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CO plays a crucial role as an intermediate in electrochemical CO2 conversion to generate multicarbon (C2+) products. However, optimizing the coverage of the CO intermediate (*CO) to improve the selectivity of C2+ products remains a great challenge. Here, we designed a hierarchically structured double hollow spherical nanoreactor featuring atomically dispersed nickel (Ni) atoms as the core and copper (Cu) nanoparticles as the shell, which can greatly improve the catalytic activity and selectivity for C2+ compounds. Within this configuration, CO generated at the active Ni sites on the inner layer accumulates in the cavity before spilling over neighboring Cu sites on the outer layer, thus enhancing CO dimerization within the cavity. Notably, this setup achieves a sustained faradaic efficiency of 74.4% for C2+ production, with partial current densities reaching 337.4 mA cm-2. In situ Raman spectroscopy and finite-element method (FEM) simulations demonstrate that the designed local CO generator can effectively increase the local CO concentration and restrict CO evolution, ultimately boosting C-C coupling. The hierarchically ordered architectural design represents a promising solution for achieving highly selective C2+ compound production in the electroreduction of CO2.
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Cation exchange (CE) in metal oxides under mild conditions remains an imperative yet challenging goal to tailor their composition and enable practical applications. Herein, we first develop an amorphization-induced strategy to achieve room-temperature CE for universally synthesizing single-atom doped In2O3 nanosheets (NSs). Density functional theory (DFT) calculations elucidate that the abundant coordination-unsaturated sites present in a-In2O3 NSs are instrumental in surmounting the energy barriers of CE reactions. Empirically, a-In2O3 NSs as the host materials successfully undergo exchange with unary cations (Cu2+, Co2+, Mn2+, Ni2+), binary cations (Co2+Mn2+, Co2+Ni2+, Mn2+Ni2+), and ternary cations (Co2+Mn2+Ni2+). Impressively, high-loading single-atom doped (over 10 atom %) In2O3 NSs were obtained. Additionally, Cu/a-In2O3 NSs exhibit an excellent ethanol yield (798.7 µmol g-1 h-1) with a high selectivity of 99.5% for the CO2 photoreduction. This work offers a new approach to induce CE reactions in metal oxides under mild conditions and constructs scalable single-atom doped catalysts for critical applications.
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A precise modulation of heterogeneous catalysts in structural and surface properties promises the development of more sustainable advanced oxidation water purification technologies. However, while catalysts with superior decontamination activity and selectivity are already achievable, maintaining a long-term service life of such materials remains challenging. Here, we propose a crystallinity engineering strategy to break the activity-stability tradeoff of metal oxides in Fenton-like catalysis. The amorphous/crystalline cobalt-manganese spinel oxide (A/C-CoMnOx) provided highly active, hydroxyl group-rich surface, with moderate peroxymonosulfate (PMS)-binding affinity and charge transfer energy and strong pollutant adsorption, to trigger concerted radical and nonradical reactions for efficient pollutant mineralization, thereby alleviating the catalyst passivation by oxidation intermediate accumulation. Meanwhile, the surface-confined reactions, benefited from the enhanced adsorption of pollutants at A/C interface, rendered the A/C-CoMnOx/PMS system ultrahigh PMS utilization efficiency (82.2%) and unprecedented decontamination activity (rate constant of 1.48 min-1) surpassing almost all the state-of-the-art heterogeneous Fenton-like catalysts. The superior cyclic stability and environmental robustness of the system for real water treatment was also demonstrated. Our work unveils a critical role of material crystallinity in modulating the Fenton-like catalytic activity and pathways of metal oxides, which fundamentally improves our understanding of the structure-activity-selectivity relationships of heterogeneous catalysts and may inspire material design for more sustainable water purification application and beyond.
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In this experiment, the effect of replacing milk fat with soybean fat body (25%, 50%, 75%, 100%) on the quality, antioxidant capacity and in vitro digestive characteristics of yogurt was investigated while maintaining the total fat content of the yogurt unchanged. The results showed that increasing the substitution amount of soy fat body for milk fat had little effect on the pH and acidity of yogurt during the storage period, while the physicochemical properties, degree of protein gel network crosslinking, saturated fatty acid content, PV value and TBARS value of the yogurt significantly decreased (p < 0.05). Meanwhile, protein content, solids content, unsaturated fatty acid content, tocopherol content and water holding capacity significantly increased (p < 0.05). Flavor analysis revealed that yogurts with soybean oil bodies were significantly different when compared to those without soybean oil bodies (p < 0.05), and yogurt with 25% substitution had the highest sensory score. After in vitro digestion, the free fatty acid release, antioxidant capacity and protein digestibility of soybean oil body yogurt were significantly higher (p < 0.05). The SDS-PAGE results showed that the protein hydrolysis of the soybean oil body yogurt was faster. Therefore, the use of an appropriate amount of soybean oil bodies to replace milk fat is able to enhance the taste of yogurt and improve the quality of the yogurt.
