ABSTRACT
Pyrethroid pesticides (PYRs) have found widespread application in agriculture for the protection of fruit and vegetable crops. Nonetheless, excessive usage or improper application may allow the residues to exceed the safe limits and pose a threat to consumer safety. Thus, there is an urgent need to develop efficient technologies for the elimination or trace detection of PYRs from vegetables. Here, a simple and efficient magnetic solid-phase extraction (MSPE) strategy was developed for the simultaneous purification and enrichment of five PYRs in vegetables, employing the magnetic covalent organic framework nanomaterial COF-SiO2@Fe3O4 as an adsorbent. COF-SiO2@Fe3O4 was prepared by a straightforward solvothermal method, using Fe3O4 as a magnetic core and benzidine and 3,3,5,5-tetraaldehyde biphenyl as the two building units. COF-SiO2@Fe3O4 could effectively capture the targeted PYRs by virtue of its abundant π-electron system and hydroxyl groups. The impact of various experimental parameters on the extraction efficiency was investigated to optimize the MSPE conditions, including the adsorbent amount, extraction time, elution solvent type and elution time. Subsequently, method validation was conducted under the optimal conditions in conjunction with gas chromatography-mass spectrometry (GC-MS). Within the range of 5.00-100 µg·kg-1 (1.00-100 µg·kg-1 for bifenthrin and 2.5-100 µg·kg-1 for fenpropathrin), the five PYRs exhibited a strong linear relationship, with determination coefficients ranging from 0.9990 to 0.9997. The limits of detection (LODs) were 0.3-1.5 µg·kg-1, and the limits of quantification (LOQs) were 0.9-4.5 µg·kg-1. The recoveries were 80.2-116.7% with relative standard deviations (RSDs) below 7.0%. Finally, COF-SiO2@Fe3O4, NH2-SiO2@Fe3O4 and Fe3O4 were compared as MSPE adsorbents for PYRs. The results indicated that COF-SiO2@Fe3O4 was an efficient and rapid selective adsorbent for PYRs. This method holds promise for the determination of PYRs in real samples.
Subject(s)
Pesticides , Pyrethrins , Silicon Dioxide , Solid Phase Extraction , Vegetables , Solid Phase Extraction/methods , Silicon Dioxide/chemistry , Vegetables/chemistry , Pyrethrins/isolation & purification , Pyrethrins/analysis , Pyrethrins/chemistry , Pesticides/isolation & purification , Pesticides/chemistry , Pesticides/analysis , Gas Chromatography-Mass Spectrometry , Adsorption , Food Contamination/analysis , Limit of Detection , Pesticide Residues/analysis , Pesticide Residues/isolation & purification , Ferric Compounds/chemistry , CobaltABSTRACT
Natural gas hydrates (NGHs) hold immense potential as a future energy resource and for sustainable applications such as gas capture and storage. Due to the challenging formation conditions, however, their mechanical properties remain poorly understood. Herein, the mechanical characteristics of tetrahydrofuran (THF) hydrates, a proxy for methane hydrates, were investigated at different ice contents, strain rates, and temperatures using uniaxial compressive experiments. The results unveil a distinct behavior in the peak strength of THF hydrates with a varying ice content, strain rate and temperature, exhibiting an increase as the strain rate and temperature decrease, in contrast to the peak strength-strain rate relationship observed in polycrystalline ice. Based on the experimental data, four machine learning (ML) models including extreme gradient boosting (XGboost), multilayer perceptron (MLP), gradient boosting decision tree (GBDT) and decision tree (DT) were developed to predict the peak strength. The XGboost model demonstrates superior predictive performance, emphasizing the significant influence of ice content and temperature on the peak strength of hydrates. Furthermore, molecular dynamics (MD) simulations were employed to gain insights into the dissociation and formation processes of clathrate cages, as well as phase transitions and amorphization occurring at grain boundaries (GBs) involving diverse unconventional clathrate cages, including 51265, 4151062, 4151064, 425861 and 425862, with 425861 and 425862 cages being predominant. This study enhances our understanding of the mechanical properties and deformation mechanisms of hydrates and provides a ML-based predictive framework for estimating the compressive strength of hydrates under diverse coupling conditions. The findings have significant implications for stability assessments of NGHs and the exploitation of NGH resources.
