This study aimed to elucidate the effects of arsenic species [As(III)/As(V)] and cadmium [Cd(II)] on nitrification and nitrogen fixation in soybean (Glycine max (L.) Merrill) cultivation, and to identify nitrogen cycle disruption mechanisms in realistic soil environments with a focus on soil-metal-plant-microbe interactions. We examined heavy metal(loid)s uptake in plant tissues, changes in nitrogen species in porewater, nitrogenase activity, the contents of essential trace metals (Mo and Fe) in nitrogenase, and nitrogen-related microbial communities.
View Article and Find Full Text PDFMountain ranges comprise heterogeneous environments and high plant diversity, but little is known about the architecture and structural complexity of trees in mountain forests. We studied the relationship between tree architecture, environmental conditions, and tree structural complexity in forests of the Annapurna region in the Himalaya. We further asked whether and how tree structural complexity translates into forest stand structural complexity.
View Article and Find Full Text PDFBackground: Plant senescence is the process of physiological maturation of plants and is important for crop yield and quality. Senescence is controlled by several factors, such as temperature and photoperiod. However, the molecular basis by which these genes promote senescence in soybeans is not well understood.
View Article and Find Full Text PDFGenomics Inform
October 2024
The molecular characterization of genetically modified organisms (GMOs) is essential for ensuring safety and gaining regulatory approval for commercialization. According to CODEX standards, this characterization involves evaluating the presence of introduced genes, insertion sites, copy number, and nucleotide sequence structure. Advances in technology have led to the increased use of next-generation sequencing (NGS) over traditional methods such as Southern blotting.
View Article and Find Full Text PDFInorganic phosphate (Pi) homeostasis plays an important role in plant growth and abiotic stress tolerance. Several MYB-CC transcription factors involved in Pi homeostasis have been identified in rice (). PHOSPHATE STARVATION RESPONSE-LIKE 7 (PHL7) is a class II MYC-CC protein, in which the MYC-CC domain is located at the N terminus.
View Article and Find Full Text PDFFront Plant Sci
December 2022
The plant hormone gibberellic acid (GA) is important for plant growth and productivity. Actin-related proteins (ARPs) also play central roles in plant growth, including cell elongation and development. However, the relationships between ARPs and GA signaling and biosynthesis are not fully understood.
View Article and Find Full Text PDFIn cultivated plants, shoot morphology is an important factor that influences crop economic value. However, the effects of gene expression patterns on shoot morphology are not clearly understood. In this study, the molecular mechanism behind shoot morphology (including leaf, stem, and node) was analyzed using RNA sequencing to compare weedy (creeper) and cultivar (stand) growth types obtained in F derived from a cross of wild and cultivated soybeans.
View Article and Find Full Text PDFPlant Signal Behav
December 2021
is a lycophyta species that survives under extremely dry conditions via the mechanism of resurrection. This phenomenon involves the regulation of numerous genes that play vital roles in desiccation tolerance and subsequent rehydration. To identify resurrection-related genes, we analyzed the transcriptome between dehydration conditions and rehydration conditions of .
View Article and Find Full Text PDFA copper-catalyzed carbochlorination of alkenes with aryl malononitriles and chloride is disclosed. This net oxidative transformation proceeds with activated and unactivated alkenes with moderate to excellent yields. Mechanism experiments suggest addition of the malononitrile radical to form a secondary carbon radical which is intercepted by a chloride source.
View Article and Find Full Text PDFWe describe herein a Cu(OTf) catalyzed oxidative arylation of a tertiary carbon-containing substrate including aryl malononitriles, 3-aryl benzofuran-2-ones, and 3-aryl oxindoles. In some cases, the nitrile groups of the aryl malononitriles undergo further reactions leading to lactones or imines. These reaction conditions are applicable for a range of arenes, including phenols, anilines, anisoles, and heteroarenes.
View Article and Find Full Text PDFWe disclose a transmetalation-initiated Ni(I)-catalyzed regioselective -vinylarylation of -alkenyl -cyanocarboxylic esters with vinyl triflates and arylzinc reagents. This reaction proceeds via contraction of six-membered nickellacycles to five-membered nickellacycles to form carbon-carbon bonds at the nonclassical homovicinal sites, and it provides expeditious access to a wide range of complex aliphatic -cyanoesters, -cyanocarboxylic acids, dicarboxylic acids, dicarboxylic acid monoamides, monocarboxylic acids, nitriles, and spirolactones. Control, deuterium labeling, and crossover experiments indicate that (i) the nickellacycle contraction occurs by -H elimination, followed by hydronickellation on transiently formed alkenes, and (ii) the Ni species are stabilized as Ni-enolates.
