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Lithium-oxygen batteries have the potential to become the most eminent solution for future energy storage with their theoretical energy density exceeding all existing batteries. However, the insulating and insoluble discharge product (lithium peroxide; Li2O2) impairs practical application. Conventional catalyst designs based on the electronic structure and interfacial charge transfer descriptors have not been able to overcome these limitations due to Li2O2. Herein, we revisit the role of heterogeneous catalysts as substrates to regulate Li2O2 growth and the formation of solid/solid reaction interfaces. We demonstrate that controlled solid/solid interfacial structure design is a critical performance parameter beyond the inherent electronic structure. In particular, the Cu2O substrate in this study induces a homogeneous deposition of Pd atoms, which leads to well-controlled growth of Li2O2 resolving mass and charge transport limits (i.e., the bottleneck of oxygen reduction/evolution reactions), thus improving reversibility, capacity, and durability of the cells by dissipating electrochemical and mechanical stress. We thus verified the essential role of solid/solid interfaces to regulate the nucleation and growth process of Li2O2 in lithium-oxygen batteries.
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The main drawback of organic electrode materials is their solubility in the electrolyte, leading to the shuttle effect. Using N,N'-dimethylphenazine (DMPZ) as a highly soluble cathode material, and its PF6 - and triflimide salts as models for its first oxidation state, a poor correlation was found between solubility and battery operability. Extensive electrochemical experiments suggest that the shuttle effect is unlikely to be mediated by molecular diffusion as commonly understood, but rather by electron-hopping via the electron self-exchange reaction based on spectroscopic results. These findings led to two counter-strategies to prevent the hopping process: the pre-treatment of the anode to form a solid-electrolyte interface and using DMPZ salt rather than neutral DMPZ as the active material. These strategies improved coulombic efficiency and capacity retention, demonstrating that solubility of organic materials does not necessarily exclude their applications in batteries.
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Development of high performance electrode materials for energy storage is one of the most important issues for our future society. However, a lack of clear analytical views limits critical understanding of electrode materials. This review covers useful analytical work using X-ray diffraction, X-ray absorption spectroscopy, microscopy and neutron diffraction for ion storage systems. The in situ observation facilitates comprehending real-time ion storage behaviour while the ion storage system is operating, which help us to understand detailed physical and chemical properties. We will discuss how the tools have been used to reveal detailed reaction mechanisms and underlying properties of electrode materials.
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Safe and effective delivery is required for siRNA and mRNA-based therapeutics to reach their potential. Here, we report on the development of poly(glycoamidoamine) brush nanoparticles as delivery vehicles for siRNA and mRNA. These polymers were capable of significant delivery of siRNA against FVII and mRNA-encoding erythropoietin (EPO) in mice. Importantly, these nanoparticles were well-tolerated at their effective dose based on analysis of tissue histology, systemic cytokine levels, and liver enzyme chemistry. The polymer brush nanoparticles reported here are promising for therapeutic applications.
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Técnicas de Transferência de Genes , Terapia Genética , Nanopartículas/administração & dosagem , RNA Mensageiro/administração & dosagem , Animais , Eritropoetina/antagonistas & inibidores , Eritropoetina/genética , Fator VII/genética , Humanos , Camundongos , Nanopartículas/efeitos adversos , RNA Interferente Pequeno/administração & dosagemRESUMO
Hard carbons are one of the most promising anode materials for next-generation sodium-ion batteries due to their high reversible capacity, long cycle life, and low cost. The advantage in terms of price of hard carbons can be further improved by using cheaper resources such as biomass waste as precursors. Lignin is one of the richest natural bio-polymer in the earth which can be obtained from woods. As the lignin has three-dimensional amorphous polymeric structure, it is considered as good precursor for producing carbonaceous materials under proper carbonization processes for energy storage devices. In this study, structural properties of lignin-derived hard carbons such as interlayer spacing, degree of disorder and surface defects are controlled. Specifically, lignin-derived hard carbons were synthesized at 1000 °C, 1250 °C, and 1500 °C, and it was confirmed that the structure gradually changed from a disordered structure to ordered structure through X-ray diffraction, Raman spectroscopy, and X-ray photoelectron spectroscopy. Hard carbons exhibit sloping regions at high voltage and plateau region at low voltage during the electrochemical processes for sodium ions. As the heat treatment temperature increases, the contribution to the overall reversible capacity of the sloping region decreases and the contribution of the plateau region increases. This trend confirms that it affects reversible capacity, rate-capability, and cycling stability, meaning that an understanding of structural properties and related electrochemical properties is necessary when developing hard carbon as a negative electrode material for sodium ion batteries.