ABSTRACT
Trichothecene (TCN) contamination in food and feed is a serious challenge due to the negative health and economic impacts. Here, we confirmed that the glutathione S-transferase (GST) Fhb7-GST could broadly catalyze type A, type B and type D TCNs into glutathione epoxide adducts (TCN-13-GSHs). To evaluate the toxicity of TCN-13-GSH adducts, we performed cell proliferation assays in vitro, which demonstrated decreased cytotoxicity of the adducts. Moreover, in vivo assays (repeated-dose treatment in mice) confirmed that TCN-13-GSH adducts were dramatically less toxic than the corresponding TCNs. To establish whether TCN-13-GSH was metabolized back to free toxin during digestion, single-dose metabolic tests were performed in rats; DON-13-GSH was not hydrolyzed in vivo, but rather was quickly metabolized to another low-toxicity compound, DON-13-N-acetylcysteine. These results demonstrate the promise of Fhb7-GST as a candidate of detoxification enzyme potentially applied in TCN-contaminated agricultural samples, minimizing the detrimental effects of the mycotoxin.
Subject(s)
Glutathione Transferase , Trichothecenes , Rats , Mice , Animals , Glutathione Transferase/genetics , Glutathione Transferase/metabolism , Trichothecenes/toxicity , Trichothecenes/metabolism , Glutathione/metabolism , CatalysisABSTRACT
The thermal transport properties of five-fold twinned (5FT) germanium-silicon (Ge-Si) heteronanowires (h-NWs) with varying cross-sectional areas, germanium (Ge) domain ratios and heterostructural patterns are investigated using homogeneous nonequilibrium molecular dynamics (HNEMD) simulations. The results demonstrate a distinctive behavior in the thermal conductivity (κ) of 5FT-NWs, characterized by a "flipped" trend at a critical cross-sectional area. This behavior is attributed to the hydrodynamic phonon flow, arising from the normal three-phonon scattering process in the low-frequency region. In addition, the composition ratio of 5FT-NWs has a significant impact on reducing the κ of 5FT-NWs and suppressing the hydrodynamic effect. Intriguingly, as the homogeneous element domains are separated, stronger phonon hydrodynamic flows are observed in comparison to the adjacent homogeneous element domains. By analyzing various phonon properties, including phonon dispersion, three-phonon scattering rate, and phonon mean free path, critical insights into the origin of the differential κ in different 5FT-NW structures are provided. The findings deepen the understanding of the thermal transport properties of nanomaterials and hold implications for the design and development of nanoelectronics and thermoelectric devices.
ABSTRACT
Understanding the mechanical properties of CO2hydrate is crucial for its diverse sustainable applications such as CO2geostorage and natural gas hydrate mining. In this work, classic molecular dynamics (MD) simulations are employed to explore the mechanical characteristics of CO2hydrate with varying occupancy rates and occupancy distributions of guest molecules. It is revealed that the mechanical properties, including maximum stress, critical strain, and Young's modulus, are not only affected by the cage occupancy rate in both large 51262and small 512cages, but also by the distribution of guest molecules within the cages. Specifically, the presence of vacancies in the 51262large cages significantly impacts the overall mechanical stability compared to 512small cages. Furthermore, four distinct machine learning (ML) models trained using MD results are developed to predict the mechanical properties of CO2hydrate with different cage occupancy rates and cage occupancy distributions. Through analyzing ML results, as-developed ML models highlight the importance of the distribution of guest molecules within the cages, as crucial contributor to the overall mechanical stability of CO2hydrate. This study contributes new knowledge to the field by providing insights into the mechanical properties of CO2hydrates and their dependence on cage occupancy rates and cage occupancy distributions. The findings have implications for the sustainable applications of CO2hydrate, and as-developed ML models offer a practical framework for predicting the mechanical properties of CO2hydrate in different scenarios.
ABSTRACT
Wheat has a large and diverse repertoire of NLRs involved in disease resistance, with over 1500 NLRs detected in some studies. These NLR genes occur as singletons or clusters containing copies of NLRs from different phylogenetic clades. The number of NLRs and cluster size can differ drastically among ecotypes and cultivars. Primarily, duplication has led to the evolution and diversification of NLR genes. Among the various mechanisms, whole genome duplication (WGD) is the most intense and leading cause, contributing to the complex evolutionary history and abundant gene set of hexaploid wheat. Tandem duplication or recombination is another major mechanism of NLR gene expansion in wheat. The diversity and divergence of duplicate NLR genes are responsible for the broad-spectrum resistance of most plant species with limited R genes. Understanding the mechanisms underlying the rapid evolution and diversification of wheat NLR genes will help improve disease resistance in crops. The present review focuses on the diversity and divergence of duplicate NLR genes and their contribution to wheat disease resistance. Moreover, we provide an overview of disease resistance-associated gene duplication and the underlying strategies in wheat.
