Symbiotic nitrogen fixation within nitrogen-fixing clade (NFC) plants is thought to have arisen from a single gain followed by massive losses in the genomes of ancestral non-nodulating plants. However, molecular evidence supporting this model is limited. Here, we confirm through bioinformatic analysis that NODULES WITH ACTIVATED DEFENSE1 (NAD1) is present only in NFC plants and is thus an NFC-specific gene.
View Article and Find Full Text PDFLegume-rhizobial symbiosis initiates the formation of root nodules, within which rhizobia reside and differentiate into bacteroids to convert nitrogen into ammonium, facilitating plant growth. This process raises a fundamental question: how is plant immunity modulated within nodules when exposed to a substantial number of foreign bacteria? In , a mutation in the () gene exclusively results in the formation of necrotic nodules combined with activated immunity, underscoring the critical role of in suppressing immunity within nodules. In this study, we employed a dual RNA-seq transcriptomic technology to comprehensively analyze gene expression from both hosts and symbionts in the mutant nodules at different developmental stages (6 dpi and 10 dpi).
View Article and Find Full Text PDFIntroducing an external visible-light field would be a promising strategy to improve the activity of the electrocatalytic CO reduction reaction (CORR), but it still remains a challenge due to the short excited-state lifetime of active sites. Herein, Ru(bpy)Cl struts as powerful photosensitive donors were immobilized into the backbones of Co-porphyrin-based covalent organic frameworks (named Co-Bpy-COF-Ru, is the molar ratio of Ru and Co species, = 1/2 and 2/3) via coordination bonds, for the photo-coupled CORR to produce CO. The optimal Co-Bpy-COF-Ru displays a high CO Faradaic efficiency of 96.
View Article and Find Full Text PDFWe propose an effective highest occupied d-orbital modulation strategy engendered by breaking the coordination symmetry of sites in the atomically precise Cu nanocluster (NC) to switch the product of CO electroreduction from HCOOH/CO to higher-valued hydrocarbons. An atomically well-defined Cu NC with symmetry-broken Cu-S N active sites (named Cu (MBD) , MBD=2-mercaptobenzimidazole) was designed and synthesized by a judicious choice of ligand containing both S and N coordination atoms. Different from the previously reported high HCOOH selectivity of Cu NCs with Cu-S sites, the Cu (MBD) with Cu-S N coordination structure shows a high Faradaic efficiency toward hydrocarbons of 65.
View Article and Find Full Text PDFThe photocatalytic conversion of CO into C products such as ethylene is a promising path toward the carbon neutral goal but remains a big challenge due to the high activation barrier for CO and similar reduction potentials of many possible multi-electron-transfer products. Herein, an effective tandem photocatalysis strategy has been developed to support conversion of CO to ethylene by construction of the synergistic dual sites in rhenium-(I) bipyridine -[Re(bpy)(CO)Cl] (Re-bpy) and copper-porphyrinic triazine framework [PTF(Cu)]. With these two catalysts, a large amount of ethylene can be produced at a rate of 73.
View Article and Find Full Text PDFWe present the first example of charged imidazolium functionalized porphyrin-based covalent organic framework (Co-iBFBim-COF-X) for electrocatalytic CO reduction reaction, where the free anions (e.g., F , Cl , Br , and I ) of imidazolium ions nearby the active Co sites can stabilize the key intermediate *COOH and inhibit hydrogen evolution reaction.
View Article and Find Full Text PDFConspectusThe continuing increase of the concentration of atmospheric CO has caused many environmental issues including climate change. Catalytic conversion of CO using thermochemical, electrochemical, and photochemical methods is a potential technique to decrease the CO concentration and simultaneously obtain value-added chemicals. Due to the high energy barrier of CO however, this method is still far from large-scale applications which requires high activity, selectivity, and stability.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
September 2021
The unique applications of porous metal-organic framework (MOF) liquids with permanent porosity and fluidity have attracted significant attention. However, fabrication of porous MOF liquids remains challenging because of the easy intermolecular self-filling of the cavity or the rapid settlement of porous hosts in hindered solvents that cannot enter their pores. Herein, we report a facile strategy for the fabrication of a MOF liquid (Im-UiO-PL) by surface ionization of an imidazolium-functionalized framework with a sterically hindered poly(ethylene glycol) sulfonate (PEGS) canopy.
View Article and Find Full Text PDFA new strategy to prepare soluble homogeneous catalysts is developed by introducing imidazolium into cationic calix[4]arene-based metal-organic cages (MOCs). The soluble MOCs show high activity and recyclability in the cycloaddition reaction of CO2 without the addition of any co-catalysts. This method provides new inspiration to design highly efficient catalysts by combining the advantages of homogeneous and heterogeneous catalysis.
View Article and Find Full Text PDFCovalent organic frameworks (COFs) are promising candidates for electrocatalytic reduction of carbon dioxide into valuable chemicals due to their porous crystalline structures and tunable single active sites, but the low conductivity leads to unmet current densities for commercial application. The challenge is to create conductive COFs for highly efficient electrocatalysis of carbon dioxide reduction reaction (CO RR). Herein, a porphyrin-based COF containing donor-acceptor (D-A) heterojunctions, termed TT-Por(Co)-COF, is constructed from thieno[3,2-b]thiophene-2,5-dicarbaldehyde (TT) and 5,10,15,20-tetrakis(4-aminophenyl)-porphinatocobalt (Co-TAPP) via imine condensation reaction.
View Article and Find Full Text PDFThree cationic capsule-shaped Zr-based metal-organic polyhedra (MOPs) with different cavity sizes were successfully constructed through the self-assembly of trinuclear zirconocene clusters and imidazolium-functionalized dicarboxylic ligands. Owing to the imidazolium groups in the MOPs, they show good CO adsorption uptake. Moreover, the halogen anions of the imidazolium groups and Brønsted acid sites (-OH) in the Zr-based knots are in close proximity, making these MOPs able to catalyze synergistically the cycloaddition reaction of CO with epoxides into cyclic carbonates.
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