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Halide solid electrolytes (SEs) are attracting great attention, owing to their high ionic conductivity and excellent high-voltage compatibility. However, severe moisture sensitivity, poor thermal stability, and instability at the lithium metal anode interface with chloride and bromide SEs retard their applications in solid-state lithium metal batteries. Fluoride SEs are expected to solve these problems, but they are now plagued by inadequate room-temperature (RT) ionic conductivity. Herein, a low-temperature molten salt (LiCl+1.33AlCl3) ablation method is proposed to enhance the ionic conductivity of monoclinic Li3GaF6 by particle boundary doping. The RT ionic conductivity of Li3GaF6 is correspondingly increased by 2 orders of magnitude, and the conductivity reaches 10-4 S cm-1 at 60 °C. The improved ionic conductivity benefits from the enhancement of interfacial ion transport, with the formation of more conductive chlorine-doped Li3GaF6-xClx and in situ binder LiAlCl4 to cement surrounding nanoparticles. The as-synthesized Li3GaF6 demonstrates outstanding humidity tolerance without conductivity degradation after exposure to a relative humidity of up to 35%. It also exhibits the widest electrochemical stability window experimentally (close to 6 V) compared with other state-of-the-art SEs. The solid-state Li/Li3GaF6/LiFePO4 cell with a stable Li+-conductive polymer interface is successfully driven for at least 200 cycles at 0.5C. Our study provides a solution to various chemical and electrochemical stability issues encountered by the halide SE family.
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Rechargeable magnesium batteries (RMBs) face with the challenge of interphase passivation between electrolytes and Mg anodes. Compared with ether electrolytes, carbonate solvents possess the superior electrochemical stability at cathode side, but their incompatibility with Mg metal, high viscosity, and desolvation energy barrier restrict their practical utilization in RMBs. Herein, the "unwanted-impurity" water with high concentration is revisited and employed as multifunctional additive in carbonate electrolyte to improve the reversibility of RMBs. Water additive enables the localized deep eutectic effect, reduces the viscosity of carbonate electrolyte, and improves the Mg ion conductivity. The water molecules also participate the solvation sheath of Mg ions, resulting in the reduction of Mg deposition overpotential and inhibition of parasitic reaction. Furthermore, the co-intercalated water molecules in V2O5 cathode layers enable the stabilization of intercalation structure and supply of additional magnesiophilic sites. Cooperated with the binder-decorated Mg powder anode, the propylene carbonate electrolyte with water additive endows Mg||Mg symmetric cells and Mg||V2O5 full cells with satisfactory cycling performance and high-voltage stability. This work revisits the impact of impurity water and provides a practical strategy for the utilization of conventional low-cost carbonate electrolyte family, broadening the design and formulation of electrolytes for chlorine-free and high-voltage RMBs.
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Therapeutic options for addressing inflammatory bowel disease (IBD) include the administration of an enema to reduce intestinal inflammation and alleviate associated symptoms. However, uncontrollable retention of enemas in the intestinal tract has posed a long-term challenge for improving their therapeutic efficacy and safety. Herein we have developed a protease-labile hydrogel system as an on-demand enema vehicle with tunable degradation and drug release rates in response to varying matrix metalloproteinase-9 (MMP-9) expression. The system, composed of three tailored hydrogel networks, is crosslinked by poly (ethylene glycol) (PEG) with 2-, 4- and 8-arms through dynamic hydrazone bonds to confer injectability and generate varying network connectivity. The retention time of the hydrogels can be tuned from 12 to 36 h in the intestine due to their different degradation behaviors induced by MMP-9. The drug-releasing rate of the hydrogels can be controlled from 0.0003 mg/h to 0.278 mg/h. In addition, injection of such hydrogels in vivo resulted in significant differences in therapeutic effects including MMP-9 consumption, colon tissue repair, reduced collagen deposition, and decreased macrophage cells, for treating a mouse model of acute colitis. Among them, GP-8/5-ASA exhibits the best performance. This study validates the effectiveness of the tailored design of hydrogel architecture in response to pathological microenvironment cues, representing a promising strategy for on-demand therapy of IBD. STATEMENT OF SIGNIFICANCE: The uncontrollable retention of enemas at the delivery site poses a long-term challenge for improving therapeutic efficacy in IBD patients. MMP-9 is highly expressed in IBD and correlates with disease severity. Therefore, an MMP-9-responsive GP hydrogel system was developed as an enema by linking multi-armed PEG and gelatin through hydrazone bonds. This forms a dynamic hydrogel characterized by in situ gelation, injectability, enhanced bio-adhesion, biocompatibility, controlled retention time, and regulated drug release. GP hydrogels encapsulating 5-ASA significantly improved the intestinal phenotype of acute IBD and demonstrated notable therapeutic differences with increasing PEG arms. This method represents a promising on-demand IBD therapy strategy and provides insights into treating diseases of varying severities using endogenous stimulus-responsive drug delivery systems.
