Search

In this update, we developed a mild, efficient and practical method using stable “F–SO2+” donor A as an environment friendly promoter for conversion of oximes to nitriles or amides via β-elimination or Beckmann rearrangement in excellent yields.

The late-stage functionalization of drugs and natural products has been identified as a promising approach to accelerate the discovery of new bioactive compounds. Due to the presence of the "Magic Methyl Effect", the direct deoxymethylation of phenolic hydroxyl groups, which are widespread in natural molecules, is a challenging task. A mild and rapid strategy for direct phenol deoxymethylation under metal catalysis using SO

A tunable and practical transformation of structurally diverse sulfonyl hydrazides into thiosulfonates in the presence of Rongalite (NaHSO2·CH2O) was developed. Transition-metal-free conditions, operational simplicity, and readily available reagents are the striking features of this protocol. It is the first example for the synthesis of thiosulfonates using sulfonyl hydrazides with the assistance of reductant. Additionally, the mechanistic studies revealed that this transformation probably undergoes via a reducing–coupling pathway.

The ability of climbing plants to grow upward along others to reach the canopy for photosynthesis is hypothesized as a key innovation in flowering plants. Most members of the Cucurbitaceae, a family containing ∼1000 species and many important crops, are climbers and have characteristic tendrils and pepo fruits. Here, we present 127 newly sequenced transcriptomes and genomes along with other datasets for a total of 136 cucurbits representing all tribes to establish a robust Cucurbitaceae phylogeny containing eight highly resolved major clades. We analyzed whole-genome duplication, diversification dynamics, and ancestral morphologies, and found that after early genome duplication event(s), a burst of diversification and morphological innovations in flower, fruit, and root characters occurred under the climate optimum in the Early Eocene. Species radiation during the Mid-Eocene Climatic Optimum also coincided with several morphological changes shared by 80% of cucurbits. We found that the cucurbit-specific tendril identity gene TEN originated from a paleo-polyploidization event at the origin of the family. Our results support the hypothesis that cucurbit diversifications were probably driven by increased genetic diversity following polyploidizations and by trait morphological innovations under paleo-climate upheavals. Our study provides a phylogenetic framework and new insights into morphological and genomic changes underlying the adaptive evolution of Cucurbitaceae.

A novel SO2F2-promoted thiocyanation method for the one-step synthesis of thiocyanates through C–O bond cleavage of readily available alcohols with ammonium thiocyanate as the thiocyanating agent was developed. The method avoids the use of additional catalyst, and a variety of (hetero)arene, alkene and aliphatic alcohols reacted with high efficiency in ethyl acetate under mild conditions to afford the corresponding thiocyanates in excellent to quantitative yields with broad functional-group compatibility.

A simple, mild and practical cascade process for the direct conversion of aldehydes to cyanamides was developed featuring a wide substrate scope and great functional group tolerability. This method allows for transformations of readily available, inexpensive, and abundant aldehydes to highly valuable cyanamides in a pot, atom, and step-economical manner with a green nitrogen source. This protocol will serve as a robust tool for the installation of the cyanamide moiety in various complicated molecules.

Adaptation to cool climates has occurred several times in different angiosperm groups. Among them, Pooideae, the largest grass subfamily with ∼3,900 species including wheat and barley, have successfully occupied many temperate regions and play a prominent role in temperate ecosystems. To investigate possible factors contributing to Pooideae adaptive evolution to cooling climates, we performed phylogenetic reconstruction using five gene sets (with 1,234 nuclear genes and their subsets) from 157 transcriptomes/genomes representing all 15 tribes and 24 of 26 subtribes. Our phylogeny supports the monophyly of all tribes (except Diarrheneae) and all subtribes with at least two species, with strongly supported resolution of their relationships. Molecular dating suggests that Pooideae originated in the late Cretaceous, with subsequent divergences under cooling conditions first among many tribes from the early middle to late Eocene and again among genera in the middle Miocene and later periods. We identified a cluster of gene duplications (CGD5) shared by the core Pooideae (with 80% Pooideae species) near the Eocene–Oligocene transition, coinciding with the transition from closed to open habitat and an upshift of diversification rate. Molecular evolutionary analyses homologs of CBF for cold resistance uncovered tandem duplications during the core Pooideae history, dramatically increasing their copy number and possibly promoting adaptation to cold habitats. Moreover, duplication of AP1/FUL-like genes before the Pooideae origin might have facilitated the regulation of the vernalization pathway under cold environments. These and other results provide new insights into factors that likely have contributed to the successful adaptation of Pooideae members to temperate regions.

