-38969191

RESUMEN

The progression of osteoarthritis (OA) includes the initial inflammation, subsequent degradation of the extracellular matrix (ECM), and chondrocyte apoptosis. Down syndrome candidate region 1 (DSCR1) is a stress-responsive gene and expresses in varied types of cells, including chondrocytes. Bioinformatics analysis of GSE103416 and GSE104739 datasets showed higher DSCR1 expression in the inflamed cartilage tissues and chondrocytes of OA. DSCR1 had two major isoforms, isoform 1 (DSCR1-1) and isoform 4 (DSCR1-4). We found that DSCR1-1 had a faster (in vitro) and higher expression (in vivo) response to OA compared to DSCR1-4. IL-1ß-induced apoptosis, inflammation, and ECM degradation in chondrocytes were attenuated by DSCR1-1 overexpression. DSCR1-1 triggered the phosphorylation of cAMP response element-binding 1 (CREB1) at 133 serine sites by decreasing calcineurin activity. Moreover, activated CREB1 moved into the cell nucleus and combined in the promoter regions of aldehyde dehydrogenase 2 (ALDH2), thus enhancing its gene transcription. ALDH2 could recover Wnt/ß-catenin signaling transduction by enhancing phosphorylation of ß-catenin at 33/37 serine sites and inhibiting the migration of ß-catenin protein from the cellular matrix to the nucleus. In vivo, adenoviruses (1 × 108 PFU) overexpressing DSCR1-1 were injected into the articular cavity of C57BL/6 mice with medial meniscus surgery-induced OA, and it showed that DSCR1-1 overexpression ameliorated cartilage injury. Collectively, our study demonstrates that DSCR1-1 may be a potential therapeutic target of OA.


Asunto(s)
Condrocitos , Proteína de Unión a Elemento de Respuesta al AMP Cíclico , Osteoartritis , Vía de Señalización Wnt , Condrocitos/metabolismo , Animales , Osteoartritis/metabolismo , Osteoartritis/patología , Proteína de Unión a Elemento de Respuesta al AMP Cíclico/metabolismo , Humanos , Ratones , Aldehído Deshidrogenasa Mitocondrial/metabolismo , Aldehído Deshidrogenasa Mitocondrial/genética , beta Catenina/metabolismo , Masculino , Ratones Endogámicos C57BL , Apoptosis/efectos de los fármacos , Proteínas de Unión al ADN/metabolismo , Proteínas de Unión al ADN/genética
9.
Angew Chem Int Ed Engl ; 63(40): e202410545, 2024 Oct 01.
Artículo en Inglés | MEDLINE | ID: mdl-38940407

RESUMEN

Rational design of efficient methanol oxidation reaction (MOR) catalyst that undergo non-CO pathway is essential to resolve the long-standing poisoning issue. However, it remains a huge challenge due to the rather difficulty in maximizing the non-CO pathway by the selective coupling between the key *CHO and *OH intermediates. Here, we report a high-performance electrocatalyst of patchy atomic-layer Pt epitaxial growth on CeO2 nanocube (Pt ALs/CeO2) with maximum electronic metal-support interaction for enhancing the coupling selectively. The small-size monolayer material achieves an optimal geometrical distance between edge Pt-O-Ce sites and *OH absorbed on CeO2, which well restrains the dehydrogenation of *CHO, resulting in the non-CO pathway. Meanwhile, the *CHO/*CO intermediate generated at inner Pt-O-Ce sites can migrate to edge, inducing the subsequent coupling reaction, thus avoiding poisoning while promoting reaction efficiency. Consequently, Pt ALs/CeO2 exhibits exceptionally catalytic stability with negligible degradation even under 1000 s pure CO poisoning operation and high mass activity (14.87 A/mgPt), enabling it one of the best-performing alkali-stable MOR catalysts.

