CWI pathway participated in vegetative growth and pathogenicity through a downstream effector AflRlm1 in Aspergillus flavus.

The cell wall is an essential dynamic structure for shielding fungus from environmental stress, and its synthesizing and remodeling are regulated by the cell wall integrity (CWI) pathway. Here, we explored the roles of a putative downstream effector AflRlm1 of CWI pathway in Aspergillus flavus. The results showed that AflRlm1 played a positive role in conidia production, sclerotium formation, aflatoxin biosynthesis, and pathogenicity. Furthermore, we provided evidence for the physical connection between AflRlm1 and AflSlt2 and determined the role of AflSlt2 in the phosphorylation of AflRlm1. Then, we discovered the importance of WSCs (cell wall integrity and stress response component) to the CWI signal and the process of AflRlm1 transferring to the nucleus after receiving the signal. Overall, this study clarified the transmission process of CWI signals and proves that the CWI pathway plays a key role in the development of A. flavus and the production of aflatoxin combined with transcriptome data analysis.

Copper(i) pyrimidine-2-thiolate cluster-based polymers as bifunctional visible-light-photocatalysts for chemoselective transfer hydrogenation of α,ß-unsaturated carbonyls.

The photoinduced chemoselective transfer hydrogenation of unsaturated carbonyls to allylic alcohols has been accomplished using cluster-based MOFs as bifunctional visible photocatalysts. Assemblies of hexanuclear clusters [Cu6(dmpymt)6] (1, Hdmpymt = 4,6-dimethylpyrimidine-2-thione) as metalloligands with CuI or (Ph3P)CuI yielded cluster-based metal organic frameworks (MOFs) {[Cu6(dmpymt)6]2[Cu2(µ-I)2]4(CuI)2} n (2), {[Cu6(dmpymt)6]2[Cu2(µ-I)2]4} n (3), respectively. Nanoparticles (NPs) of 2 and 3 served both as photosensitizers and photocatalysts for the highly chemoselective reduction of unsaturated carbonyl compounds to unsaturated alcohols with high catalytic activity under blue LED irradiation. The photocatalytic system could be reused for several cycles without any obvious loss of efficiency.

miR-34b/c regulates doxorubicin-induced myocardial cell injury through ITCH.

Objective: To determine the underlying mechanism of miR-34b/c in regulating doxorubicin (Dox)-induced myocardial cell injury.Methods: The viability of mouse myocardial cells HL-1 was detected by MTT assay. The apoptosis of HL-1 cells was detected by TUNEL assay. mRNA expressions of ITCH, TNF-α and IL-6 were measured by qRT-PCR. Protein levels of ITCH, NF-κB, TNF-α and IL-6 were measured by western blot. Dual luciferase assay was performed to detect the regulation of miR-34b/c on ITCH. Mouse model of cardiomyopathy was induced by intraperitoneal injection of Dox.Results: Dox reduced HL-1 cell viability and activated NF-κB pathway in HL-1 cells. miR-34b/c expressions were gradually up-regulated and ITCH expression was gradually down-regulated in Dox-treated HL-1 cells. miR-34b/c expression had negative correlation with the mRNA expression of ITCH. Besides, ITCH was a target of miR-34b/c. miR-34b/c mimic reduced cell viability, suppressed ITCH expression, increased TNF-α and IL-6 level, and promoted NF-κB expression in nucleus and cytoplasm of HL-1 cells. Whereas silencing miR-34 protected HL-1 cells through regulating ITCH. Finally, we demonstrated miR-34 antagomir-protected myocardial cells in mouse model of cardiomyopathy.Conclusion: miR-34b/c decreased HL-1 cell viability and promoted the secretion of proinflammatory cytokines in Dox-induced myocardial cells through ITCH/NF-κB pathway.

Reaction condition controlled nickel(ii)-catalyzed C-C cross-coupling of alcohols.

