π-Diamond: A Diamondoid Superstructure Driven by π-Interactions.

Modulating the arrangement of superstructures through noncovalent interactions has a significant impact on macroscopic shape and the expression of unique properties. Constructing π-interaction-driven hierarchical three-dimensional (3D) superstructures poses challenges on account of limited directional control and weak intermolecular interactions. Here we report the construction of a 3D diamondoid superstructure, named π-Diamond, employing a ditopic strained Z-shaped building block comprising a porphyrin unit as bow-limb double-strapped with two m-xylylene units as bowstring. This superstructure, reminiscent of diamond's tetrahedral carbon composition, is composed of double-walled tetrahedron (DWT) driven solely by π-interactions. Hetero-π-stacking between porphyrin and m-xylylene panels drive the assembly of four building blocks predominantly into a DWT, which undergoes extension to create an adamantane unit and eventually a diamondoid superstructure wherein each porphyrin panel is shared by two neighboring tetrahedra through hetero-π-stacking. π-Diamond exhibits a solid-state fluorescent quantum yield 44 times higher than that of tetraphenylporphyrin along with excellent photocatalytic performance. The precise 3D directionality of π-interactions, achieved through strained multipanel building blocks, revolutionizes the assembly of hierarchical 3D superstructures driven by π-interactions.

Strain-Driven Formal [1,3]-Aryl Shift within Molecular Bows.

Delving into the influence of strain on organic reactions in small molecules at the molecular level can unveil valuable insight into developing innovative synthetic strategies and structuring molecules with superior properties. Herein, we present a molecular-strain engineering approach to facilitate the consecutive [1,2]-aryl shift (formal [1,3]-aryl shift) in molecular bows (MBs) that integrate 1,4-dimethoxy-2,5-cyclohexadiene moieties. By introducing ring strain into MBs through tethering the bow limb, we can harness the intrinsic mechanical forces to drive multistep aryl shifts from the para- to the meta- to the ortho-position. Through the use of precise intramolecular strain, the seemingly impractical [1,3]-aryl shift was realized, resulting in the formation of ortho-disubstituted products. The solvent and temperature play a crucial role in the occurrence of the [1,3]-aryl shift. The free energy calculations with inclusion of solvation support a feasible mechanism, which entails multistep carbocation rearrangements, for the formal [1,3]-aryl shift. By exploring the application of molecular strain in synthetic chemistry, this research offers a promising direction for developing new tools and strategies towards precision organic synthesis.

Cascade Synthesis of Benzotriazulene with Three Embedded Azulene Units and Large Stokes Shifts.

We report here the one-pot synthesis of benzo[1,2-a : 3,4-a' : 5,6-a'']triazulene (BTA), wherein three azulene units are embedded through a tandem reaction comprising two steps, Suzuki coupling and Knoevenagel condensation, between a readily available triborylated truxene precursor and 8-bromo-1-naphthaldehyde. Its nitration leads to a regioselective trinitrated product, namely, BTA-NO2 . Single-crystal X-ray crystallography revealed that the superstructure of BTA consists of a dimer stacked by two enantiomeric helicene conformers, while that of BTA-NO2 consists of an unprecedented π-tetramer stacked from two enantiomeric dimers, that is, four distinct helicene conformers. Both compounds show excellent stability and fluorescence with large Stokes shifts of up to 5100 cm-1 . In addition, BTA-NO2 exhibits a unique solvatochromic effect in different solvents and hydrogen-bonding-induced emission transfer in different ratios of THF/H2 O solutions.

Infinite Twisted Polycatenanes.

Poly[n]catenanes have exceptional mechanical bonding properties that give them tremendous potential for use in the development of molecular machines and soft materials. Synthesizing these compounds has, however, proven to be a formidable challenge. Herein, we describe a concise method for the construction of twisted polycatenanes. Our approach involves using preorganized double helicates as templates, linked crosswise in a linear fashion by either silver ions or triple bonds. By using this approach, we successfully synthesized twisted polycatenanes with both coordination and covalent bonding employing Ag(I) ions and ethynylene units, respectively, as the linkages and leveraging the same Ag(I)-templated double helicate in both cases. Synthesis with Ag(I) ions formed a single-crystalline one-dimensional (1D) coordination poly[n]catenane, and synthesis using ethynylene units generated 1D fibers which self-assembled with solvents to form a gel. Our results confirm the potential of multi-stranded metallohelicates for creating sophisticated mechanically interlocked molecules and polymers, which could pave the way for exploration in the realms of molecular nanotopology and materials design.

