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Understanding the structure and dynamic process of water at the solid-liquid interface is an extremely important topic in surface science, energy science and catalysis1-3. As model catalysts, atomically flat single-crystal electrodes exhibit well-defined surface and electric field properties, and therefore may be used to elucidate the relationship between structure and electrocatalytic activity at the atomic level4,5. Hence, studying interfacial water behaviour on single-crystal surfaces provides a framework for understanding electrocatalysis6,7. However, interfacial water is notoriously difficult to probe owing to interference from bulk water and the complexity of interfacial environments8. Here, we use electrochemical, in situ Raman spectroscopic and computational techniques to investigate the interfacial water on atomically flat Pd single-crystal surfaces. Direct spectral evidence reveals that interfacial water consists of hydrogen-bonded and hydrated Na+ ion water. At hydrogen evolution reaction (HER) potentials, dynamic changes in the structure of interfacial water were observed from a random distribution to an ordered structure due to bias potential and Na+ ion cooperation. Structurally ordered interfacial water facilitated high-efficiency electron transfer across the interface, resulting in higher HER rates. The electrolytes and electrode surface effects on interfacial water were also probed and found to affect water structure. Therefore, through local cation tuning strategies, we anticipate that these results may be generalized to enable ordered interfacial water to improve electrocatalytic reaction rates.
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Chronic inflammatory and immune responses play key roles in the development and progression of chronic obstructive pulmonary disease (COPD). PANoptosis, as a unique inflammatory cell death modality, is involved in the pathogenesis of many inflammatory diseases. We aim to identify critical PANoptosis-related biomarkers and explore their potential effects on respiratory tract diseases and immune infiltration landscapes in COPD. Total microarray data consisting of peripheral blood and lung tissue datasets associated with COPD were obtained from the GEO database. PANoptosis-associated genes in COPD were identified by intersecting differentially expressed genes (DEGs) with genes involved in pyroptosis, apoptosis, and necroptosis after normalizing and removing the batch effect. Furthermore, GO, KEGG, PPI network, WGCNA, LASSO-COX, and ROC curves analysis were conducted to screen and verify hub genes, and the correlation between PYCARD and infiltrated immune cells was analyzed. The effect of PYCARD on respiratory tract diseases and the potential small-molecule agents for the treatment of COPD were identified. PYCARD expression was verified in the lung tissue of CS/LPS-induced COPD mice. PYCARD was a critical PANoptosis-related gene in all COPD patients. PYCARD was positively related to NOD-like receptor signaling pathway and promoted immune cell infiltration. Moreover, PYCARD was significantly activated in COPD mice mainly by targeting PANoptosis. PANoptosis-related gene PYCARD is a potential biomarker for COPD diagnosis and treatment.
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Nanomaterials with biomimetic catalytic abilities have attracted significant attention. However, the stereoselectivity of natural enzymes determined by their unique configurations is difficult to imitate. In this work, a kind of chiral CuxCoyS-CuzS nanoflowers (L/D-Pen-NFs) is developed, using porous CuxCoyS nanoparticles (NPs) as stamens, CuzS sheets as petals, and chiral penicillamine as surface stabilizers. Compared to the natural laccase enzyme, L/D-Pen-NFs exhibit significant advantages in catalytic efficiency, stability against harsh environments, recyclability, and convenience in construction. Most importantly, they display high enantioselectivity toward chiral neurotransmitters, which is proved by L- and D-Pen-NFs' different catalytic efficiencies toward chiral enantiomers. L-Pen-NFs are more efficient in catalyzing the oxidation of L-epinephrine and L-dopamine compared with D-Pen-NFs. However, their catalytic efficiency in oxidizing L-norepinephrine and L-DOPA is lower than that of D-Pen-NFs. The reason for the difference in catalytic efficiency is the distinct binding affinities between CuxCoyS-CuzS nano-enantiomers and chiral molecules. This work can spur the development of chiral nanostructures with biomimetic functions.
