Panchromatic Light-Absorbing [70]Fullerene-Perylene-BODIPY Triad with Cascade of Energy Transfer as an Efficient Singlet Oxygen Sensitizer.

A panchromatic light-absorbing [70]fullerene-perylene-BODIPY triad (C70-P-B) was synthesized and applied as a heavy atom-free organic triplet photosensitizer for photooxidation. The photophysical processes were comprehensively investigated by the methods of steady-state spectroscopy, time-resolved spectroscopy, as well as theoretical calculations. C70-P-B shows a strong absorption ability from 300-620 nm. Efficient cascading intramolecular singlet-singlet energy transfer in C70-P-B was confirmed by the luminescence study. The backward triplet excited state energy transfer from C70 moiety to perylene then occurs to populate 3perylene*. Thus, the triplet excited states of C70-P-B are distributed on both C70 and perylene moiety with lifetimes of 23 ± 1 µs and 175 ± 17 µs, respectively. C70-P-B exhibits excellent photooxidation capacity, and its yield of singlet oxygen reaches 0.82. The photooxidation rate constant of C70-P-B is 3.70 times that of C70-Boc and 1.58 times that of MB, respectively. The results in this paper are useful for designing efficient heavy atom-free organic triplet photosensitizers for practical application in photovoltaics, photodynamic therapy, etc.

Metabolite profiling and genome-wide association studies reveal response mechanisms of phosphorus deficiency in maize seedling.

Inorganic phosphorus (Pi) is an essential element in numerous metabolic reactions and signaling pathways, but the molecular details of these pathways remain largely unknown. In this study, metabolite profiles of maize (Zea mays L.) leaves and roots were compared between six low-Pi-sensitive lines and six low-Pi-tolerant lines under Pi-sufficient and Pi-deficient conditions to identify pathways and genes associated with the low-Pi stress response. Results showed that under Pi deprivation the concentrations of nucleic acids, organic acids and sugars were increased, but that the concentrations of phosphorylated metabolites, certain amino acids, lipid metabolites and nitrogenous compounds were decreased. The levels of secondary metabolites involved in plant immune reactions, including benzoxazinoids and flavonoids, were significantly different in plants grown under Pi-deficient conditions. Among them, the 11 most stable metabolites showed significant differences under low- and normal-Pi conditions based on the coefficient of variation (CV). Isoleucine and alanine were the most stable metabolites for the identification of Pi-sensitive and Pi-resistant maize inbred lines. With the significant correlation between morphological traits and metabolites, five low-Pi-responding consensus genes associated with morphological traits and simultaneously involved in metabolic pathways were mined by combining metabolites profiles and genome-wide association study (GWAS). The consensus genes induced by Pi deficiency in maize seedlings were also validated by reverse-transcription quantitative polymerase chain reaction (RT-qPCR). Moreover, these genes were further validated in a recombinant inbred line (RIL) population, in which the glucose-6-phosphate-1-epimerase encoding gene mediated yield and correlated traits to phosphorus availability. Together, our results provide a framework for understanding the metabolic processes underlying Pi-deficient responses and give multiple insights into improving the efficiency of Pi use in maize.

A new trifluoromethylated sulfonamide phosphine ligand for Ag(i)-catalyzed enantioselective [3 + 2] cycloaddition of azomethine ylides.

A newly developed Ming-Phos ligand with a 3,5-bis(trifluoromethyl)phenyl substituent was demonstrated to be highly efficient for Ag-catalyzed asymmetric [3 + 2] cycloaddition reactions of azomethine ylides with maleimides, cyclopentene-1,3-diones, and N-(2-t-butylphenyl)maleimide. Being easily prepared on the gram scale in one step, the ligand in combination with a Ag catalyst enables the synthesis of a variety of highly functionalized bicyclic pyrrolidine derivatives in good yields and excellent enantioselectivities under mild conditions.

Enantioselective Dicarbofunctionalization of Unactivated Alkenes by Palladium-Catalyzed Tandem Heck/Suzuki Coupling Reaction.

