RESUMO
In the presence of water, the electrically conductive metal-organic framework (MOF) Cu3HHTT2 (H6HHTT = 2,3,7,8,12,13-hexahydroxy-4b1,5,10,15-tetraazanaphtho[1,2,3-gh]tetraphene) provides a conduit for proton transport, thereby becoming a dual ionic-electronic conductor. Owing to its dual conducting nature and its high density of imine and open metal sites, the MOF operates as a particularly sensitive chemiresistor, whose sensing mechanism changes with relative humidity. Thus, the interaction of NH3 gas with the MOF under low humidity promotes proton transport, which translates to high sensitivity for ammonia detection. Conversely, NO2 gas hinders proton conductivity, even under high relative humidity conditions, leading to large resistance variations in the humid regime. This dual ionic-electronic conduction-based gas sensor provides superior sensitivity compared to other conventional chemiresistors under similar conditions and highlights its potential as a platform for room-temperature gas sensors.
RESUMO
Metal-organic frameworks (MOFs) are promising materials for gas sensing but are often limited to single-use detection. A hybridization strategy is demonstrated synergistically deploying conductive MOFs (cMOFs) and conductive polymers (cPs) as two complementary mixed ionic-electronic conductors in high-performing stand-alone chemiresistors. This work presents significant improvement in i) sensor recovery kinetics, ii) cycling stability, and iii) dynamic range at room temperature. The effect of hybridization across well-studied cMOFs is demonstrated based on 2,3,6,7,10,11-hexahydroxytriphenylene (HHTP) and 2,3,6,7,10,11-hexaiminotriphenylene (HITP) ligands with varied metal nodes (Co, Cu, Ni). A comprehensive mechanistic study is conducted to relate energy band alignments at the heterojunctions between the MOFs and the polymer with sensing thermodynamics and binding kinetics. The findings reveal that hole enrichment of the cMOF component upon hybridization leads to selective enhancement in desorption kinetics, enabling significantly improved sensor recovery at room temperature, and thus long-term response retention. This mechanism is further supported by density functional theory calculations on sorbate-analyte interactions. It is also found that alloying cPs and cMOFs enables facile thin film co-processing and device integration, potentially unlocking the use of these hybrid conductors in diverse electronic applications.
RESUMO
BACKGROUND: This study aimed to validate apparent diffusion coefficient (ADC) values and thresholds to predict poor neurological outcomes in out-of-hospital cardiac arrest (OHCA) survivors by quantitatively analysing the ADC values via brain magnetic resonance imaging (MRI). METHODS: This observational study used prospectively collected data from two tertiary academic hospitals. The derivation cohort comprised 70% of the patients randomly selected from one hospital, whereas the internal validation cohort comprised the remaining 30%. The external validation cohort used the data from another hospital, and the MRI data were restricted to scans conducted at 3 T within 72-96 h after an OHCA experience. We analysed the percentage of brain volume below a specific ADC value at 50-step intervals ranging from 200 to 1200 × 10-6 mm2/s, identifying thresholds that differentiate between good and poor outcomes. Poor neurological outcomes were defined as cerebral performance categories 3-5, 6 months after experiencing an OHCA. RESULTS: A total of 448 brain MRI scans were evaluated, including a derivation cohort (n = 224) and internal/external validation cohorts (n = 96/128, respectively). The proportion of brain volume with ADC values below 450, 500, 550, 600, and 650 × 10-6 mm2/s demonstrated good to excellent performance in predicting poor neurological outcomes in the derivation group (area under the curve [AUC] 0.89-0.91), and there were no statistically significant differences in performances among the derivation, internal validation, and external validation groups (all P > 0.5). Among these, the proportion of brain volume with an ADC below 600 × 10-6 mm2/s predicted a poor outcome with a 0% false-positive rate (FPR) and 76% (95% confidence interval [CI] 68-83) sensitivity at a threshold of > 13.2% in the derivation cohort. In both the internal and external validation cohorts, when using the same threshold, a specificity of 100% corresponded to sensitivities of 71% (95% CI 58-81) and 78% (95% CI 66-87), respectively. CONCLUSIONS: In this validation study, by consistently restricting the MRI types and timing during quantitative analysis of ADC values in brain MRI, we observed high reproducibility and sensitivity at a 0% FPR. Prospective multicentre studies are necessary to validate these findings.