View Article and Find Full Text PDFWe disclose unprecedented synergistic bimetallic Ni/Ag and Ni/Cu catalysts for regioselective γ,δ-diarylation of unactivated alkenes in simple ketimines with aryl halides and arylzinc reagents. The bimetallic synergy, which generates cationic Ni(II) species during reaction, promotes migratory insertion and transmetalation steps and suppresses β-H elimination and cross-coupling, the major side reactions that cause serious problems during alkene difunctionalization. This diarylation reaction proceeds at remote locations to imines to afford, after simple H workup, diversely substituted γ,δ-diaryl ketones that are otherwise difficult to access readily with existing methods.
View Article and Find Full Text PDFWe disclose a [(PhO)P]/NiBr-catalyzed regioselective β,δ-diarylation of unactivated olefins in ketimines with aryl halides and arylzinc reagents. This diarylation proceeds at remote locations to the carbonyl group to afford, after simple H workup, diversely substituted β,δ-diarylketones that are otherwise difficult to access readily with existing methods. Deuterium-labeling and crossover experiments indicate that diarylation proceeds by ligand-enabled contraction of transient nickellacycles.
View Article and Find Full Text PDFTransition metal (TM)-catalyzed difunctionalization of unactivated olefins with two carbon-based entities is a powerful method to construct complex molecular architectures rapidly from simple and readily available feedstock chemicals. While dicarbofunctionalization of unactivated olefins has a long history typically with the use of either carbon monoxide to intercept C(sp )-[M] (alkyl-TM) species or substrates lacking in β-hydrogen (β-Hs), development of this class of reaction still remains seriously limited due to complications of β-H elimination arising from the in situ-generated C(sp )-[M] intermediates. Over the years, different approaches have been harnessed to suppress β-H elimination, which have led to the development of various types of olefin dicarbofunctionalization reactions even in substrates that generate C(sp )-[M] intermediates bearing β-Hs with a wide range of electrophiles and nucleophiles.
View Article and Find Full Text PDFWe disclose a (terpy)NiBr-catalyzed reaction protocol that regioselectively difunctionalizes unactivated olefins with tethered alkyl halides and arylzinc reagents. The reaction shows an excellent functional group tolerance (such as ketones, esters, nitriles, and halides) and a moderate to good level of diastereoselectivity. The current cyclization/cross-coupling also tolerates molecules containing base-sensitive racemizable stereocenters, which are preserved without racemization during the reaction.
View Article and Find Full Text PDFWe disclose a strategy for Ni-catalyzed dicarbofunctionalization of olefins in styrenes by intercepting Heck C(sp)-NiX intermediates with arylzinc reagents. This approach utilizes a readily removable imine as a coordinating group that plays a dual role of intercepting oxidative addition species derived from aryl halides and triflates to promote Heck carbometalation and stabilizing the Heck C(sp)-NiX intermediates as transient metallacycles to suppress β-hydride elimination and facilitate transmetalation/reductive elimination steps. This method affords diversely substituted 1,1,2-triarylethyl products that occur as structural motifs in various natural products.
View Article and Find Full Text PDFWe present a strategy that difunctionalizes unactivated olefins in 1,2-positions with two carbon-based entities. This method utilizes alkyl/arylzinc reagents derived from olefin-tethered alkyl/aryl halides that undergo radical cyclization to generate C(sp)-Cu complexes in situ, which are intercepted with aryl and heteroaryl iodides. A variety of (arylmethyl)carbo- and heterocycles (N, O) can be synthesized with this new method.
View Article and Find Full Text PDFWe disclose a Pd-catalyzed reaction protocol that regioselectively difunctionalizes unactivated olefins with aryl iodides and tethered enolates. The current method allows the rapid synthesis of a variety of 1,3,4-trisubstituted pyrrolidinones from simple and readily available amides. We further demonstrate this new method's application by postsynthetically modifying the arylacetic acid side chains of two commercial nonsteroidal anti-inflammatory drugs, indomethacin and tolmetin, to highly decorated 4-benzylpyrrolidinone frameworks.
View Article and Find Full Text PDFWe report the first example of Cu(I)-catalysed coupling of alkylboron reagents with aryl and heteroaryl iodides that affords products in good to excellent yields. Preliminary mechanistic studies with alkylborates indicate that the anionic (alkoxy)(alkyl)borates, generated from alkyllithium and alkoxyboron reagents, undergo disproportionation to anionic dialkylborates and that both anionic alkylborates are active for transmetalation to a Cu(I)-catalyst. Results from a radical clock experiment and the Hammett plot imply that the reaction likely proceeds via a non-radical pathway.
View Article and Find Full Text PDFChem Commun (Camb)
March 2015
An unprecedented Cu(I)-catalysed cross-coupling of arylzirconium reagents with aryl and heteroaryl iodides is reported. Mechanistic studies with a Cp2ZrAr2 complex revealed that Cp2Zr(Ar)(Cl) is the reactive species that undergoes transmetalation with (PN-1)CuI. In addition, experiments with radical probes indicated that the reaction proceeds via a non-radical pathway.
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