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Cobre , Catálise , Cobre/química , Estereoisomerismo , Nanoestruturas/química , Biomimética/métodos , Oxirredução , Lacase/química , Lacase/metabolismoRESUMO
BACKGROUND: Prospective observational studies have demonstrated that the machine learning (ML) -guided noninvasive chromosome screening (NICS) grading system, which we called the noninvasive chromosome screening-artificial intelligence (NICS-AI) grading system, can be used embryo selection. The current prospective interventional clinical study was conducted to investigate whether this NICS-AI grading system can be used as a powerful tool for embryo selection. METHODS: Patients who visited our centre between October 2018 and December 2021 were recruited. Grade A and B embryos with a high probability of euploidy were transferred in the NICS group. The patients in the control group selected the embryos according to the traditional morphological grading. Finally, 90 patients in the NICS group and 161 patients in the control group were compared statistically for their clinical outcomes. RESULTS: In the NICS group, the clinical pregnancy rate (70.0% vs. 54.0%, p < 0.001), the ongoing pregnancy rate (58.9% vs. 44.7%, p = 0.001), and the live birth rate (56.7% vs. 42.9%, p = 0.001) were significantly higher than those of the control group. When the female was ≥ 35 years old, the clinical pregnancy rate (67.7% vs. 32.1%, p < 0.001), ongoing pregnancy rate (56.5% vs. 25.0%, p = 0.001), and live birth rate (54.8% vs. 25.0%, p = 0.001) in the NICS group were significantly higher than those of the control group. Regardless of whether the patients had a previous record of early spontaneous abortion or not, the live birth rate of the NICS group was higher than that of the control group (61.0% vs. 46.9%; 57.9% vs. 34.8%; 33.3% vs. 0%) but the differences were not statistically significant. CONCLUSIONS: NICS-AI was able to improve embryo utilisation rate, and the live birth rate, especially for those ≥ 35 years old, with transfer of Grade A embryos being preferred, followed by Grade B embryos. NICS-AI can be used as an effective tool for embryo selection in the future.
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Aprendizado de Máquina , Taxa de Gravidez , Humanos , Feminino , Gravidez , Adulto , Estudos Prospectivos , Transferência de Embrião Único/métodos , Diagnóstico Pré-Implantação/métodos , Transferência Embrionária/métodos , Infertilidade Feminina/terapia , Infertilidade Feminina/genética , Infertilidade Feminina/diagnóstico , Resultado do Tratamento , Infertilidade/terapia , Infertilidade/diagnóstico , Infertilidade/genéticaRESUMO
OBJECTIVES: Blood-brain barrier (BBB) disruption is an important pathological change after cerebral infarction that exacerbates brain injury. We aimed to investigate and compare the predictive utility of pre-treatment BBB permeability (BBBP) and BBBP within 1 h after endovascular treatment (EVT) for hemorrhagic transformation (HT) and 90-day prognosis. METHODS: Patients underwent preoperative computed tomography perfusion (CTP) and non-contrast CT (NCCT) within 1 h after EVT. Preoperative BBBP was determined by the relative permeability surface area product (rPS) in the hypoperfusion area. Postoperative BBBP was determined by the post-EVT Alberta Stroke Program Early CT Score (Post-ASPECTS), which is based on brain parenchymal hyperdensity on the postoperative NCCT. OUTCOMES: We included 100 patients. Univariate logistic regression analysis revealed correlations of preoperative rPS with HT, poor outcomes, and death. However, these correlations were not observed in multivariate logistic regression. A Post-ASPECTS ≤7 and could independently predict poor outcomes, while Post-ASPECTS ≤6 could independently predict death and HT. The baseline National Institutes of Health Stroke Scale (NIHSS) score could independently predict poor outcomes and death but not HT. A combined model using the baseline NIHSS and Post-ASPECTS scores had better predictive performance for poor outcomes and death than baseline NIHSS score alone; however, it was not superior to the predictive performance of the Post-ASPECTS score. CONCLUSION: The preoperative rPS cannot independently predict clinical outcomes in EVT-treated patients; contrastingly, the Post-ASPECTS score could independently predict poor outcomes, death, and HT. This parameter could inform prompt postoperative treatment decisions.
