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Oxides with a face-centred cubic (fcc) anion sublattice are generally not considered as solid-state electrolytes as the structural framework is thought to be unfavourable for lithium (Li) superionic conduction. Here we demonstrate Li superionic conductivity in fcc-type oxides in which face-sharing Li configurations have been created through cation over-stoichiometry in rocksalt-type lattices via excess Li. We find that the face-sharing Li configurations create a novel spinel with unconventional stoichiometry and raise the energy of Li, thereby promoting fast Li-ion conduction. The over-stoichiometric Li-In-Sn-O compound exhibits a total Li superionic conductivity of 3.38 × 10-4 S cm-1 at room temperature with a low migration barrier of 255 meV. Our work unlocks the potential of designing Li superionic conductors in a prototypical structural framework with vast chemical flexibility, providing fertile ground for discovering new solid-state electrolytes.
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Lithium-rich cathodes are promising energy storage materials due to their high energy densities. However, voltage hysteresis, which is generally associated with transition metal migration, limits their energy efficiency and implementation in practical devices. Here we reveal that voltage hysteresis is related to the collective migration of metal ions, and that isolating the migration events from each other by creating partial disorder can create high-capacity reversible cathode materials, even when migrating transition metal ions are present. We demonstrate this on a layered Li-rich chromium manganese oxide that in its fully ordered state displays a substantial voltage hysteresis (>2.5 V) associated with collective transition metal migration into Li layers, but can be made to achieve high capacity (>360 mAh g-1) and energy density (>1,100 Wh kg-1) when the collective migration is perturbed by partial disorder. This study demonstrates that partially cation-disordered cathode materials can accommodate a high level of transition metal migration, which broadens our options for redox couples to those of mobile cations.
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Non-Saccharomyces (NSc) yeasts have great potential in improving wine qualities. In this study, two NSc and two Saccharomyces cerevisiae (Sc) samples were tested on their performance of mono-inoculated and composite culture in the fermentation of Chunjian citrus wine. The cell count, Brix degree, total sugar, total acidity, alcohol level, pH value, color intensity (CI), and tonality were determined to evaluate the contribution of NSc to the quality of citrus wine in the mixed fermentation. Volatile compounds were analyzed by HS-SPME-GC-MS, and sensory evaluation was carried out. During the 9-day fermentation, the mixed-culture wine exhibited a higher cell concentration than the pure culture. After the fermentation, mixed-culture wine specifically decreased the concentrations of unfavorable volatile compounds, such as isobutanol and octanoic acid, and increased favorable volatile compounds, including ethyl octanoate, ethyl decanoate, and phenylethyl acetate. The quality category of the citrus wine was improved compared with the Sc mono-inoculated wines, mainly in regard to aroma, retention, and sweetness. The study shows that the mixed fermentation of NSc and Sc has positive impacts on reducing alcohol level and total acidity and increasing CI. The present work demonstrates that the mixed fermentation of NSc and Sc has enormous beneficial impacts on improving the quality of citrus wine.
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Saccharomyces , Vinho , Saccharomyces cerevisiae , Vinho/análise , Fermentação , Etanol/análiseRESUMO
Transition-metal dichalcogenides (TMDs) have long been attractive to researchers for their diverse properties and high degree of tunability. Most recently, interest in magnetically intercalated TMDs has resurged due to their potential applications in spintronic devices. While certain compositions featuring the absence of inversion symmetry such as Fe1/3NbS2 and Cr1/3NbS2 have garnered the most attention, the diverse compositional space afforded through the host matrix composition as well as intercalant identity and concentration is large and remains relatively underexplored. Here, we report the magnetic ground state of Fe1/4NbS2 that was determined from low-temperature neutron powder diffraction as an A-type antiferromagnet. Despite the presence of overall inversion symmetry, the pristine compound manifests spin polarization induced by the antiferromagnetic order at generic k points, based on density functional theory band-structure calculations. Furthermore, by combining synchrotron diffraction, pair distribution function, and magnetic susceptibility measurements, we find that the magnetic properties of Fe1/4NbS2 are sensitive to the Fe site order, which can be tuned via electrochemical lithiation and thermal history.