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As a natural active ingredient, lactic acid bacteria have potential anti-inflammatory effects. In this study, male C57BL/6J mice were given a high-fat diet (HFD) to establish an obese mouse model. Lactobacillus plantarum 23-1 (LP23-1) with prebiotic characteristics was intervened for 8 weeks to evaluate its remission effect on obese animals and related mechanisms. The effects of LP23-1 on lipid accumulation and intestinal inflammation in HFD-fed mice were systematically evaluated by detecting lipid accumulation, blood lipid level, pathological changes in the liver and small intestine, oxidative stress and inflammatory cell level, lipid transport-related gene expression, the inflammatory signaling pathway, and intestinal tight junction (TJ) mRNA and protein expression. The results showed that LP23-1 could significantly reduce the body weight and fat index of HFD-fed mice, improve the lipid levels of serum and liver, reduce the histopathological damage to the liver and small intestine, and alleviate oxidative stress and inflammatory response caused by obesity. In addition, reverse transcription-polymerase chain reaction and western blot analysis showed that LP23-1 could regulate the mRNA expression of lipid transport-related genes; activate the TLR4/NF-κB signaling pathway; reduce intestinal inflammation; improve the mRNA and protein expression of intestinal TJ proteins zona occludens-1 (ZO-1), occludin, claudin-1, and Muc2; repair intestinal mucosal injury; and enhance intestinal barrier function. The aforementioned results showed that LP23-1 through the TLR4/NF-κB signaling pathway and intestinal barrier function reduced obesity symptoms. This study provided new insights into the mechanism of LP23-1 in reducing obesity and provided a theoretical basis for developing new functional foods.
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Lactobacillus plantarum , Animales , Inflamación/metabolismo , Mucosa Intestinal/metabolismo , Lactobacillus plantarum/metabolismo , Lípidos , Masculino , Ratones , Ratones Endogámicos C57BL , Ratones Obesos , FN-kappa B/genética , FN-kappa B/metabolismo , Obesidad/metabolismo , ARN Mensajero/metabolismo , Transducción de Señal , Receptor Toll-Like 4/genética , Receptor Toll-Like 4/metabolismoRESUMEN
Reports concerning the characteristics of soybean oil bodies (SOBs) isolated from high protein genotypes and high oil genotypes of soybeans available in the literature are insufficient and limiting. In this study, fatty acid compositions, total phenol and tocopherol contents, antioxidant capacity, and physicochemical stability of SOB emulsions recovered from three high-protein and three high-oil genotype soybeans were comparatively investigated. Principal component analysis showed that all six SOB samples could be easily discriminated based on the cultivar characteristics. Overall, the SOBs derived from the high-protein soybeans exhibited higher polyunsaturated fatty acid (PUFA) contents, while the SOBs derived from the high-oil soybeans had higher extraction yields and tocopherol contents; the tocopherol content was also positively correlated with the antioxidant capacity of the lipophilic fraction, but the difference in the total phenolic content between the two genotypes was not significant. The SOBs derived from the high-protein soybeans were more easily oxidized during storage, with 1.38- and 4-fold higher accumulation rates of lipid hydroperoxides (LPO) and thiobarbituric acid reactive substances (TBARS), respectively, in the high-protein-derived SOBs than in the high-oil-derived SOBs. In addition, the SOBs from the high-protein soybeans exhibited pronounced coalescence during storage, which was corroborated by focused confocal microscopy. These results confirmed that SOBs obtained from high-oil soybean genotypes are more suitable to manufacture OB-based products due to their superior physicochemical stability.
