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SiOx anode has a more durable cycle life than Si, being considered competitive to replace the conventional graphite. SiOx usually serves as composites with carbon to achieve more extended cycle life. However, the carbon microstructure dependent Li-ion storage behaviors in SiOx /C anode have received insufficient attention. Herein, this work demonstrates that the disorder of carbon can determine the ratio of inter- and intragranular Li-ion diffusions. The resulted variation of platform characteristics will result in different compatibility when matching SiOx . Rational disorder induced intergranular diffusion can benefit phase transition of SiOx /C, benefiting the electrochemical performance. Through a series of quantitative calculations and in situ X-ray diffraction characterizations, this work proposes the rational strategy for the future optimization, thus achieving preferable performance of SiOx /C anode.
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Tin chalcogenides are regarded as promising anode materials for potassium ion batteries (PIBs) due to their considerable specific capacity. However, the severe volume effect, limited electronic conductivity, and the shuttle effect of the potassiation product restrict the application prospect. Herein, based on the metal evaporation reaction, a facile structural engineering strategy for yolk-shell SnSe encapsulated in carbon shell (SnSe@C) is proposed. The internal void can accommodate the volume change of the SnSe core and the carbon shell can enhance the electronic conductivity. Combining qualitative and quantitative electrochemical analyses, the distinguished electrochemical performance of SnSe@C anode is attributed to the contribution of enhanced capacitive behavior. Additionally, first-principles calculations elucidate that the heteroatomic doped carbon exhibits a preferable affinity toward potassium ions and the potassiation product K2 Se, boosting the rate performance and capacity retention consequently. Furthermore, the phase evolution of SnSe@C electrode during the potassiation/depotassiation process is clarified by in situ X-ray diffraction characterization, and the crystal transition from the SnSe Pnma(62) to Cmcm(63) point group is discovered unpredictably. This work demonstrates a pragmatic avenue to tailor the SnSe@C anode via a facile structural engineering strategy and chemical regulation, providing substantial clarification for the phase evolution mechanism of SnSe-based anode for PIBs.
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The treatment of high salt organic sewage is considered to be a high energy consumption process, and it is difficult to degrade organic matter and separate salt and water simultaneously. In this study, a gradient structure titanium oxide nanowire film is developed, which can realize the thorough treatment of sewage under sunlight. Among the film, part TiO2-x has enhanced photocatalytic properties and can completely degrade 0.02 g·L-1 methylene blue in 90 min under 2 sun. Part TinO2n-1 has excellent photothermal conversion efficiency and can achieve 1.833 kg·m-2·h-1 water evaporation rate at 1 sun. Through the special structure design, salt positioning crystallization can be realized to ensure the film's stable operation for a long time. The gradient hydrophilicity of the film ensures adequate and rapid water transfer, while the water flow can induce a significant hydrovoltaic effect. The measured VOC is positively correlated with light intensity and photothermal area and corresponds to the water evaporation rate.
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As a novel energy harvesting method, generating electricity from the interaction of liquid-solid interface has attracted growing interest. Although several functional materials have been carried out to improve the performance of the flow-induced hydrovoltaic generators, there are few reports on influencing the droplet flow behavior to excavate its electricity generation by governing the device structure. Here, the output performance of the graphene microfluidic channel (GMC) structure is â¼13 times higher than that of the flat-open space graphene morphology. The strong slip flow and high surface charge density near the graphene-droplet interface originate from the GMC structure, which produces an effective liquid-solid interaction and rapid relative movement of the droplet. Additionally, based on the GMC structure a self-powered pressure sensor is designed. The droplet motion is regulated by external forces to generate specific voltages, which provide a new approach for the development of wearable self-powered electronics.
