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Global warming will significantly affect grapevine growth and development. To analyze the effects of high temperature on the leaf tissue structure of grapevines in the field, 19 representative cultivars were selected from the grapevine germplasm resources garden in Turpan Research Institute of Agricultural Sciences, XAAS. Twelve tissue structure indexes of grapevine leaves, including the thickness of the upper epidermis (TUE), the thickness of palisade tissue (TPT), leaf vein (LV), the thickness of spongy tissue (TST), the thickness of the lower epidermis (TLE), stoma (St), guard cell (GC), cuticle (Cu), leaf tissue compactness (CTR) and leaf tissue porosity (SR), were measured during the natural high-temperature period in Turpan. The results showed significant differences in the leaf tissue structure of the 19 grapevine cultivars under natural high temperature. Based on the comprehensive comparative analysis of the leaf phenotype in the field, we identified that the leaves of some cultivars, including ‘Zaoxia Wuhe’, ‘Centennial Seedless’ and ‘Kyoho’ showed strong heat tolerance, whereas grapevine cultivars ‘Golden Finger’, ‘Shine Muscat’, ‘Flame Seedless’, ‘Bixiang Wuhe’ and ‘Thompson Seedless’ showed sensitivity to high temperature. We further evaluated the heat tolerance of different grapevine cultivars by principal component analysis and the optimal segmentation clustering of ordered samples. These findings provide a theoretical basis for adopting appropriate cultivation management measures to reduce the effect of high temperatures and offer fundamental knowledge for future breeding strategies for heat-tolerant grapevine varieties.

The electrochemical N2 reduction reaction (NRR) under ambient conditions is attractive in replacing the current Haber-Bosch process toward sustainable ammonia production. Metal-heteroatom-doped carbon-rich materials have emerged as the most promising NRR electrocatalysts. However, simultaneously boosting their NRR activity and selectivity remains a grand challenge, while the principle for precisely tailoring the active sites has been elusive. Herein, we report the first case of crystalline two-dimensional conjugated covalent organic frameworks (2D c-COFs) incorporated with M–N4–C centers as novel, defined, and effective catalysts, achieving simultaneously enhanced activity and selectivity of electrocatalytic NRR to ammonia. Such 2D c-COFs are synthesized based on metal-phthalocyanine (M = Fe, Co, Ni, Mn, Zn, and Cu) and pyrene units bonded by pyrazine linkages. Significantly, the 2D c-COFs with Fe–N4–C center exhibit higher ammonia yield rate (33.6 μg h–1 mgcat–1) and Faradaic efficiency (FE, 31.9%) at −0.1 V vs reversible hydrogen electrode than those with other M–N4–C centers, making them among the best NRR electrocatalysts (yield rate >30 μg h–1 mgcat–1 and FE > 30%). In situ X-ray absorption spectroscopy, Raman spectroelectrochemistry, and theoretical calculations unveil that Fe–N4–C centers act as catalytic sites. They show a unique electronic structure with localized electronic states at Fermi level, allowing for stronger interaction with N2 and thus faster N2 activation and NRR kinetics than other M–N4–C centers. Our work opens the possibility of developing metal–nitrogen-doped carbon-rich 2D c-COFs as superior NRR electrocatalyst and provides an atomic understanding of the NRR process on M–Nx–C based electrocatalysts for designing high-performance NRR catalysts.

The electrocatalytic oxygen reduction reaction (ORR) is the vital process at the cathode of next-generation electrochemical storage and conversion technologies, such as metal–air batteries and fuel cells. Single-metal-atom and nitrogen co-doped carbonaceous electrocatalysts (M–N–C) have emerged as attractive alternatives to noble-metal platinum for catalyzing the kinetically sluggish ORR due to their high electrical conductivity, large surface area, and structural tunability at the atomic level, however, their application is limited by the low intrinsic activity of the metal–nitrogen coordination sites (M–Nx) and inferior site density. In this Perspective, we summarize the recent progress and milestones relating to the active site engineering of single atom carbonous electrocatalysts for enhancing the ORR activity. Particular emphasis is placed on the emerging strategies for regulating the electronic structure of the single metal site and populating the site density. In addition, challenges and perspectives are provided regarding the future development of single atom carbonous electrocatalysts for the ORR and their utilization in practical use., This Perspective summarizes and highlights the recent progress and milestones relating to the active site engineering of single atom carbonous electrocatalysts for enhancing the electrocatalytic oxygen reduction reaction activity.