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Hidrogeles , Enfermedades Inflamatorias del Intestino , Metaloproteinasa 9 de la Matriz , Hidrogeles/química , Hidrogeles/farmacología , Animales , Metaloproteinasa 9 de la Matriz/metabolismo , Ratones , Enfermedades Inflamatorias del Intestino/tratamiento farmacológico , Enfermedades Inflamatorias del Intestino/patología , Polietilenglicoles/química , Ratones Endogámicos C57BL , Colitis/tratamiento farmacológico , Colitis/patologíaRESUMEN
The immune system has a strong connection to tumors. When a tumor cell is recognized as an abnormal cell by the immune system, the immune system may initiate an immune response to kill the tumor cell. In this study, RNA sequencing was performed on multiple myeloma (MM) cells treated with the proteasome inhibitor FHND6091. The transcriptional changes induced by FHND6091 in RPMI8226 cells aligned notably with immune response activation and results indicated upregulation of cGAS-STING pathway-related genes in the FHND6091-treated group. In vivo and in vitro experiments had demonstrated that FHND6091 stimulated the immunoreaction of MM cells via activation of the cyclic guanosine monophosphate-adenosine synthase/stimulator of interferon genes (cGAS-STING) pathway. This activation resulted in the generation of type-I interferons and the mobilization of natural killer (NK) cells. Notably, FHND6091 upregulated the levels of calreticulin and the protein ligands UL16-binding protein 2/5/6, MHC class I chain-related A (MICA), and MICB on the surface of MM cells. Subsequently, upon engaging with the surface activation receptors of NK cells, these ligands triggered NK cell activation, leading to the subsequent elimination of tumor cells. Thus, our findings elucidated the mechanism whereby FHND6091 exerted its immunotherapeutic activity as a STING agonist, enhancing the killing ability of NK cells against tumor cells.