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Barreira Hematoencefálica , Procedimentos Endovasculares , Humanos , Masculino , Feminino , Idoso , Barreira Hematoencefálica/diagnóstico por imagem , Pessoa de Meia-Idade , Prognóstico , Resultado do Tratamento , Tomografia Computadorizada por Raios X , Estudos Retrospectivos , Idoso de 80 Anos ou maisRESUMO
Chiral nanoscale enantiomers exhibit different biological effects in living systems. However, their chirality effect on the detection sensitivity for chiral biological targets still needs to be explored. Here, we discovered that Co2+ can modulate the luminescence performance of L/D-glutathione (GSH)-modified copper nanoclusters (L/D-Cu NCs) and induce strong chiroptical activities as the asymmetric factor was enhanced 223-fold with their distribution regulating from the ultraviolet to visible region. One Co2+ coordinated with two GSH molecules that modified on the surface of Cu NCs in the way of CoN2O2. On this basis, dual-modal chiral and luminescent signals of Co2+ coordinated L/D-Cu NCs (L/D-Co-Cu NCs) were used to detect the chiral adenosine triphosphate (ATP) based on the competitive interaction between surficial GSH and ATP molecules with Co2+. The limits of detection of ATP obtained with fluorescence and circular dichroism intensity were 9.15â µM and 15.75â nM for L-Co-Cu NCs, and 5.35â µM and 4.69â nM for D-Co-Cu NCs. This demonstrated that selecting suitable chiral configurations of nanoprobes effectively enhances detection sensitivity. This study presents not only a novel method to modulate and enhance the chiroptical activity of nanomaterials but also a unique perspective of chirality effects on the detection performances for bio-targets.
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Cobre , Nanoestruturas , Trifosfato de Adenosina , Luminescência , GlutationaRESUMO
The encapsulation of functional colloidal nanoparticles (100â nm) into single-crystalline ZSM-5 zeolites, aiming to create uniform core-shell structures, is a highly sought-after yet formidable objective due to significant lattice mismatch and distinct crystallization properties. In this study, we demonstrate the fabrication of a core-shell structured single-crystal zeolite encompassing an Fe3O4 colloidal core via a novel confinement stepwise crystallization methodology. By engineering a confined nanocavity, anchoring nucleation sites, and executing stepwise crystallization, we have successfully encapsulated colloidal nanoparticles (CN) within single-crystal zeolites. These grafted sites, alongside the controlled crystallization process, compel the zeolite seed to nucleate and expand along the Fe3O4 colloidal nanoparticle surface, within a meticulously defined volume (1.5×107≤V≤1.3×108â nm3). Our strategy exhibits versatility and adaptability to an array of zeolites, including but not restricted to ZSM-5, NaA, ZSM-11, and TS-1 with polycrystalline zeolite shell. We highlight the uniformly structured magnetic-nucleus single-crystalline zeolite, which displays pronounced superparamagnetism (14â emu/g) and robust acidity (~0.83â mmol/g). This innovative material has been effectively utilized in a magnetically stabilized bed (MSB) reactor for the dehydration of ethanol, delivering an exceptional conversion rate (98 %), supreme ethylene selectivity (98 %), and superior catalytic endurance (in excess of 100â hours).
