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Self-trapped exciton (STE) luminescence, typically associated with structural deformation of excited states, has attracted significant attention in metal halide materials recently. However, the mechanism of multiexciton STE emissions in certain metal halide crystals remains largely unexplored. This study investigates dual luminescence emissions in HCOO- doped Cs3Cu2I5 single crystals using transient and steady-state spectroscopy. The dual emissions are attributed to intrinsic STE luminescence originating from the host lattice and extrinsic STE luminescence induced by external dopants, respectively, each of which can be triggered independently at distinct energy levels. Theoretical calculations reveal that multiexciton emission originates from structural distortion of the host and dopant STEs within the 0D lattice in their respective excited states. By meticulously tuning the excitation wavelength and selectively exciting different STEs, the dynamic alteration of color change in Cs3Cu2I5:HCOO- crystals is demonstrated. Ultimately, owing to an extraordinarily high photoluminescence quantum yield (99.01%) and a diminished degree of self-absorption in Cs3Cu2I5:HCOO- crystals, they exhibit remarkable X-ray scintillation characteristics with light yield being improved by 5.4 times as compared to that of pristine Cs3Cu2I5 crystals, opening up exciting avenues for achieving low-dose X-ray detection and imaging.
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2D semiconductors (2SEM) can transform many sectors, from information and communication technology to healthcare. To date, top-down approaches to their fabrication, such as exfoliation of bulk crystals by "scotch-tape," are widely used, but have limited prospects for precise engineering of functionalities and scalability. Here, a bottom-up technique based on epitaxy is used to demonstrate high-quality, wafer-scale 2SEM based on the wide band gap gallium selenide (GaSe) compound. GaSe layers of well-defined thickness are developed using a bespoke facility for the epitaxial growth and in situ studies of 2SEM. The dominant centrosymmetry and stacking of the individual van der Waals layers are verified by theory and experiment; their optical anisotropy and resonant absorption in the UV spectrum are exploited for photon sensing in the technological UV-C spectral range, offering a scalable route to deep-UV optoelectronics.
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BACKGROUND: Atherogenic index of plasma (AIP), a marker of atherosclerosis and cardiovascular disease (CVD). However, few studies have investigated association between AIP and all-cause mortality and specific-mortality in the general population. METHODS: This study included data from 14,063 American adults. The exposure variable was the AIP, which was defined as log10 (triglycerides/high-density lipoprotein cholesterol). The outcome variables included all-cause mortality and specific-mortality. Survey-weighted cox regressions were performed to evaluate the relation between AIP and all-cause mortality and specific-mortality. Weighted restricted cubic spline was conducted to examin the non-linear relationship. RESULTS: During 10 years of follow-up, we documented 2,077, 262, 854, and 476 cases of all-cause mortality, diabetes mortality, CVD mortality and cancer mortality, respectively. After adjustment for potential confounders, we found that atherogenic index of plasma (AIP) was significantly associated with an increased risk of diabetes mortality when comparing the highest to the lowest quantile of AIP in female (p for trend = 0.001) or participants older than 65 years (p for trend = 0.002). AIP was not significantly associated with all-cause mortality, CVD mortality and cancer mortality (p > 0.05). Moreover, a non-linear association was observed between AIP and all-cause mortality in a U-shape (p for non-linear = 0.0011), while a linear relationship was observed with diabetes mortality and non-diabetes mortality (p for linear < 0.0001). CONCLUSIONS: In this study, there is a no significant association between high AIP levels and a high risk of all-cause and cardiovascular mortality. Besides, a higher AIP was significantly associated with an increased risk of diabetes mortality, which only found in women older than 65 years. AIP was associated with all-cause mortality in a U-shape. This association could be explained by the finding that higher AIP predicted a higher risk of death from diabetes, and that lower AIP predicted a higher risk of death from non-diabetes causes.
We used a large national database and a prospective cohort study with a long follow-up period. Higher AIP was significantly associated with an increased risk of diabetes mortality, only in women older than 65 years. There is a no significant association between high AIP levels and a high risk of all-cause and cardiovascular mortality. AIP was associated with all-cause mortality in a U-shape. This finding suggest that controlling AIP levels may have a positive effect on reducing diabetes mortality.