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Electrochemical ion storage behaviors of Fe3O4 nanoparticles, as a representative transition metal oxide for an environmentally benign and low-cost anode for a sodium-ion battery, are thoroughly investigated through a combination of electrochemical analysis and diagnostics of Fe3O4 electrode cells, X-ray-based and spectroscopic analysis of material structure evolution as functions of depth of discharge (DoD) and state of charge (SoC), and first principle modeling. The gravimetric capacity is found to be 50 mA h/g for bulk Fe3O4 (50 nm average crystallite size) and 100 mA h/gâabout a tenth of the theoretical prediction for complete conversionâfor Fe3O4 nanoparticles (8.7 nm average particle size), respectively. A fundamental and mechanistic study of material evolution as functions of DoD and SoC shows that Fe3O4 does not allow electrochemical incorporation of Na+ ions into the empty cation positions of the inverse spinel structure, leading to our assertion that electrochemical intercalation of Na+ ions to conversion of the Fe3O4 anode in sodium-ion batteries is nonviable. A density functional theory investigation points to the impracticality of the intercalation of Na+ ions into Fe3O4 and further validates our experimental findings. We propose several possible mechanisms corresponding to the observed low capacity, including formation of solid electrolyte interphases with unfavorable properties and adsorption of Na+ ions onto surfaces of nanoparticles and/or at heterointerfaces in Fe3O4 composite electrodes in a NaPF6-based electrolyte system.
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Shape memory polymers (SMPs) are attracting attention for their use in wearable displays and biomedical materials due to their good biocompatibility and excellent moldability. SMPs also have the advantage of being lightweight with excellent shape recovery due to their low density. However, they have not yet been applied to a wide range of engineering fields because of their inferior physical properties as compared to those of shape memory alloys (SMAs). In this study, we attempt to find optimized shape memory polymer composites. We also investigate the shape memory performance and physical properties according to the filler type and amount of hardener. The shape memory composite was manufactured by adding nanocarbon materials of graphite and non-carbon additives of Cu. The shape-recovery mechanism was compared, according to the type and content of the filler. The shape fixation and recovery properties were analyzed, and the physical properties of the shape recovery composite were obtained through mechanical strength, thermal conductivity and differential scanning calorimetry analysis.
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Na3V2(PO4)3 is regarded as one of the promising cathode materials for next-generation sodium ion batteries, but its undesirable electrochemical performances due to inherently low electrical conductivity have limited its direct use for applications. Motivated by the limit, this study employed a porous carbon network to obtain a porous carbon network-Na3V2(PO4)3 composite by using poly(vinylalcohol) assised sol-gel method. Compared with the typical carbon-coating approach, the formation of a porous carbon network ensured short ion diffusion distances, percolating electrolytes by distributing nanosized Na3V2(PO4)3 particles in the porous carbon network and suppressing the particle aggregation. As a result, the porous carbon network-Na3V2(PO4)3 composite exhibited improved electrochemical performances, i.e., a higher specific discharge capacity (~110 mAh g-1 at 0.1 C), outstanding kinetic properties (~68 mAh g-1 at 50 C), and stable cyclic stability (capacity retention of 99% over 100 cycles at 1 C).
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We present a unique composite assembly of rhombohedral Li3V2(PO4)3 and carbon nanofiber, which simultaneously facilitates Li-ion transport as well as electron transfer. For the synthesis of this composite, the inorganic precursors were confined in electron-spun nanofibers, and then, through controlled annealing, Na3V2(PO4)3 particulates were grown with controllable crystallite size and partially embedded into carbon nanofibers with precisely controlled diameter. The rhombohedral Li3V2(PO4)3 could be successfully obtained by ion exchange from Na to Li in the prepared Na3V2(PO4)3. The final rhombohedral Li3V2(PO4)3 particles anchored onto the carbon nanofibers exhibited excellent electrochemical performance with fast kinetics for Li-ion batteries. Suprisingly it maintains 69 and 41 mAh/g even at 100C as cathode and anode. Several advanced characterizations revealed that its ultrafast kinetics could be attributed to synergistic effect resulting from the distinctive microstructure of the composite and the structural superiority of highly symmetric rhombohedral Li3V2(PO4)3 over its monoclinic homologue for Li-ion transport.