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Grafite , Fontes de Energia Elétrica , Eletricidade , Eletrônica , MicrofluídicaRESUMO
PURPOSE: This study aimed to investigate whether axial or radial functionally graded root analog implants can optimize the stress and strain distribution near the implant-bone interface in alveolar bone models under static loads using finite element analysis (FEA). MATERIALS AND METHODS: The 3D profile of the root analog implant was captured from a natural tooth in CBCT data. The implant was separated into different layers (3, 5, and 10 layers) to vary the Young modulus axially or radially. The variation in Young modulus was designed to be linear, exponential, or parabolic. Different occlusal loads were applied. The von Mises stress and strain were used to evaluate the system risk of failure. RESULTS: The difference in the numbers of layers had no significant effect on the alveolar bone. In the radial functionally graded implant models, the maximum von Mises stress of the alveolar bone decreased as the outer layer's elastic modulus increased; however, in the vertical functionally graded implants, this stress varied little. The maximum von Mises stress of the cancellous bone changed only slightly, from 2 to 5 MPa in all models. The maximum strain of the alveolar bone varied from 0.001478 mm to 0.003999 mm. Those FEA results were in line with previous findings. CONCLUSION: The functionally graded root analog implants show no significant biomechanical advantages over dense zirconia implants. Radial functionally graded root analog implants should optimize the peri-implant stresses and are biomechanically favorable for design.
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Implantes Dentários , Fenômenos Biomecânicos , Simulação por Computador , Implantes Dentários/efeitos adversos , Análise do Estresse Dentário , Análise de Elementos Finitos , Humanos , Estresse MecânicoRESUMO
BACKGROUND: Differentially expressed microRNAs (miRNAs) in the blood of breast cancer patients may serve as diagnostic biomarkers. METHODS: In this study, miRNA microarray of the blood of breast cancer patients and healthy controls was performed. Candidate differentially expressed miRNAs were further verified by real-time polymerase chain reaction in 68 breast cancer patients and 13 healthy controls. RESULTS: Six upregulated blood miRNAs (miR-26b-5p, miR-106b-5p, miR-142-3p, miR-142-5p, miR-185-5p, and miR-362-5p) were identified in breast cancer patients. These six miRNAs could discriminate breast cancer patients from healthy controls, with areas under the receiver operating characteristic curve (AUCs) of 0.8891, 0.8158, 0.8529, 0.8507, 0.9050, and 0.9333, respectively. Bioinformatic analysis showed that the six miRNAs were potentially involved in numerous cancer-related pathways, including the mitogen-activated protein kinase signaling pathway, nuclear factor-kappa B signaling pathway, and the transforming growth factor-beta signaling pathway. Importantly, two miRNAs (miR-185-5p and miR-362-5p) were used to construct a two-miRNA panel by logistic regression. The two-miRNA panel displayed a better diagnostic performance than each of the miRNAs alone, with a higher AUC (0.957), sensitivity (92.65 %), and specificity (92.31 %). Additionally, the high expression of the six miRNAs or the two-miRNA panel was associated with poor prognosis of breast cancer. CONCLUSIONS: We identified six upregulated miRNAs and a two-miRNA panel in the blood as potential biomarkers for the diagnosis and prognosis of breast cancer.
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Biomarcadores Tumorais/metabolismo , Neoplasias da Mama/genética , Regulação Neoplásica da Expressão Gênica/genética , MicroRNAs/genética , Neoplasias da Mama/metabolismo , MicroRNA Circulante/genética , Biologia Computacional , Perfilação da Expressão Gênica/métodos , Humanos , PrognósticoRESUMO
Designing efficient and robust nonprecious metal-based electrocatalysts for overall water electrolysis, which is mainly limited by the oxygen evolution reaction (OER), for hydrogen production remains a major challenge for the hydrogen economy. In this work, a bimetallic NiFeP catalyst is coated on nickel phosphide rods grown on nickel foam (NiFeP@NiP@NF). This self-supported and interfacially connected electrode structure is favorable for mass transfer and reducing electrical resistance during electrocatalysis. The preparation of NiFeP@NiP@NF is optimized in terms of (i) the coprecipitation time of the NiFe Prussian blue analogue layer that serves as phosphides precursor and (ii) the phosphidation temperature. The optimized sample exhibits excellent OER performance delivering current densities of 10 and 100 mA cm-2 at low overpotentials of 227 and 252 mV in 1.0 M KOH, respectively, and maintaining 10 mA cm-2 for more than 120 h without obvious degradation. Moreover, it can also be operated as a hydrogen evolution electrocatalyst, requiring an overpotential of 105 mV at 10 mA cm-2 in the same medium. Thus, the as-prepared material was tentatively utilized as a bifunctional electrocatalyst in a symmetric electrolyzer, requiring a voltage bias of 1.57 V to afford 10 mA cm-2 in 1.0 M KOH, while exhibiting outstanding stability.