ABSTRACT
The oxygen evolution reaction (OER) is a key process in various energy storage/generation technologies. Tuning the electronic structures of catalysts is an effective approach to improve the catalyst's activity. In this work, we synthesized Ce-doped cobalt-organic frameworks with benzene-1, 4-dicarboxylic acid (BDC) as the ligand as efficient OER electrocatalysts (denoted as Co3Ce1 BDC) with excellent stability and improved catalytic performance. The introduced Ce in Co3Ce1 BDC changes the surface configuration and tunes electronic structures of the active Co site, leading to enhanced interaction between intermediates and catalysts. Besides, the specific surface area, reaction kinetics, charge transfer efficiency, and turnover frequency are also improved in the presence of Ce. As a result, the Co3Ce1 BDC demonstrated excellent performance with a low overpotential of 285 mV at a current of 10 mA·cm-2, a preferable Tafel slope of 56.1 mV·dec-1, and an excellent durability in 1 M KOH, indicating the potential for practical applications in water splitting and other energy storage technologies wherein the OER plays a critical role. Comprehensive theoretical calculations and modeling further identified the key role of Ce in modulating the electronic structure and OER activity of cobalt-organic frameworks. Most importantly, this work provides a new strategy to the development of efficient cobalt-organic framework catalysts in OER-related applications.
ABSTRACT
We propose an approach that can accurately predict the heat conductivity of liquid water. On the one hand, we develop an accurate machine-learned potential based on the neuroevolution-potential approach that can achieve quantum-mechanical accuracy at the cost of empirical force fields. On the other hand, we combine the Green-Kubo method and the spectral decomposition method within the homogeneous nonequilibrium molecular dynamics framework to account for the quantum-statistical effects of high-frequency vibrations. Excellent agreement with experiments under both isobaric and isochoric conditions within a wide range of temperatures is achieved using our approach.
ABSTRACT
Grain size is a key trait associated with bread wheat yield. It is also the most frequently selected trait during domestication. After the phenotypic characterization of 768 bread wheat accessions in three plots for at least two years, the present study shows that the improved variety showed significantly higher grain size but lower grain protein content than the landrace. Using 55K SNP assay genotyping and large-scale phenotyping population and GWAS data, we identified 5, 6, 6, and 6 QTLs associated with grain length, grain weight, grain area, and thousand grain weight, respectively. Seven of the 23 QTLs showed common association within different locations or years. Most significantly, the key locus associated with grain length, qGL-2D, showed the highest association after years of multi-plot testing. Haplotype and evolution analysis indicated that the superior allele of qGL-2D was mainly hidden in the improved variety rather than in landrace, which may contribute to the significant difference in grain length. A comprehensive analysis of transcriptome and homolog showed that TraesCS2D02G414800 could be the most likely candidate gene for qGL-2D. Overall, this study presents several reliable grain size QTLs and candidate gene for grain length associated with bread wheat yield.
ABSTRACT
Here, using homogeneous nonequilibrium molecular dynamics simulations, we report the thermal transport characteristics of thin Si nanowires (NWs) with varying size and isotope doping ratio. It is identified that crossover in the thermal conductivity (κ) of both isotope doping-free and isotope doped Si-NWs appears at critical sizes, below whichκis enlarged with decreasing size because the hydrodynamic phonon flow predominates, above which, due to the dominant phonon boundary scattering, opposite behavior is observed. With increasing isotope doping, however, the critical size in minimizing theκis moved to small values because the phonon impurity scattering caused by isotope doping is critically involved. Moreover, there is a critical isotope doping (<50%) in the critical size motion, originating from that, above which, the critical size no longer moves due to the persistence of hydrodynamic phonon flow. This study provides new insights into the thermal transport behaviors of quasi-1D structures.