Exploring efficient electrocatalysts for the oxygen reduction reaction (ORR) is key to realize the application of fuel cells and metal–air batteries. Identifying the key intermediate and optimizing its adsorption have been a valued approach to guide the catalyst development. Here, based on the linear scaling relation between the adsorption free energy of intermediates and the finding that the antibonding state promotes the adsorption of intermediates, we rationally propose a design concept of ORR electrocatalysts: the electron donating element is applied to regulate the bonding–antibonding property, promote the electron transfer from the active site to adsorbates, optimize the adsorption of intermediates, and thus enhance the ORR activity. The calculation results indiate that B-doped Ni–N4 systems (Ni–N4–B) possess a stronger antibonding state than the Ni–N4 structure, exhibiting superior ORR activity. In particular, the Ni–N4–2B-2 nanoribbon shows a lower theoretical overpotential (0.35 V). The two-fold coordinated B doping can induce the transformation from the bonding state to the antibonding state of the Ni–N bond accompanied by the optimization of multiple descriptors towards the ORR including a higher charge and spin density, a larger d-band center value, a narrower d-bandwidth and a weaker coordination strength of Ni–N, thus greatly enhancing the electrocatalytic activity.

2D conjugated metal-organic frameworks (2D c-MOFs) are emerging as electroactive materials for chemiresistive sensors, but selective sensing with fast response/recovery is a challenge. Phthalocyanine-based Ni

A highly effective electrocatalyst is the central component of advanced electrochemical energy conversion. Recently, two-dimensional conjugated metal-organic frameworks (2D c-MOFs) have emerged as a class of promising electrocatalysts because of their advantages including 2D layered structure with high in-plane conjugation, intrinsic electrical conductivity, permanent pores, large surface area, chemical stability, and structural diversity. In this Review, we summarize the recent advances of 2D c-MOF electrocatalysts for electrochemical energy conversion. First, we introduce the chemical design principles and synthetic strategies of the reported 2D c-MOFs, as well as the functional design for the electrocatalysis. Subsequently, we present the representative 2D c-MOF electrocatalysts in various electrochemical reactions, such as hydrogen/oxygen evolution, and reduction reactions of oxygen, carbon dioxide, and nitrogen. We highlight the strategies for the structural design and property tuning of 2D c-MOF electrocatalysts to boost the catalytic performance, and we offer our perspectives in regard to the challenges to be overcome.

In viticulture, grafting has been practiced widely and influences grape development as well as berry and wine quality. However, there is limited understanding of the effects of rootstocks on grape phenolic compounds, which are located primarily in the berry skin and contribute to certain sensory attributes of wine. In this study, scion–rootstock interactions were investigated at the green-berry stage and the veraison stage when grapevines were hetero-grafted with three commonly used rootstock genotypes (5BB, 101-14MG, and SO4). Physiological investigations showed that hetero-grafts, especially CS/5BB, contained higher concentrations of total proanthocyanidins (PAs) and various PA components in berry skins compared with the auto-grafted grapevines. Further metabolomics analysis identified 105 differentially accumulated flavonoid compounds, the majority of which, including anthocyanins, PAs, and flavonols, were significantly increased in the berry skins of hetero-grafted grapevines compared with auto-grafted controls. In addition, transcriptomic analysis of the same samples identified several thousand differentially expressed genes between hetero-grafted and auto-grafted vines. The three rootstocks not only increased the transcript levels of stilbene, anthocyanin, PA, and flavonol synthesis genes but also affected the expression of numerous transcription factor genes. Taken together, our results suggest that hetero-grafting can promote phenolic compound accumulation in grape berry skin during development. These findings provide new insights for improving the application value of grafting by enhancing the accumulation of nutritious phenolic components in grape.