Assuntos
Parada Cardíaca Extra-Hospitalar , Humanos , Feminino , Masculino , Pessoa de Meia-Idade , Idoso , Parada Cardíaca Extra-Hospitalar/diagnóstico por imagem , Estudos Prospectivos , Prognóstico , Sobreviventes/estatística & dados numéricos , Estudos de Coortes , Imageamento por Ressonância Magnética/métodos , Imagem de Difusão por Ressonância Magnética/métodos , Valor Preditivo dos Testes , Encéfalo/diagnóstico por imagem , Encéfalo/fisiopatologiaRESUMO
Exciton complexes in two-dimensional semiconductors, encompassing bright and dark excitons, biexcitons, and defect-bound excitons, have shown significant potential across a wide range of research areas. These applications range from exploring quantum many-body phenomena to developing nonclassical light sources and quantum transport devices. To fully leverage their dynamic and interactive properties and extend the capabilities of excitonic devices, realizing systematic engineering and mixing of the exciton complexes are crucial. Unlike conventional material methods, which often lead to undesired changes in the electronic band structure and binding energy, optical methods provide a means to manipulate the radiative decay dynamics of individual exciton complexes in a purely environmental manner. Here, we employ a specialized photonic platform, analogous to an artist's palette, to arrange and mix exciton complexes on an identical two-dimensional transition metal dichalcogenide medium. Essentially, a gradient thickness mirror (GTM) continuously tunes the local distribution of optical vacuum field interference. The GTM platform enables us to create and examine five distinct compositions of the exciton complexes of the WSe2 monolayer and their contributions to the photoluminescence spectrum. Moreover, the exciton complex palette facilitates the observation of dark and defect-bound excitons, even at high temperatures of 70 K, and its performance can be further managed by simple postprocessing manipulations.
RESUMO
In this study, the development and characterization of 2D ferroelectric field-effect transistor (2D FeFET) devices are presented, utilizing nanoscale ferroelectric HfZrO2 (HZO) and 2D semiconductors. The fabricated device demonstrated multi-level data storage capabilities. It successfully emulated essential biological characteristics, including excitatory/inhibitory postsynaptic currents (EPSC/IPSC), Pair-Pulse Facilitation (PPF), and Spike-Timing Dependent Plasticity (STDP). Extensive endurance tests ensured robust stability (107 switching cycles, 105 s (extrapolated to 10 years)), excellent linearity, and high Gmax/Gmin ratio (>105), all of which are essential for realizing multi-level data states (>7-bit operation). Beyond mimicking synaptic functionalities, the device achieved a pattern recognition accuracy of ≈94% on the Modified National Institute of Standards and Technology (MNIST) handwritten dataset when incorporated into a neural network, demonstrating its potential as an effective component in neuromorphic systems. The successful implementation of the 2D FeFET device paves the way for the development of high-efficiency, ultralow-power neuromorphic hardware which is in sub-femtojoule (48 aJ/spike) and fast response (1 µs), which is 104 folds faster than human synapse (≈10 ms). The results of the research underline the potential of nanoscale ferroelectric and 2D materials in building the next generation of artificial intelligence technologies.
RESUMO
Electrosynthesis of acetate from CO offers the prospect of a low-carbon-intensity route to this valuable chemical--but only once sufficient selectivity, reaction rate and stability are realized. It is a high priority to achieve the protonation of the relevant intermediates in a controlled fashion, and to achieve this while suppressing the competing hydrogen evolution reaction (HER) and while steering multicarbon (C2+) products to a single valuable product--an example of which is acetate. Here we report interface engineering to achieve solid/liquid/gas triple-phase interface regulation, and we find that it leads to site-selective protonation of intermediates and the preferential stabilization of the ketene intermediates: this, we find, leads to improved selectivity and energy efficiency toward acetate. Once we further tune the catalyst composition and also optimize for interfacial water management, we achieve a cadmium-copper catalyst that shows an acetate Faradaic efficiency (FE) of 75% with ultralow HER (<0.2% H2 FE) at 150 mA cm-2. We develop a high-pressure membrane electrode assembly system to increase CO coverage by controlling gas reactant distribution and achieve 86% acetate FE simultaneous with an acetate full-cell energy efficiency (EE) of 32%, the highest energy efficiency reported in direct acetate electrosynthesis.