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Aterosclerosis , Biomarcadores , Causas de Muerte , HDL-Colesterol , Diabetes Mellitus , Triglicéridos , Humanos , Femenino , Masculino , Persona de Mediana Edad , Anciano , Medición de Riesgo , Biomarcadores/sangre , Aterosclerosis/mortalidad , Aterosclerosis/sangre , Aterosclerosis/diagnóstico , Factores de Riesgo , Factores de Tiempo , Adulto , Diabetes Mellitus/mortalidad , Diabetes Mellitus/sangre , Diabetes Mellitus/diagnóstico , Diabetes Mellitus/epidemiología , HDL-Colesterol/sangre , Estados Unidos/epidemiología , Triglicéridos/sangre , Pronóstico , Neoplasias/mortalidad , Neoplasias/sangre , Neoplasias/diagnóstico , Enfermedades Cardiovasculares/mortalidad , Enfermedades Cardiovasculares/sangre , Enfermedades Cardiovasculares/diagnósticoRESUMEN
BACKGROUND: Dietary diversity has been suggested as a potential preventive measure against frailty in older adults, but the effect of changes in dietary diversity on frailty is unclear. This study was conducted to examine the association between the dietary diversity score (DDS) and frailty among older Chinese adults. METHODS: A total of 12,457 adults aged 65 years or older were enrolled from three consecutive and nonoverlapping cohorts from the Chinese Longitudinal Healthy Longevity Survey (the 2002 cohort, the 2005 cohort, and the 2008 cohort). DDS was calculated based on nine predefined food groups, and DDS changes were assessed by comparing scores at baseline and the first follow-up survey. We used 39 self-reported health items to assess frailty. Cox proportional hazard models were performed to examine the association between DDS change patterns and frailty. RESULTS: Participants with low-to-low DDS had the highest frailty incidence (111.1/1000 person-years), while high-to-high DDS had the lowest (41.1/1000 person-years). Compared to the high-to-high group of overall DDS pattern, participants in other DDS change patterns had a higher risk of frailty (HRs ranged from 1.25 to 2.15). Similar associations were observed for plant-based and animal-based DDS. Compared to stable DDS changes, participants with an extreme decline in DDS had an increased risk of frailty, with HRs of 1.38 (1.24, 1.53), 1.31 (1.19, 1.44), and 1.29 (1.16, 1.43) for overall, plant-based, and animal-based DDS, respectively. CONCLUSIONS: Maintaining a lower DDS or having a large reduction in DDS was associated with a higher risk of frailty among Chinese older adults. These findings highlight the importance of improving a diverse diet across old age for preventing frailty in later life.
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Dieta , Fragilidad , Humanos , Anciano , Femenino , Masculino , Fragilidad/epidemiología , China/epidemiología , Dieta/estadística & datos numéricos , Dieta/métodos , Estudios de Cohortes , Anciano Frágil/estadística & datos numéricos , Estudios Longitudinales , Anciano de 80 o más Años , Pueblo Asiatico/estadística & datos numéricos , Modelos de Riesgos Proporcionales , Evaluación Geriátrica/métodos , Evaluación Geriátrica/estadística & datos numéricos , Pueblos del Este de AsiaRESUMEN
BACKGROUND: There is limited understanding regarding prospective associations of insomnia symptoms and trajectories with functional disability. We aimed to investigate the associations of insomnia symptoms and trajectories with functional disability. METHOD: A total of 13 197 participants were eligible from the Health and Retirement Study. Insomnia symptoms included non-restorative sleep, difficulty initiating sleep, early morning awakening, and difficulty maintaining sleep. We also identified four distinct trajectories of insomnia symptoms: low, decreasing, increasing, and high insomnia symptoms. Functional status was assessed through activities of daily living (ADL) and instrumental activities of daily living (IADL). RESULTS: Participants experiencing one (HR, 1.21; 95% CI, 1.13-1.29), two (HR, 1.43; 95% CI, 1.29-1.57), or three to four (HR, 1.41; 95% CI, 1.25-1.60) insomnia symptoms had a higher risk of ADL disability than asymptomatic respondents. Similarly, participants with one or more insomnia symptoms had a higher risk of IADL disability. Furthermore, using the trajectory with low insomnia symptoms as the reference, decreasing insomnia symptoms (HR, 1.22; 95% CI, 1.12-1.34), increasing insomnia symptoms (HR, 1.21; 95% CI, 1.05-1.41), and high insomnia symptoms (HR, 1.36; 95% CI, 1.18-1.56) were all associated with an increased risk of ADL disability. CONCLUSION: Both a single measurement and dynamic trajectory of insomnia symptoms are associated with the onset of ADL disability. Increased awareness and management of insomnia symptoms may contribute to the prevention of functional disability occurrence.