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Glycine max/química , Gotas Lipídicas/química , Aceite de Soja/química , Proteínas de Soja/análisis , Antioxidantes/análisis , Emulsiones/química , Ácidos Grasos , Ácidos Grasos Omega-3/análisis , Peróxidos Lipídicos/análisis , Microscopía Confocal , Oxidación-Reducción , Tamaño de la Partícula , Fenoles/análisis , Análisis de Componente Principal , Semillas/química , Sustancias Reactivas al Ácido Tiobarbitúrico/análisis , Tocoferoles/análisisRESUMEN
BACKGROUND: Oil bodies (OBs) are a kind of natural and stable oil nucleate microcapsule in which the triglyceride matrix can be used as an appropriate carrier of hydrophobic molecules. Astaxanthin has high antioxidant properties but is extremely sensitive to oxidation, causing the loss of its bioactive properties. RESULTS: The purpose of this study was to clarify the effects of environmental factors (light, oxygen, temperature, and pH) on the physical and oxidative stability of astaxanthin microcapsules prepared with peanut oil bodies (POBs). After 14 days of storage, the retention rate of astaxanthin in peanut oil microcapsules (POMs) was significantly increased. The astaxanthin retention rate of POMs stored under light conditions was higher than under dark conditions. Similarly, the retention rate of astaxanthin in POMs was significantly increased during vacuum storage. The astaxanthin retention rate was also the highest when POMs were stored at 4 °C, whereas it was the lowest at pH 3.0. CONCLUSION: The experiment demonstrated that microcapsulation could improve the astaxanthin retention rate and storage stability, and recombinant OBs were potential ideal wall materials for astaxanthin embedding. © 2022 Society of Chemical Industry.
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Liposomas , Xantófilas , Cápsulas/química , Estrés Oxidativo , Xantófilas/químicaRESUMEN
Vesicular neurotransmitter transporters (VNTs) mediate the selective uptake and enrichment of small-molecule neurotransmitters into synaptic vesicles (SVs) and are therefore a major determinant of the synaptic output of specific neurons. To identify novel VNTs expressed on SVs (thus identifying new neurotransmitters and/or neuromodulators), we conducted localization profiling of 361 solute carrier (SLC) transporters tagging with a fluorescent protein in neurons, which revealed 40 possible candidates through comparison with a known SV marker. We parallelly performed proteomics analysis of immunoisolated SVs and identified seven transporters in overlap. Ultrastructural analysis further supported that one of the transporters, SLC35D3, localized to SVs. Finally, by combining metabolite profiling with a radiolabeled substrate transport assay, we identified UDP-glucose as the principal substrate for SLC35D3. These results provide new insights into the functional role of SLC transporters in neurotransmission and improve our understanding of the molecular diversity of chemical transmitters.
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Transporte Biológico/fisiología , Neuronas/metabolismo , Proteómica , Vesículas Sinápticas/metabolismo , Uridina Difosfato Glucosa/metabolismo , Animales , Glucosa/metabolismo , Células HEK293 , Humanos , Ratones , Proteínas de Transporte de Monosacáridos/metabolismo , Neurotransmisores/metabolismo , Ratas , Ratas Sprague-Dawley , Transmisión Sináptica/fisiologíaRESUMEN
Lithium-sulfur batteries show great potential to achieve high-energy-density storage, but their long-term stability is still limited due to the shuttle effect caused by the dissolution of polysulfides into electrolyte. Herein, we report a strategy of significantly improving the polysulfides adsorption capability of cobaltous oxide by amorphization-induced surface electronic states modulation. The amorphous cobaltous oxide nanosheets as the cathode additives for lithium-sulfur batteries demonstrates the rate capability and cycling stability with an initial capacity of 1248.2 mAh g-1 at 1 C and a substantial capacity retention of 1037.3 mAh g-1 after 500 cycles. X-ray absorption spectroscopy analysis reveal that the coordination structures and symmetry of ligand field around Co atoms of cobaltous oxide nanosheets are notably changed after amorphization. Moreover, DFT studies further indicate that amorphization-induced re-distribution of d orbital makes more electrons occupy high energy level, thereby resulting in a high binding energy with polysulfides for favorable adsorption.
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Heterogeneous noble-metal-based catalysis plays an essential role in the production of fine chemicals. Rh-based catalysts are one of the most active candidates for indole synthesis. However, it is still highly desired to develop heterogeneous Rh-based catalysts with high activity and selectivity. In this work, a general, facile wet-chemical method is reported to synthesize ultrathin amorphous/crystalline heterophase Rh and Rh-based bimetallic alloy nanosheets (NSs), including RhCu, RhZn, and RhRu. Impressively, the amorphous/crystalline heterophase Rh NSs exhibit enhanced catalytic activity toward the direct synthesis of indole compared to the crystalline counterpart. Importantly, the obtained amorphous/crystalline heterophase RhCu alloy NSs can further enhance the selectivity to indole of >99.9% and the conversion is 100%. This work demonstrates the importance of phase engineering and metal alloying in the rational design and synthesis of tandem heterogeneous catalysts toward fine chemical synthesis.