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Rechargeable Li-air (O2) batteries have attracted a great deal of attention because of their high theoretical energy density and been regarded as a promising next-generation energy storage technology. Among numerous obstacles to Li-air (O2) batteries preventing their use in practical applications, water is a representative impurity for Li-air (O2), which could hasten the deterioration of the anode and accelarate the premature death of cells. Here, we report an effective in situ high-current pretreatment process to enhance the cycling performance of Li-O2 batteries in a wet tetraethylene glycol dimethyl ether-based electrolyte. With the help of certain levels of H2O (from 100 to 2000 ppm) in the electrolyte, adequate Li2O formed on the lithium anode surface after high-current pretreatment, which is necessary for a robust and uniform solid electrolyte interphase layer to protect Li metal during the long-term discharge-charge cycling process. This in situ high-current pretreatment method in a wet electrolyte is shown to be an effective approach for enhancing the cycling performance of Li-O2 batteries with a stable Li metal anode and promoting the realization of practical Li-air batteries.
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Two-dimensional materials have been extensively investigated in the fields of electrochemical sensors, field-effect transistors, and other electronic devices due to their large surface areas, high compatibility with device integration, and so on. Conventional electrodes, such as precious metal layers that are deposited on polymer or silicon wafers, have gradually revealed increasing difficulties in adapting to various device structures, especially for two-dimensional materials, which prefer high exposure of surface atoms. Here, we demonstrate a tailorable metal-ceramic (Cu-TiC0.5) layered structure as novel electrodes with high mechanical property and conductivity and fabricate a highly sensitive gas sensor with graphene lying on this proposed electrodes. The Cu-TiC0.5 layered structure exhibits remarkably high tensile yield strength and compressive yield strength, which increase 7 and 8 times than those of the pure copper, respectively. Meanwhile, excellent flexibility and conductivity could also be obtained with the further thinning of the Cu-TiC0.5 layered composite, which shows its potential applications in flexible electronics. Finally, we demonstrated that a graphene-based gas sensor fabricated on tailored metal-ceramic electrodes was ultrasensitive and robust, which benefits from the good thermal conductivity and peculiar gas channels etched on the surface of copper alloy electrodes.
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Rechargeable lithium-oxygen (Li-O2) batteries (LOBs) with extremely high theoretical energy density have been regarded as a promising next-generation energy storage technology. However, the limited cycle life, undesirable corrosion, and safety hazards are seriously limiting the practical application of the lithium metal anode in LOBs. Here, we demonstrate a rational design of the Li-Al alloy (LiAlx) anode that successfully achieves ultralong cycling life of LOBs with stable Li cycling. Through in situ high-current pretreatment technology, Al atoms accumulates, and a stable Al2O3-containing solid electrolyte interphase protective film formed on the LiAlx anode surface to suppress side reactions and O2 crossover. The cycling life of LOB with the protected LiAlx anode increases to 667 cycles under a fixed capacity of 1000 mA h g-1, as compared to 17 cycles without pretreatment. We believe that this in situ high-current pretreatment strategy presents a new vision to protect the lithium-containing alloy anodes, such as Li-Al, Li-Mg, Li-Sn, and Li-In alloys for stable and safe lithium metal batteries (Li-O2 and Li-S batteries).