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Capsaicin stress, along with salt stress, could be considered the main stressors for lactic acid bacteria in traditional fermented pepper products. Until now, insufficient attention has been paid to salt stress, while the effect of capsaicin on the aroma-producing properties of Lactobacillus plantarum (L. plantarum) is unclear. The present study attempted to illustrate the effect of capsaicin stress on the aroma-producing properties of L. plantarum CL-01 isolated from traditionally fermented peppers based on E-nose and GC-IMS. The results showed that E-nose could clearly distinguish the overall flavor differences of L. plantarum CL-01 under capsaicin stress. A total of 48 volatile compounds (VOCs) were characterized by means of GC-IMS, and the main VOCs belonged to acids and alcohols. Capsaicin stress significantly promoted L. plantarum CL-01 to produce alpha-pinene, ethyl crotonate, isobutyric acid, trans-2-pentenal, 2-methyl-1-butanol, 3-methyl-3-buten-1-ol, 1-penten-3-one, 2-pentanone, 3-methyl-1-butanol-D, and 2-heptanone (p < 0.05). In addition, under capsaicin stress, the contents of 1-penten-3-one, 3-methyl-3-buten-1-ol, 5-methylfurfuryl alcohol, isobutanol, 2-furanmethanethiol, 2,2,4,6,6-pentamethylheptane, 1-propanethiol, diethyl malonate, acetic acid, beta-myrcene, 2-pentanone, ethyl acetate, trans-2-pentenal, 2-methylbutyl acetate, and 2-heptanone produced by L. plantarum CL-01 were significantly increased along with the fermentation time (p < 0.05). Furthermore, some significant correlations were observed between the response values of specific E-nose sensors and effective VOCs.
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Aldeídos , Butanóis , Nariz Eletrônico , Cetonas , Lactobacillus plantarum , Pentanonas , Odorantes , Capsaicina/farmacologiaRESUMO
High-entropy (HE) ceramics, by analogy with HE metallic alloys, are an emerging class of solid solutions composed of a large number of species. These materials offer the benefit of large compositional flexibility and can be used in a wide variety of applications, including thermoelectrics, catalysts, superionic conductors and battery electrodes. We show here that the HE concept can lead to very substantial improvements in performance in battery cathodes. Among lithium-ion cathodes, cation-disordered rocksalt (DRX)-type materials are an ideal platform within which to design HE materials because of their demonstrated chemical flexibility. By comparing a group of DRX cathodes containing two, four or six transition metal (TM) species, we show that short-range order systematically decreases, whereas energy density and rate capability systematically increase, as more TM cation species are mixed together, despite the total metal content remaining fixed. A DRX cathode with six TM species achieves 307 mAh g-1 (955 Wh kg-1) at a low rate (20 mA g-1), and retains more than 170 mAh g-1 when cycling at a high rate of 2,000 mA g-1. To facilitate further design in this HE DRX space, we also present a compatibility analysis of 23 different TM ions, and successfully synthesize a phase-pure HE DRX compound containing 12 TM species as a proof of concept.
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An amendment to this paper has been published and can be accessed via the original article.