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Células Asesinas Naturales , Proteínas de la Membrana , Mieloma Múltiple , Inhibidores de Proteasoma , Humanos , Células Asesinas Naturales/efectos de los fármacos , Células Asesinas Naturales/inmunología , Células Asesinas Naturales/metabolismo , Inhibidores de Proteasoma/farmacología , Línea Celular Tumoral , Proteínas de la Membrana/genética , Proteínas de la Membrana/metabolismo , Animales , Mieloma Múltiple/tratamiento farmacológico , Mieloma Múltiple/inmunología , Nucleotidiltransferasas/metabolismo , Nucleotidiltransferasas/genética , Ratones , Antígenos de Histocompatibilidad Clase I/metabolismo , Antígenos de Histocompatibilidad Clase I/genética , Calreticulina/metabolismo , Calreticulina/genética , Transducción de Señal/efectos de los fármacos , Citotoxicidad Inmunológica/efectos de los fármacos , Interferón Tipo I/metabolismoRESUMEN
BACKGROUND: The parallel evolution of similar traits or species provides strong evidence for the role of natural selection in evolution. Traits or species that evolved repeatedly can be driven by separate de novo mutations or interspecific gene flow. Although parallel evolution has been reported in many studies, documented cases of parallel evolution caused by gene flow are scarce by comparison. Aquilegia ecalcarata and A. kansuensis belong to the genus of Aquilegia, and are the closest related sister species. Mutiple origins of A. ecalcarata have been reported in previous studies, but whether they have been driven by separate de novo mutations or gene flow remains unclear. RESULTS: In this study, We conducted genomic analysis from 158 individuals of two repeatedly evolving pairs of A. ecalcarata and A. kansuensis. All samples were divided into two distinct clades with obvious geographical distribution based on phylogeny and population structure. Demographic modeling revealed that the origin of the A. ecalcarata in the Eastern of China was caused by gene flow, and the Eastern A. ecalcarata occurred following introgression from Western A. ecalcarata population. Analysis of Treemix and D-statistic also revealed that a strong signal of gene flow was detected from Western A. ecalcarata to Eastern A. ecalcarata. Genetic divergence and selective sweep analyses inferred parallel regions of genomic divergence and identified many candidate genes associated with ecologically adaptive divergence between species pair. Comparative analysis of parallel diverged regions and gene introgression confirms that gene flow contributed to the parallel evolution of A. ecalcarata. CONCLUSIONS: Our results further confirmed the multiple origins of A. ecalcarata and highlighted the roles of gene flow. These findings provide new evidence for parallel origin after hybridization as well as insights into the ecological adaptation mechanisms underlying the parallel origins of species.
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Aquilegia , Flujo Génico , Aquilegia/genética , Genómica , China , Filogenia , Hibridación GenéticaRESUMEN
Autoantibodies against apolipoprotein A-I (ApoA-I) are associated with cardiovascular disease risks. We aimed to examine the 4-hydroxy-2-nonenal (HNE) modification of ApoA-I in coronary artery disease (CAD) and evaluate the potential risk of autoantibodies against their unmodified and HNE-modified peptides. We assessed plasma levels of ApoA-I, HNE-protein adducts, and autoantibodies against unmodified and HNE-peptide adducts, and significant correlations and odds ratios (ORs) were examined. Two novel CAD-specific HNE-peptide adducts, ApoA-I251-262 and ApoA-I70-83, were identified. Notably, immunoglobulin G (IgG) anti-ApoA-I251-262 HNE, IgM anti-ApoA-I70-83 HNE, IgG anti-ApoA-I251-262, IgG anti-ApoA-I70-83, and HNE-protein adducts were significantly correlated with triglycerides, creatinine, or high-density lipoprotein in CAD with various degrees of stenosis (<30% or >70%). The HNE-protein adduct (OR = 2.208-fold, p = 0.020) and IgM anti-ApoA-I251-262 HNE (2.046-fold, p = 0.035) showed an increased risk of progression from >30% stenosis in CAD. HNE-protein adducts and IgM anti-ApoA-I251-262 HNE may increase the severity of CAD at high and low levels, respectively.
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PURPOSE: To enhance the predictive risk model for all-cause mortality in individuals with Type 2 Diabetes (T2DM) and prolonged Atherosclerotic Cardiovascular Disease (ASCVD) risk factors. Despite the utility of the Coronary Artery Calcium (CAC) score in assessing cardiovascular risk, its capacity to predict all-cause mortality remains limited. METHODS: A retrospective cohort study included 1929 asymptomatic T2DM patients with ASCVD risk factors, aged 40-80. Variables encompassed demographic attributes, clinical parameters, CAC scores, comorbidities, and medication usage. Factors predicting all-cause mortality were selected to create a predictive scoring system. By using stepwise selection in a multivariate Cox proportional hazards model, we divided the patients into three risk groups. RESULTS: In our analysis of all-cause mortality in T2DM patients with extended ASCVD risk factors over 5 years, we identified significant risk factors, their adjusted hazard ratios (aHR), and scores: e.g., CAC score > 1000 (aHR: 1.57, score: 2), CAC score 401-1000 (aHR: 2.05, score: 2), and more. These factors strongly predict all-cause mortality, with varying risk groups (e.g., very low-risk: 2.0%, very high-risk: 24.0%). Significant differences in 5-year overall survival rates were observed among these groups (log-rank test < 0.001). CONCLUSION: The Poh-Ai Predictive Scoring System excels in forecasting mortality and cardiovascular events in individuals with Type 2 Diabetes Mellitus and extended ASCVD risk factors.