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BACKGROUND: The authors compare the effectiveness and safety of endovascular treatment (EVT) versus best medical management (BMM) in strokes attributable to acute basilar artery occlusion (BAO). METHODS: The present analysis was based on the ongoing, prospective, multicenter ATTENTION (Endovascular Treatment for Acute Basilar Artery Occlusion) trial registry in China. Our analytic sample comprised 2134 patients recruited at 48 sites between 2017 and 2021 and included 462 patients who received BMM and 1672 patients who received EVT. We performed an inversed probability of treatment weighting analysis. Qualifying patients had to present within 24 hours of estimated BAO. The primary clinical outcome was favorable functional outcome (modified Rankin Scale score, 0-3) at 90 days. We also performed a sensitivity analysis with the propensity score matching-based and the instrumental variable-based analysis. RESULTS: In our primary analysis using the inversed probability of treatment weighting-based analysis, there was a significantly higher rate of favorable outcome at 90 days among EVT patients compared with BMM-treated patients (adjusted relative risk, 1.42 [95% CI, 1.19-1.65]; absolute risk difference, 11.8% [95% CI, 6.9-16.7]). The mortality was significantly lower (adjusted relative risk, 0.78 [95% CI, 0.69-0.88]; absolute risk difference, -10.3% [95% CI, -15.8 to -4.9]) in patients undergoing EVT. Results were generally consistent across the secondary end points. Similar associations were seen in the propensity score matching-based and instrumental variable-based analysis. CONCLUSIONS: In this real-world study, EVT was associated with significantly better functional outcomes and survival at 90 days. Well-designed randomized studies comparing EVT with BMM in the acute BAO are needed. REGISTRATION: URL: www.chictr.org.cn; Unique identifier: ChiCTR2000041117.
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Arteriopatias Oclusivas , Procedimentos Endovasculares , Acidente Vascular Cerebral , Arteriopatias Oclusivas/terapia , Artéria Basilar , Procedimentos Endovasculares/efeitos adversos , Procedimentos Endovasculares/métodos , Humanos , Estudos Prospectivos , Sistema de Registros , Trombectomia/métodos , Resultado do TratamentoRESUMO
BACKGROUND: In acute ischemic stroke, there is uncertainty regarding the benefit and risk of administering intravenous alteplase before endovascular thrombectomy. METHODS: We conducted a trial at 41 academic tertiary care centers in China to evaluate endovascular thrombectomy with or without intravenous alteplase in patients with acute ischemic stroke. Patients with acute ischemic stroke from large-vessel occlusion in the anterior circulation were randomly assigned in a 1:1 ratio to undergo endovascular thrombectomy alone (thrombectomy-alone group) or endovascular thrombectomy preceded by intravenous alteplase, at a dose of 0.9 mg per kilogram of body weight, administered within 4.5 hours after symptom onset (combination-therapy group). The primary analysis for noninferiority assessed the between-group difference in the distribution of the modified Rankin scale scores (range, 0 [no symptoms] to 6 [death]) at 90 days on the basis of a lower boundary of the 95% confidence interval of the adjusted common odds ratio equal to or larger than 0.8. We assessed various secondary outcomes, including death and reperfusion of the ischemic area. RESULTS: Of 1586 patients screened, 656 were enrolled, with 327 patients assigned to the thrombectomy-alone group and 329 assigned to the combination-therapy group. Endovascular thrombectomy alone was noninferior to combined intravenous alteplase and endovascular thrombectomy with regard to the primary outcome (adjusted common odds ratio, 1.07; 95% confidence interval, 0.81 to 1.40; P = 0.04 for noninferiority) but was associated with lower percentages of patients with successful reperfusion before thrombectomy (2.4% vs. 7.0%) and overall successful reperfusion (79.4% vs. 84.5%). Mortality at 90 days was 17.7% in the thrombectomy-alone group and 18.8% in the combination-therapy group. CONCLUSIONS: In Chinese patients with acute ischemic stroke from large-vessel occlusion, endovascular thrombectomy alone was noninferior with regard to functional outcome, within a 20% margin of confidence, to endovascular thrombectomy preceded by intravenous alteplase administered within 4.5 hours after symptom onset. (Funded by the Stroke Prevention Project of the National Health Commission of the People's Republic of China and the Wu Jieping Medical Foundation; DIRECT-MT ClinicalTrials.gov number, NCT03469206.).