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BACKGROUND: Circular RNAs (circRNAs) represent a subclass of regulatory RNAs that have been shown to have significant regulatory roles in cancer progression. However, the biological functions of circRNAs in bladder cancer (BCa) are largely unknown. METHODS: Cell invasion models were established, and invasion-related circRNAs were detected by qPCR. Using above method, circ-ZKSCAN1 was picked out for further study. Circ-ZKSCAN1 expression and survival analyses were performed through qPCR. The survival curves were generated by the Kaplan-Meier method, and the log-rank test was used to assess the significance. Cell proliferation, migration and invasion were examined to investigate the function of circ-ZKSCAN1. Tumorigenesis in nude mice was assessed to determine the effect of circ-ZKSCAN1 in bladder cancer. Biotin-coupled probe pull-down assays, FISH and luciferase reporter assays were conducted to confirm the relationship between circ-ZKSCAN1 and microRNA. RNA-seq revealed different molecular changes in downstream genes. RESULTS: Here, we found that circ-ZKSCAN1 was downregulated in BCa tissues and cell lines. Circ-ZKSCAN1 levels were associated with survival, tumor grade, pathological T stage and tumor recurrence. Overexpressed circ-ZKSCAN1 inhibits cell proliferation, migration, invasion and metastasis in vitro and in vivo. Mechanistically, we demonstrated that circ-ZKSCAN1 upregulated p21 expression by sponging miR-1178-3p, which suppressed the aggressive biological behaviors in bladder cancer. CONCLUSIONS: These results reveal that Circ-ZKSCAN1 acts as a tumor suppressor via a novel circ-ZKSCAN1/miR-1178-3p/p21 axis, which have the important role in the proliferation, migration and invasion ablitities of BCa cells and provide a novel perspective on circRNAs in BCa progression.
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MicroRNAs/genética , RNA Circular , Neoplasias da Bexiga Urinária/genética , Dedos de Zinco/genética , Idoso , Idoso de 80 Anos ou mais , Animais , Biomarcadores Tumorais , Linhagem Celular Tumoral , Movimento Celular/genética , Proliferação de Células , Feminino , Regulação Neoplásica da Expressão Gênica , Humanos , Masculino , Camundongos , Pessoa de Meia-Idade , Gradação de Tumores , Estadiamento de Neoplasias , Prognóstico , Interferência de RNA , Neoplasias da Bexiga Urinária/diagnóstico , Neoplasias da Bexiga Urinária/mortalidadeRESUMO
Metal-containing nanocrystals with well-designed surface structures represent a class of model systems for revealing the fundamental physical and chemical processes involved in heterogeneous catalysis. Herein it is shown how surface modification can be utilized as an efficient strategy for controlling the surface electronic state of catalysts and, thus, for tuning their catalytic activity. As model catalysts, the Pd-tetrahedron-TiO2 nanostructures, modified on the surface with different foreign atoms, showed a varied activity in the catalytic decomposition of formic acid towards H2 production. The catalytic activity increases with a reduction in the work function of modified atoms; this reduction can be well explained by a surface polarization mechanism. In this hybrid system, the difference in the work functions of Pd and modified atoms results in surface polarization on the Pd surface and, thus, in the tuning of its charge state. Together with the Schottky junction between TiO2 and metals, the tuned charge state enables the promotion of catalytic efficiency in the catalytic decomposition of formic acid to H2 and CO2 .
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OBJECTIVE: Raf kinase inhibitor protein (RKIP) appears to control cancer cell metastasis and its expression in colonic tissue is related to colonic cancer development. We sought to identify the roles of RKIP in maintaining homeostasis of GI tract. DESIGN: The expression of RKIP was determined by immunohistochemistry and western blot analysis. RKIP knockout and wild-type mice were administered dextran sulfate sodium (DSS) or 2,4,6-trinitrobenzenesulfonic acid (TNBS) to induce experimental colitis, and the mice were assessed based on colitis symptoms and biochemical approaches. The mechanism was analysed using immunoprecipitation and pull-down experiments. RESULTS: The RKIP expression is positively correlated with the severity of IBD. RKIP deficiency protects mice from DSS-induced or TNBS-induced colitis and accelerated recovery from colitis. RKIP deficiency inhibits DSS-induced infiltration of acute-phase immune cells and reduces production of proinflammatory cytokines and chemokines in colon. RKIP deficiency inhibits DSS-induced or TNBS-induced colonic epithelial barrier damage and intestinal epithelial cell (IEC) apoptosis. RKIP deficiency also inhibits tumour necrosis factor-alpha-induced IEC apoptosis and colitis. Mechanistically, RKIP enhances the induction of P53-upregulated modulator of apoptosis by interacting with TGF-ß-activated kinase 1 (TAK1) and promoting TAK1-mediated NF-κB activation. This is supported by the observation that TAK1 activation is positively correlated with the expression of RKIP in human clinical samples and the development of IBD. CONCLUSIONS: RKIP contributes to colitis development by promoting inflammation and mediating IEC apoptosis and might represent a therapeutic target of IBD.