A highly enantioselective dicarbofunctionalization of unactivated alkenes was implemented by a Pd-catalyzed asymmetric tandem Heck/Suzuki coupling reaction. This reaction represents the first example of a highly enantioselective intramolecular cyclization/cross-coupling of olefin-tethered aryl halides with alkyl-, alkenyl- or arylboronic acids, and provides rapid access to a number of chiral compounds, such as dihydrobenzofurans, indolines, chromanes, and indanes bearing a quaternary stereocenter, in good yields with excellent enantioselectivities. The practicality of this reaction was validated in the modification of biologically complex molecules such as peptides, piperitol, CB2 receptor agonists, etc. Moreover, the synthesis of two enantiomers can be easily realized by simple change in the order of the steps in the coupling sequence.

Temperature and photoperiod changes affect cucumber sex expression by different epigenetic regulations.

BACKGROUND: Cucumbers (Cucumis sativus) are known for their plasticity in sex expression. DNA methylation status determines gene activity but is susceptible to environmental condition changes. Thus, DNA methylation-based epigenetic regulation may at least partially account for the instability of cucumber sex expression. Do temperature and photoperiod that are the two most important environmental factors have equal effect on cucumber sex expression by similar epigenetic regulation mechanism? To answer this question, we did a two-factor experiment of temperature and photoperiod and generated methylome and transcriptome data from cucumber shoot apices. RESULTS: The seasonal change in the femaleness of a cucumber core germplasm collection was investigated over five consecutive years. As a result, 71.3% of the 359 cucumber accessions significantly decreased their femaleness in early autumn when compared with spring. High temperature and long-day photoperiod treatments, which mimic early autumn conditions, are both unfavorable for female flower formation, and temperature is the predominant factor. High temperatures and long-day treatments both predominantly resulted in hypermethylation compared to demethylation, and temperature effect was decisive. The targeted cytosines shared in high-temperature and long-day photoperiod treatment showed the same change in DNA methylation level. Moreover, differentially expressed TEs (DETs) and the predicted epiregulation sites were clustered across chromosomes, and importantly, these sites were reproducible among different treatments. Essentially, the photoperiod treatment preferentially and significantly influenced flower development processes, while temperature treatment produced stronger responses from phytohormone-pathway-related genes. Cucumber AGAMOUS was likely epicontrolled exclusively by photoperiod while CAULIFLOWER A and CsACO3 were likely epicontrolled by both photoperiod and temperature. CONCLUSIONS: Seasonal change of sex expression is a germplasm-wide phenomenon in cucumbers. High temperature and long-day photoperiod might have the same effect on the methylome via the same mechanism of gene-TE interaction but resulted in different epicontrol sites that account for different mechanisms between temperature- and photoperiod-dependent sex expression changes.

Evolutionary conservation and functional divergence of the LFK gene family play important roles in the photoperiodic flowering pathway of land plants.

ZEITLUPE (ZTL), LOV KELCH PROTEIN 2 (LKP2), and FLAVIN-BINDING KELCH REPEAT F-BOX 1 (FKF1)-blue-light photoreceptors-play important roles in regulating the circadian clock and photoperiodic flowering pathway in plants. In this study, phylogenetic analysis revealed that the LOV (Light, Oxygen, or Voltage) and Kelch repeat-containing F-box (LFK) gene family can be classified into two clades, ZTL/LKP2 and FKF1, with clear differentiation between monocots and dicots within each clade. The LFK family genes underwent strong purifying selection; however, signatures of positive selection to adapt to local conditions still existed in 18 specific codons. In 87 diverse maize inbred lines, significant differences were identified (P ≤ 0.01) for days to female flowering between the haplotypes consisting of eight positive selection sites at ZmFKF1b corresponding to tropical and temperate maize groups of the phylogenetic tree, indicating a key role of ZmFKF1b in maize adaptive evolution. In addition, positive coevolution was detected in the domains of the LFK family for long-term cooperation to targets. The Type-I and Type-II functional divergence analysis revealed subfunctionalization or neofunctionalization of the LFKs, and the ZTL subfamily is most likely to maintain the ancestral function of LFKs. Over 50% of critical amino acid sites involved in the functional divergence were identified in the Kelch repeat domain, resulting in the distinction of substrates for ubiquitination and degradation. These results suggest that evolutionary conservation contributes to the maintenance of critical physiological functions, whereas functional divergence after duplication helps to generate diverse molecular regulation mechanisms.