10.
Nat Ecol Evol ; 8(7): 1248-1258, 2024 Jul.
Artículo en Inglés | MEDLINE | ID: mdl-38862784

RESUMEN

Morphological disparity and taxonomic diversity are distinct measures of biodiversity, typically expected to evolve synergistically. However, evidence from mass extinctions indicates that they can be decoupled, and while mass extinctions lead to a drastic loss of diversity, their impact on disparity remains unclear. Here we evaluate the dynamics of morphological disparity and extinction selectivity across the Permian-Triassic mass extinction. We developed an automated approach, termed DeepMorph, for the extraction of morphological features from fossil images using a deep learning model and applied it to a high-resolution temporal dataset encompassing 599 genera across six marine clades. Ammonoids, brachiopods and ostracods experienced a selective loss of complex and ornamented forms, while bivalves, gastropods and conodonts did not experience morphologically selective extinctions. The presence and intensity of morphological selectivity probably reflect the variations in environmental tolerance thresholds among different clades. In clades affected by selective extinctions, the intensity of diversity loss promoted the loss of morphological disparity. Conversely, under non-selective extinctions, the magnitude of diversity loss had a negligible impact on disparity. Our results highlight that the Permian-Triassic mass extinction had heterogeneous morphological selective impacts across clades, offering new insights into how mass extinctions can reshape biodiversity and ecosystem structure.


Asunto(s)
Organismos Acuáticos , Biodiversidad , Evolución Biológica , Extinción Biológica , Fósiles , Animales , Fósiles/anatomía & histología , Organismos Acuáticos/clasificación , Invertebrados/anatomía & histología , Invertebrados/clasificación , Aprendizaje Profundo
11.
mSphere ; 9(6): e0018224, 2024 Jun 25.
Artículo en Inglés | MEDLINE | ID: mdl-38738873

RESUMEN

The appearance and prevalence of multidrug-resistance (MDR) Gram-negative bacteria (GNB) have limited our antibiotic capacity to control bacterial infections. The clinical efficacy of colistin (COL), considered as the "last resort" for treating GNB infections, has been severely hindered by its increased use as well as the emergence and prevalence of mobile colistin resistance (MCR)-mediated acquired drug resistance. Identifying promising compounds to restore antibiotic activity is becoming an effective strategy to alleviate the crisis of increasing MDR. We first demonstrated that the combination of berberine (BBR) and EDTA substantially restored COL sensitivity against COL-resistant Salmonella and Escherichia coli. Molecular docking indicated that BBR can interact with MCR-1 and the efflux pump system AcrAB-TolC, and BBR combined with EDTA downregulated the expression level of mcr-1 and tolC. Mechanically, BBR combined with EDTA could increase bacterial membrane damage, inhibit the function of multidrug efflux pump, and promote oxidative damage, thereby boosting the action of COL. In addition, transcriptome analysis found that the combination of BBR and EDTA can accelerate the tricarboxylic acid cycle, inhibit cationic antimicrobial peptide (CAMP) resistance, and attenuate Salmonella virulence. Notably, the combination of BBR and EDTA with COL significantly reduced the bacterial load in the liver and spleen of a mice model infected with Salmonella. Our findings revealed that BBR and EDTA can be used as adjuvants collectively with COL to synergistically reverse the COL resistance of bacteria. IMPORTANCE: Colistin is last-resort antibiotic used to treat serious clinical infections caused by MDR bacterial pathogens. The recent emergence of transferable plasmid-mediated COL resistance gene mcr-1 has raised the specter of a rapid worldwide spread of COL resistance. Coupled with the fact of barren antibiotic development pipeline nowadays, a critical approach is to revitalize existing antibiotics using antibiotic adjuvants. Our research showed that berberine combined with EDTA effectively reversed COL resistance both in vivo and in vitro through multiple modes of action. The discovery of berberine in combination with EDTA as a new and safe COL adjuvant provides a therapeutic regimen for combating Gram-negative bacteria infections. Our findings provide a potential therapeutic option using existing antibiotics in combination with antibiotic adjuvants and address the prevalent infections caused by MDR Gram-negative pathogens worldwide.