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Developing highly stable and efficient catalysts toward the oxygen reduction reaction is important for the long-term operation in proton exchange membrane fuel cells. Reported herein is a facile synthesis of two-dimensional coplanar Pt-carbon nanomeshes (NMs) that are composed of highly distorted Pt networks (neck width of 2.05±0.72â nm) and carbon. X-ray absorption fine structure spectroscopy demonstrated the metallic state of Pt in the coplanar Pt/C NMs. Fuel cell tests verified the excellent activity of the coplanar Pt/C NM catalyst with the peak power density of 1.21â W cm-2 and current density of 0.360â A cm-2 at 0.80â V in the H2 /O2 cell. Moreover, the coplanar Pt/C NM electrocatalysts showed superior stability against aggregation, with NM structures preserved intact for a long-term operation of over 30 000â cycles for electrode measurement, and the working voltage loss was negligible after 120â h in the H2 /O2 single cell operation. Density-functional theory analysis indicates the increased vacancy formation energy of Pt atoms for coplanar Pt/C NMs, restraining the tendency of Pt dissolution and aggregation.
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The sintering of supported metal nanoparticles is a major route to the deactivation of industrial heterogeneous catalysts, which largely increase the cost and decrease the productivity. Here, we discover that supported palladium/gold/platinum nanoparticles distributed at the interface of oxide supports and nitrogen-doped carbon shells would undergo an unexpected nitrogen-doped carbon atomization process against the sintering at high temperatures, during which the nanoparticles can be transformed into more active atomic species. The in situ transmission electron microscopy images reveal the abundant nitrogen defects in carbon shells provide atomic diffusion sites for the mobile atomistic palladium species detached from the palladium nanoparticles. More important, the catalytic activity of sintered and deactivated palladium catalyst can be recovered by this unique N-doped carbon atomization process. Our findings open up a window to preparation of sintering-resistant single atoms catalysts and regeneration of deactivated industrial catalysts.
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Noble metal nanomaterials have been widely used as catalysts. Common techniques for the synthesis of noble metal often result in crystalline nanostructures. The synthesis of amorphous noble metal nanostructures remains a substantial challenge. We present a general route for preparing dozens of different amorphous noble metal nanosheets with thickness less than 10 nm by directly annealing the mixture of metal acetylacetonate and alkali salts. Tuning atom arrangement of the noble metals enables to optimize their catalytic properties. Amorphous Ir nanosheets exhibit a superior performance for oxygen evolution reaction under acidic media, achieving 2.5-fold, 17.6-fold improvement in mass activity (at 1.53 V vs. reversible hydrogen electrode) over crystalline Ir nanosheets and commercial IrO2 catalyst, respectively. In situ X-ray absorption fine structure spectra indicate the valance state of Ir increased to less than + 4 during the oxygen evolution reaction process and recover to its initial state after the reaction.
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Background The temporal sequence between serum calcium and insulin resistance (IR) and their effects on hypertension are unclear. We studied the association between serum calcium and IR, with risk of hypertension events in a longitudinal cohort conducted in China. Methods and Results Data from 8653 subjects aged 20 to 74 years with an average follow-up of 5.3 years were analyzed. Serum calcium, and fasting and 2-hour serum glucose and insulin were measured at baseline and follow-up. Cross-lagged panel and mediation analysis were used to examine the temporal relationship between serum calcium and IR and its impact on hypertension incidence. The conjoint effects of serum calcium and IR at baseline on hypertension at follow-up were observed ( P=0.029 for HOMA_IR [hepatic IR] and P=0.009 for Gutt index [peripheral IR]). The cross-lagged path coefficient (ß2) from baseline serum calcium to follow-up peripheral IR were significantly greater than path coefficient (ß1) from baseline peripheral insulin resistance to follow-up serum calcium (ß2 =-0.354 versus ß1=-0.005; P=0.027). However, no directional relationships were observed in the serum calciumâhepatic IR analysis. The mediation effect of peripheral IR on the association of serum calcium at baseline with hypertension at follow-up was estimated at 16.4% ( P<0.001). Conclusions Our findings demonstrate that higher serum calcium levels probably precede peripheral IR, and this 1-directional relation plays a role in the development of hypertension.