ABSTRACT
Even frequently used in wheat breeding, we still have an insufficient understanding of the biology of the products via distant hybridization. In this study, a transcriptomic analysis was performed for six Triticum aestivum-Thinopyrum elongatum substitution lines in comparison with the host plants. All the six disomic substitution lines showed much stronger "transcriptomic-shock" occurred on alien genomes with 57.43-69.22% genes changed expression level but less on the recipient genome (2.19-8.97%). Genome-wide suppression of alien genes along chromosomes was observed with a high proportion of downregulated genes (39.69-48.21%). Oppositely, the wheat recipient showed genome-wide compensation with more upregulated genes, occurring on all chromosomes but not limited to the homeologous groups. Moreover, strong co-upregulation of the orthologs between wheat and Thinopyrum sub-genomes was enriched in photosynthesis with predicted chloroplastic localization, which indicates that the compensation happened not only on wheat host genomes but also on alien genomes.
ABSTRACT
BACKGROUND: Bread wheat (Triticum aestivum) is an important staple cereal grain worldwide. The ever-increasing environmental stress makes it very important to mine stress-resistant genes for wheat breeding programs. Therefore, dehydrin (DHN) genes can be considered primary candidates for such programs, since they respond to multiple stressors. RESULTS: In this study, we performed a genome-wide analysis of the DHN gene family in the genomes of wheat and its three relatives. We found 55 DHN genes in T. aestivum, 31 in T. dicoccoides, 15 in T. urartu, and 16 in Aegilops tauschii. The phylogenetic, synteny, and sequence analyses showed we can divide the DHN genes into five groups. Genes in the same group shared similar conserved motifs and potential function. The tandem TaDHN genes responded strongly to drought, cold, and high salinity stresses, while the non-tandem genes respond poorly to all stress conditions. According to the interaction network analysis, the cooperation of multiple DHN proteins was vital for plants in combating abiotic stress. CONCLUSIONS: Conserved, duplicated DHN genes may be important for wheat being adaptable to a different stress conditions, thus contributing to its worldwide distribution as a staple food. This study not only highlights the role of DHN genes help the Triticeae species against abiotic stresses, but also provides vital information for the future functional studies in these crops.
Subject(s)
Bread , Triticum , Gene Expression Regulation, Plant , Genome, Plant , Multigene Family , Phylogeny , Plant Breeding , Plant Proteins/genetics , Plant Proteins/metabolism , Stress, Physiological/genetics , Triticum/genetics , Triticum/metabolismABSTRACT
Glutathione S-transferases (GSTs) are ancient proteins encoded by a large gene family in plants, which play multiple roles in plant growth and development. However, there has been little study on the GST genes of common wheat (Triticum aestivum) and its relatives (Triticum durum, Triticum urartu, and Aegilops tauschii), which are four important species of Triticeae. Here, a genome-wide comprehensive analysis of this gene family was performed on the genomes of common wheat and its relatives. A total of 346 GST genes in T. aestivum, 226 in T. durum, 104 in T. urartu, and 105 in Ae. tauschii were identified, and all members were divided into ten classes. Transcriptome analysis was used to identify GST genes that respond to salt stress in common wheat, which revealed that the reaction of GST genes is not sensitive to low and moderate salt concentrations but is sensitive to severe concentrations of the stressor, and the GST genes related to salt stress mainly come from the Tau and Phi classes. Six GST genes which respond to different salt concentrations were selected and validated by a qRT-PCR assay. These findings will not only provide helpful information about the function of GST genes in Triticeae species but also offer insights for the future application of salt stress resistance breeding in common wheat.
ABSTRACT
KEY MESSAGE: A single dominant powdery mildew resistance gene MlNFS10 was identified in wild emmer wheat and mapped within a 0.3cM genetic interval spanning a 2.1Mb physical interval on chromosome arm 4AL. Wheat powdery mildew caused by Blumeria graminis forma specialis tritici (Bgt) is a globally devastating disease. The use of powdery mildew resistance genes from wild relatives of wheat is an effective method of disease management. Our previous research has shown that disruptive ecological selection has driven the discrete adaptations of the wild emmer wheat population on the south facing slope (SFS) and north facing slope (NFS) at the microsite of "Evolution Canyon" at Mount Carmel, Israel and demonstrated that 16 accessions in the NFS population display high resistance to 11 powdery mildew isolates (collected from different wheat fields in China). Here, we constructed bi-parental population by crossing the accession NFS-10 (resistant to 22 Bgt races collected from China in seedling resistance screen) and the susceptible line SFS2-12. Genetic analysis indicated that NFS-10 carries a single dominant gene, temporarily designated MlNFS10. Ultimately, 13 markers were successfully located within the long arm of chromosome 4A, thereby delineating MlNFS10 to a 0.3 cM interval covering 2.1 Mb (729275816-731365462) in the Chinese Spring reference sequence. We identified disease resistance-associated genes based on the RNA-seq analysis of both parents. The tightly linked InDel marker XWsdau73447 and SSR marker XWsdau72928 were developed and used for marker-assisted selection when MlNFS10 was introgressed into a hexaploid wheat background. Therefore, MlNFS10 can be used for improvement of germplasm in breeding programs for powdery mildew resistant cultivars.