Water lilies belong to the angiosperm order Nymphaeales. Amborellales, Nymphaeales and Austrobaileyales together form the so-called ANA-grade of angiosperms, which are extant representatives of lineages that diverged the earliest from the lineage leading to the extant mesangiosperms1–3. Here we report the 409-megabase genome sequence of the blue-petal water lily (Nymphaea colorata). Our phylogenomic analyses support Amborellales and Nymphaeales as successive sister lineages to all other extant angiosperms. The N. colorata genome and 19 other water lily transcriptomes reveal a Nymphaealean whole-genome duplication event, which is shared by Nymphaeaceae and possibly Cabombaceae. Among the genes retained from this whole-genome duplication are homologues of genes that regulate flowering transition and flower development. The broad expression of homologues of floral ABCE genes in N. colorata might support a similarly broadly active ancestral ABCE model of floral organ determination in early angiosperms. Water lilies have evolved attractive floral scents and colours, which are features shared with mesangiosperms, and we identified their putative biosynthetic genes in N. colorata. The chemical compounds and biosynthetic genes behind floral scents suggest that they have evolved in parallel to those in mesangiosperms. Because of its unique phylogenetic position, the N. colorata genome sheds light on the early evolution of angiosperms., The genome of the tropical blue-petal water lily Nymphaea colorata and the transcriptomes from 19 other Nymphaeales species provide insights into the early evolution of angiosperms.

A novel tetraploid S. spontaneum with basic chromosome x = 10 was discovered, providing us insights in the origin and evolution in Saccharum species. Sugarcane (Saccharum spp., Poaceae) is a leading crop for sugar production providing 80% of the world's sugar. However, the genetic and genomic complexities of this crop such as its high polyploidy level and highly variable chromosome numbers have significantly hindered the studies in deciphering the genomic structure and evolution of sugarcane. Here, we developed the first set of oligonucleotide (oligo)-based probes based on the S. spontaneum genome (x = 8), which can be used to simultaneously distinguish each of the 64 chromosomes of octaploid S. spontaneum SES208 (2n = 8x = 64) through fluorescence in situ hybridization (FISH). By comparative FISH assay, we confirmed the chromosomal rearrangements of S. spontaneum (x = 8) and S. officinarum (2n = 8x = 80), the main contributors of modern sugarcane cultivars. In addition, we examined a S. spontaneum accession, Np-X, with 2n = 40 chromosomes, and we found that it was a tetraploid with the unusual basic chromosome number of x = 10. Assays at the cytological and DNA levels demonstrated its close relationship with S. spontaneum with basic chromosome number x = 8 (the most common accessions in S. spontaneum), confirming its S. spontaneum identity. Population genetic structure and phylogenetic relationship analyses between Np-X and 64 S. spontaneum accessions revealed that Np-X belongs to the ancient Pan-Malaysia group, indicating a close relationship to S. spontaneum with basic chromosome number of x = 8. This finding of a tetraploid S. spontaneum with basic chromosome number of x = 10 suggested a parallel evolution path of genomes and polyploid series in S. spontaneum with different basic chromosome numbers.

A rapid, simple and mild process for the dehydration of aldoximes to give the corresponding nitriles, which utilizes SO2F2 as an efficient reagent, has been developed. A variety of (hetero)arene, alkene, alkyne and aliphatic aldoximes proceeded with high efficiency to afford nitriles in excellent to quantitative yields with great functional group compatibilities in acetonitrile under ambient conditions. Furthermore, an eco-friendly synthetic protocol to access nitriles from aldehydes with ortho-, meta- and para-nitrile groups was also described in aqueous methanol by using inorganic base Na2CO3, and a one-pot synthetic strategy to generate nitriles from aldehydes was proved to be feasible.

A simple, mild and practical process for the direct conversion of nitriles to cyanamides was newly discovered and exhibited a wide substrate scope as well as great functional group-tolerability (36 examples). In this efficient strategy, the in situ generated amidoximes obtained from the reaction of nitriles with hydroxylamine subsequently underwent Tiemann rearrangement, producing the corresponding cyanamides with great isolated yields under SO2F2. Additionally, the control experiments reportedly shed light on the tentative mechanism involved in the formation and elimination of the key intermediate: a sulfonyl ester.

