Nitroalkanes as Thioacyl Equivalents to Access Thioamides and Thiopeptides

Thioamides are an important, but a largely underexplored class of amide bioisostere in peptides. Replacement of oxoamide units with thioamides in peptide therapeutics is a valuable tactic to improve biological activity and resistance to enzymatic hydrolysis. This tactic, however, has been hampered by insufficient methods to introduce thioamide bonds into peptide or protein backbones in a site-specific and stereo-retentive fashion. In this work, we developed an efficient and mild thioacylation method to react nitroalkanes with amines directly in the presence of elemental sulfur and sodium sulfide to form a diverse range of thioamides in high yields. Notably, this convenient method can be employed for the controlled thioamide coupling of multifunctionalized peptides without epimerization of stereocenters, including the late stage thioacylation of advanced compounds of biological and medicinal interest. Experimental interrogation of postulated mechanisms currently supports the intermediacy of thioacyl species

Phosphine-catalyzed activation of cyclopropenones: a versatile C3 synthon for (3+2) annulations with unsaturated electrophiles

We herein report a phosphine-catalyzed (3 + 2) annulation of cyclopropenones with a wide variety of electrophilic π systems, including aldehydes, ketoesters, imines, isocyanates, and carbodiimides, offering products of butenolides, butyrolactams, maleimides, and iminomaleimides, respectively, in high yields with broad substrate scope. An α-ketenyl phosphorous ylide is validated as the key intermediate, which undergoes preferential catalytic cyclization with aldehydes rather than stoichiometric Wittig olefinations. This phosphine-catalyzed activation of cyclopropenones thus supplies a versatile C3 synthon for formal cycloadditon reactions

Regioselective SN2' Mitsunobu reaction of Morita–Baylis–Hillman alcohols: A facile and stereoselective synthesis of α-alkylidene-β-hydrazino acid derivatives

A highly regioselective SN2' Mitsunobu reaction between Morita–Baylis–Hillman (MBH) alcohols, azodicarboxylates, and triphenylphosphine is developed, which provides an easy access to α-alkylidene-β-hydrazino acid derivatives in high yields and good stereoselectivity. This reaction represents the first direct transformation of MBH alcohols into hydrazines

Th17/1-Biased Inflammatory Environment Involved in the Response of Epithelial Cells to Antigen Stimuli in Nasal Polyps

Several studies showed that IL-17A was significantly increased in nasal polyps (NPs). However, the source and characteristics of IL-17A-producing cells in NPs were not fully understood. We isolated mononuclear cells from NPs and uncinate tissues and analyzed them using flow cytometry. The results indicated that IL-17A was increased in NP tissues compared to uncinate tissues. The main IL-17A-expressing cells were CD3+ T cells in NP tissues, including Th17 cells, Tc17 cells, and γδT17 cells. Not similar to those in uncinate tissues, the majority of Th17 cells highly coexpressed IFN-γ in NP tissues, such as Th17/1 cells, which highly expressed CXCR3, CCR6, RORγt, and T-bet. Furthermore, Th17/1-biased environment increased the response of nasal epithelial cells to bacterial and viral stimuli, implying that Th17/1 cells play a greater role in the pathological development of NPs than Th17 or Th1 cells

Comparative Analysis of the Glutathione S-Transferase Gene Family of Four Triticeae Species and Transcriptome Analysis of GST Genes in Common Wheat Responding to Salt Stress

Glutathione S-transferases (GSTs) are ancient proteins encoded by a large gene family in plants, which play multiple roles in plant growth and development. However, there has been little study on the GST genes of common wheat (Triticum aestivum) and its relatives (Triticum durum, Triticum urartu, and Aegilops tauschii), which are four important species of Triticeae. Here, a genome-wide comprehensive analysis of this gene family was performed on the genomes of common wheat and its relatives. A total of 346 GST genes in T. aestivum, 226 in T. durum, 104 in T. urartu, and 105 in Ae. tauschii were identified, and all members were divided into ten classes. Transcriptome analysis was used to identify GST genes that respond to salt stress in common wheat, which revealed that the reaction of GST genes is not sensitive to low and moderate salt concentrations but is sensitive to severe concentrations of the stressor, and the GST genes related to salt stress mainly come from the Tau and Phi classes. Six GST genes which respond to different salt concentrations were selected and validated by a qRT-PCR assay. These findings will not only provide helpful information about the function of GST genes in Triticeae species but also offer insights for the future application of salt stress resistance breeding in common wheat

The Effects of Plant and Soil Characteristics on Partitioning Different Rainfalls to Soil in a Subtropical Chinese Fir Forest Ecosystem