Grafting, which joins a scion from a cultivar with the stem of a rootstock from a grapevine wild relative, is commonly used in viticulture. Grafting has crucial effects on various phenotypes of the cultivar, including its phenology, biotic and abiotic resistance, berry metabolome, and coloration, but the underlying genetics and regulatory mechanisms are largely unexplored. In this study, we investigated the phenotypic, metabolomic, and transcriptomic profiles at three developmental stages (45, 75, and 105 days after flowering) of the Crimson Seedless cultivar (Vitis vinifera) grafted onto four rootstocks (three heterografts, CS/101-14, CS/SO4, and CS/110R and one self-graft, CS/CS) with own-rooted graft-free Crimson Seedless (CS) as the control. All the heterografts had a significant effect on berry reddening as early as ~45 days after flowering. The grafting of rootstocks promoted anthocyanin biosynthesis and accumulation in grape berries. The metabolomic features showed that cyanidin 3-O-glucoside, delphinidin 3-O-glucoside, malvidin 3-O-glucoside, peonidin 3-O-glucoside, and petunidin 3-O-glucoside were the pigments responsible for the purplish-red peel color. Transcriptomic analyses revealed that anthocyanin biosynthesis-related genes, from upstream (phenylalanine ammonia-lyase) to downstream (anthocyanidin 3-O-glucosyltransferase and anthocyanidin synthase), were upregulated with the accumulation of anthocyanins in the heterografted plants. At the same time, all these genes were also highly expressed and more anthocyanin was accumulated in self-grafted CS/CS samples compared with own-rooted graft-free CS samples, suggesting that self-grafting may also have promoted berry reddening in grapevine. Our results reveal global transcriptomic and metabolomic features in berry color regulation under different grafting conditions that may be useful for improving berry quality in viticulture.

Background Acute lung injury is an important factor that leads to the death of patients with pneumonia. Previous studies have shown that nicotinamide (NAM) plays a role in reducing cell damage, so this study explored the mechanism by which NAM functions in acute lung injury. Methods We explored the mechanism by which NAM affects acute lung injury in vivo and in vitro by qRT-PCR, western blotting and ELISA. Results The results showed that NAM could significantly reduce lung injury and proinflammatory mediator accumulation. Further mechanistic studies showed that NAM could significantly inhibit the MAPK and AKT/NF-κB signaling pathways. Conclusion These results suggested that NAM may reduce the release of proinflammatory mediators by inhibiting the MAPK and AKT/NF-κB signaling pathways and ultimately alleviate lung injury.

In recent years a massive increase in publications on conventional 2D materials (graphene, h-BN, MoS2) is documented, accompanied by the transfer of the 2D concept to porous (crystalline) materials, such as ordered 2D layered polymers, covalent-organic frameworks, and metal–organic frameworks. Over the years, the 3D frameworks have gained a lot of attention for use in applications, ranging from electronic devices to catalysis, and from information to separation technologies, mostly due to the modular construction concept and exceptionally high porosity. A key challenge lies in the implementation of these materials into devices arising from the deliberate manipulation of properties upon delamination of their layered counterparts, including an increase in surface area, higher diffusivity, better access to surface sites and a change in the band structure. Within this minireview, we would like to highlight recent achievements in the synthesis of 2D framework materials and their advantages for certain applications, and give some future perspectives., In recent years the 2D concept has been transferred from conventional 2D materials to porous 2D framework materials. This minireview takes a closer look onto the preparation of 2D framework materials and their merits for energy applications.

Layered two-dimensional (2D) conjugated metal-organic frameworks (MOFs) represent a family of rising electrocatalysts for the oxygen reduction reaction (ORR), due to the controllable architectures, excellent electrical conductivity, and highly exposed well-defined molecular active sites. Herein, we report a copper phthalocyanine based 2D conjugated MOF with square-planar cobalt bis(dihydroxy) complexes (Co-O4 ) as linkages (PcCu-O8 -Co) and layer-stacked structures prepared via solvothermal synthesis. PcCu-O8 -Co 2D MOF mixed with carbon nanotubes exhibits excellent electrocatalytic ORR activity (E1/2 =0.83 V vs. RHE, n=3.93, and jL =5.3 mA cm-2 ) in alkaline media, which is the record value among the reported intrinsic MOF electrocatalysts. Supported by in situ Raman spectro-electrochemistry and theoretical modeling as well as contrast catalytic tests, we identified the cobalt nodes as ORR active sites. Furthermore, when employed as a cathode electrocatalyst for zinc-air batteries, PcCu-O8 -Co delivers a maximum power density of 94 mW cm-2 , outperforming the state-of-the-art Pt/C electrocatalysts (78.3 mW cm-2 ).