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Fibrinolíticos/uso terapêutico , Acidente Vascular Cerebral/tratamento farmacológico , Acidente Vascular Cerebral/cirurgia , Trombectomia/métodos , Ativador de Plasminogênio Tecidual/uso terapêutico , Idoso , Hemorragia Cerebral/etiologia , China , Terapia Combinada , Intervalos de Confiança , Procedimentos Endovasculares , Feminino , Fibrinolíticos/efeitos adversos , Humanos , Infusões Intravenosas , Masculino , Pessoa de Meia-Idade , Reperfusão/métodos , Trombectomia/efeitos adversos , Tempo para o Tratamento , Ativador de Plasminogênio Tecidual/efeitos adversos , Resultado do TratamentoRESUMO
BACKGROUND: Hepatitis E virus (HEV) infection causes serious adverse pregnancy outcomes during pregnancy. However, the maternal and fetal damage induced by HEV infection is rarely reported. METHODS: A BALB/c pregnant mouse model was established to explore the maternal and fetal pathological damage and inflammatory responses caused by HEV infection. RESULTS: Notably, miscarriages and stillbirths were observed in HEV-infected pregnant mice. HEV infections were identified by qRT-PCR, immunohistochemical analysis and immunofluorescence assay in the uterus, placenta, umbilical cords and livers and brains of fetuses. Serious inflammatory responses and pathological damage were triggered in the uterus and placenta of HEV-infected pregnant mice. Vertical transmission of HEV resulted in severe pathological damage and inflammatory responses in the livers and brains of fetuses, as well as emerging apoptosis cells in the brains of fetuses. Most of the cytokines/chemokines in the sera were significantly increased in the HEV-infected pregnant mice. Remarkably, cytokines/chemokines were significantly different between HEV-infected pregnant and miscarriage mice; IL9, GM-CSF and IL1α were the most important three cytokines/chemokines in determining the pregnancy outcomes. CONCLUSION: HEV infections cause serious maternal/fetal pathological damage, inflammatory responses and apoptosis, which may be responsible for adverse pregnancy outcomes.
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Aborto Espontâneo , Vírus da Hepatite E , Hepatite E , Complicações Infecciosas na Gravidez , Animais , Feminino , Camundongos , Gravidez , Aborto Espontâneo/etiologia , Citocinas , Hepatite E/complicações , Hepatite E/patologia , Camundongos Endogâmicos BALB CRESUMO
Optical metamaterials, sensing, nonlinear optics, and surface-enhanced spectroscopies have witnessed the remarkable potential of the anapole mode. While dielectric particles with a high refractive index have garnered significant attention in recent years, the exploration of plasmonic anapole modes with intense localized electric field enhancements in the visible frequency range remains limited. In this study, we present a theoretical investigation on the relationship between the strongest near-field response and magnetic anapole modes, along with their substantial enhancement of Raman signals from probing molecules. These captivating findings arise from the design of a practical metallic oblate spheroid-film plasmonic system that generates magnetic anapole resonances at frequencies within the visible-near-infrared range. This research not only sheds light on the underlying mechanisms in a wide range of plasmon-enhanced spectroscopies but also paves the way for innovative nano-device designs.
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Methyl acetate (MA) has a wide range of applications as an important industrial chemical. Traditional MOR zeolite for carbonylation of DME to MA accumulated carbon easily because of a 12-membered ring (12 MR) channel. In this work, we innovatively developed the method of recrystallization ferrierite (FER) zeolite using special chelating ligand sodium oleate which can affect ions other than alkali metals. The characterization results of N2 adsorption, transmission electron microscopy (TEM), and Fourier transform infrared spectroscopy (FT-IR) show that hydrothermal recrystallization of ferrierite using sodium oleate resulted in a higher Si/Al ratio, a bigger specific surface area and a larger number of Brønsted acid sites in the eight MR channels, which was more efficient in the reaction of carbonylation of dimethyl ether than ordinary alkali treatment.