The climate-induced changes in soil water patterns pose a serious threat to subtropical plantations. Mixed species stands have been advocated as an efficient way to enhance ecosystem stability. However, little is known about their possible impact on the soil water-holding capacity in the subtropics. In this study, we employed a stable hydrogen isotope to assess the contribution of rainfall to soil water (CRSW) in a pure Chinese fir (Cunninghamia lanceolata) plantation and in two mixtures of Chinese fir with Cinnamomum camphora or with Alnus cremastogyne after three different magnitudes of rainfall events in subtropical China. Furthermore, we used structure equation modeling (SEM) to quantify the relative importance of vegetation and soil properties on the CRSW. The results indicated that the CRSW did not differ among these three Chinese fir plantations after light rainfall, whereas the CRSW of moderate and heavy rainfall to soil water were 15.95% and 26.06% higher in Chinese fir plantation with Cinnamomum camphora, and 22.67% and 22.93% higher in Chinese fir plantation with Alnus cremastogyne than that in the pure Chinese fir plantation, respectively. SEM analysis showed that the vegetation biomass and soil properties significantly affected the CRSW following light rainfall, but the soil properties were the most important factors influencing the CRSW under moderate and heavy rainfall. Our findings demonstrate that the mixed conifer–broad-leaved plantation is a more effective strategy for improving the soil water-holding capacity than the pure conifer plantation in subtropical regions, which is conducive to coping with the frequent seasonal droughts and extreme precipitation events.Forestry, Faculty ofNon UBCForest and Conservation Sciences, Department ofReviewedFacultyResearcherOthe

Design and Validation of Lifetime Prediction Model for Lithium-Thiocarbonyl Chloride Batteries Based on Accelerated Aging Experiments

The purpose of this study is to establish a life prediction model of lithium-thiocarbonyl chloride batteries by semi-empirical method. In the experiment, accelerated life tests on several groups of batteries at different temperatures were conducted. After a period of operation in the range from 25 °C to 74 °C, it was found that the higher the temperature, the less the remaining capacity of the batteries. According to the study of the battery aging mechanism, the characteristic parameter impedance of an aging battery would change exponentially with the increase of storage time and environmental temperature. The established life prediction model showed that the change in battery impedance spectrum had a good law, which made it possible to predict the state of charge (SOC) of the battery according to the local change characteristics of the electrochemical impedance spectroscopy (EIS) spectrum. The experimental data were compared with the fitted prediction curve, and the maximum deviation of the prediction was only 4.1036%, which indicated that the constructed model had high accuracy

Divergent Amine-Catalyzed [4 + 2] Annulation of Morita–Baylis–Hillman Allylic Acetates with Electron-Deficient Alkenes

An amine-catalyzed [4 + 2] annulation of Morita–Baylis–Hillman allylic acetates <b>2</b> with electron-deficient alkenes or diazenes has been developed for efficient syntheses of highly functionalized cyclohexenes, tetrahydropyridazines, and important spirocycles. This reaction unveils a new reactivity pattern of the intensely studied allylic compounds <b>2</b> acting as a <i>C</i>₄ synthon in Lewis base catalyzed annulation reactions and also showcases divergent catalysis between tertiary amines and phosphines

Alterations of Cortisol and Melatonin Production by the Theca Interna Cells of Porcine Cystic Ovarian Follicles

(1) Background: Cortisol and melatonin (MT) act in regulating follicular development. We hypothesized that abnormal levels of cortisol, MT, and steroids in theca interna cells might be involved in the development of follicular cysts in sows. (2) Methods: To test this hypothesis, we measured the mRNA levels of enzymes involved in steroid hormone synthesis, the glucocorticoid receptor (GR), and melatonin receptors (MTRs) in theca interna cells of cystic and normal porcine follicles. (3) Results: The concentrations of estradiol, progesterone, and cortisol were greater in cystic follicles than in control ones (p = 0.034, p = 0.020, p = 0.000), but the concentration of MT was significantly lower (p = 0.045). The levels of GR, 11&beta;-HSD1, and 11&beta;-HSD2 were higher in cystic follicles than in control l follicles. MT types 1 and 2 were significantly lower in cystic follicles (p &lt; 0.05). The mRNA expression levels of genes encoding the steroid hormone synthesis enzymes, steroidogenic acute regulatory protein (StAR), recombinant cytochrome P45011A1 (CYP11A1), and 3&beta;-hydroxysteroid dehydrogenase (3&beta;-HSD) in theca interna cells of cystic follicles were significantly higher than in control follicles. Thus, there was disruption of hormone secretion in the fluid of cystic follicles in sows. (4) Conclusions: The levels of steroid hormones, cortisol and MT are disrupted in porcine cystic follicles