A simple, one-step and amplified Hg2+ detection strategy based on DNAzyme motor was described here. Fluorophore labeled DNA probes and long arm DNA are immobilized on the AuNPs by Au-S bond. The fluorescent signal of DNA probe is significantly quenched by AuNPs. In the presence of Hg2+, thymine-Hg2+-thymine (T-Hg2+-T) interaction can causes the duplex structure of split E-DNA and then form an entire E-DNA. Then the E-DNA can bind with fluorophore labeled DNA to form Mg2+-dependent DNAzyme structure. With the assistance of Mg2+, the fluorophore labeled DNA can be circularly cleaved by DNAzyme and then leave from the AuNPs surface. The recycling cleavage and binding processes caused processive moving of E-DNA on AuNPs surface and significant fluorescent signal recovery. A good linear relationship was obtained between fluorescence intensity and Hg2+ concentration in the range from 0.1 nM to 5 nM. The limit of detection was calculated to be 30 pM. This strategy was successfully used for detection of Hg2+ in Chinese herbs (Atractylodes macrocephala Koidz), showing a promising practical application future.

Large blue rectangular crystals of the 2D layered coordination polymer 1 have been obtained. The interest for this complex is two-fold. First, complex 1 is made of 2D layers packing along the (0–11) direction favored by the presence of lattice and coordinated water molecules. And second, nanostructures that could be derived by delamination are potentially suitable for catalytic purposes. Therefore it represents an excellent example to study the role of interlayer solvent molecules on the ultrasound-assisted delamination of functionally-active 2D metal-organic frameworks in water, a field of growing interest. With this aim, ultrasound-assisted delamination of the crystals was optimized with time, leading to stable nanosheet colloidal water suspensions with very homogeneous dimensions. Alternative bottom-up synthesis of related nanocrystals under ultrasound sonication yielded similar shaped crystals with much higher size dispersions. Finally, experimental results evidence that the nanostructures have higher catalytic activities in comparison to their bulk counterparts, due to larger metallic center exposition. These outcomes confirm that the combination of liquid phase exfoliation and a suitable synthetic design of 2D coordination polymers represents a very fruitful approach for the synthesis of functional nanosheets with an enhancement of catalytic active sites, and in general, with boosted functional properties., This work was supported by grant RTI2018-098027-B-C21 from the Spanish Government funds and by the European Regional Development Fund (ERDF). The ICN2 is funded by the CERCA programme/Generalitat de Catalunya. The ICN2 is supported by the Severo Ochoa Centres of Excellence programme, funded by the Spanish Research Agency (AEI, grant no. SEV-2017-0706). Noemí Contreras Pereda’s project that gave rise to these results received the support of a fellowship from “laCaixa” Foundation (ID 100010434). The fellowship code is LCF/BQ/ES17/11600012. Renhao Dong acknowledgements the financial support from ERC Starting Grant (FC2DMOF, No. 852909) and DFG project (SPP 1928, COORNETs).

Two-dimensional conjugated covalent organic frameworks (2D

Correction to: Nature Communications https://doi.org/10.1038/s41467-020-15141-y, published online 16 March 2020. The original version of this Article did not acknowledge Renhao Dong as a corresponding author. This has now been corrected in both the PDF and HTML versions of the Article.