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OBJECTIVES: The aim of this study was to observe the radiographic healing of periapical lesions after root canal treatment via volumetric measurements based on cone-beam computed tomography (CBCT) over 4 years. METHODS: In total, 162 single-root teeth from patients with chronic periapical periodontitis who underwent primary root canal treatment were included in this retrospective study. Follow-up visits were scheduled at 1, 2, and 4 years after treatment. The volume of radiolucency at pretreatment and follow-up were measured, and the radiographic outcomes were classified into 4 categories: absence, reduction, uncertain or enlargement. Reduction or enlargement was considered when the volumetric change in radiolucency was 20 % or more. RESULTS: During the 4-year follow-up period, 128 teeth were reviewed at least once, including 3 extracted teeth. Of the remaining 125 teeth, the volume of radiolucency was reduced in 116 teeth (90.6 %), uncertain in 5, and enlarged in 4 teeth during 1 to 4 years after treatment. Among the 43 teeth with reduced radiolucency at 1 year after treatment, 42 (97.7 %) had continuing reduced lesions at 4 years. In the 2 teeth with enlarged radiolucency at 1 year, the volume of radiolucency doubled at 4 years. Cox regression analysis revealed that the preoperative radiolucency size was a risk factor for persistent periapical radiolucency. CONCLUSIONS: The efficacy of root canal treatment for apical periodontitis was predictable. When the radiolucency changed by 20 % or more in volume on CBCT scans at 1 year after treatment, reversal of the radiographic healing tendency was rare. CLINICAL SIGNIFICANCE: The volumetric changes in radiolucency on CBCT could reflect trends in the healing process and may foster early clinical decision-making.
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Tomografía Computarizada de Haz Cónico , Periodontitis Periapical , Tratamiento del Conducto Radicular , Cicatrización de Heridas , Humanos , Tomografía Computarizada de Haz Cónico/métodos , Periodontitis Periapical/diagnóstico por imagen , Periodontitis Periapical/terapia , Tratamiento del Conducto Radicular/métodos , Femenino , Masculino , Estudios Retrospectivos , Estudios Longitudinales , Persona de Mediana Edad , Adulto , Resultado del Tratamiento , Anciano , Estudios de SeguimientoRESUMEN
Increasing grain yield is a major goal of breeders due to the rising global demand for food. We previously reported that the miR397-LACCASE (OsLAC) module regulates brassinosteroid (BR) signaling and grain yield in rice (Oryza sativa). However, the precise roles of laccase enzymes in the BR pathway remain unclear. Here, we report that OsLAC controls grain yield by preventing the turnover of TRANSTHYRETIN-LIKE (OsTTL), a negative regulator of BR signaling. Overexpressing OsTTL decreased BR sensitivity in rice, while loss-of-function of OsTTL led to enhanced BR signaling and increased grain yield. OsLAC directly binds to OsTTL and regulates its phosphorylation-mediated turnover. The phosphorylation site Ser226 of OsTTL is essential for its ubiquitination and degradation. Overexpressing the dephosphorylation-mimic form of OsTTL (OsTTLS226A) resulted in more severe defects than did overexpressing OsTTL. These findings provide insight into the role of an ancient laccase in BR signaling and suggest that the OsLAC-OsTTL module could serve as a target for improving grain yield.