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Actividades Cotidianas , Trastornos del Inicio y del Mantenimiento del Sueño , Humanos , Trastornos del Inicio y del Mantenimiento del Sueño/epidemiología , Trastornos del Inicio y del Mantenimiento del Sueño/diagnóstico , Femenino , Masculino , Estudios Prospectivos , Anciano , Persona de Mediana Edad , Personas con Discapacidad , Estudios de Cohortes , Evaluación de la Discapacidad , Factores de RiesgoRESUMEN
RF-based gesture recognition systems outperform computer vision-based systems in terms of user privacy. The integration of Wi-Fi sensing and deep learning has opened new application areas for intelligent multimedia technology. Although promising, existing systems have multiple limitations: (1) they only work well in a fixed domain; (2) when working in a new domain, they require the recollection of a large amount of data. These limitations either lead to a subpar cross-domain performance or require a huge amount of human effort, impeding their widespread adoption in practical scenarios. We propose Wi-AM, a privacy-preserving gesture recognition framework, to address the above limitations. Wi-AM can accurately recognize gestures in a new domain with only one sample. To remove irrelevant disturbances induced by interfering domain factors, we design a multi-domain adversarial scheme to reduce the differences in data distribution between different domains and extract the maximum amount of transferable features related to gestures. Moreover, to quickly adapt to an unseen domain with only a few samples, Wi-AM adopts a meta-learning framework to fine-tune the trained model into a new domain with a one-sample-per-gesture manner while achieving an accurate cross-domain performance. Extensive experiments in a real-world dataset demonstrate that Wi-AM can recognize gestures in an unseen domain with average accuracy of 82.13% and 86.76% for 1 and 3 data samples.
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Gestos , Reconocimiento de Normas Patrones Automatizadas , Humanos , Reconocimiento en Psicología , Tecnología de la Información , Inteligencia , AlgoritmosRESUMEN
BACKGROUND: Oxidative stress indicators affect chronic orofacial pain (COFP), but how to reduce these effects is uncertain. OBJECTIVES: 11 oxidative stress biomarkers were collected as exposures, while four forms of COFP were chosen as outcomes for Mendelian randomization (MR) study. METHODS: The effect estimates between oxidative stress and COFP were calculated using inverse variance-weighted MR (IVW-MR). Then, functional mapping and annotation (FUMA) was utilized in order to carry out SNP-based functional enrichment analyses. In addition, the IVW-MR method was applied to combine effect estimates when using genetic variants associated with oxidative stress biomarkers as an instrument for exploring potential druggable targets. RESULTS: The results indicated that oxidative stress biomarkers (causal OR of uric acid (UA), 0.998 for myofascial pain, 95% CI 0.996-1.000, p < .05; and OR of glutathione transferase (GST), 1.002 for dentoalveolar pain, 95% CI 1.000-1.003, p < .05) were significantly linked with the probability of COFP. Functional analysis also demonstrated that UA and myofascial pain genes were prominent in nitrogen and uracil metabolism, while GST and dentoalveolar pain genes were enriched in glutathione metabolism. Also, the study provided evidence that solute carrier family 2 member 9 (SLC2A9) and glutathione S-transferase alpha 2 (GSTA2) cause discomfort in the myofascial pain (OR = 1.003, 95% CI 1.000-1.006; p < .05) and dentoalveolar region (OR = 1.001, 95% CI 1.000-1.002; p < .05), respectively. CONCLUSIONS: In conclusion, this MR study indicates that genetically predicted myofascial pain was significantly associated with decreased UA and dentoalveolar pain was significantly associated with increased GST level. SLC2A9 inhibitor and GSTA2 inhibitor were novel chronic orofacial pain therapies and biomarkers, but clinical trials are called to examine if these oxidative biomarkers have the protective effect against orofacial pain, and further research are needed to explore the underlying mechanisms.