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Éteres Metílicos , Zeolitas , Zeolitas/química , Espectroscopia de Infravermelho com Transformada de FourierRESUMO
Vascular dementia (VD) is the second most common dementia syndrome worldwide, and effective treatments are lacking. Gastrodia elata Blume (GEB) has been used in traditional Chinese herbal medicine for centuries to treat cognitive impairment, ischemic stroke, epilepsy, and dizziness. Gastrodin (p-hydroxymethylphenyl-b-D-glucopyranoside, Gas) and Gastrodigenin (p-hydroxybenzyl alcohol, HBA) are the main bioactive components of GEB. This study explored the effects of Gas and HBA on cognitive dysfunction in VD and their possible molecular mechanisms. The VD model was established by bilateral common carotid artery ligation (2-vessel occlusion, 2-VO) combined with an intraperitoneal injection of sodium nitroprusside solution. One week after modeling, Gas (25 and 50 mg/kg, i.g.) and HBA (25 and 50 mg/kg, i.g.) were administered orally for four weeks, and the efficacy was evaluated. A Morris water maze test and passive avoidance test were used to observe their cognitive function, and H&E staining and Nissl staining were used to observe the neuronal morphological changes; the expressions of Aß1-42 and p-tau396 were detected by immunohistochemistry, and the changes in energy metabolism in the brain tissue of VD rats were analyzed by targeted quantitative metabolomics. Finally, a Hippocampus XF analyzer measured mitochondrial respiration in H2O2-treated HT-22 cells. Our study showed that Gas and HBA attenuated learning memory dysfunction and neuronal damage and reduced the accumulation of Aß1-42, P-Tau396, and P-Tau217 proteins in the brain tissue. Furthermore, Gas and HBA improved energy metabolism disorders in rats, involving metabolic pathways such as glycolysis, tricarboxylic acid cycle, and the pentose phosphate pathway, and reducing oxidative damage-induced cellular mitochondrial dysfunction. The above results indicated that Gas and HBA may exert neuroprotective effects on VD by regulating energy metabolism and mitochondrial function.
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Demência Vascular , Ratos , Animais , Demência Vascular/tratamento farmacológico , Demência Vascular/metabolismo , Peróxido de Hidrogênio/metabolismo , Metabolismo Energético , Mitocôndrias/metabolismo , Hipocampo/metabolismoRESUMO
Noncovalent interactions are essential in the formation and properties of a diverse range of hybrid materials. However, reliably identifying the noncovalent interactions in nanocrystalline materials remains challenging using conventional methods such as X-ray diffraction and spectroscopy. Here, we demonstrate that accurate atomic positions including hydrogen atoms can be determined using three-dimensional electron diffraction (3D ED), from which the entire range of noncovalent interactions in a nanocrystalline aluminophosphate hybrid material SCM-34 are directly visualized. The protonation states of both the inorganic and organic components in SCM-34 are determined from the hydrogen positions. All noncovalent interactions, including hydrogen-bonding, electrostatic, π-π stacking, and van der Waals interactions, are unambiguously identified, which provides detailed insights into the formation of the material. The 3D ED data also allow us to distinguish different types of covalent bonds based on their bond lengths and to identify an elongated terminal PâO π-bond caused by noncovalent interactions. Our results show that 3D ED can be a powerful tool for resolving detailed noncovalent interactions in nanocrystalline materials. This can improve our understanding of hybrid systems and guide the development of novel functional materials.