Palladium-Catalyzed Enantioselective Reductive Heck Reactions: Convenient Access to 3,3-Disubstituted 2,3-Dihydrobenzofuran.

The first example of highly enantioselective intramolecular hydroarylation of allyl aryl ethers was realized by palladium-catalyzed reductive heck reactions utilizing a new chiral sulfinamide phosphine ligand (N-Me-XuPhos). N-Me-XuPhos can be easily prepared on gram scale from readily available starting materials in a one-pot synthesis approach. A series of optically active 2,3-dihydrobenzofurans bearing a quaternary stereocenter were obtained in good yields and with excellent enantioselectivities. The practicality of this reaction was validated in the straightforward synthesis of CB2 receptor agonists. Moreover, deuterium was efficiently incorporated into the products.

Modulation of metal species as control point for Ni-catalyzed stereodivergent semihydrogenation of alkynes with water.

A base-assisted metal species modulation mechanism enables Ni-catalyzed stereodivergent transfer semihydrogenation of alkynes with water, delivering both olefinic isomers smoothly using cheap and nontoxic catalysts and additives. Different from most precedents, in which E-alkenes derive from the isomerization of Z-alkene products, the isomers were formed in orthogonal catalytic pathways. Mechanistic studies suggest base as a key early element in modulation of the reaction pathways: by adding different bases, nickel species with disparate valence states could be accessed to initiate two catalytic cycles toward different stereoisomers. The practicability of the method is showcased with nearly 70 examples, including internal and terminal triple bonds, enynes and diynes, affording semi-hydrogenated products in high yields and selectivity.

Enantioselective difunctionalization of alkenes by a palladium-catalyzed Heck/borylation sequence.

A palladium catalyzed enantioselective Heck/borylation reaction of alkene-tethered aryl iodides was realized, delivering a variety of 2,3-dihydrobenzofuranyl boronic esters in high yield with excellent enantioselectivity. Asymmetric synthesis of chromane boronic ester, indane boronic ester and indoline boronic ester was also accomplished. The protocol offers an efficient access to the corresponding chiral benzocyclic boronic esters, which are notably important chemical motifs in synthetic transformations.

Identification of microbial markers across populations in early detection of colorectal cancer.

Associations between gut microbiota and colorectal cancer (CRC) have been widely investigated. However, the replicable markers for early-stage adenoma diagnosis across multiple populations remain elusive. Here, we perform an integrated analysis on 1056 public fecal samples, to identify adenoma-associated microbial markers for early detection of CRC. After adjusting for potential confounders, Random Forest classifiers are constructed with 11 markers to discriminate adenoma from control (area under the ROC curve (AUC) = 0.80), and 26 markers to discriminate adenoma from CRC (AUC = 0.89), respectively. Moreover, we validate the classifiers in two independent cohorts achieving AUCs of 0.78 and 0.84, respectively. Functional analysis reveals that the altered microbiome is characterized with increased ADP-L-glycero-beta-D-manno-heptose biosynthesis in adenoma and elevated menaquinone-10 biosynthesis in CRC. These findings are validated in a newly-collected cohort of 43 samples using quantitative real-time PCR. This work proves the validity of adenoma-specific markers across multi-populations, which would contribute to the early diagnosis and treatment of CRC.

Putative Familial Transmissible Bacteria of Various Body Niches Link with Home Environment and Children's Immune Health.