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Regulación de la Expresión Génica de las Plantas , Lacasa , MicroARNs , Oryza , Proteínas de Plantas , Oryza/genética , Oryza/metabolismo , Oryza/crecimiento & desarrollo , Oryza/enzimología , Lacasa/metabolismo , Lacasa/genética , Proteínas de Plantas/metabolismo , Proteínas de Plantas/genética , MicroARNs/genética , MicroARNs/metabolismo , Fosforilación , Grano Comestible/crecimiento & desarrollo , Grano Comestible/genética , Grano Comestible/metabolismo , Transducción de Señal , Plantas Modificadas Genéticamente , Brasinoesteroides/metabolismoRESUMEN
Triple-negative breast cancer (TNBC) is a highly invasive and metastatic subtype of breast cancer that often recurs after surgery. Herein, we developed a cyclodextrin-based tumor-targeted nano delivery system that incorporated the photosensitizer chlorin e6 (Ce6) and the chemotherapeutic agent lonidamine (LND) to form the R6RGD-CMßCD-se-se-Ce6/LND nanoparticles (RCC/LND NPS). This nanosystem could target cancer cells, avoid lysosomal degradation and further localize within the mitochondria. The RCC/LND NPS had pH and redox-responsive to control the release of Ce6 and LND. Consequently, the nanosystem had a synergistic effect by effectively alleviating hypoxia, enhancing the production of cytotoxic reactive oxygen species (ROS) and amplifying the efficacy of photodynamic therapy (PDT). Furthermore, the RCC/LND NPS + light weakened anoikis resistance, disrupted extracellular matrix (ECM), activated both the intrinsic apoptotic pathway (mitochondrial pathway) and extrinsic apoptotic pathway (receptor death pathway) of anoikis. In addition, the nanosystem showed significant anti-TNBC efficacy in vivo. These findings collectively demonstrated that RCC/LND NPS + light enhanced the anticancer effects, induced anoikis and inhibited tumor cell migration and invasion through a synergistic effect of chemotherapy and PDT. Overall, this study highlighted the promising potential of the RCC/LND NPS + light for the treatment of TNBC.
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Anoicis , Apoptosis , Clorofilidas , Nanopartículas , Fotoquimioterapia , Fármacos Fotosensibilizantes , Porfirinas , Neoplasias de la Mama Triple Negativas , Neoplasias de la Mama Triple Negativas/tratamiento farmacológico , Neoplasias de la Mama Triple Negativas/patología , Humanos , Fotoquimioterapia/métodos , Femenino , Porfirinas/farmacología , Porfirinas/uso terapéutico , Animales , Línea Celular Tumoral , Fármacos Fotosensibilizantes/farmacología , Fármacos Fotosensibilizantes/uso terapéutico , Anoicis/efectos de los fármacos , Nanopartículas/química , Nanopartículas/uso terapéutico , Apoptosis/efectos de los fármacos , Indazoles/farmacología , Indazoles/uso terapéutico , Especies Reactivas de Oxígeno/metabolismo , Antineoplásicos/farmacología , Antineoplásicos/uso terapéutico , RatonesRESUMEN
Diabetic retinopathy (DR) is a kind of ocular complication of diabetes, and its degree grade is an essential basis for early diagnosis of patients. Manual diagnosis is a long and expensive process with a specific risk of misdiagnosis. Computer-aided diagnosis can provide more accurate and practical treatment recommendations. In this paper, we propose a multi-view joint learning DR diagnostic model called RT2Net, which integrates the global features of fundus images and the local detailed features of vascular images to reduce the limitations of single fundus image learning. Firstly, the original image is preprocessed using operations such as contrast-limited adaptive histogram equalization, and the vascular structure of the extracted DR image is segmented. Then, the vascular image and fundus image are input into two branch networks of RT2Net for feature extraction, respectively, and the feature fusion module adaptively fuses the feature vectors' output from the branch networks. Finally, the optimized classification model is used to identify the five categories of DR. This paper conducts extensive experiments on the public datasets EyePACS and APTOS 2019 to demonstrate the method's effectiveness. The accuracy of RT2Net on the two datasets reaches 88.2% and 85.4%, and the area under the receiver operating characteristic curve (AUC) is 0.98 and 0.96, respectively. The excellent classification ability of RT2Net for DR can significantly help patients detect and treat lesions early and provide doctors with a more reliable diagnosis basis, which has significant clinical value for diagnosing DR.