Asunto(s)
Antibacterianos , Berberina , Colistina , Ácido Edético , Escherichia coli , Salmonella , Colistina/farmacología , Berberina/farmacología , Escherichia coli/efectos de los fármacos , Escherichia coli/genética , Antibacterianos/farmacología , Animales , Ratones , Ácido Edético/farmacología , Salmonella/efectos de los fármacos , Salmonella/genética , Farmacorresistencia Bacteriana Múltiple/genética , Pruebas de Sensibilidad Microbiana , Infecciones por Escherichia coli/tratamiento farmacológico , Infecciones por Escherichia coli/microbiología , Femenino , Proteínas de Escherichia coli/genética , Simulación del Acoplamiento Molecular , Farmacorresistencia Bacteriana/genética , Quimioterapia Combinada , Ratones Endogámicos BALB C , Sinergismo Farmacológico
12.
Adv Mater ; 36(31): e2404672, 2024 Aug.
Artículo en Inglés | MEDLINE | ID: mdl-38634272

RESUMEN

The performance of single-atom catalysts is greatly influenced by the chemical environment surrounding the central atom. Here, a salt-assisted method is employed to transform the tetrahedral coordination structure of zeolitic imidazolate frameworks - 8 (ZIF-8) into a planar square coordination structure without altering the ligands. During the subsequent carbonization process, concurrent with the evaporation of zinc atoms, the structure of the nitrogen and carbon carriers (NC carriers) undergoes a transition from five-membered rings to six-membered rings to preserve the 2D structure. This transition results in the generation of additional defect sites on the 2D-NC substrates. Hence, the Pt single-atom catalysts with planar square coordination symmetries can be precisely prepared via electrodeposition (denoted as 2D-Pt SAC). The Pt loading of 2D-Pt SAC is 0.49 ± 0.03 µg cm-2, higher than that of 3D-Pt SAC (0.37 ± 0.04 µg cm-2). In the context of the hydrogen oxidation reaction electrocatalysis, under an overpotential of 50 mV, these single-atom catalysts with 2D coordination exhibit mass activities of 2396 A gPt -1 (32 times higher than commercial Pt/C catalyst, 2 times higher than 3D-PtNC).

13.
Nat Commun ; 15(1): 3416, 2024 Apr 22.
Artículo en Inglés | MEDLINE | ID: mdl-38649713

RESUMEN

In-depth comprehension and modulation of the electronic structure of the active metal sites is crucial to enhance their intrinsic activity of electrocatalytic oxygen evolution reaction (OER) toward anion exchange membrane water electrolyzers (AEMWEs). Here, we elaborate a series of amorphous metal oxide catalysts (FeCrOx, CoCrOx and NiCrOx) with high performance AEMWEs by high-valent chromium dopant. We discover that the positive effect of the transition from low to high valence of the Co site on the adsorption energy of the intermediate and the lower oxidation barrier is the key factor for its increased activity by synchrotron radiation in-situ techniques. Particularly, the CoCrOx anode catalyst achieves the high current density of 1.5 A cm-2 at 2.1 V and maintains for over 120 h with attenuation less than 4.9 mV h-1 in AEMWE testing. Such exceptional performance demonstrates a promising prospect for industrial application and providing general guidelines for the design of high-efficiency AEMWEs systems.