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Potassium- (PIBs) and sodium-ion batteries (SIBs) are emerging as promising alternatives to lithium-ion batteries owing to the low cost and abundance of K and Na resources. However, the large radius of K+ and Na+ lead to sluggish kinetics and relatively large volume variations. Herein, a surface-confined strategy is developed to restrain SnS2 in self-generated hierarchically porous carbon networks with an inâ situ reduced graphene oxide (rGO) shell (SnS2 @C@rGO). The as-prepared SnS2 @C@rGO electrode delivers high reversible capacity (721.9â mAh g-1 at 0.05â A g-1 ) and superior rate capability (397.4â mAh g-1 at 2.0â A g-1 ) as the anode material of SIB. Furthermore, a reversible capacity of 499.4â mAh g-1 (0.05â A g-1 ) and a cycling stability with 298.1â mAh g-1 after 500â cycles at a current density of 0.5â A g-1 were achieved in PIBs, surpassing most of the reported non-carbonaceous anode materials. Additionally, the electrochemical reactions between SnS2 and K+ were investigated and elucidated.
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High efficient adsorption of radioiodine in nuclear waste has attracted extensive attentions all over the world. In this work, we fabricated sulfur and nitrogen co-doped graphene aerogels (SN-GA) through one-step hydrothermal method, and investigated its iodine adsorption behavior including adsorption kinetics and isotherms in water. Our results reveal that SN-GA exhibits a 3D porous architecture with thiophene-S, oxidized-S, pyridine-N, pyrrole-N and graphite-N co-doped into the sp2 carbon frameworks. The adsorption experiment showed SN-GA has a maximum iodine adsorption capacity of 999 mg g-1 determined by Langmuir isotherm, and the adsorption process could be better described by the pseudo-second-order model.
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3D porous sulfur and nitrogen co-doped graphene aerogel has been fabricated by a facile one-pot process. Both experimental and theoretical studies have demonstrated that sulfur and nitrogen co-doping could synergistically enhance the catalytic performance for activating peroxydisulfate (PDS) compared to the original and N doped graphene aerogels. The ratio of sulfur/nitrogen in the aerogel can be controlled by regulating the additions of thiourea and urea sources, and the aerogel with the S/N ratio of about 1:2.5 shows a better catalytic effect due to more significant changes in the electrostatic potential and the surface charge distribution, as revealed by the theoretical simulations. The radical quenching tests indicated that both SO4·- and ·OH radicals could be formed in the SN-rGO aerogel + PDS system and contribute most to RhB degradation.
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Corantes/química , Grafite/química , Poluentes Químicos da Água/química , Catálise , Cor , Nitrogênio/química , Enxofre/químicaRESUMO
Amphiphilic block copolymer templating strategies are extensively used for syntheses of mesoporous materials. However, monodisperse tubular nanostructures are limited. Here, a general method is developed to synthesize monodisperse nanotubes with narrow diameter distribution induced by self-assembly of block copolymer. 3-Aminophenol (AP) and formaldehyde (F) polymerize and self-assemble with cylindrical PS-b-PEO micelles into worm-like PS-b-PEO@APF composites with uniform diameter (49 ± 3 nm). After template extraction, worm-like APF polymer nanotubes are formed. The structure and morphology of the polymer nanotubes can be tuned by regulating the synthesis conditions. Furthermore, PS-b-PEO@APF composites are uniformly converted to isomorphic carbon nanotubes with large surface area of 662 m2 g-1 , abundant hierarchical porous frameworks and nitrogen doping. The synthesis can be extended to silica nanotubes. These findings open an avenue to the design of porous materials with controlled structural framework, composition, and properties for a wide range of applications.