RESUMO
The instability of the surface chemistry in transition metal oxide perovskites is the main factor hindering the long-term durability of oxygen electrodes in solid oxide electrochemical cells. The instability of surface chemistry is mainly due to the segregation of A-site dopants from the lattice to the surface. Here we report that cathodic potential can remarkably improve the stability in oxygen reduction reaction and electrochemical activity, by decomposing the near-surface region of the perovskite phase in a porous electrode made of La1-xSrxCo1-xFexO3 mixed with Sm0.2Ce0.8O1.9. Our approach combines X-ray photoelectron spectroscopy and secondary ion mass spectrometry for surface and sub-surface analysis. Formation of Ruddlesden-Popper phase is accompanied by suppression of the A-site dopant segregation, and exsolution of catalytically active Co particles onto the surface. These findings reveal the chemical and structural elements that maintain an active surface for oxygen reduction, and the cathodic potential is one way to generate these desirable chemistries.
RESUMO
Despite recent progress in medical and endovascular therapy, the prognosis for patients with critical limb ischemia (CLI) remains poor. In response, various stem cells and growth factors have been assessed for use in therapeutic neovascularization and limb salvage in CLI patients. However, the clinical outcomes of cell-based therapeutic angiogenesis have not provided the promised benefits, reinforcing the need for novel cell-based therapeutic angiogenic strategies to cure untreatable CLI. In the present study, we investigated genetically engineered mesenchymal stem cells (MSCs) derived from human bone marrow that continuously secrete stromal-derived factor-1α (SDF1α-eMSCs) and demonstrated that intramuscular injection of SDF1α-eMSCs can provide long-term paracrine effects in limb ischemia and effectively contribute to vascular regeneration as well as skeletal muscle repair through increased phosphorylation of ERK and Akt within the SDF1α/CXCR4 axis. These results provide compelling evidence that genetically engineered MSCs with SDF-1α can be an effective strategy for successful limb salvage in limb ischemia.
Assuntos
Transplante de Células-Tronco Mesenquimais , Células-Tronco Mesenquimais , Animais , Humanos , Quimiocina CXCL12/genética , Quimiocina CXCL12/metabolismo , Quimiocina CXCL12/farmacologia , Membro Posterior/irrigação sanguínea , Isquemia/terapia , Isquemia/metabolismo , Células-Tronco Mesenquimais/metabolismo , Músculo Esquelético/metabolismo , Neovascularização FisiológicaRESUMO
Inflammatory bowel disease (IBD) affects millions of people worldwide and is considered a significant risk factor for colorectal cancer. Recent in vivo and in vitro studies reported that ellagic acid (EA) exhibits important antioxidant and anti-inflammatory properties. In this study, we investigated the preventive effects of EA against dextran sulfate sodium (DSS)-induced acute colitis, liver, and brain injury in mice through the gut-liver-brain axis. Acute colitis, liver, and brain injury were induced by treatment with 5% (w/v) DSS in the drinking water for 7 days. Freshly prepared EA (60 mg/kg/day) was orally administered, while control (CON) group mice were treated similarly by daily oral administrations with a vehicle (water). All the mice were euthanized 24 h after the final treatment with EA. The blood, liver, colon, and brain samples were collected for further histological and biochemical analyses. Co-treatment with a physiologically relevant dose (60 mg/kg/day) of EA for 7 days significantly reduced the DSS-induced gut barrier dysfunction; endotoxemia; and inflammatory gut, liver, and brain injury in mice by modulating gut microbiota composition and inhibiting the elevated oxidative and nitrative stress marker proteins. Our results further demonstrated that the preventive effect of EA on the DSS-induced IBD mouse model was mediated by blocking the NF-κB and mitogen-activated protein kinase (MAPK) pathway. Therefore, EA co-treatment significantly attenuated the pro-inflammatory and oxidative stress markers by suppressing the activation of NF-κB/MAPK pathways in gut, liver, and brain injury. These results suggest that EA, effective in attenuating IBD in a mouse model, deserves further consideration as a potential therapeutic for the treatment of inflammatory diseases.