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Elétrons , Nanopartículas , Hidrogênio , Ligação de Hidrogênio , Eletricidade EstáticaRESUMO
Metal-dielectric heterostructures have shown great application potentials in physics, chemistry and material science. In this work, we have designed and manufactured ordered metal-dielectric multiple heterostructures with tunable optical properties, which can be as large as the order of square centimeters in size. We experimentally realized that the surface-enhanced Raman scattering signal of the periodic multiple heterostructures increased 50 times compared with the silicon nanodisk-gold film arrays, which is attributed to the large-scale hotspots and high efficient coupling between the optical cavities and surface plasmon resonance modes. More importantly, the substrate also features a good uniformity and an excellent reproducible fabrication, which is very promising for practical applications.
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Zeolites with large cavities that are accessible via wide pore windows are desirable but very rare. They have been dominantly used as catalysts in industry. Here we report a novel porous germanosilicate SCM-25, the zeolite structure containing ordered meso-cavities (29.9 × 7.6 × 6.0 Å3) interconnected by 10- and 12-ring channels. SCM-25 was synthesized as nanosized crystals by using a simple organic structure-directing agent (OSDA). Three-dimensional (3D) electron diffraction shows that SCM-25 crystallizes in the orthorhombic space group Cmmm with a = 14.62 Å, b = 51.82 Å, c = 13.11 Å, which is one of the zeolites with the largest unit cell dimensions. We demonstrate that 3D electron diffraction is a powerful technique for determining the complex structure of SCM-25, including the disorders and distributions of framework atoms silicon and germanium. SCM-25 has a high surface area (510 m2/g) and high thermal stability (700 °C). Furthermore, we propose a potential postsynthetic strategy for the preparation of zeolites with ordered meso-cavities by applying the ADOR (assembly-disassembly-organization-reassembly) approach.
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Hierarchical zeolites combine the intrinsic catalytic properties of microporous zeolites and the enhanced access and transport of the additional meso- and/or macroporous system. These materials are the most desirable catalysts and sorbents for industry and become a highly evolving field of important current interests. In addition to the enhanced mass transfer leading to high activity, selectivity, and cycle time, another essential merit of the hierarchical structure in zeolite materials is that it can significantly improve the utilization effectiveness of zeolite materials resulting in the minimum energy, time, and raw materials consumption. Substantial progress has been made in the synthesis, characterization, and application of hierarchical zeolites. Herein, we provide an overview of recent achievements in the field, highlighting the significant progress in the past decade on the development of novel and remarkable strategies to create an additional pore system in zeolites. The most innovative synthesis approaches are reviewed according to the principle, versatility, effectiveness, and degree of reality while establishing a firm link between the preparation route and the resultant hierarchical pore quality in zeolites. Zeolites with different hierarchically porous structures, i.e., micro-mesoporous structure, micro-macroporous structure, and micro-meso-macroporous structure, are then analyzed in detail with concrete examples to illustrate their benefits and their fabrications. The significantly improved performances in catalytic, environmental, and biological applications resulting from enhanced mass transport properties are discussed through a series of representative cases. In the concluding part, we envision the emergence of "material-properties-by-quantitative and real rational design" based on the "generalized Murray's Law" that enables the predictable and controlled productions of bioinspired hierarchically structured zeolites. This Review is expected to attract important interests from catalysis, separation, environment, advanced materials, and chemical engineering fields as well as biomedicine for artificial organ and drug delivery systems.