14.
Materials (Basel) ; 17(6)2024 Mar 21.
Artículo en Inglés | MEDLINE | ID: mdl-38541589

RESUMEN

The slag entrapment defect has become a big issue for the IF steel casting process. In this study, the mechanism of mold flux entrapment in deep oscillation mark of an IF steel shell was studied by a high-temperature mold simulator. Results show that both temperature and heat flux in a copper mold become lower when mold flux B with lower melting and viscosity is used, compared with these when mold flux A with higher melting and viscosity is used. The average thickness of the slag film for mold fluxes A and B is 1.31 mm and 1.63 mm, and the consumption of them is 0.33 kg/m2 and 0.35 kg/m2, respectively. The shell for mold flux A exhibits sharper oscillation marks, while the shell for mold flux B has shallower oscillation marks. These deeper oscillation marks capture the mold flux by overflow of molten steel at the meniscus, which finally produces the slag entrapment defect in the shell.

15.
Nano Lett ; 24(10): 3213-3220, 2024 Mar 13.
Artículo en Inglés | MEDLINE | ID: mdl-38426819

RESUMEN

Rational design of well-defined active sites is crucial for promoting sluggish oxygen reduction reactions. Herein, leveraging the surfactant-oriented and solvent-ligand effects, we develop a facile self-assembly strategy to construct a core-shell catalyst comprising a high-index Pt shell encapsulating a PtCu3 intermetallic core with efficient oxygen-reduction performance. Without undergoing a high-temperature route, the ordered PtCu3 is directly fabricated through the accelerated reduction of Cu2+, followed by the deposition of the remaining Pt precursor onto its surface, forming high-index steps oriented by the steric hindrance of surfactant. This approach results in a high half-wave potential of 0.911 V versus reversible hydrogen electrode, with negligible deactivation even after 15000-cycle operation. Operando spectroscopies identify that this core-shell catalyst facilitates the conversion of oxygen-involving intermediates and ensures antidissolution ability. Theoretical investigations rationalize that this improvement is attributed to reinforced electronic interactions around high-index Pt, stabilizing the binding strength of rate-determining OHads species.

17.
J Phys Chem Lett ; 15(11): 3071-3077, 2024 Mar 21.
Artículo en Inglés | MEDLINE | ID: mdl-38466813

RESUMEN

The comprehensive understanding toward the dealloying process is crucial for designing alloy catalysts employed in the oxygen reduction reaction (ORR). However, the specific leaching procedure and subsequent reconstruction of the dealloyed catalyst still remain unclear. Herein, we employ in situ X-ray absorption fine structure spectroscopy to monitor the dealloying process of a two-dimensional PtTe ordered alloy, known for its enhanced ORR activity. Our findings reveal the unsynchronous evolutions of Pt and Te sites, wherein the Pt component undergoes a structural transformation prior to the complete leaching of Te, leading to the formation of a defect-rich Pt catalyst. This dealloyed catalyst exhibits a significant enhancement in ORR activity, featuring a half-wave potential of 0.90 V versus the reversible hydrogen electrode and a mass activity of 0.62 A mgPt-1, outperforming the performance of commercial Pt/C counterpart. This in-depth understanding of the dealloying mechanism enriches our knowledge for the development of high-performance Pt-based alloy catalysts.

18.
Sci Rep ; 14(1): 2941, 2024 Feb 05.
Artículo en Inglés | MEDLINE | ID: mdl-38316944

RESUMEN

This study aims to delineate landslide susceptibility maps using the Analytical Hierarchy Process (AHP) method for the Great Xi'an Region, China, which is a key planning project for urban construction in Shaanxi Province, China from 2021 to 2035. Multiple data as elevation, slope, aspect, curvature, river density, soil, lithology, and land use have been considered for delineating the landslide susceptibility maps. Spatially thematic layers and distributed maps of all the aforementioned parameters were created in a GIS environment. Determine the relative importance of these thematic layers in the occurrence of landslides in the study area concerning historical landslide data to assign appropriate weights. Landslide sensitivity maps were generated by a weighted combination in a GIS environment after being analyzed by the AHP method. The sensitivity maps were categorized as "very high (11.06%), high (19.41%), moderate (23.03%), low (28.70%), and very low (17.80%)". Overlay analysis of the test data with the LSM showed that the moderate to very high landslide susceptibility zones were able to contain 82.58% of the historic landslides. The results of the study help determine the landslide-prone areas in the area and provide a reference for subsequent construction. In addition, the analysis of landslide susceptibility in the area contributes to the study of landslides in similar loess sites.