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Aminofenóis/química , Formaldeído/química , Nanotubos de Carbono/química , Polietilenoglicóis/química , Polímeros/química , Poliestirenos/química , Micelas , Microscopia Eletrônica de Varredura , Microscopia Eletrônica de Transmissão , Nanoestruturas/química , Nanoestruturas/ultraestrutura , Nanotubos de Carbono/ultraestrutura , Polímeros/síntese química , Porosidade , Dióxido de Silício/químicaRESUMO
The electrode-electrolyte interface stability is a critical factor influencing cycle performance of All-solid-state lithium batteries (ASSLBs). Here, we propose a LiF- and Li3N-enriched artificial solid state electrolyte interphase (SEI) protective layer on metallic lithium (Li). The SEI layer can stabilize metallic Li anode and improve the interface compatibility at the Li anode side in ASSLBs. We also developed a Li1.5Al0.5Ge1.5(PO4)3-poly(ethylene oxide) (LAGP-PEO) concrete structured composite solid electrolyte. The symmetric Li/LAGP-PEO/Li cells with SEI-protected Li anodes have been stably cycled with small polarization at a current density of 0.05 mA cm-2 at 50 °C for nearly 400 h. ASSLB-based on SEI-protected Li anode, LAGP-PEO electrolyte, and LiFePO4 (LFP) cathode exhibits excellent cyclic stability with an initial discharge capacity of 147.2 mA h g-1 and a retention of 96% after 200 cycles.
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Three-dimensional (3D) carbon-wrapped iron sulfide interlocked graphene (Fe7S8@C-G) composites for high-performance sodium-ion storage are designed and produced through electrostatic interactions and subsequent sulfurization. The iron-based metal-organic frameworks (MOFs, MIL-88-Fe) interact with graphene oxide sheets to form 3D networks, and carbon-wrapped iron sulfide (Fe7S8@C) nanoparticles with high individual-particle conductivity are prepared following a sulfurization process, surrounded by interlocked graphene sheets to enhance the interparticle conductivity. The prepared Fe7S8@C-G composites exhibit not only improved individual-particle and interparticle conductivity to shorten electron/ion diffusion pathways, but also enhanced structural stability to prevent the aggregation of active materials and buffer large volume changes during sodiation/desodiation. As a sodium-ion storage material, the Fe7S8@C-G composites exhibit a reversible capacity of 449 mA h g-1 at 500 mA g-1 after 150 cycles and a retention capacity of 306 mA h g-1 under a current density of 2000 mA g-1. The crucial factors related to the structural changes and stability during cycles have been further investigated. These results demonstrate that the high-performance sodium-ion storage properties are mainly attributed to the uniquely designed three-dimensional configuration.
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3D porous N-doped reduced graphene oxide (N-rGO) aerogels were synthesized by a hydrothermal reduction of graphene oxide (GO) with urea and following freeze-drying process. N-rGO aerogels have a high BET surface of 499.70 m2/g and a high N doping content (5.93-7.46 at%) including three kinds of N (graphitic, pyridinic and pyrrolic). Their high catalytic performance for phenol oxidation in aqueous solution was investigated by catalytic activation of persulfate (PS). We have demonstrated that N-rGO aerogels are promising metal-free catalysts for phenol removal. Kinetics studies indicate that phenol degradation follows first-order reaction kinetics with the reaction rate constant of 0.16799 min-1 for N-rGO-A(1:30). Interestingly, the comparison of direct catalytic oxidation with adsorption-catalytic oxidation experiments indicates that adsorption plays an important role in the catalytic oxidation of phenol by decreasing the phenol degradation time. Spin density and adsorption modeling demonstrates that graphitic N in N-rGO plays the most important role for the catalytic performance by inducing high positive charge densities to adjacent carbon atoms and facilitating phenol adsorption on these carbon sites. Furthermore, the activation mechanism of persulfate (PS) on N-rGO was first investigated by DFT method and PS can be activated to generate strongly oxidative radical (SO4·-) by transferring electrons to N-rGO.