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Biomarcadores , Dolor Crónico , Dolor Facial , Análisis de la Aleatorización Mendeliana , Estrés Oxidativo , Polimorfismo de Nucleótido Simple , Humanos , Dolor Facial/genética , Dolor Facial/fisiopatología , Dolor Crónico/genética , Dolor Crónico/metabolismo , Glutatión Transferasa/genética , Ácido Úrico/sangreRESUMEN
Herein, we report a synthesis of cyclohexanones bearing multi-continuous stereocenters by combining copper-catalyzed asymmetric conjugate addition of dialkylzinc reagents to cyclic enones with iridium-catalyzed asymmetric allylic substitution reaction. Good to excellent yields, diastereoselectivity and enantioselectivity can be obtained. Unlike the stereodivergent construction of adjacent stereocenters (1,2-position) reported in the literature, the current reaction can achieve the stereodivergent construction of nonadjacent stereocenters (1,3-position) by a proper combination of two chiral catalysts with different enantiomers.
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Recognition of structure prototypes from tremendous known inorganic crystal structures has been an important subject beneficial for materials science research and new materials design. The existing databases of inorganic crystal structure prototypes were mostly constructed by classifying materials in terms of the crystallographic space group information. Herein, we employed a distinct strategy to construct the inorganic crystal structure prototype database, relying on the classification of materials in terms of local atomic environments (LAEs) accompanied by unsupervised machine learning method. Specifically, we adopted a hierarchical clustering approach onto all experimentally known inorganic crystal structure data to identify structure prototypes. The criterion for hierarchical clustering is the LAE represented by the state-of-the-art structure fingerprints of the improved bond-orientational order parameters and the smooth overlap of atomic positions. This allows us to build up a LAE-based Inorganic Crystal Structure Prototype Database (LAE-ICSPD) containing 15,613 structure prototypes with defined stoichiometries. In addition, we have developed a Structure Prototype Generator Infrastructure (SPGI) package, which is a useful toolkit for structure prototype generation. Our developed SPGI toolkit and LAE-ICSPD are beneficial for investigating inorganic materials in a global way as well as accelerating the materials discovery process in the data-driven mode.
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Correction for 'A first-principles study of the stability, electronic structure, and optical properties of halide double perovskite Rb2Sn1-xTexI6 for solar cell applications' by Muhammad Faizan et al., Phys. Chem. Chem. Phys., 2021, 23, 4646-4657, DOI: 10.1039/D0CP05827K.
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Owing to their emerging role in solar cell technology, lead halide perovskites have aroused significant research interest in the recent past. However, due to its obvious toxicity, looking for a potential alternative to lead is becoming one of the most important pursuits in present times. We present our work based on density functional theory (DFT) investigating lead free defect perovskites (Rb2Sn1-xTexI6 (0 ≤x≤ 1)). In particular, we explore the crystal structure, thermodynamic stability, electronic structure, and optical properties of Rb2Sn1-xTexI6 (0 ≤x≤ 1) as a function of increasing Te concentration. Our results show that the Sn-Te alloyed perovskites exhibit considerable stability, a suitable band gap, small effective mass, and excellent light absorption. Especially, Rb2Sn0.75Te0.25I6 and Rb2Sn0.50Te0.50I6 have a direct band gap of 1.35 and 1.44 eV, respectively, which is highly favorable for use in a single-junction photovoltaic cell. We hope that our work will arouse the interest of experimental as well as theoretical scientists for synthesizing new materials and/or exploring the Sn-Te mix as a potential substitute for lead in photovoltaic materials.