19.
J Am Chem Soc ; 146(7): 4883-4891, 2024 Feb 21.
Artículo en Inglés | MEDLINE | ID: mdl-38326284

RESUMEN

Nonprecious transition metal catalysts have emerged as the preferred choice for industrial alkaline water electrolysis due to their cost-effectiveness. However, their overstrong binding energy to adsorbed OH often results in the blockage of active sites, particularly in the cathodic hydrogen evolution reaction. Herein, we found that single-atom sites exhibit a puncture effect to effectively alleviate OH blockades, thereby significantly enhancing the alkaline hydrogen evolution reaction (HER) performance. Typically, after anchoring single Ru atoms onto tungsten carbides, the overpotential at 10 mA·cm-2 is reduced by more than 130 mV (159 vs 21 mV). Also, the mass activity is increased 16-fold over commercial Pt/C (MA100 = 17.3 A·mgRu-1 vs 1.1 A·mgPt-1, Pt/C). More importantly, such electrocatalyst-based alkaline anion-exchange membrane water electrolyzers can exhibit an ultralow potential (1.79 Vcell) and high stability at an industrial current density of 1.0 A·cm-2. Density functional theory (DFT) calculations reveal that the isolated Ru sites could weaken the surrounding local OH binding energy, thus puncturing OH blockage and constructing bifunctional interfaces between Ru atoms and the support to accelerate water dissociation. Our findings exhibit generality to other transition metal catalysts (such as Mo) and contribute to the advancement of industrial-scale alkaline water electrolysis.

20.
medRxiv ; 2024 Jan 27.
Artículo en Inglés | MEDLINE | ID: mdl-38343837

RESUMEN

Background: Multisystem inflammatory syndrome in children (MIS-C) is a severe post-acute sequela of SARS-CoV-2 infection. The highly diverse clinical features of MIS-C necessities characterizing its features by subphenotypes for improved recognition and treatment. However, jointly identifying subphenotypes in multi-site settings can be challenging. We propose a distributed multi-site latent class analysis (dMLCA) approach to jointly learn MIS-C subphenotypes using data across multiple institutions. Methods: We used data from the electronic health records (EHR) systems across nine U.S. children's hospitals. Among the 3,549,894 patients, we extracted 864 patients < 21 years of age who had received a diagnosis of MIS-C during an inpatient stay or up to one day before admission. Using MIS-C conditions, laboratory results, and procedure information as input features for the patients, we applied our dMLCA algorithm and identified three MIS-C subphenotypes. As validation, we characterized and compared more granular features across subphenotypes. To evaluate the specificity of the identified subphenotypes, we further compared them with the general subphenotypes identified in the COVID-19 infected patients. Findings: Subphenotype 1 (46.1%) represents patients with a mild manifestation of MIS-C not requiring intensive care, with minimal cardiac involvement. Subphenotype 2 (25.3%) is associated with a high risk of shock, cardiac and renal involvement, and an intermediate risk of respiratory symptoms. Subphenotype 3 (28.6%) represents patients requiring intensive care, with a high risk of shock and cardiac involvement, accompanied by a high risk of >4 organ system being impacted. Importantly, for hospital-specific clinical decision-making, our algorithm also revealed a substantial heterogeneity in relative proportions of these three subtypes across hospitals. Properly accounting for such heterogeneity can lead to accurate characterization of the subphenotypes at the patient-level. Interpretation: Our identified three MIS-C subphenotypes have profound implications for personalized treatment strategies, potentially influencing clinical outcomes. Further, the proposed algorithm facilitates federated subphenotyping while accounting for the heterogeneity across hospitals.

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