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Retinopatía Diabética , Diagnóstico por Computador , Retinopatía Diabética/diagnóstico por imagen , Retinopatía Diabética/diagnóstico , Humanos , Diagnóstico por Computador/métodos , Interpretación de Imagen Asistida por Computador/métodos , Aprendizaje AutomáticoRESUMEN
The accurate and effective detection of moisture in coal gravels is crucial. Conventional air oven-drying method suffers from prolonged processing times and their disruptive nature. This paper proposes a deep learning-based adaptive fusion method for multiple microwave spectra to non-destructively detect the moisture content of coal gravels. First, a purpose-built free-space measurement platform is employed to acquire microwave spectra of coal samples, encompassing the magnitude and phase spectra of reflection coefficients (S11) and transmission coefficients (S21). Subsequently, a Monte-Carlo cross-validation-based method is adopted to detect and eliminate outliers in the spectra. Furthermore, a novel feature extraction module is proposed, enhancing the traditional U-shaped network using residual learning (ResNet) and the convolutional block attention module (CBAM) to extract and reconstruct subtle spectral features. Inspired by the high-level data fusion, an adaptive spectra fusion method is then introduced that can autonomously balance the contributions between different spectra. The experimental results underscore the advantages of the proposed method, with narrow frequency intervals between 2.50-3.25 GHz, 3.75-4.00 GHz, and 4.75-5.00 GHz exhibiting superior detection accuracy compared to the entire frequency band, achieving R2 = 0.9034, MAE = 1.0254, RMSE = 1.2948 and RPIQ = 6.0630.
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Background: Demographics of pulmonary hypertension (PH) has changed a lot over the past forty years. Several recent registries noted an increase in mean age of PH but only a few of them investigated the characteristics of elderly patients. Thus, we aimed to analyze the characteristics of PH in such a population in this study. Methods: This multicenter study enrolled patients diagnosed with PH in group 1, 3, 4, and 5 consecutively from January 1, 2019 to December 31, 2020. A total of 490 patients was included, and patients were divided into three groups by age (≤45 years, 45-65 years, and >65 years). Results: The mean age of PH patients diagnosed with PH was 55.3 ± 16.3 years of age. There was higher proportion of elderly patients classified as group 3 PH (≤45: 1.3, 45-65: 4.5, >65: 8.1 %; p = 0.0206) and group 4 PH (≤45: 8.4, 45-65: 14.5, >65: 31.6 %; p < 0.0001) than young patients. Elderly patients had shorter 6-min walking distance (6 MWD) (≤45 vs. >65, mean difference, 77.8 m [95% confidence interval (CI), 2.1-153.6 m]), lower mean pulmonary arterial pressure (mPAP) (≤45 vs. >65, mean difference, 10.8 mmHg [95% CI, 6.37-15.2 mmHg]), and higher pulmonary arterial wedge pressure (PAWP) (≤45 vs. 45-65, mean difference, -2.1 mmHg [95% CI, -3.9 to -0.3 mmHg]) compared to young patients. Elderly patients had a poorer exercise capacity despite lower mPAP level compared to young population, but they received combination therapy less frequently compared to young patients (triple therapy in group 1 PH, ≤45: 16.7, 45-65: 11.3, >65: 3.8 %; p = 0.0005). Age older than 65 years was an independent predictor of high mortality for PH patients. Conclusions: Elderly PH patients possess unique hemodynamic profiles and epidemiologic patterns. They had higher PAWP, lower mPAP, and received combination therapy less frequently. Moreover, ageing is a predictor of high mortality for PH patients. Exercise capacity-hemodynamics mismatch and inadequate treatment are noteworthy in the approach of elderly population with PH.