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Herein we report a Pd-catalyzed dearomative methoxyallylation of 3-nitroindoles with readily available allyl carbonates. Good yields (up to 86 %) and diastereoselectivity (up to >20:1 dr) are obtained for a wide range of substrates. The compatibility of gram-scale synthesis and the relatively low catalyst loading (down to 1â mol % of [Pd]) enhance the practicality of this method. The kinetic experiments indicate that the rate-determining step of this reaction is the nucleophilic attack of the alkoxide anion.
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Herein we report a catalytic asymmetric dearomatization reaction of electron-deficient heteroarenes with α-substituted isocyanoacetates through an interrupted Barton-Zard reaction. A range of optically active pyrrolo[3,4-b]indole derivatives was obtained in good yields (up to 97 %) with high stereoselectivities (up to >20:1 dr and 97 % ee), using a catalytic system consisting of a cinchona-derived amino-phosphine and silver oxide. This reaction features wide substrate scope and mild conditions, and provides a new strategy for developing asymmetric dearomatization reactions.
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Spirocyclic hexadienones with multiple stereogenic centers are frequently found in natural products but remain challenging targets to synthesize. Herein, we report the enantioselective desymmetrization of bisphenol derivatives via Ir-catalyzed allylic dearomatization reactions, affording spirocyclic hexadienone derivatives with up to three contiguous stereogenic centers in good yields (up to 90%) and excellent enantioselectivity (up to 99% ee). The high efficiency of this reaction is exemplified by the short reaction time (30 min), low catalyst loading (down to 0.2 mol %), and ability to perform the reaction on a gram-scale. The total syntheses of (+)-tatanan B and (+)-tatanan C were also realized using this Ir-catalyzed allylic dearomatization reaction as a key step.
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Dearomatization of anthranils with vinylcyclopropanes (VCPs) by Pd-catalyzed [4+3] cyclization reaction has been realized. In the presence of a catalytic amount of borane as an activator, bridged cyclic products were obtained in good to excellent yields with excellent stereoselectivities. By introducing a chiral PHOX ligand (L5), asymmetric dearomatization reactions of anthranils with vinylcyclopropanes proceeded with excellent enantioselectivity. Borane plays a key role for the reactivity, likely owing to the formation of a borane-anthranil complex which has been confirmed by NMR experiments.
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Myocardial infarction (MI)-induced impaired cardiomyocyte (CM) mitochondrial function and microenvironmental inflammatory cascades severely accelerate the progression of heart failure for compromised myocardial repair. Modulation of the crosstalk between CM mitochondrial DNA (mtDNA) and STING has been recently identified as a robust strategy in enhancing MI treatment, but remains seldom explored. To develop a novel approach that can address persistent myocardial injury using this crosstalk, we report herein construction of a biomimetic hydrogel system, Rb1/PDA-hydrogel comprised of ginsenoside Rb1/polydopamine nanoparticles (Rb1/PDA NPs)-loaded carboxylated chitosan, 4-arm-PEG-phenylboronic acid (4-arm-PEG-PBA), and 4-arm-PEG-dopamine (4-arm-PEG-DA) crosslinked networks. An optimized hydrogel formulation presents not only desired adhesion properties to the surface of the myocardium, but also adaptability for deep myocardial injection, resulting in ROS scavenging, CM mitochondrial function protection, M1 macrophage polarization inhibition through the STING pathway, and angiogenesis promotion via an internal-external spatial combination. The enhanced therapeutic efficiency is supported by the histological analysis of the infarcted area, which shows that the fibrotic area of the MI rats decreases from 58.4% to 5.5%, the thickness of the left ventricular wall increases by 1-fold, and almost complete recovery of cardiac function after 28 days of treatment. Overall, this study reported the first use of a strong adhesive and injectable hydrogel with mtDNA and STING signaling characteristics for enhanced MI treatment via an internal-external spatial combination strategy.
