Coughlinharbo3363

Endophytic fungi have proven to be prolific producers of bioactive secondary metabolites with agricultural applications. In this study, bioassay-guided isolation of the endophytic fungus Acremonium vitellinum yielded four anthraquinone derivatives (compounds 1-4), including a previously undescribed dimethylated derivative of bipolarin, 6,8-di-O-methylbipolarin (1). Their structures were determined by 1D and 2D nuclear magnetic resonance analysis as well as high-resolution electrospray ionization mass spectrometry data, and the absolute configuration of 1 was established by comparing the calculated and experimental electronic circular dichroism spectra. https://www.selleckchem.com/mTOR.html The insecticidal activity of the isolated compounds against the cotton bollworm Helicoverpa armigera was evaluated. The new compound 1 showed the strongest larvicidal activity against the 3rd instar larvae of H. armigera with an LC50 value of 0.72 mg/mL. In addition, transcriptome sequencing was performed to evaluate the molecular mechanism of the insecticidal activity. In total, 5732 differentially expressed genes were found, among which 2904 downregulated genes and 2828 upregulated genes were mainly involved in cell autophagy, apoptosis, and DNA mismatch repair and replication. The results presented in this study reveal how 1 exerts its insecticidal effects against H. armigera via genome-wide differential gene expression analyses. Our findings suggest that anthraquinone derivatives are potential biopesticides for cotton bollworm control.Ubiquitination and SUMOylation of protein are crucial for various biological responses. The recent unraveling of cross-talk between SUMO and ubiquitin (Ub) has shown the pressing needs to develop the platform for the synthesis of Ub tagged SUMO2 dimers to decipher its biological functions. Still, the platforms for facile synthesis of dimers under native condition are less explored and remain major challenges. Here, we have developed the platform that can expeditiously synthesize all eight Ub tagged SUMO2 and SUMOylated proteins under native condition. Expanding genetic code (EGC) method was employed to incorporate Se-alkylselenocysteine at lysine positions. Oxidative selenoxide elimination generates the electrophilic center, dehydroalanine, which upon Michael addition with C-terminal modified ubiquitin, a nucleophile, yield Ub tagged SUMO2. The dimers were further interrogated with USP7, a SUMO2 deubiquitinase, which is involved in DNA repair, to understand specificity toward the Ub tagged SUMO2 dimer. Our results have shown that the C-terminal domain of USP7 is crucial for USP7 efficiency and selectivity for the Ub tagged SUMO2 dimer.An atom- and step-economic synthesis of aryliminophosphoranes bearing ortho urea was achieved via unprecedented Ph3P-I2 mediated ring-opening of 1,3-dihydro-1H-benzimidazol-2-ones with secondary amines. Tandem aza-Wittig/heterocyclization of the functionalized aryliminophosphoranes upon treatment with isothiocyanates enables a facile access to a single regioisomer of N1-substituted 2-aminobenzimidazoles as well as fused tetracyclic quinazolinone derivatives in one-pot. 31P1H NMR studies suggested that the urea C-N bond of benzimidazolone is weakened by N-phosphorylation, leading to aminolysis rather than the expected deoxygenative amination.N-Heterocyclic carbene (NHC) gold(I) complexes offer great prospects in medicinal chemistry as antiproliferative, anticancer, and antibacterial agents. However, further development requires a thorough understanding of their reaction behavior in aqueous media. Herein, we report the conversion of the bromido[3-ethyl-4-(4-methoxyphenyl)-5-(2-methoxypyridin-5-yl)-1-propylimidazol-2-ylidene]gold(I) ((NHC)AuIBr, 1) complex in acetonitrile/water mixtures to the bis[3-ethyl-4-(4-methoxyphenyl)-5-(2-methoxypyridin-5-yl)-1-propylimidazol-2-ylidene]gold(I) ([(NHC)2AuI]+, 7), which is subsequently oxidized to the dibromidobis[3-ethyl-4-(4-methoxyphenyl)-5-(2-methoxypyridin-5-yl)-1-propylimidazol-2-ylidene]gold(III) ([(NHC)2AuIIIBr2]+, 9). By combining experimental data from HPLC, NMR, and (LC-)/HR-MS with computational results from DFT calculations, we outline a detailed ligand scrambling reaction mechanism. The key step is the formation of the stacked ((NHC)AuIBr)2 dimer (2) that rearranges to the T-shaped intermediate Br(NHC)2AuI-AuIBr (3). The dissociation of Br- from 3 and recombination lead to (NHC)2AuI-AuIBr2 (5) followed by the separation into [(NHC)2AuI]+ (7) and [AuIBr2]- (8). [AuIBr2]- is not stable in an aqueous environment and degrades in an internal redox reaction to Au0 and Br2. The latter in turn oxidizes 7 to the gold(III) species 9. The reported ligand rearrangement of the (NHC)AuIBr complex differs from that found for related silver(I) analogous. A detailed understanding of this scrambling mechanism is of utmost importance for the interpretation of their biological activity and will help to further optimize them for biomedical and other applications.Iron oxide nanocrystals have the potential for use in a wide variety of applications if we can finely control and tune the diverse structural attributes that lead to specific, desired properties. At the high temperatures utilized for thermal decomposition based syntheses, commonly used Fe(III) alkylcarboxylate precursors are inadvertently reduced and produce wüstite (FeO), which is paramagnetic, as opposed to the desired ferrimagnetic spinel phases of magnetite (Fe3O4) and maghemite (γ-Fe2O3). To circumvent this issue, we carried out syntheses at lower temperatures (∼230 °C) using an esterification-mediated approach. Under these conditions, formation of the FeO phase can be avoided. However, we found that the precursor oxidation state and ligation had a surprisingly strong influence on the morphologies of the resulting nanocrystals. To investigate the cause of these morphological effects, we carried out analogous nanocrystal syntheses with a series of precursors. The use of Fe(III) oleate precursors yielded highly crystalline, largely twin-free nanocrystals; however, small amounts of acetylacetonate ligation yielded nanocrystals with morphologies characteristic of twin defects. During synthesis at 230 °C, the Fe(III) oleate precursor is partially reduced, providing sufficient quantities of Fe(II) that are needed to grow the Fe3O4 nanocrystals (wherein one-third of the iron atoms are in the Fe(II) state) without twinning. Our investigations suggest that the acetylacetonate ligands prevent reduction of Fe(III) to Fe(II), leading to twinned structures during synthesis. Harnessing this insight, we identified conditions to predictably and continuously grow octahedral, spinel nanocrystals as well as conditions to synthesize highly twinned nanocrystals. These findings also help explain observations in the thermal decomposition synthesis literature which suggest that iron oxide nanocrystals produced from Fe(acac)3 are less prone to FeO contamination in comparison to those produced from Fe(III) alkylcarboxylates.