Subject(s)
Ascomycota/physiology , Chromosome Mapping/methods , Disease Resistance/genetics , Gene Expression Regulation, Plant , Plant Diseases/genetics , Plant Proteins/genetics , Triticum/genetics , Chromosomes, Plant/genetics , Disease Resistance/immunology , Genetic Linkage , Genetic Markers , Plant Diseases/microbiology , Triticum/immunology , Triticum/microbiologyABSTRACT
Molecular dynamics studies have revealed that the nucleation pathway of clathrate hydrates involves the evolution from amorphous to crystalline hydrates. In this study, complete cages are further classified into the standard edge-saturated cages (SECs) and nonstandard edge-saturated cages (non-SECs). Centered on studying the structure and evolution of non-SECs and SECs, we propose a novel and efficient algorithm, iterative cup overlapping (ICO), to monitor hydrate nucleation and growth in molecular simulations by identifying SECs and discuss possible causes of the instability of non-SECs. Manipulation of topological information makes it possible for ICO to avoid the repeated searches for identified cages and deduce all SECs with low time costs, improving the efficiency of identification significantly. The accuracy and efficiency of ICO were verified by comparing the identification results with other well-proven algorithms. Furthermore, it was found that non-SECs have short lifetimes and eventually decompose or reorganize into more stable structures. Some evidence suggests that the instability of non-SECs is closely related to the hydrogen-bonding configuration of water-ring aggregations that they contain. The spontaneous evolution of the hydrogen-bonding network into the tetrahedral network may be the main factor that causes the conversion of QWRAs and the evolution of non-SECs.
ABSTRACT
Fusarium head blight (FHB), a fungal disease caused by Fusarium species that produce food toxins, currently devastates wheat production worldwide, yet few resistance resources have been discovered in wheat germplasm. Here, we cloned the FHB resistance gene Fhb7 by assembling the genome of Thinopyrum elongatum, a species used in wheat distant hybridization breeding. Fhb7 encodes a glutathione S-transferase (GST) and confers broad resistance to Fusarium species by detoxifying trichothecenes through de-epoxidation. Fhb7 GST homologs are absent in plants, and our evidence supports that Th. elongatum has gained Fhb7 through horizontal gene transfer (HGT) from an endophytic Epichloë species. Fhb7 introgressions in wheat confers resistance to both FHB and crown rot in diverse wheat backgrounds without yield penalty, providing a solution for Fusarium resistance breeding.
Subject(s)
Disease Resistance/genetics , Epichloe/genetics , Fusarium/pathogenicity , Gene Transfer, Horizontal , Glutathione Transferase/genetics , Plant Diseases/microbiology , Triticum/genetics , Triticum/microbiology , Cloning, Molecular , Plant Breeding , Poaceae/geneticsABSTRACT
Plant epidermis serves important functions in shoot growth, plant defense and lipid metabolism, though mechanisms of related transcriptional regulation are largely unknown. Here, we identified cis-elements specific to shoot epidermis expression by dissecting the promoter of Triticum aestivum lipid transfer protein 1 (TaLTP1). A preliminary promoter deletion analysis revealed that a truncated fragment within 400 bp upstream from the translation start site was sufficient to confer conserved epidermis-specific expression in transgenic Brachypodium distachyon and Arabidopsis thaliana. Further, deletion or mutation of a GC(N4)GGCC motif at position -380 bp caused a loss of expression in pavement cells. With an electrophoretic mobility shift assay (EMSA) and transgenic reporter assay, we found that a light-responsive CcATC motif at position -268 bp was also involved in regulating pavement cell-specific expression that is evolutionary conserved. Moreover, expression specific to leaf trichome cells was found to be independently regulated by a CCaacAt motif at position -303 bp.