Poaceae (the grasses) includes rice, maize, wheat, and other crops, and is the most economically important angiosperm family. Poaceae is also one of the largest plant families, consisting of over 11 000 species with a global distribution that contributes to diverse ecosystems. Poaceae species are classified into 12 subfamilies, with generally strong phylogenetic support for their monophyly. However, many relationships within subfamilies, among tribes and/or subtribes, remain uncertain. To better resolve the Poaceae phylogeny, we generated 342 transcriptomic and seven genomic datasets; these were combined with other genomic and transcriptomic datasets to provide sequences for 357 Poaceae species in 231 genera, representing 45 tribes and all 12 subfamilies. Over 1200 low-copy nuclear genes were retrieved from these datasets, with several subsets obtained using additional criteria, and used for coalescent analyses to reconstruct a Poaceae phylogeny. Our results strongly support the monophyly of 11 subfamilies; however, the subfamily Puelioideae was separated into two non-sister clades, one for each of the two previously defined tribes, supporting a hypothesis that places each tribe in a separate subfamily. Molecular clock analyses estimated the crown age of Poaceae to be ∼101 million years old. Ancestral character reconstruction of C

Freezing tolerance is a significant trait in plants that grow in cold environments and survive through the winter. Apple (Malus domestica Borkh.) is a cold-tolerant fruit tree, and the cold tolerance of its bark is important for its survival at low temperatures. However, little is known about the gene activity related to its freezing tolerance. To better understand the gene expression and regulation properties of freezing tolerance in dormant apple trees, we analyzed the transcriptomic divergences in the bark from 1-year-old branches of two apple cultivars, “Golden Delicious” (G) and “Jinhong” (H), which have different levels of cold resistance, under chilling and freezing treatments. “H” can safely overwinter below −30 °C in extremely low-temperature regions, whereas “G” experiences severe freezing damage and death in similar environments. Based on 28 bark transcriptomes (from the epidermis, phloem, and cambium) from 1-year-old branches under seven temperature treatments (from 4 to −29 °C), we identified 4173 and 7734 differentially expressed genes (DEGs) in “G” and “H”, respectively, between the chilling and freezing treatments. A gene coexpression network was constructed according to this expression information using weighted gene correlation network analysis (WGCNA), and seven biologically meaningful coexpression modules were identified from the network. The expression profiles of the genes from these modules suggested the gene regulatory pathways that are responsible for the chilling and freezing stress responses of “G” and/or “H.” Module 7 was probably related to freezing acclimation and freezing damage in “H” at the lower temperatures. This module contained more interconnected hub transcription factors (TFs) and cold-responsive genes (CORs). Modules 6 and 7 contained C-repeat binding factor (CBF) TFs, and many CBF-dependent homologs were identified as hub genes. We also found that some hub TFs had higher intramodular connectivity (KME) and gene significance (GS) than CBFs. Specifically, most hub TFs in modules 6 and 7 were activated at the beginning of the early freezing stress phase and maintained upregulated expression during the whole freezing stress period in “G” and “H”. The upregulation of DEGs related to methionine and carbohydrate biosynthetic processes in “H” under more severe freezing stress supported the maintenance of homeostasis in the cellular membrane. This study improves our understanding of the transcriptional regulation patterns underlying freezing tolerance in the bark of apple branches.

A simple, mild and practical cascade process for the direct conversion of aldehydes to cyanamides was developed featuring a wide substrate scope and great functional group tolerability. This method allows for transformations of readily available, inexpensive, and abundant aldehydes to highly valuable cyanamides in a pot, atom, and step-economical manner with a green nitrogen source. This protocol will serve as a robust tool for the installation of the cyanamide moiety in various complicated molecules.

Fabaceae are the third largest angiosperm family, with 765 genera and ∼19 500 species. They are important both economically and ecologically, and global Fabaceae crops are intensively studied in part for their nitrogen-fixing ability. However, resolution of the intrasubfamilial Fabaceae phylogeny and divergence times has remained elusive, precluding a reconstruction of the evolutionary history of symbiotic nitrogen fixation in Fabaceae. Here, we report a highly resolved phylogeny using >1500 nuclear genes from newly sequenced transcriptomes and genomes of 391 species, along with other datasets, for a total of 463 legumes spanning all 6 subfamilies and 333 of 765 genera. The subfamilies are maximally supported as monophyletic. The clade comprising subfamilies Cercidoideae and Detarioideae is sister to the remaining legumes, and Duparquetioideae and Dialioideae are successive sisters to the clade of Papilionoideae and Caesalpinioideae. Molecular clock estimation revealed an early radiation of subfamilies near the K/Pg boundary, marked by mass extinction, and subsequent divergence of most tribe-level clades within ∼15 million years. Phylogenomic analyses of thousands of gene families support 28 proposed putative whole-genome duplication/whole-genome triplication events across Fabaceae, including those at the ancestors of Fabaceae and five of the subfamilies, and further analyses supported the Fabaceae ancestral polyploidy. The evolution of rhizobial nitrogen-fixing nodulation in Fabaceae was probed by ancestral character reconstruction and phylogenetic analyses of related gene families and the results support the hypotheses of one or two switch(es) to rhizobial nodulation followed by multiple losses. Collectively, these results provide a foundation for further morphological and functional evolutionary analyses across Fabaceae.