Rice qGL3/OsPPKL1 Functions with the GSK3/SHAGGY-Like Kinase OsGSK3 to Modulate Brassinosteroid Signaling.

Brassinosteroids (BRs) are steroid hormones that play essential roles in plant growth and development. We previously cloned qGL3, a major quantitative trait locus regulating grain length in rice (Oryza sativa). The O. sativa japonica var N411 has extra-large grains compared with the O. sativa indica var 9311, and the recessive qgl3 allele from N411 contributes positively to grain length. qGL3 encodes a putative protein phosphatase with Kelch-like repeat domains, an ortholog of Arabidopsis (Arabidopsis thaliana) brassinosteroid-insensitive1 SUPPRESSOR1 (BSU1). BSU1 positively regulates BR signaling, while overexpression of qGL3 induced BR loss-of-function phenotypes. Both qGL3N411 and qGL39311 physically interact with the rice glycogen synthase kinase 3 (GSK3)/SHAGGY-like kinase 3 (OsGSK3), an ortholog of Arabidopsis BR INSENSITIVE2 (BIN2). qGL39311 dephosphorylates OsGSK3, but qGL3N411 lacks this activity. Knocking out OsGSK3 enhances BR signaling and induces nuclear localization of O. sativa BRASSINAZOLE RESISTANT1 (OsBZR1). Unlike the dephosphorylation of BIN2 (which leads to protein degradation) in Arabidopsis, qGL3 dephosphorylates and stabilizes OsGSK3 in rice. These results demonstrate that qGL3 suppresses BR signaling by regulating the phosphorylation and stability of OsGSK3, which modulates OsBZR1 phosphorylation and subcellular distribution. Our study clarifies the role of qGL3 in the regulation of grain length and provides insight into BR signaling, including the differences between rice and Arabidopsis.

Leaf Mutant 7 Encoding Heat Shock Protein OsHSP40 Regulates Leaf Size in Rice.

Leaf size is an important agronomic trait directly affecting yield in rice, and thus understanding the genes determining leaf size is important in breeding. In this study, one Leaf Mutant 7 (lm7) with small leaf size was isolated using ethyl methane sulphonate (EMS) mutagenesis from the japonica Zhenggeng 1925. MutMap by whole genome resequencing of phenotypic bulks revealed that LM7 is likely located in the 133 kb region on chromosome 7 using F2 population from a cross between lm7 and wild-type (WT) Zhenggeng 1925. The candidate gene encoding heat shock protein OsHSP40 for LM7 was functionally validated. Disruption of this gene in Oshsp40 mutants significantly reduced the leaf size compared with that of WT in rice. Microscopic examination showed that OsHSP40 modulated leaf size via regulating the veins formation and cell size/cell number. Nucleotide diversity analysis indicated that a single nucleotide polymorphism (SNP) variation of C to T in the coding region of OsHSP40 may cause small leaves among rice accessions. Therefore, the natural variation of OsHSP40 contributing to leaf size might be useful for rice breeding.

Linear Nonalternant Isomers of Acenes Fusing Multiple Azulene Units.

A modular approach to azulene building blocks was developed starting from readily available aryl-substituted cyclopentadiene and ortho-haloaryl aldehyde by dehydration condensation followed by palladium-catalyzed C-H coupling. It facilitates the synthesis of four nonalternant isomers of pentacene and hexacene, namely, dibenzo[e,g]azulene, benzo[1,2-f : 5,4-f']diazulene, benzo[1,2-f : 4,5-f']diazulene, and naphtho[2,3-f : 6,7-f']diazulene, which exhibit narrow band gaps with high stability in addition to protonation-caused enhanced near-infrared fluorescence. We discovered that in these isomers, i) constitutional isomerism influences significantly their photoelectric properties and ii) the elongation of the conjugation system does not necessarily lead to a narrowing in the band gap. Due to the easy modifiability of the nonazulene building blocks, this strategy can be extended to modularly prepare numerous multiazulene-fused aromatics.

A New Insight into 6-Pentyl-2H-pyran-2-one against Peronophythora litchii via TOR Pathway.