Owing to their significant impact on children's long-term health, familial factors in the microbiomes of children have attracted increasing attention. However, the mechanism underlying microbiome transmission across generations remains unclear. A significantly lower alpha diversity was observed in the gut flora of children than in the gut flora of parents and grandparents; the alpha diversity of oral and skin microbiota was relatively higher in children than in their predecessors. Gut, oral, and skin microbiome was more similar between family members than between unrelated individuals. Meanwhile, 55.05%, 61.09%, and 76.73% of amplicon sequence variants (ASVs) in children's gut, oral, and skin microbiomes, respectively, were transmitted from all family members. Among these, the most transmissible ASVs belonged to Methylophilaceae, Solimonadaceae, Neisseriaceae, and Burkholderiaceae, which were defined as "putative familial transmissible bacteria." Furthermore, we found that the time spent with parents/grandparents and children's dietary preferences were important factors that influenced the proportion of the transmissible microbiome. Moreover, the majority of transmissible ASVs (85.06%), especially those of Ruminococcaceae and Lachnospiraceae, were significantly associated with the immune indices, such as CD3+, CD4+, CD8+, IgG, and IgA. IMPORTANCE Our study revealed that the children's microbiota was partially transmitted from their family members and specific putative transmissible ASVs were associated with the immune system of children. These findings suggest that home life plays a key role in the shaping of young children's microbiomes and has long-term health benefits.

Catalytic C-C Cleavage/Alkyne-Carbonyl Metathesis Sequence of Cyclobutanones.

A ring-opening/alkyne-carbonyl metathesis sequence of alkyne-tethered cyclobutanones catalyzed by AgSbF6 is realized for the first time to furnish multisubstituted naphthyl ketones under mild conditions. A range of substrates decorated with various substituents at different positions were all well accommodated. Preliminary mechanistic studies show that silver salt acted as a Lewis acid to facilitate both C-C cleavage of the cyclobutanone moiety and the subsequent metathesis between C═O and C≡C bonds.

A new species of Rhinogobius (Pisces: Gobiidae), with analyses of its DNA barcode.

The genus Rhinogobius Gill 1859 is widely distributed in fresh waters along the Western Pacific coast of tropical and temperate Asia. A new species, Rhinogobius maxillivirgatus, is described from Anhui Province in Eastern China. This species can be differentiated from all congeners by a combination of the following characters: up to 6 longitudinal brown to black stripes along the side of the body; pectoral-fin rays modally 14; predorsal scale series 5-9; lateral scale series 28-30; transverse scale series 6-7; branchiostegal membrane with about 20 red round spots in males; and 2 black oblique stripes parallel along the upper jaw on the anterior portion of the cheek. Analyzing sequences of cytochrome c oxidase subunit I revealed that the new species is closely related to, but distinct, from Rhinogobius wuyanlingensis.

[Effect of waterlogging on physical traits and yield of wheat in Sichuan, China].

Following a two-factor split plot design, two popular varieties ( Neimai836 and Chuanmail04) were used to study the effects of waterlogging at four growth stages (seedling, jointing, booting and anthesis) on wheat growth and yield formation during two growing seasons (2011-2012 and 2012-2013). The resulted showed that the greatest yield penalty occurred when waterlogging happened at the seedling stage (10% - 15% decrease), and it was alleviated when waterlogging happened at the other stages. Waterlogging during the seedling stage significantly reduced SPAD of 2nd-6th leaves, tillers and spike number per plant, productive ears, dry matter accumulation after flowering and dry matter at maturity. Waterlogging during the jointing stage decreased SPAD of 4th-7th leaves, and waterlogging during the booting stage reduced the SPAD of top 2nd, 3rd, 4th leaves. Waterlogging during the jointing and booting stages reduced the SPAD of flag leaf, the rate of grain filling during the gradual increase stage, the average filling rate and the 1000-grain mass. Waterlogging during the flowering stage produced limited change in yield. Therefore, waterlogging during the seedling stage was identified to have the most critical influence on wheat production under wheat/rice cropping rotations in Sichuan Province.