Subject(s)
Gene Expression Regulation, Plant , Plant Epidermis/genetics , Promoter Regions, Genetic , Triticum/genetics , Arabidopsis , Base Sequence , Brachypodium , Plant Epidermis/metabolism , Plants, Genetically Modified , Sequence Alignment , Sequence Analysis, DNAABSTRACT
In plants, the mechanism for ecological sympatric speciation (SS) is little known. Here, after ruling out the possibility of secondary contact, we show that wild emmer wheat, at the microclimatically divergent microsite of "Evolution Canyon" (EC), Mt. Carmel, Israel, underwent triple SS. Initially, it split following a bottleneck of an ancestral population, and further diversified to three isolated populations driven by disruptive ecological selection. Remarkably, two postzygotically isolated populations (SFS1 and SFS2) sympatrically branched within an area less than 30 m at the tropical hot and dry savannoid south-facing slope (SFS). A series of homozygous chromosomal rearrangements in the SFS1 population caused hybrid sterility with the SFS2 population. We demonstrate that these two populations developed divergent adaptive mechanisms against severe abiotic stresses on the tropical SFS. The SFS2 population evolved very early flowering, while the SFS1 population alternatively evolved a direct tolerance to irradiance by improved ROS scavenging activity that potentially accounts for its evolutionary fate with unstable chromosome status. Moreover, a third prezygotically isolated sympatric population adapted on the abutting temperate, humid, cool, and forested north-facing slope (NFS), separated by 250 m from the SFS wild emmer wheat populations. The NFS population evolved multiple resistant loci to fungal diseases, including powdery mildew and stripe rust. Our study illustrates how plants sympatrically adapt and speciate under disruptive ecological selection of abiotic and biotic stresses.
Subject(s)
Disease Resistance/genetics , Sympatry/genetics , Triticum/genetics , Ascomycota , Basidiomycota , Chromosomes, Plant , Gene Flow , Genes, Plant/genetics , Homozygote , Israel , Karyotyping , Plant Diseases/microbiology , Stress, PhysiologicalABSTRACT
KEY MESSAGE: Eight environmentally stable QTL for grain yield-related traits were detected by four RIL populations, and two of them were validated by a natural wheat population containing 580 diverse varieties or lines. Yield and yield-related traits are important factors in wheat breeding. In this study, four RIL populations derived from the cross of one common parent Yanzhan 1 (a Chinese domesticated cultivar) and four donor parents including Hussar (a British domesticated cultivar) and three semi-wild wheat varieties in China were phenotyped for 11 yield-related traits in eight environments. An integrated genetic map containing 2009 single-nucleotide polymorphism (SNP) markers generated from a 90 K SNP array was constructed to conduct quantitative trait loci (QTL) analysis. A total of 161 QTL were identified, including ten QTL for grain yield per plant (GYP) and yield components, 49 QTL for spike-related traits, 43 QTL for flag leaf-related traits, 22 QTL for plant height (PH), and 37 QTL for heading date and flowering date. Eight environmentally stable QTL were validated in individual RIL population where the target QTL was notably detected, and six of them had a significant effect on GYP. Furthermore, Two QTL, QSPS-2A.4 and QSL-4A.1, were also validated in a natural wheat population containing 580 diverse varieties or lines, which provided valuable resources for further fine mapping and genetic improvement in yield in wheat.
Subject(s)
Edible Grain/genetics , Quantitative Trait Loci , Triticum/genetics , Alleles , China , Chromosome Mapping , Chromosomes, Plant , Edible Grain/growth & development , Flowers/genetics , Flowers/growth & development , Flowers/physiology , Genetic Linkage , Genome, Plant , Genotype , Phenotype , Plant Breeding , Plant Leaves/genetics , Plant Leaves/growth & development , Plant Leaves/physiology , Polymorphism, Single Nucleotide , Triticum/growth & developmentABSTRACT
The fabrication of cost effective and efficient electrocatalysts with functional building blocks to replace noble metal ones is of great importance for energy related applications yet remains a great challenge. Herein, we report the fabrication of a hierarchical structure containing CNTs/graphene/transition-metal hybrids (h-NCNTs/Gr/TM) with excellent bifunctional oxygen electrocatalytic activity. The synthesis was rationally designed by the growth of shorter nitrogen-doped CNTs (S-NCNTs) on longer NCNTs arrays (L-NCNTs), while graphene layers were in situ generated at their interconnecting sites. The hybrid material shows excellent OER and ORR performance, and was also demonstrated to be a highly active bifunctional catalyst for Zn-air batteries, which could be due to rapid electron transport and full exposure of active sites in the hierarchical structure.