RESUMO
Single-atom catalysts feature interesting catalytic activity toward applications that rely on surface reactions such as electrochemical energy storage, catalysis, and gas sensors. However, conventional synthetic approaches for such catalysts require extended periods of high-temperature annealing in vacuum systems, limiting their throughput and increasing their production cost. Herein, we report an ultrafast flash-thermal shock (FTS)-induced annealing technique (temperature > 2850 °C, <10 ms duration, and ramping/cooling rates of â¼105 K/s) that operates in an ambient-air environment to prepare single-atom-stabilized N-doped graphene. Melamine is utilized as an N-doping source to provide thermodynamically favorable metal-nitrogen bonding sites, resulting in a uniform and high-density atomic distribution of single metal atoms. To demonstrate the practical utility of the single-atom-stabilized N-doped graphene produced by the FTS method, we showcased their chemiresistive gas sensing capabilities and electrocatalytic activities. Overall, the air-ambient, ultrafast, and versatile (e.g., Co, Ni, Pt, and Co-Ni dual metal) FTS method provides a general route for high-throughput, large area, and vacuum-free manufacturing of single-atom catalysts.
RESUMO
We present a thermally stable, mechanically compliant, and sensitive polymer-based NO2 gas sensor design. Interconnected nanoscale morphology driven from spinodal decomposition between conjugated polymers tethered with polar side chains and thermally stable matrix polymers offers judicious design of NO2-sensitive and thermally tolerant thin films. The resulting chemiresitive sensors exhibit stable NO2 sensing even at 170 °C over 6 h. Controlling the density of polar side chains along conjugated polymer backbone enables optimal design for coupling high NO2 sensitivity, selectivity, and thermal stability of polymer sensors. Lastly, thermally stable films are used to implement chemiresistive sensors onto flexible and heat-resistant substrates and demonstrate a reliable gas sensing response even after 500 bending cycles at 170 °C. Such unprecedented sensor performance as well as environmental stability are promising for real-time monitoring of gas emission from vehicles and industrial chemical processes.
Assuntos
Temperatura Alta , Dióxido de Nitrogênio , PolímerosRESUMO
Alcoholic liver disease (ALD) is damage to the liver and mainly caused by binge alcohol. ALD have decreased junctional protein expression and modulated intestinal permeability. We investigated whether plant-releasing exosome-like nanovesicles can prevent liver damage and leaky gut from binge alcohol. In this study, we characterized the exosome-like nanovesicles from pomegranate juice and confirmed the round shape of a lipid bilayer. After 14 days of pomegranate-derived exosome-like nanovesicle (PNVs) pretreatment, binge alcohol (6 g/kg/dose) was administered to mice three times orally every 12 h. Exposure to binge alcohol increased levels of oxidative and nitric oxide stress marker proteins such as CYP2E1, 3-Nitrotyrosine, and inducible nitric oxide synthase in both liver and gut damage. Also, binge alcohol significantly elevated the plasma endotoxemia, inflammatory fatty liver, and leaky gut. However, PNVs reduced the oxidative stress and apoptosis marker proteins and prevented the leaky gut and endotoxemia. Markedly, PNV treatment significantly prevented a decrease in the amount of intestinal junctional proteins and an increase in leaky gut in mice exposed to alcohol. These results showed that PNVs can prevent leaky gut and liver damage caused by binge alcohol and suggest that it may be useful hepatoprotective or intestinal protective agents for the first time.
RESUMO
Lysine-specific demethylase 1 (LSD1) is crucial for regulating gene expression by catalyzing the demethylation of mono- and di-methylated histone H3 lysine 4 (H3K4) and lysine 9 (H3K9) and non-histone proteins through the amine oxidase activity with FAD+ as a cofactor. It interacts with several protein partners, which potentially contributes to its diverse substrate specificity. Given its pivotal role in numerous physiological and pathological conditions, the function of LSD1 is closely regulated by diverse post-translational modifications (PTMs), including phosphorylation, ubiquitination, methylation, and acetylation. In this review, we aim to provide a comprehensive understanding of the regulation and function of LSD1 following various PTMs. Specifically, we will focus on the impact of PTMs on LSD1 function in physiological and pathological contexts and discuss the potential therapeutic implications of targeting these modifications for the treatment of human diseases.