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Layered P2-type Na0.8 Mn0.5 Fe0.5 O2 cathode material is a promising candidate for next-generation sodium-ion batteries due to the economical and environmentally benign characteristics of Mn and Fe. The poor cycling stability of the material, however, is still a problem that must be solved. To address the problem, electrochemically inactive Mg2+ was introduced into the structure by substituting some of the Fe ions. It was shown that Mg substitution led to a smoother voltage profile with improved cycling performance and rate capability. These observations were attributed to the suppressed structural changes during electrochemical processes. Detailed redox mechanisms, associated local structural changes, and phase transitions were investigated by X-ray absorption spectroscopy and X-ray diffraction. From the detailed analysis of electrochemical behaviors, it was also identified how the redox reactions and structural disordering occurred in the high- and low-voltage regions and how Mg substitution stabilized the structure.
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Irreversible phase transformation of layered structure into spinel structure is considered detrimental for most of the layered structure cathode materials. Here we report that this presumably irreversible phase transformation can be rendered to be reversible in sodium birnessite (NaxMnO2·yH2O) as a basic structural unit. This layered structure contains crystal water, which facilitates the formation of a metastable spinel-like phase and the unusual reversal back to layered structure. The mechanism of this phase reversibility was elucidated by combined soft and hard X-ray absorption spectroscopy with X-ray diffraction, corroborated by first-principle calculations and kinetics investigation. These results show that the reversibility, modulated by the crystal water content between the layered and spinel-like phases during the electrochemical reaction, could activate new cation sites, enhance ion diffusion kinetics and improve its structural stability. This work thus provides in-depth insights into the intercalating materials capable of reversible framework changes, thereby setting the precedent for alternative approaches to the development of cathode materials for next-generation rechargeable batteries.
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The effects of surface charge density on DNA hybridization have been investigated on a mixture of hydrogen-, oxygen-, and amine-terminated diamond surfaces. A difference in the hybridization efficiencies of complementary and mismatched DNA was clearly observed by fluorescence and potentiometric observations at a particular coverage of oxygen. In the fluorescence observation, singly mismatched DNA was detected with high contrast after appropriate hybridization on the surface with 10-20% oxygen coverage. The amount of oxygen in the form of C-O(-) (deprotonated C-OH) producing the surface negative-charge density was estimated by X-ray photoelectron spectroscopy. Electrolyte solution gate field-effect transistors (SGFETs) were used for potentiometric observations. The signal difference (change in gate potential) on the SGFET, which was as large as approximately 20 mV, was caused by the difference in the hybridization efficiencies of complementary target DNA (cDNA) and singly mismatched (1MM) target DNA with a common probe DNA immobilized on the same SGFET. The reversible change in gate potential caused by the hybridization and denaturation cycles and discriminating between the complementary and 1MM DNA targets was very stable throughout the cyclical detections. Moreover, the ratio of signals caused by hybridization of the cDNA and 1MM DNA targets with the probe DNA immobilized on the SGFET was determined to be 3:1 when hybridization had occurred (after 15 min on SGFET), as determined by real-time measurements. From the viewpoint of hybridization kinetics, the rate constant for hybridization of singly mismatched DNA was a factor of approximately 3 smaller than that of cDNA on this functionalized (oxidized and aminated) diamond surface.
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DNA/química , Sequência de Bases , Sondas de DNA/química , Modelos Moleculares , Conformação de Ácido Nucleico , Desnaturação de Ácido Nucleico , Potenciometria , Espectrofotometria , Propriedades de SuperfícieRESUMO
The development of next-generation energy-storage devices with high power, high energy density, and safety is critical for the success of large-scale energy-storage systems (ESSs), such as electric vehicles. Rechargeable sodium-oxygen (Na-O2 ) batteries offer a new and promising opportunity for low-cost, high-energy-density, and relatively efficient electrochemical systems. Although the specific energy density of the Na-O2 battery is lower than that of the lithium-oxygen (Li-O2 ) battery, the abundance and low cost of sodium resources offer major advantages for its practical application in the near future. However, little has so far been reported regarding the cell chemistry, to explain the rate-limiting parameters and the corresponding low round-trip efficiency and cycle degradation. Consequently, an elucidation of the reaction mechanism is needed for both lithium-oxygen and sodium-oxygen cells. An in-depth understanding of the differences and similarities between Li-O2 and Na-O2 battery systems, in terms of thermodynamics and a structural viewpoint, will be meaningful to promote the development of advanced metal-oxygen batteries. State-of-the-art battery design principles for high-energy-density lithium-oxygen and sodium-oxygen batteries are thus reviewed in depth here. Major drawbacks, reaction mechanisms, and recent strategies to improve performance are also summarized.