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Presión Sanguínea/fisiología , Calcio/sangre , Hipertensión/sangre , Resistencia a la Insulina/fisiología , Adulto , Anciano , Biomarcadores/sangre , Índice de Masa Corporal , China/epidemiología , Femenino , Estudios de Seguimiento , Humanos , Hipertensión/epidemiología , Hipertensión/fisiopatología , Incidencia , Masculino , Persona de Mediana Edad , Pronóstico , Estudios Prospectivos , Factores de Riesgo , Factores de Tiempo , Adulto JovenRESUMEN
The correct establishment and maintenance of unidirectional Notch signaling are critical for the homeostasis of various stem cell lineages. However, the molecular mechanisms that prevent cell-autonomous ectopic Notch signaling activation and deleterious cell fate decisions remain unclear. Here we show that the retromer complex directly and specifically regulates Notch receptor retrograde trafficking in Drosophila neuroblast lineages to ensure the unidirectional Notch signaling from neural progenitors to neuroblasts. Notch polyubiquitination mediated by E3 ubiquitin ligase Itch/Su(dx) is inherently inefficient within neural progenitors, relying on retromer-mediated trafficking to avoid aberrant endosomal accumulation of Notch and cell-autonomous signaling activation. Upon retromer dysfunction, hypo-ubiquitinated Notch accumulates in Rab7+ enlarged endosomes, where it is ectopically processed and activated in a ligand-dependent manner, causing progenitor-originated tumorigenesis. Our results therefore unveil a safeguard mechanism whereby retromer retrieves potentially harmful Notch receptors in a timely manner to prevent aberrant Notch activation-induced neural progenitor dedifferentiation and brain tumor formation.
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Carcinogénesis/metabolismo , Proteínas de Drosophila/metabolismo , Complejos Multiproteicos/metabolismo , Células-Madre Neurales/metabolismo , Receptores Notch/metabolismo , Animales , Carcinogénesis/genética , Proteínas de Drosophila/genética , Drosophila melanogaster/genética , Drosophila melanogaster/metabolismo , Endosomas/metabolismo , Células HEK293 , Humanos , Complejos Multiproteicos/genética , Mutación , Unión Proteica , Transporte de Proteínas , Receptores Notch/genética , Proteínas de Transporte Vesicular/genética , Proteínas de Transporte Vesicular/metabolismoRESUMEN
The inhibin/activin subunits (α, ßA and ßB) have been found in epididymal tissue of many mammals, but there have been no data available for wild seasonal breeders so far. The aim of this study was to investigate the immunoreactivities of inhibin/activin α, ßA and ßB subunits in the epididymis of wild ground squirrels during the breeding and nonbreeding seasons. Immunohistochemistry and Western blotting were performed to detect the epididymal immunolocalizations and immunoreactivities of the three subunits. Strong immunostaining of α subunit was present in the interstitial part of the caput epididymis and epithelial parts of the corpus epididymis and cauda epididymis during the breeding season, whereas no α subunit was found in the nonbreeding season. ßA and ßB subunits were expressed in all cell types of the epithelium throughout the whole seasonal cycle, and immunostaining in the breeding season was likely stronger compared with that of the nonbreeding season. These results suggested that the epididymis might be a potential source of inhibin and activin in the wild male ground squirrel, and the secretion of epididymal inhibin and activin showed distinct seasonal changes. Furthermore, inhibin and activin might function as paracrine and/or autocrine factors that have an effect on the epididymis.
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Activinas/metabolismo , Epidídimo/metabolismo , Regulación de la Expresión Génica , Inhibinas/metabolismo , Estaciones del Año , Animales , Inmunohistoquímica , Subunidades beta de Inhibinas/metabolismo , Masculino , Sciuridae , Testículo/metabolismo , Distribución TisularRESUMEN
The PBAN (pheromone biosynthesis activating neuropeptide)/pyrokinin peptides comprise a major neuropeptide family characterized by a common FXPRL amide at the C-terminus. These peptides are actively involved in many essential endocrine functions. For the first time, we reported the cDNA cloning and sequence determination of the PBAN from the seabuckthorn carpenterworm, Holcocerus hippophaecolus, by using rapid amplification of cDNA ends. The full-length cDNA of Hh-DH-PBAN contained five peptides: diapause hormone (DH) homolog, α-neuropeptide (NP), ß-NP, PBAN, and γ-NP. All of the peptides were amidated at their C-terminus and shared a conserved motif, FXPR (or K) L. Moreover, Hh-DH-PBAN had high homology to the other members of the PBAN peptide family: 56% with Manduca sexta, 66% with Bombyx mori, 77% with Helicoverpa zea, and 47% with Plutella xylostella. Phylogenetic analysis revealed that Hh-DH-PBAN was closely related to PBANs from Noctuidae, demonstrated by the relatively higher similarity compared with H. zea. In addition, real-time quantitative PCR (qRT-PCR) analysis showed that Hh-DH-PBAN mRNA expression peaked in the brain-subesophageal ganglion (Br-SOG) complex, and was also detected at high levels during larval and adult stages. The expression decreased significantly after pupation. These results provided information concerning molecular structure characteristics of Hh-DH-PBAN, whose expression profile suggested that the Hh-DH-PBAN gene might be correlated with larval development and sex pheromone biosynthesis in females of the H. hippophaecolus.