Electrocatalytic oxygen reduction reaction (ORR) is the vital process for next-generation electrochemical energy storage and conversion technologies, e.g., metal-air batteries and fuel cells. During the ORR, the O-2* and O* intermediates principally combine with protons to form OOH* and OH* species, respectively, which are the proton-coupled electron transfer processes. Unfortunately, under alkaline conditions, the protons are essentially generated from the sluggish water dissociation process, which unavoidably limits the ORR kinetics. Herein, we design and synthesize a nitrogen-doped hierarchically porous carbon with homogeneously distributed ultrafine alpha-MoC nanoparticles (alpha-MoC/NHPC) as a model electrocatalyst. Theoretical investigations unveil that alpha-MoC on NHPC could efficiently reduce the energy barrier of the water dissociation process to generate protons, eventually promoting the proton-coupled ORR kinetics. In a 0.1 M KOH aqueous solution, alpha-MoC/NHPC exhibits excellent ORR performance with a high half-wave potential of 0.88 V (vs. reversible hydrogen electrode), which outperforms those for NHPC and commercial Pt/C. Moreover, as the air electrode in a zinc-air battery, alpha-MoC/NHPC presents a large peak power density of 200.3 mW cm(-2)and long-term stability. Thereby, our approach to engineering proton-feeding centers paves a new avenue towards the understanding of ORR kinetics and the development of high-performance ORR electrocatalysts.

Highly effective electrocatalysts promoting CO2 reduction reaction (CO2RR) is extremely desirable to produce value-added chemicals/fuels while addressing current environmental challenges. Herein, we develop a layer-stacked, bimetallic two-dimensional conjugated metal-organic framework (2D c-MOF) with copper-phthalocyanine as ligand (CuN4) and zinc-bis(dihydroxy) complex (ZnO4) as linkage (PcCu-O8-Zn). The PcCu-O8-Zn exhibits high CO selectivity of 88%, turnover frequency of 0.39 s−1 and long-term durability (>10 h), surpassing thus by far reported MOF-based electrocatalysts. The molar H2/CO ratio (1:7 to 4:1) can be tuned by varying metal centers and applied potential, making 2D c-MOFs highly relevant for syngas industry applications. The contrast experiments combined with operando spectroelectrochemistry and theoretical calculation unveil a synergistic catalytic mechanism; ZnO4 complexes act as CO2RR catalytic sites while CuN4 centers promote the protonation of adsorbed CO2 during CO2RR. This work offers a strategy on developing bimetallic MOF electrocatalysts for synergistically catalyzing CO2RR toward syngas synthesis., Effective electrocatalyst is crucial in promoting CO2 reduction to address current energy/environmental issue. Here, the authors develop bimetallic layered two-dimensional conjugated metal-organic framework to synergistically and efficiently electro-catalyze CO2 to CO toward syngas synthesis.

A novel fluorescent and colorimetric strategy with enzyme-free dual amplification was developed for ultra-sensitively detection of uranyl in river waters samples. The enzyme-strand recycling and hairpin catalytic assembly (HCA) reaction were used as dual enzyme-free amplification strategies. Three hairpins labeled with fluorophore can absorb on the surface of gold nanoparticles (AuNPs) to prevent them from aggregation in salt solution and quench the fluorescent signal simultaneously. In the presence of UO22+, the HCA reaction between hairpins was induced to form rigid DNA triangles, resulting in the aggregation of AuNPs with a red to blue color change and a “turn-on” fluorescent signal. The limit of detection was as low as 0.1 pM. Importantly, this strategy provided colorimetric and fluorescent dual signals for lower false-positives and higher anti-interference ability. It was successfully used for detection of uranyl in real waters samples.

Herein, a fast and visible colorimetric method for bisphenol A (BPA) detection was developed using hemin-functionalized reduced graphene oxide (H–rGO) composites and aptamer. The aptamer can be stably adsorbed on the surface of H–rGO, preventing H–rGO from salt-induced aggregation. However, in the presence of BPA, the aptamer can bind with BPA; this results in the aggregation of H–rGO. Consequently, the supernatant contains a little H–rGO and shows light blue color after the chromogenic reaction. The color difference can be used for the quantitative detection of BPA. The designed aptasensor displayed a linear response for BPA in the range from 5 nM to 100 nM with a detection limit of 2 nM. This colorimetric aptasensing platform offered great advantages, including label-free conditions and visible result readout platform, for quick screening of BPA for on-site analysis and in-house diagnosis.