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Apoptose , Colite/genética , Doença de Crohn/metabolismo , Células Epiteliais/química , MAP Quinase Quinase Quinases/metabolismo , Proteína de Ligação a Fosfatidiletanolamina/genética , Proteína de Ligação a Fosfatidiletanolamina/metabolismo , Animais , Apoptose/efeitos dos fármacos , Apoptose/genética , Colite/induzido quimicamente , Colite/metabolismo , Colite/patologia , Colite Ulcerativa/metabolismo , Sulfato de Dextrana , Células Epiteliais/efeitos dos fármacos , Células HCT116 , Homeostase/genética , Humanos , Mucosa Intestinal/citologia , Camundongos , Camundongos Knockout , Proteína de Ligação a Fosfatidiletanolamina/análise , Fosforilação , Índice de Gravidade de Doença , Ácido Trinitrobenzenossulfônico , Fator de Necrose Tumoral alfa/farmacologiaRESUMO
Kiwi wine (KW) is tipically made by fermenting juice from peeled kiwifruit, resulting in the disposal of peel and pomace as by-products. However, the peel contains various beneficial compounds, like phenols and flavonoids. Since the peel is edible and rich in these compounds, incorporating it into the fermentation process of KW presents a potential solution to minimize by-product waste. This study compared the aroma and taste profiles of KW from peeled (PKW) and unpeeled (UKW) kiwifruits by combining intelligent sensory technology, GC-MS, and 1H-NMR. Focusing on aroma profiles, 75 volatile organic compounds (VOCs) were identified in KW fermented with peel, and 73 VOCs in KW without peel, with 62 VOCs common to both. Among these compounds, rose oxide, D-citronellol, and bornylene were more abundant in UKW, while hexyl acetate, isoamyl acetate, and 2,4,5-trichlorobenzene were significantly higher in PKW. For taste profiles, E-tongue analysis revealed differences in the taste profiles of KW from the two sources. A total of 74 molecules were characterized using 1H-NMR. UKW exhibited significantly higher levels of tartrate, galactarate, N-acetylserotonin, 4-hydroxy-3-methoxymandelate, fumarate, and N-acetylglycine, along with a significantly lower level of oxypurinol compared to PKW. This study seeks to develop the theoretical understanding of the fermentation of kiwifruit with peel in sight of the utilization of the whole fruit for KW production, to increase the economic value of kiwifruit production.
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In situ carbon dioxide (CO2) outgassing is a common phenomenon in lithium-ion batteries (LiBs), primarily due to parasitic side reactions at the cathode-electrolyte interface. However, little is known about the chemical origins of the in situ CO2 released from emerging Li-excess cation-disordered rock salt (DRX) cathodes. In this study, we selectively labeled various carbon sources with 13C in cathodes containing a representative DRX material, Li1.2Mn0.4Ti0.4O2 (LMTO), and performed differential electrochemical mass spectrometry (DEMS) during galvanostatic cycling in a carbonate-based electrolyte. When charging LMTO cathodes, electrolyte solvent (EC) decomposition is the dominant source of the CO2 outgassing. The amount of EC-originated CO2 is strongly correlated with the total surface area of carbon black in the electrode, revealing the critical role of electron-conducting carbon additives in the electrolyte degradation mechanisms. In addition, unusual bimodal CO2 evolution during the first cycle is found to originate from carbon black oxidation. Overall, the underlying chemical origin of in situ CO2 release during battery cycling is highly voltage- and cycle-dependent. This work further provides insights into improving the stability of DRX cathodes in LiBs and is envisioned to help guide future relevant material design to mitigate parasitic reactions in DRX-based batteries.