Assuntos
Histonas , Lisina , Humanos , Histonas/metabolismo , Lisina/metabolismo , Histona Desmetilases/metabolismo , Processamento de Proteína Pós-Traducional , MetilaçãoRESUMO
High-entropy alloys (HEAs) provide unprecedented physicochemical properties over unary nanoparticles (NPs). According to the conventional alloying guideline (Hume-Rothery rule), however, only size-and-structure similar elements can be mixed, limiting the possible combinations of alloying elements. Recently, it has been reported that based on carbon thermal shocks (CTS) in a vacuum atmosphere at high temperature, ultrafast heating/cooling rates and high-entropy environment play a critical role in the synthesis of HEAs, ruling out the possibility of phase separation. Since the CTS requires conducting supports, the Joule-heating efficiencies rely on the carbon qualities, featuring difficulties in uniform heating along the large area. This work proposes a photo-thermal approach as an alternative and innovative synthetic method that is compatible with ambient air, large-area, remote process, and free of materials selection. Single flash irradiation on carbon nanofibers induced momentary high-temperature annealing (>1800 °C within 20 ms duration, and ramping/cooling rates >104 K s-1 ) to successfully decorate HEA NPs up to nine elements with excellent compatibility for large-scale synthesis (6.0 × 6.0 cm2 of carbon nanofiber paper). To demonstrate their feasibility toward applications, senary HEA NPs (PtIrFeNiCoCe) are designed and screened, showing high activity (ηoverall = 777 mV) and excellent stability (>5000 cycles) at the water splitting, including hydrogen evolution reactions and oxygen evolution reactions.
RESUMO
Osteoblasts and osteoclasts play crucial roles in bone formation and bone resorption. We found that plum-derived exosome-like nanovesicles (PENVs) suppressed osteoclast activation and modulated osteoblast differentiation. PENVs increased the proliferation, differentiation, and mineralization of osteoblastic MC3T3-E1 cells and osteoblasts from mouse bone marrow cultures. Notably, PENVs elevated the expression of osteoblastic transcription factors and osteoblast differentiation marker proteins in MC3T3-E1 cells. Higher levels of phosphorylated BMP-2, p38, JNK, and smad1 proteins were detected in PENV-treated MC3T3-E1 cells. Additionally, the number of TRAP-positive cells was significantly decreased in PENV-treated osteoclasts isolated from osteoblasts from mouse bone marrow cultures. Importantly, osteoclastogenesis of marker proteins such as PPAR-gamma, NFATc1, and c-Fos were suppressed by treatment with PENVs (50 µg/mL). Taken together, these results demonstrate that PENVs can be used as therapeutic targets for treating bone-related diseases by improving osteoblast differentiation and inhibiting osteoclast activation for the first time.
Assuntos
Doenças Ósseas , Exossomos , Prunus domestica , Animais , Camundongos , Osteoclastos , Osteoblastos , Diferenciação CelularRESUMO
During exercise, skeletal muscle is exposed to a low oxygen condition, hypoxia. Under hypoxia, the transcription factor hypoxia-inducible factor-1α (HIF-1α) is stabilized and induces expressions of its target genes regulating glycolytic metabolism. Here, using a skeletal muscle-specific gene ablation mouse model, we show that Brg1/Brm-associated factor 155 (Baf155), a core subunit of the switch/sucrose non-fermentable (SWI/SNF) complex, is essential for HIF-1α signaling in skeletal muscle. Muscle-specific ablation of Baf155 increases oxidative metabolism by reducing HIF-1α function, which accompanies the decreased lactate production during exercise. Furthermore, the augmented oxidation leads to high intramuscular adenosine triphosphate (ATP) level and results in the enhancement of endurance exercise capacity. Mechanistically, our chromatin immunoprecipitation (ChIP) analysis reveals that Baf155 modulates DNA-binding activity of HIF-1α to the promoters of its target genes. In addition, for this regulatory function, Baf155 requires a phospho-signal transducer and activator of transcription 3 (pSTAT3), which forms a coactivator complex with HIF-1α, to activate HIF-1α signaling. Our findings reveal the crucial role of Baf155 in energy metabolism of skeletal muscle and the interaction between Baf155 and hypoxia signaling.