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ADN Mitocondrial , Hidrogeles , Infarto del Miocardio , Miocitos Cardíacos , Polímeros , Animales , Infarto del Miocardio/tratamiento farmacológico , Infarto del Miocardio/metabolismo , Hidrogeles/administración & dosificación , Hidrogeles/química , Miocitos Cardíacos/efectos de los fármacos , Miocitos Cardíacos/metabolismo , Masculino , Polímeros/química , Polímeros/administración & dosificación , Indoles/administración & dosificación , Indoles/química , Nanopartículas/administración & dosificación , Nanopartículas/química , Quitosano/química , Quitosano/administración & dosificación , Ratas Sprague-Dawley , Polietilenglicoles/química , Polietilenglicoles/administración & dosificación , Ratas , Proteínas de la Membrana , Especies Reactivas de Oxígeno/metabolismo , Ácidos Borónicos , GinsenósidosRESUMEN
In the post-Moore's law era, the progress of electronics relies on discovering superior semiconductor materials and optimizing device fabrication. Computational methods, augmented by emerging data-driven strategies, offer a promising alternative to the traditional trial-and-error approach. In this Perspective, we highlight data-driven computational frameworks for enhancing semiconductor discovery and device development by elaborating on their advances in exploring the materials design space, predicting semiconductor properties and optimizing device fabrication, with a concluding discussion on the challenges and opportunities in these areas.
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An asymmetric allylic dearomatization reaction of 1-nitro-2-naphthol derivatives with Morita-Baylis-Hillman (MBH) adducts has been developed. By utilizing Pd catalyst derived from Pd(OAc)2 and Trost ligand (R,R)-L1, the reaction proceeded smoothly in 1,4-dioxane at room temperature, affording substituted ß-naphthalenones in good yields (up to 92%) and enantioselectivity (up to 90% ee). A range of substituted 1-nitro-2-naphthols and MBH adducts were found to be compatible under the optimized conditions. This reaction provides a convenient method for the synthesis of enantioenriched 1-nitro-ß-naphthalenone derivatives.
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Fluorination of carbohydrates has been one of the strategies to increase their enzymatic and chemical stabilities and reduce their hydrophilicities, making this modification attractive for drug discovery purposes. The synthesis of monofluorinated carbohydrates was achieved under mild conditions by using SO2F2 as the deoxyfluorination reagent in the presence of a base without extra fluoride additives. This method features low toxicity, easy availability, low cost, and high efficiency and can be subjected to diverse sugar units.
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Transition metal alloys have emerged as promising catalysts for oxygen reduction/evolution reactions (ORR/OER) because of their intermetallic synergy and tunable redox properties. However, for alloy nanoparticles, it is quite challenging to suppress the self-aggregation and promote the bifunctional activity. Anchoring alloys in heteroatoms-doped carbon matrix with excellent electro-conductibility is a powerful strategy to form strongly-coupled alloy-carbon nanohybrids. Here, highly-dispersed NiFe alloys are evenly in-situ anchored on the surface of Co, N co-doped carbon nanotubes (NiFe/Co-N@CNTs) via a gravity-guided chemical vapor deposition and self-assembly strategy. Stably-structured NiFe/Co-N@CNTs possesses a tubular skeleton with diameters of 80-100 nm and a hydrophilic surface. For ORR, half-wave potential of NiFe/Co-N@CNTs (0.87 V vs RHE) is higher than that of Pt/C (0.85 V). Strong synergies between NiFe alloys and Co-Nx species facilitate the charge transfer on one-dimensional conductive structure to boost the 4e- ORR kinetics. For OER, NiFe/Co-N@CNTs has a lower overpotential (300 mV) than RuO2 (400 mV) at 10 mA cm-2 due to in-situ formation of highly-active NiOOH/FeOOH species (as indicated by in-situ X-ray diffraction) at the catalytic sites on NiFe alloy. Rechargeable Zn-air battery (ZAB) with NiFe/Co-N@CNTs-based air-cathode exhibits promising open-circuit potential (1.52 V) and charge-discharge cycling stability (350 h). This alloy-carbon integrating strategy is meaningful for promoting dispersion, activity and stability of non-noble metal alloys for oxygen electrocatalysis.