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BACKGROUND: Previous studies show that using 12-lead electrocardiogram (ECG) or 24-h ECG monitor for the detection of cardiac arrhythmia events in patients with stroke or syncope is ineffective. HYPOTHESIS: The 14-day continuous ECG patch has higher detection rates of arrhythmias compared with conventional 24-h ECG monitoring in patients with ischemic stroke or syncope. METHODS: This cross-sectional study of patients with newly diagnosed ischemic stroke or syncope received a 24-h ECG monitoring and 14-day continuous cardiac monitoring patch and the arrhythmia events were measured. RESULTS: This study enrolled 83 patients with ischemic stroke or syncope. The detection rate of composite cardiac arrhythmias was significantly higher for the 14-day ECG patch than 24-h Holter monitor (69.9% vs. 21.7%, p = .006). In patients with ischemic stroke, the detection rates of cardiac arrhythmias were 63.4% for supraventricular tachycardia (SVT), 7% for ventricular tachycardia (VT), 5.6% for atrial fibrillation (AF), 4.2% for atrioventricular block (AVB), and 1.4% for pause by 14-day ECG patch, respectively. The significant difference in arrhythmic detection rates were found for SVT (45.8%), AF (6%), pause (1.2%), AVB (2.4%), and VT (9.6%) by 14-day ECG patch but not by 24-h Holter monitor in patients with ischemic stroke or syncope. CONCLUSIONS: A 14-day ECG patch can be used on patients with ischemic stroke or syncope for the early detection of AF or other cardiac arrhythmia events. The patch can be helpful for physicians in planning medical or mechanical interventions of patients with ischemic stroke and occult AF.
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Fibrilación Atrial , Bloqueo Atrioventricular , Accidente Cerebrovascular Isquémico , Taquicardia Ventricular , Humanos , Estudios Transversales , Síncope/diagnóstico , Síncope/etiología , ElectrocardiografíaRESUMEN
Batteries taking conversion-type iron fluorides as energy-dense cathodes provide the possibility for the power electrification of the transportation and aviation industries. However, a safe and low-toxicity synthesis method for fluorides and the design of a compatible electrolyte formula are still challenging. Here, we propose a dual strategy of mild C-F scissoring fluorination and a local high-concentration electrolyte (LHCE) to enable highly reversible Li-Fe-F conversion batteries. A facile and safe scissoring strategy at a low temperature (95 °C) enables the preparation of a carbon-iron fluoride composite with a porous cubic cage-like structure. CFx plays a double role as a solid fluorination agent and an in situ conductive network after defluorination. The as-prepared fluoride cathode delivers a reversible capacity as high as 300 mA h g-1 over 100 cycles. The further LHCE strategy not only enhances the oxidation stable voltage of the electrolyte (>5 V) and the transference number of Li+ (0.74), but also realizes dual protection of the fluoride cathode and Li metal anode by facilitating the construction of robust cathode- and anode-electrolyte interfaces, respectively. The LHCE-assisted fluoride battery releases a higher reversible capacity of 335 mA h g-1 after 130 cycles. This work provides a solution to high-performance carbon-fluoride conversion cathodes by a synergetic effect of tailored synthesis, electroactive particle texture and electrolyte formula.