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Grafite/química , Fenol/química , Adsorção , Carbono/química , Catálise , Géis , Cinética , Oxirredução , Óxidos , ÁguaRESUMO
In an animal body, coronary arteries cover around the whole heart and supply the necessary oxygen and nutrition so that the heart muscle can survive as well as can pump blood in and out very efficiently. Inspired by this, we have designed a novel heart-coronary arteries structured electrode by electrospinning carbon nanofibers to cover active anode graphene/silicon particles. Electrospun high conductive nanofibers serve as veins and arteries to enhance the electron transportation and improve the electrochemical properties of the active "heart" particles. This flexible binder free carbon nanofibers/graphene/silicon electrode consists of millions of heart-coronary arteries cells. Besides, in the graphene/silicon "hearts", graphene network improves the electrical conductivity of silicon nanopaticles, buffers the volume change of silicon, and prevents them from directly contacting with electrolyte. As expected, this novel composite electrode demonstrates excellent lithium storage performance with a 86.5% capacity retention after 200 cycles, along with a high rate performance with a 543 mAh g-1 capacity at the rate of 1000 mA g-1.
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Accumulating evidence indicates that human circulating microRNAs (miRNAs) could serve as diagnostic and prognostic biomarkers in various cancers. We aimed to explore novel miRNA biomarkers in the blood of breast cancer patients based on miRNA profiling. A miRCURY™ LNA Array was used to identify differentially altered miRNAs in the whole blood of breast cancer patients (n=6) and healthy controls (n=6). Levels of candidate miRNAs were quantified by quantitative reverse transcription-polymerase chain reaction (qRT-PCR) in whole blood specimens of 15 breast cancer patients and 13 age-matched healthy control individuals. The miRWalk database was used to predict miRNA targets and the DAVID tool was used to identify significant enrichment pathways. A total of 171 differentially expressed miRNAs were identified by microarray, including 169 upregulated and 2 downregulated miRNAs in breast cancer. Five upregulated miRNAs (miR-30b-5p, miR-96-5p, miR-182-5p, miR-374b-5p, and miR-942-5p) were confirmed by qRT-PCR. The areas under the receiver operating characteristic curve of miR-30b-5p, miR-96-5p, miR-182-5p, miR-374b-5p, and miR-942-5p were 0.9333, 0.7692, 0.7590, 0.8256, and 0.8128, respectively. Importantly, upregulation of these five miRNAs was observed even in patients with very early-stage breast cancer. A total of 855 genes were predicted to be targeted by the five miRNAs, and the one cut domain family member 2 gene (ONECUT2) was a shared target of the five miRNAs. Analysis of publicly available data revealed that these dysregulated miRNAs and the target genes were associated with the survival of breast cancer patients. Furthermore, the five miRNAs were significantly enriched in numerous cancer-related pathways, including "MicroRNAs in cancer", "Pathways in cancer", "FoxO signaling pathway", "Ras signaling pathway", "Rap1 signaling pathway", "MAPK signaling pathway", and "PI3K-Akt signaling pathway". Our data support the potential of the five identified miRNAs as novel biomarkers for the detection of breast cancer, and indicate that they may be involved in breast cancer development and progression.
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Biomarcadores Tumorais/genética , Neoplasias da Mama/genética , MicroRNAs/genética , Adulto , Biomarcadores Tumorais/sangue , Neoplasias da Mama/sangue , Neoplasias da Mama/patologia , Estudos de Casos e Controles , Feminino , Humanos , MicroRNAs/sangue , Pessoa de Meia-Idade , Análise de Sobrevida , TranscriptomaRESUMO
Nanoporous gold (NPG) obtained via dealloying of Au alloys has potential applications in a range of fields, and in particular in bioelectrochemistry. NPG possesses a three dimensional bicontinuous network of interconnected pores with typical pore diameters of ca. 30-40 nm, features that are useful for the immobilisation of enzymes. This review describes the common routes of fabrication and characterization of NPG, the use of NPG as a support for oxidoreductases for applications in biosensors and biofuel cells together with recent progress in the use of NPG electrodes for applications in bioelectrochemistry.