Assuntos
Subunidade alfa do Fator 1 Induzível por Hipóxia , Músculo Esquelético , Fatores de Transcrição , Animais , Camundongos , Regulação da Expressão Gênica , Hipóxia/metabolismo , Subunidade alfa do Fator 1 Induzível por Hipóxia/genética , Subunidade alfa do Fator 1 Induzível por Hipóxia/metabolismo , Músculo Esquelético/metabolismo , Transdução de Sinais , Fatores de Transcrição/genética , Fatores de Transcrição/metabolismoRESUMO
Owing to its pseudocapacitive, unidimensional, rapid ion channels, TiO2(B) is a promising material for application to battery electrodes. In this study, we align these channels by epitaxially growing TiO2(B) films with the assistance of an isostructural VO2(B) template layer. In a liquid electrolyte, binder-free TiO2(B) epitaxial electrodes exhibit a supercapacity near the theoretical value of 335 mA h g-1 and an excellent charge-discharge reproducibility for ≥200 cycles, which outperform those of other TiO2(B) nanostructures. For the all-solid-state configuration employing the LiPON solid electrolyte, excellent stability persists. Our findings suggest excellent potential for miniaturizing all-solid-state nanobatteries in self-powered integrated circuits.
RESUMO
To allow a high quality factor (Q-factor) to a sub-wavelength dielectric resonator, quasi-bound states in the continuum (Q-BICs) have gained much interest. However, the Q-BIC resonance condition is too sensitive to the geometry of the resonator, and its practical broadband generation on a single-wafer platform has been limited. Here we present that, employing the base angle as a structural degree of freedom, the truncated nano-cone resonator supports the Q-BIC resonance with a high Q-factor of >150 over a wide wavelength range of >100â nm. We expect our approach will boost the utilization of the Q-BIC resonance for various applications requiring broadband spectral tuning.
RESUMO
Objective: Shoulder pain is a common complaint in outpatient clinics and can result in an inability to work or perform household activities, leading to significant socioeconomic burden. Acupotomy, as one kind acupuncture that has flat knife-shaped tip, has been widely used for treating shoulder pain. However, despite the widespread use of acupotomy in primary medical institutions, large sample size clinical trials have not sufficiently been performed. In this respect, this multi-center retrospective study aimed to investigate the effectiveness and safety of acupotomy in reducing shoulder pain and disability using data from multi-center primary care clinics. Methods: This study was conducted in 25 Korean medicine clinics affiliated with the Korean Medical Society of Acupotomology, Republic of Korea, from August 2021 to December 2021. The medical records of patients who visited the clinics complaining of shoulder pain were gathered, and among them were those of patients who underwent acupotomy treatment and those who received acupuncture combined therapy. The Numeric Rating Scale (NRS), SPADI (Shoulder Pain and Disability Index), Range of Motion (ROM) and adverse event were evaluated at each visit. A linear mixed-effects models and paired t-test were used to identify the effectiveness of the treatment. Results: Overall analysis showed that the NRS score of patients decreased from 4.95 ± 1.97 before treatment to 3.78 ± 2.03 after treatment (n = 332, difference in NRS score, 1.17; 95% CI: 0.96-1.38, t = 10.89 p < 0.001). SPADI score decreased from 19.05 ± 20.44 at baseline before treatment to 12.12 ± 17.26 after the last visit, which was statistically significant (n = 332, mean difference in SPADI score, 6.93; 95% CI: 4.71-9.15, t = 6.150, p < 0.001). No serious adverse event was reported in both groups. Conclusion: This study showed the effectiveness of acupotomy therapy for shoulder pain, and as the treatment sessions increased, the effect of pain reduction and shoulder function improvement were also increased.