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Introduction: Tumor hypoxia and invasion present significant challenges for the efficacy of photodynamic therapy (PDT) in triple-negative breast cancer (TNBC). This study developed a mitochondrial targeting strategy that combined PDT and gene therapy to promote each other and address the challenges. Methods: The positively charged amphiphilic material triphenylphosphine-tocopherol polyethylene glycol succinate (TPP-TPGS, TPS) and the photosensitizer chloride e6 (Ce6) formed TPS@Ce6 nanoparticles (NPs) by hydrophobic interaction. They electrostatically condensed microRNA-34a (miR-34a) to form stable TPS@Ce6/miRNA NPs. Results: Firstly, Ce6 disrupted the lysosomal membrane, followed by successful delivery of miR-34a by TPS@Ce6/miRNA NPs. Meanwhile, miR-34a reduced ROS depletion and further enhanced the effectiveness of PDT. Consequently, the mutual promotion between PDT and gene therapy led to enhanced anti-tumor effects. Furthermore, the TPS@Ce6/miRNA NPs promoted apoptosis by down-regulating Caspase-3 and inhibited tumor cell migration and invasion by down-regulating N-Cadherin. In addition, in vitro and in vivo experiments demonstrated that the TPS@Ce6/miRNA NPs achieved excellent anti-tumor effects. These findings highlighted the enhanced anticancer effects and reduced migration of tumor cells through the synergistic effects of PDT and gene therapy. Conclusion: Taken together, the targeted co-delivery of Ce6 and miR-34a will facilitate the application of photodynamic and genic nanomedicine in the treatment of aggressive tumors, particularly TNBC.
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MicroARNs , Nanopartículas , Fotoquimioterapia , Porfirinas , Neoplasias de la Mama Triple Negativas , Humanos , Animales , Ratones , Neoplasias de la Mama Triple Negativas/genética , Neoplasias de la Mama Triple Negativas/terapia , Fármacos Fotosensibilizantes/química , MicroARNs/genética , Modelos Animales de Enfermedad , Línea Celular Tumoral , Porfirinas/química , Nanopartículas/químicaRESUMEN
Rechargeable fluoride ion batteries (FIBs) as an emerging anion shuttle system are attracting much attention due to their potential advantages in terms of energy density, cost and safety. A liquid electrolyte system enables the FIB operation at low or room temperature due to its higher ionic conductivity than that of a solid F-ion electrolyte. However, the insolubility of fluoride salts in aprotic solvents limits the development of liquid F-ion electrolytes. Although the boron-based anion acceptors (AAs) can facilitate the dissolution of F-ion salts, they are prone to lead to a tough desolvation process for F- due to strong Lewis acidity and therefore an inferior electrochemical performance. Here, a new non-boron AA (6-thioguanine) with moderate Lewis acidity is proposed to dissolve F- in the sulfone solvent. The ionic conductivity of the corresponding electrolytes reaches a level of mS cm-1 at room temperature. A model FIB coin cell is successfully operated with high conversion reaction reversibility based on the coupled defluorination/fluorination mechanism of electrodes, enabling a low overpotential of 0.36 V and a reversible capacity of 126 mA h g-1 after 40 cycles.
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Magnesium metal batteries (MMBs) currently face challenges suffering from severe Mg metal passivation and extremely high overpotential in conventional electrolytes. Herein, a strategy of using a low-cost deep eutectic solution (DES) is proposed to modify Mg anode with the monolithic and compact coating of a MgCl2 -Al-MgCl2 sandwich structure, enabling the stable and reversible Mg plating-stripping behavior. An organic/nanocrystal hybrid interphase is in-situ built through a facile Mg-Al displacement reaction between aluminum-chloro clusters and Mg in AlCl3 /Et3 NHCl solution, and it can effectively minimize the adverse interfacial passivation reaction and surface diffusion barrier, affording the high ion-conduction and electronic insulation. This DES-assisted method guarantees a highly reversible cycling of Mg metal anode (over 5000 h at 0.1 mA cm-2 and 400 h at 2.0 mAh cm-2 ) in Mg(TFSI)2 /DME electrolyte with the improved interfacial kinetics and low overpotential. Even at a much higher current density of 1 mA cm-2 , the overpotential only undergoes a slight increase from 0.2 V (at 0.1 mA cm-2 ) to 0.23 V. The corresponding full cells with CuS and phenanthraquinone cathodes deliver satisfactory cyclic performance. The DES modification strategy provides a new solution to the design of robust and conductive solid electrolyte interphase for achieving high-voltage and durable MMBs.