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Fast lithium ion and electron transport inside electrode materials are essential to realize its superb electrochemical performances for lithium rechargeable batteries. Herein, a distinctive structure of cathode material is proposed, which can simultaneously satisfy these requirements. Nanosized Li3V2(PO4)3 (LVP) particles can be successfully grown up on the carbon nanofiber via electrospinning method followed by a controlled heat-treatment. Herein, LVP particles are anchored onto the surface of carbon nanofiber, and with this growing process, the size of LVP particles as well as the thickness of carbon nanofiber can be regulated together. The morphological features of this composite structure enable not only direct contact between electrolytes and LVP particles that can enhance lithium ion diffusivity, but also fast electron transport through 1D carbon network along nanofibers simultaneously. Finally, it is demonstrated that this unique structure is an ideal one to realize high electron transport and ion diffusivity together, which are essential for enhancing the electrochemical performances of electrode materials.
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A series of indolo[3,2-b]indole (IDID) derivatives are designed as a novel structural platform for thermally activated delayed fluorescence (TADF) emitters. Intramolecular charge transfer (ICT)-type molecules consisting of IDID donor (D) and various acceptor (A) moieties are synthesized and characterized in the protocol of the systematical structure-property correlation. IDID derivatives exhibit high efficiency, prompt fluorescence as well as TADF with emission ranges tuned by the chemical structure of the acceptor units. Interestingly, almost all of the IDID derivatives show an identical energy level of the lowest triplet excited state (T1) attributed to the locally excited triplet state of the IDID backbone (3LEID), while that of their lowest singlet excited state (S1) is largely tuned by varying the acceptor units. Thus, we demonstrate the underlying mechanism in terms of the molecular engineering. Among the compounds, Tria-phIDID and BP-phIDID generate efficient delayed fluorescence based on the small energy gap between the lowest singlet and triplet excited states (ΔEST) and mediation of the 3LEID state. Organic light-emitting diodes with these Tria-phIDID and BP-phIDID as a dopant in the emitting layer show highly efficient electroluminescence with maximum external quantum efficiencies of 20.8% and 13.9%, respectively.
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Cyclins and cyclin-dependent kinases (CDKs) are hyperactivated in numerous human tumors. To identify means of interfering with cyclins/CDKs, we performed nine genome-wide screens for human microRNAs (miRNAs) directly regulating cell-cycle proteins. We uncovered a distinct class of miRNAs that target nearly all cyclins/CDKs, which are very effective in inhibiting cancer cell proliferation. By profiling the response of over 120 human cancer cell lines, we derived an expression-based algorithm that can predict the response of tumors to cell-cycle-targeting miRNAs. Using systemic administration of nanoparticle-formulated miRNAs, we inhibited tumor progression in seven mouse xenograft models, including three treatment-refractory patient-derived tumors, without affecting normal tissues. Our results highlight the utility of using cell-cycle-targeting miRNAs for treatment of refractory cancer types.
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Ciclo Celular/genética , Regulação Neoplásica da Expressão Gênica , MicroRNAs/genética , Regiões 3' não Traduzidas , Algoritmos , Animais , Antineoplásicos/farmacologia , Neoplasias da Mama/tratamento farmacológico , Neoplasias da Mama/genética , Linhagem Celular Tumoral , Sistemas de Liberação de Medicamentos/métodos , Feminino , Estudo de Associação Genômica Ampla , Humanos , Camundongos Endogâmicos , MicroRNAs/administração & dosagem , MicroRNAs/farmacologia , Mutação , Nanopartículas , Proteínas Proto-Oncogênicas p21(ras)/genética , Ensaios Antitumorais Modelo de XenoenxertoRESUMO
Charge detection biosensors have recently become the focal point of biosensor research, especially field-effect-transistors (FETs) that combine compactness, low cost, high input, and low output impedances, to realize simple and stable in vivo diagnostic systems. However, critical evaluation of the possibility and limitations of charge detection of label-free DNA hybridization using silicon-based ion-sensitive FETs (ISFETs) has been introduced recently. The channel surface of these devices must be covered by relatively thick insulating layers ( SiO2, Si3N4, Al2O3, or Ta2O5) to protect against the invasion of ions from solution. These thick insulating layers are not suitable for charge detection of DNA and miniaturization, as the small capacitance of thick insulating layers restricts translation of the negative DNA charge from the electrolyte to the channel surface. To overcome these difficulties, thin-gate-insulator FET sensors should be developed. Here, we report diamond solution-gate FETs (SGFETs), where the DNA-immobilized channels are exposed directly to the electrolyte solution without gate insulator. These SGFETs operate stably within the large potential window of diamond (>3.0 V). Thus, the channel surface does not need to be covered by thick insulating layers, and DNA is immobilized directly through amine sites, which is a factor of 30 more sensitive than existing Si-ISFET DNA sensors. Diamond SGFETs can rapidly detect complementary, 3-mer mismatched (10 pM) and has a potential for the detection of single-base mismatched oligonucleotide DNA, without biological degradation by cyclically repeated hybridization and denature.