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Na Super Ionic Conductor (NASICON) materials are an important class of solid-state electrolytes owing to their high ionic conductivity and superior chemical and electrochemical stability. In this paper, we combine first-principles calculations, experimental synthesis and testing, and natural language-driven text-mined historical data on NASICON ionic conductivity to achieve clear insights into how chemical composition influences the Na-ion conductivity. These insights, together with a high-throughput first-principles analysis of the compositional space over which NASICONs are expected to be stable, lead to the successful synthesis and electrochemical investigation of several new NASICONs solid-state conductors. Among these, a high ionic conductivity of 1.2 mS cm-1 could be achieved at 25 °C. We find that the ionic conductivity increases with average metal size up to a certain value and that the substitution of PO4 polyanions by SiO4 also enhances the ionic conductivity. While optimal ionic conductivity is found near a Na content of 3 per formula unit, the exact optimum depends on other compositional variables. Surprisingly, the Na content enhances the ionic conductivity mostly through its effect on the activation barrier, rather than through the carrier concentration. These deconvoluted design criteria may provide guidelines for the design of optimized NASICON conductors.
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Physicochemical properties, bacterial communities, and volatile compounds of mutton sausage produced from Jianzhou Big-Eared goat meat during natural ripening were investigated. Firmicutes and Bacteroidetes accounted for over 66% of all operational taxonomic units (OTUs) throughout the whole process, with Lachnospiraceae_NK4A136_group and Staphylococcus as the predominant genus during the early and later ripening periods, respectively. The evolution of microbial composition became less rich and diverse. The uncultured bacterium, the Lachnospiraceae_NK4A136_group, and Staphylococcus were marker bacteria on days 0, 7, and 26, respectively, with none on day 16. The bacteria distribution seemed to influence the volatile profile of mutton sausage throughout processing, with the bacterial composition on day 0 and day 7 clustered separately from day 16 and day 26, and the same pattern for the volatile profile. Meanwhile, the concentration of total volatile fraction significantly increased, and the majority of the volatile compounds were generated during late ripening. Non-anal, hexanal, decanal, heptanal, dodecyl aldehyde, benzaldehyde, 3-methylbutanal, γ-dodecalactone, 2-pentylfuran, and 1-octen-3-ol were key volatile compounds, contributing to the overall mutton sausage flavors. Based on Spearman's correlation analysis, Staphylococcus as well as Psychrobacter were positively correlated with the production of the key volatile compounds, and other bacteria such as Lachnospiraceae_NK4A136_group, Bacteroides, Lactobacillus, Prevotella_1, Odoribacter, and so on were associated with the production of most alcohols and esters.
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Advances in solid-state batteries have primarily been driven by the discovery of superionic conducting structural frameworks that function as solid electrolytes. We demonstrate the ability of high-entropy metal cation mixes to improve ionic conductivity in a compound, which leads to less reliance on specific chemistries and enhanced synthesizability. The local distortions introduced into high-entropy materials give rise to an overlapping distribution of site energies for the alkali ions so that they can percolate with low activation energy. Experiments verify that high entropy leads to orders-of-magnitude higher ionic conductivities in lithium (Li)-sodium (Na) superionic conductor (Li-NASICON), sodium NASICON (Na-NASICON), and Li-garnet structures, even at fixed alkali content. We provide insight into selecting the optimal distortion and designing high-entropy superionic conductors across the vast compositional space.