The challenge in the C-C cross-coupling of secondary and primary alcohols using acceptorless dehydrogenation coupling (ADC) is the difficulty in accurately controlling product selectivities. Herein, we report a controlled approach to a diverse range of ß-alkylated secondary alcohols, α-alkylated ketones and α,ß-unsaturated ketones using the ADC methodology employing a Ni(ii) 4,6-dimethylpyrimidine-2-thiolate cluster catalyst under different reaction conditions. This catalyst could tolerate a wide range of substrates and exhibited a high activity for the annulation reaction of secondary alcohols with 2-aminobenzyl alcohols to yield quinolines. This work is an example of precise chemoselectivity control by careful choice of reaction conditions.

Switchable Chemoselective Transfer Hydrogenations of Unsaturated Carbonyls Using Copper(I) N-Donor Thiolate Clusters.

Unsaturated alcohols and saturated carbonyls are important chemical, pharmaceutical, and biochemical intermediates. We herein report an efficient transfer hydrogenation protocol in which conversion of unsaturated carbonyl compounds to either unsaturated alcohols or saturated carbonyls was catalyzed by Cu(I) N-donor thiolate clusters along with changing hydrogen source (isopropanol or butanol) and base (NaOH or K2CO3). Mechanistic studies supported by DFT transition state modeling indicate that such a chemoselectivity can be explained by the relative concentrations of Cu(I) monohydride and protonated Cu(I) hydride complexes in each catalytic system.

Copper(i) 5-phenylpyrimidine-2-thiolate complexes showing unique optical properties and high visible light-directed catalytic performance.

Solvothermal reactions of 5-phenylpyrimidine-2-thiol (5-phpymtH) with equimolar CuBr afforded one hexanuclear cluster [Cu6(µ3-5-phpymt)6] (1) along with a tetranuclear by-product [{(Cu2Br)(µ-5-phpymtH)}(µ3-5-phpymt)]2 (2). A two dimensional (2D) polymer [Cu4(µ5-5-phpymt)2(µ-Br)2]n (3) was isolated from the reaction of 5-phpymtH with two equiv. of CuBr. Analogous reactions of 5-phpymtH with one or four equiv. of CuI produced one tetranuclear cluster [{Cu2(µ-5-phpymtH)(µ-5-phpymt)}(µ3-I)]2 (4) and one 2D polymer [Cu6I2(µ4-I)2(µ4-5-phpymt)2]n (5). Compound 1 possesses a water-wheel-shaped hexameric structure. Compound 2 has an H-shaped tetrameric structure. Compound 3 possesses a 2D network in which unique 1D [Cu8(µ-Br)2(µ5-5-phpymt)4]n chains are connected by µ-Br- ions. Compound 4 has another tetrameric structure in which two {Cu2(µ-5-phpymtH)2(µ-5-phpymt)} fragments are linked by a pair of µ3-I- ions. Compound 5 contains another 2D network in which hexanuclear {Cu6I2(µ4-I)2} units are linked by µ4-5-phpymt bridges. The 5-phpymt ligand shows four coordination modes: µ-κ1(S)-κ1(N) (4), µ3-κ2(S)-κ1(N) (1 and 2), µ4-κ1(N)-κ2(S)-κ1(N') (5) and µ5-κ1(N)-κ3(S)-κ1(N') (3). Complex 1 shows strong solvatochromic behaviour and displays reversible luminescence switching upon alternate addition of CF3COOH and Et3N into its CHCl3 solution. Complexes 1-5 exhibit a high photocatalytic activity towards the aerobic oxidative hydroxylation of arylboronic acids to phenols under visible light irradiation. Catalyst 5 can be reused in several cycles without any obvious decay of the catalytic efficiency. These results offer an interesting insight into how the CuX/5-phpymtH molar ratios and X- ions exert great impacts on the coordination modes of the 5-phpymt- ligand, the structures of the final complexes, and the luminescence and catalytic properties.