The litchi downy blight disease of litchi caused by Peronophythora litchii accounts for severe losses in the field and during storage. While ample quantitative studies have shown that 6-pentyl-2H-pyran-2-one (6PP) possesses antifungal activities against multiple plant pathogenic fungi, the regulatory mechanisms of 6PP-mediated inhibition of fungal pathogenesis and growth are still unknown. Here, we investigated the potential molecular targets of 6PP in the phytopathogenic oomycetes P. litchii through integrated deployment of RNA-sequencing, functional genetics, and biochemical techniques to investigate the regulatory effects of 6PP against P. litchii. Previously we demonstrated that 6PP exerted significant oomyticidal activities. Also, comparative transcriptomic evaluation of P. litchii strains treated with 6PP Revealed significant up-regulations in the expression profile of TOR pathway-related genes, including PlCytochrome C and the transcription factors PlYY1. We also noticed that 6PP treatment down-regulated putative negative regulatory genes of the TOR pathway, including PlSpm1 and PlrhoH12 in P. litchii. Protein-ligand binding analyses revealed stable affinities between PlYY1, PlCytochrome C, PlSpm1, PlrhoH12 proteins, and the 6PP ligand. Phenotypic characterization of PlYY1 targeted gene deletion strains generated in this study using CRISPR/Cas9 and homologous recombination strategies significantly reduced the vegetative growth, sporangium, encystment, zoospore release, and pathogenicity of P. litchii. These findings suggest that 6PP-mediated activation of PlYY1 expression positively regulates TOR-related responses and significantly influences vegetative growth and the virulence of P. litchii. The current investigations revealed novel targets for 6PP and underscored the potential of deploying 6PP in developing management strategies for controlling the litchi downy blight pathogen.

UDP-glucosyltransferase OsUGT75A promotes submergence tolerance during rice seed germination.

Submergence stress represents a major obstacle limiting the application of direct seeding in rice cultivation. Under flooding conditions, coleoptile elongation can function as an escape strategy that contributes to submergence tolerance during seed germination in rice; however, the underlying molecular bases have yet to be fully determined. Herein, we report that natural variation of rice coleoptile length subjected to submergence is determined by the glucosyltransferase encoding gene OsUGT75A. OsUGT75A regulates coleoptile length via decreasing free abscisic acid (ABA) and jasmonic acid (JA) levels by promoting glycosylation of these two phytohormones under submergence. Moreover, we find that OsUGT75A accelerates coleoptile length through mediating the interactions between JASMONATE ZIMDOMAIN (OsJAZ) and ABSCISIC ACID-INSENSITIVE (OsABI) proteins. Last, we reveal the origin of the haplotype that contributes to coleoptile length in response to submergence and transferring this haplotype to indica rice can enhance coleoptile length in submergence conditions. Thus, we propose that OsUGT75A is a useful target in breeding of rice varieties suitable for direct seeding cultivation.

Dynamic RNA-Seq Study Reveals the Potential Regulators of Seed Germination in Paris polyphylla var. yunnanensis.

Paris polyphylla var. yunnanensis is an important traditional Chinese medicine, but poor seed germination limits its large-scale artificial cultivation. Thus, it is crucial to understand the regulators of seed germination to obtain clues about how to improve the artificial cultivation of Paris polyphylla. In this study, the seeds at three germination stages, including ungerminated seeds (stage 1), germinated seeds with a 0.5 cm radicel length (stage 2), and germinated seeds with a 2.0 cm radicel length (stage 3) after warm stratification (20 °C) for 90 days were used for RNA sequencing. Approximately 220 million clean reads and 447,314 annotated unigenes were obtained during seed germination, of which a total of 4454, 5150, and 1770 differentially expressed genes (DEGs) were identified at stage 1 to stage 2, stage 1 to stage 3, and stage 2 to stage 3, respectively. Encyclopedia of Genes and Genomes (KEGG) analysis revealed that the DEGs were significantly enriched in carbohydrate metabolism, lipid metabolism, signal transduction, and translation. Of them, several genes encoding the glutamate decarboxylase, glutamine synthetase, alpha-galactosidase, auxin-responsive protein IAA30, abscisic-acid-responsive element binding factor, mitogen-activated protein kinase kinase 9/18, and small and large subunit ribosomal proteins were identified as potentially involved in seed germination. The identified genes provide a valuable resource to study the molecular basis of seed germination in Paris polyphylla var. yunnanensis.