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Technological, safety-related and volatile properties were analyzed in coagulase-negative staphylococci (CNS) isolates from Chinese spontaneously fermented meat products. A total of 107 CNS isolates were identified via 16 S rRNA sequencing, and the most recovered species were S. saprophyticus (53.3 %), S. edaphicus (12.1 %), and S. epidermidis (10.3 %). Among them, 58 CNS isolates belonging to 9 species were selected with higher activities of catalase, nitrate reductase, proteolysis, and lipolysis, as well as higher tolerance to stressful environmental conditions. Then, 7 CNS isolates belonging to 4 species were further selected based upon excellent technological characteristics, lack of hemolysis and antibiotic resistance, and a low production of biogenic amines. The volatile profiles of these 7 strains cultivated in pork broth was determined. S. casei No. 1 produced significant amounts of phenethyl alcohol, geraniol, and 3-methyl-butanol. S. xylosus No. 120 produced the highest amount of methyl ketones with the potential to provide dry-cured odor of fermented meats. The volatile profile was highly strain dependent. Several CNS identified in this study have the potential to be used as the starter cultures for fermented meat products.
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Produtos da Carne , China , Coagulase/metabolismo , Fermentação , Microbiologia de Alimentos , Staphylococcus/genética , Staphylococcus/metabolismoRESUMO
The development of a materials synthesis route is usually based on heuristics and experience. A possible new approach would be to apply data-driven approaches to learn the patterns of synthesis from past experience and use them to predict the syntheses of novel materials. However, this route is impeded by the lack of a large-scale database of synthesis formulations. In this work, we applied advanced machine learning and natural language processing techniques to construct a dataset of 35,675 solution-based synthesis procedures extracted from the scientific literature. Each procedure contains essential synthesis information including the precursors and target materials, their quantities, and the synthesis actions and corresponding attributes. Every procedure is also augmented with the reaction formula. Through this work, we are making freely available the first large dataset of solution-based inorganic materials synthesis procedures.
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It is the heterogeneous changes of hypothalamic functions that determine the chronological sequence of aging in mammals. Recently, it was hypothesized by Cai the decrease in slow-wave sleep (SWS) resulting from skin aging as responsible for the degeneration of hypothalamic suprachiasmatic nucleus (SCN). It was soon hypothesized by the European people in television that the increase in body fat as responsible for the degeneration of male preoptic sexually dimorphic nucleus (SDN-POA), via the aromatase converting testosterone to estradiol as proposed by Cohen. It is the hypothalamic paraventricular nucleus (PVN) that remains unchanged in neuron number during aging for psychological stress. In this chapter, it is briefly reviewed more manifestations of hypothalamic related mammalian aging processes, including (1) the aging of ovary by lipid, estradiol and hypothalamus; (2) the aging of muscle, stomach, intestine, thymus, and the later aging of brain, regulated by growth hormone/insulin-like growth factor 1(GH/IGF1); (3) the cardiovascular hypertension from PVN activation, the bone and other peripheral aging by psychological stress, and that of kidney by vasopressin. It is classified these aging processes by the primary regulation from one of the three hypothalamic nuclei, although still necessary to investigate and supplement their secondary regulation by the hypothalamic nuclei in future. It is the hypothalamic structural changes that shift the functional balance among these three hypothalamic systems toward aging.
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Hipotálamo , Núcleo Supraquiasmático , Envelhecimento/fisiologia , Animais , Estradiol , Feminino , Humanos , Hipotálamo/fisiologia , Masculino , Núcleo Hipotalâmico Paraventricular/fisiologia , Núcleo Supraquiasmático/fisiologiaRESUMO
Structure plays a vital role in determining materials properties. In lithium ion cathode materials, the crystal structure defines the dimensionality and connectivity of interstitial sites, thus determining lithium ion diffusion kinetics. In most conventional cathode materials that are well-ordered, the average structure as seen in diffraction dictates the lithium ion diffusion pathways. Here, we show that this is not the case in a class of recently discovered high-capacity lithium-excess rocksalts. An average structure picture is no longer satisfactory to understand the performance of such disordered materials. Cation short-range order, hidden in diffraction, is not only ubiquitous in these long-range disordered materials, but fully controls the local and macroscopic environments for lithium ion transport. Our discovery identifies a crucial property that has previously been overlooked and provides guidelines for designing and engineering cation-disordered cathode materials.