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Técnicas Biossensoriais/instrumentação , DNA/análise , DNA/genética , Eletroquímica/instrumentação , Hibridização In Situ/instrumentação , Análise de Sequência com Séries de Oligonucleotídeos/instrumentação , Transistores Eletrônicos , Técnicas Biossensoriais/métodos , Diamante/química , Eletroquímica/métodos , Desenho de Equipamento , Análise de Falha de Equipamento , Hibridização In Situ/métodos , Análise de Sequência com Séries de Oligonucleotídeos/métodos , Reprodutibilidade dos Testes , Sensibilidade e Especificidade , SoluçõesRESUMO
The combination of Cas9, guide RNA and repair template DNA can induce precise gene editing and the correction of genetic diseases in adult mammals. However, clinical implementation of this technology requires safe and effective delivery of all of these components into the nuclei of the target tissue. Here, we combine lipid nanoparticle-mediated delivery of Cas9 mRNA with adeno-associated viruses encoding a sgRNA and a repair template to induce repair of a disease gene in adult animals. We applied our delivery strategy to a mouse model of human hereditary tyrosinemia and show that the treatment generated fumarylacetoacetate hydrolase (Fah)-positive hepatocytes by correcting the causative Fah-splicing mutation. Treatment rescued disease symptoms such as weight loss and liver damage. The efficiency of correction was >6% of hepatocytes after a single application, suggesting potential utility of Cas9-based therapeutic genome editing for a range of diseases.
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Sistemas CRISPR-Cas/genética , Genoma Humano , Edição de RNA , Tirosinemias/terapia , Animais , Modelos Animais de Doenças , Técnicas de Transferência de Genes , Vetores Genéticos , Humanos , Lipídeos/química , Camundongos , Mutação , Nanopartículas/química , Tirosinemias/genética , Vírus/genéticaRESUMO
BACKGROUND: The appropriate indication for coronary computed tomographic angiography (CTA) as a part of preoperative evaluation has not been defined yet. We investigated the value of coronary CTA in patients undergoing noncardiac surgery. METHODS AND RESULTS: We included 844 patients (median age, 67 years; male sex, 62%) who underwent coronary CTA for screening of coronary artery disease before noncardiac surgery. Clinically determined revised cardiac risk index were compared with the extent and severity of coronary artery disease assessed by coronary CTA. Perioperative major cardiac event (PMCE), defined as cardiac death, myocardial infarction, or pulmonary edema within postoperative 30 days, developed in 25 patients (3.0%). Significant coronary CTA finding was defined as >3 any lesions with ≥1 (diameter stenosis ≥70%) stenosis based on the relationship between the severity of coronary artery disease and PMCE risk. The risk of PMCE was 14.0% in patients with significant CTA findings, whereas 2.2% of patients without significant CTA findings regardless of revised cardiac risk index score. The predictive performance of revised cardiac risk index could be improved significantly after addition of significant coronary CTA findings (c-statistics=0.631 versus 0.757; net reclassification improvement=0.923; integrated discrimination improvement=0.051). On the basis of revised cardiac risk index and coronary CTA, the risk of PMCE could be estimated with sensitivity, specificity, positive predictive value, and negative predictive value of 76%, 73%, 8%, and 99%, respectively. CONCLUSIONS: Addition of coronary CTA to clinical risk improved perioperative risk stratification. Absence of significant coronary CTA findings conferred low PMCE risk with high specificity and negative predictive value regardless of clinical risk. Coronary CTA may improve perioperative risk stratification in patients undergoing noncardiac surgery.