A mild, simple process for the effective aerobic oxidative deoximation of a wide range of ketoximes and aldoximes has been developed that utilizes Fe(NO3)3·9H2O as the single catalyst and molecular oxygen as the green oxidant. The environmentally benign protocol provides moderate to excellent yield and broad functional groups tolerance and is a valuable synthetic method for practical applications. According the relevant verification experiment, a plausible mechanism has been proposed.

A simple and efficient cationic Fe(III)/TEMPO-catalyzed oxidative cyclization of aroyl hydrazones has been developed for the synthesis of 2,5-disubstituted 1,3,4-oxadiazole derivatives. The reaction offers a broad scope, good functional-group tolerance, and high yields under mild conditions in the presence of O2.

Germplasms resources of wild strawberry are rich in Motuo country of Tibet, China. In this study, we assessed genetic diversity of seventy wild strawberry germplasms from different geographical regions using simple sequence repeat (SSR) markers. The genetic diversity of wild strawberry was demonstrated by 189 polymorphic SSR-PCR bands obtained using ten selective primers. Additionally, the average polymorphic information content ( PIC ), total gene diversity and population diversity were 0.941, 0.331 and 0.214, respectively. At the population level, variation of strawberry accessions among population was higher than that within population. Based on arithmetic mean (UPGMA) dendrogram method, all samples were clustered into 6 groups and two subgroups. Combined with the results of UPGMA and Principle coordinate analysis, wild strawberry accessions tended to group by geographic origin. Thus, these findings will benefit for the protection and exploitation of wild strawberry, and provide theoretical basis for further study in the origin and phylogenetic systematics of wild strawberry.

To provide physicians with an objective and quantitative measurement of single-sided facial paralysis, the paper presents a computer-based approach that is different from the nine existing, subjective and hand-performed international scales, such as House-Brackman. For voluntary expressions of a patient, this approach used Pface, which stems from Dface, to measure the asymmetry between two sides of the face and used eigenflow to measure the expression variations between the patient and normal subjects. The results from Pface and eigenflow were then combined by the support vector machine produce to Pdegree. A study of 25 subjects revealed that Pdegree could differentiate paralysis states (Pdegreeor = 0) and normal states (Pdegree0), with the ability to grade facial paralysis automatically. Moreover, the Pface of specific facial areas can be used in the supervision of the rehabilitation process.

To investigate the role and possible mechanisms of platelets in liver cancer metastasis.The optimum conditions of hepatoma cell adhesion to the extracellular matrix (ECM) were determined. The ability of cells to adhere to the ECM was compared between human hepatoma cell lines with a highly metastatic potential (MHCC97) and human hepatoma cell lines with a lower metastatic potential (SMMC7721). By using adhesion assays and inhibition studies in vitro, the effects of platelets and their specific adhesive molecules were compared via the ability of MHCC97 and SMMC7721 to adhere to ECM protein.The SMMC7721 cell adhesion rate to vitronectin, fibronectin, and fibrinogen, respectively, was significantly lower than that of MHCC97 cells (44.9% vs 73.6%, 47.4% vs 76.4%, and 59.3% vs 80.6%, P0.05). Both hepatoma cell adhesion to the ECM-bound platelets was unchanged whether the platelets were activated or not. SMMC7721 cell adhesion to the ECM was not affected by platelets, but MHCC97 cell adhesion to the ECM was significantly enhanced by platelets ( P0.01). In addition, this effect was significantly reduced when either P-selectin or GP IIb-IIIa was blocked by monoclonal antibodies ( P0.05, P0.01). In the inhibition studies, the ability of SMMC7721 to adhere to the ECM-bound activated platelets was also lower than that of MHCC97 ( P0.05). However, when GP IIb was blocked by antibody, the adhesion ability of both cells was similar ( P0.05).Human hepatoma cells with a highly metastatic potential proved to have a highly adhesive ability. MHCC97 cell adhesion to the ECM was significantly enhanced by platelets. The interaction of MHCC97 cells with the ECM-bound activated platelets may be mediated by platelet P-selectin and GP IIb-IIIa.