Apple (Malus × domestica) trees are vulnerable to freezing temperatures. However, there has been only limited success in developing cold-hardy cultivars. This lack of progress is due at least partly to lack of understanding of the molecular mechanisms of freezing tolerance in apple. In this study, we evaluated the potential roles for two R2R3 MYB transcription factors (TFs), MYB88 and the paralogous FLP (MYB124), in cold stress in apple and Arabidopsis. We found that MYB88 and MYB124 positively regulate freezing tolerance and cold-responsive gene expression in both apple and Arabidopsis. Chromatin-Immunoprecipitation-qPCR and electrophoretic mobility shift assays showed that MdMYB88/MdMYB124 act as direct regulators of the COLD SHOCK DOMAIN PROTEIN 3 (MdCSP3) and CIRCADIAN CLOCK ASSOCIATED 1 (MdCCA1) genes. Dual luciferase reporter assay indicated that MdCCA1 but not MdCSP3 activated the expression of MdCBF3 under cold stress. Moreover, MdMYB88 and MdMYB124 promoted anthocyanin accumulation and H O detoxification in response to cold. Taken together, our results suggest that MdMYB88 and MdMYB124 positively regulate cold hardiness and cold-responsive gene expression under cold stress by C-REPEAT BINDING FACTOR (CBF)-dependent and CBF-independent pathways.
Non-precious-metal or metal-free catalysts with stability are desirable but challenging for proton exchange membrane fuel cells. Here we partially unzip a multiwall carbon nanotube to synthesize zigzag-edged graphene nanoribbons with a carbon nanotube backbone for electrocatalysis of oxygen reduction in proton exchange membrane fuel cells. Zigzag carbon exhibits a peak areal power density of 0.161 W cm−2 and a peak mass power density of 520 W g−1, superior to most non-precious-metal electrocatalysts. Notably, the stability of zigzag carbon is improved in comparison with a representative iron-nitrogen-carbon catalyst in a fuel cell with hydrogen/oxygen gases at 0.5 V. Density functional theory calculation coupled with experimentation reveal that a zigzag carbon atom is the most active site for oxygen reduction among several types of carbon defects on graphene nanoribbons in acid electrolyte. This work demonstrates that zigzag carbon is a promising electrocatalyst for low-cost and durable proton exchange membrane fuel cells.
Simultaneously increasing the activity and stability of the single-atom active sites of M–N–C catalysts is critical but remains a great challenge. Here, we report an Fe–N–C catalyst with nitrogen-coordinated iron clusters and closely surrounding Fe–N4 active sites for oxygen reduction reaction in acidic fuel cells. A strong electronic interaction is built between iron clusters and satellite Fe–N4 due to unblocked electron transfer pathways and very short interacting distances. The iron clusters optimize the adsorption strength of oxygen reduction intermediates on Fe–N4 and also shorten the bond amplitude of Fe–N4 with incoherent vibrations. As a result, both the activity and stability of Fe–N4 sites are increased by about 60% in terms of turnover frequency and demetalation resistance. This work shows the great potential of strong electronic interactions between multiphase metal species for improvements of single-atom catalysts.
The active sites of Fe–N–C catalysts are nitrogen coordinated iron atoms, FeNx(x = 1–5), that have five possible coordination numbers, corresponding to different ORR activities and PEMFC performances.
The surprising properties of biomaterials are the results of billions of years of evolution. Generally, biomaterials are assembled under mild conditions with very limited supply of constituents available for living organism, and their amazing properties largely result from the sophisticated hierarchical structures. Following the biomimetic principles to prepare manmade materials has drawn great research interests in materials science and engineering. In this review, we summarize the recent progress in fabricating bioinspired materials with the emphasis on mimicking the structure from one to three dimensions. Selected examples are described with a focus on the relationship between the structural characters and the corresponding functions. For one-dimensional materials, spider fibers, polar bear hair, multichannel plant roots and so on have been involved. Natural structure color and color shifting surfaces, and the antifouling, antireflective coatings of biomaterials are chosen as the typical examples of the two-dimensional biomimicking. The outstanding protection performance, and the stimuli responsive and self-healing functions of biomaterials based on the sophisticated hierarchical bulk structures are the emphases of the three-dimensional mimicking. Finally, a summary and outlook are given.
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