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Dióxido de Carbono/isolamento & purificação , Desenho de Fármacos , Compostos Orgânicos Voláteis/isolamento & purificação , Águas Residuárias/química , Poluentes Químicos da Água/isolamento & purificação , Zeolitas/síntese química , Adsorção , Dióxido de Carbono/química , Tamanho da Partícula , Porosidade , Compostos Orgânicos Voláteis/química , Poluentes Químicos da Água/química , Zeolitas/químicaRESUMO
Plasmonic metals under photoexcitation can generate energetic hot electrons to directly induce chemical reactions. However, the capability and fundamental insights of the transportation of these hot electrons at plasmonic metal-2D material interfaces remain unclear. Herein, hot-electron transfer at Au-graphene interfaces has been in situ studied using surface-enhanced Raman spectroscopy (SERS) with atomic layer accuracy. Combining in situ SERS studies with density functional theory calculations, it is proved that hot electrons can be injected from plasmonic Au nanoparticles to graphene and directly penetrate graphene to trigger photocatalytic reactions. With increasing graphene layers, the transportation of hot electrons decays rapidly and would be completely blocked after five layers of graphene. Moreover, the transfer of hot electrons can be modulated by applying an external electric field, and the hot-electron transfer efficiency under electrochemical conditions is improved by over three times in the presence of a monolayer of graphene.
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OBJECTIVE: Surgical ablation of atrial fibrillation (AF) has become a routine procedure during concomitant cardiac surgery, however, the extension of lesion sets remain controversial. We sought to compare the relative benefit and risk of different lesion sets through a Bayesian network meta-analysis (NMA). METHODS: Pubmed, Embase, and Cochrane Trials databases were searched for randomized controlled trials (RCTs) comparing the rhythm outcome of AF patients undergoing pulmonary vein isolation (PVI), left atrial Maze (LAM), bi-atrial Maze (BAM), or no ablation during concomitant cardiac surgery. An NMA was conducted to explore the difference of over 1 year AF freedom as well as risks for early mortality and permanent pacemaker implantation (PPMI). RESULTS: A total of 2031 patients of 19 RCTs were included. PVI, LAM, and BAM (OR [95% Cr.I]: 5.02 [2.72, 10.02], 7.97 [4.93, 14.29], 8.29 [4.90, 14.86], p < .05) demonstrated higher freedom of AF compared with no ablation, however, no significant difference of rhythm outcome was found among the three ablation strategies based on the random-effects model. BAM was associated with an increase in early mortality when compared with no ablation (OR [95% Cr.I]: 4.08 [1.23, 17.30], p < .05), while none of the remaining comparisons reached statistical difference in terms of early mortality and PPMI. CONCLUSION: Bi-atrial ablation is not superior to left atrial ablation strategies in reducing AF recurrence for un-selected surgical patients. BAM has a higher risk of early mortality than no ablation, but no difference was found between bi-atrial and left atrial ablation in regard to early mortality and PPMI based on the current evidence.
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Fibrilação Atrial , Procedimentos Cirúrgicos Cardíacos , Ablação por Cateter , Veias Pulmonares , Fibrilação Atrial/diagnóstico , Fibrilação Atrial/cirurgia , Ablação por Cateter/efeitos adversos , Humanos , Metanálise em Rede , Veias Pulmonares/cirurgia , Ensaios Clínicos Controlados Aleatórios como Assunto , Resultado do TratamentoRESUMO
Understanding the reaction mechanism for the catalytic process is essential to the rational design and synthesis of highly efficient catalysts. MoS2 has been reported to be an efficient catalyst toward the electrochemical hydrogen evolution reaction (HER), but it still lacks direct experimental evidence to reveal the mechanism for MoS2-catalyzed electrochemical HER process at the atomic level. In this work, we develop a wet-chemical synthetic method to prepare the single-layer MoS2-coated polyhedral Ag core-shell heterostructure (Ag@MoS2) with tunable sizes as efficient catalysts for the electrochemical HER. The Ag@MoS2 core-shell heterostructures are used as ideal platforms for the real-time surface-enhanced Raman spectroscopy (SERS) study owing to the strong electromagnetic field generated in the plasmonic Ag core. The in situ SERS results provide solid Raman spectroscopic evidence proving the S-H bonding formation on the MoS2 surface during the HER process, suggesting that the S atom of MoS2 is the catalytic active site for the electrochemical HER. It paves the way on the design and synthesis of heterostructures for exploring their catalytic mechanism at atomic level based on the in situ SERS measurement.