Search

Precisely controlling the product selectivity of a reaction is an important objective in organic synthesis. α‐Ketoamides are vital intermediates in chemical transformations and privileged motifs in numerous drugs, natural products, and biologically active molecules. The selective synthesis of α‐ketoamides from feedstock chemicals in a safe and operationally simple manner under mild conditions is a long‐standing catalysis challenge. Herein, an unprecedented TBD‐switched Pd‐catalyzed double isocyanide insertion reaction for assembling ketoamides in aqueous DMSO from (hetero)aryl halides and pseudohalides under mild conditions is reported. The effectiveness and utility of this protocol are demonstrated by its diverse substrate scope (93 examples), the ability to late‐stage modify pharmaceuticals, scalability to large‐scale synthesis, and the synthesis of pharmaceutically active molecules. Mechanistic studies indicate that TBD is a key ligand that modulates the Pd‐catalyzed double isocyanide insertion process, thereby selectively providing the desired α‐ketoamides in a unique manner. In addition, the imidoylpalladium(II) complex and α‐ketoimine amide are successfully isolated and determined by X‐ray analysis, confirming that they are probable intermediates in the catalytic pathway. [ABSTRACT FROM AUTHOR]

Objective To explore the effect of zerumbone on proliferation, migration and invasion of non-small cell lung cancer cell line and underline mechanism. Methods Human non-small cell lung cancer cells line A549 was divided into control group, zingerone-low dose group, zingerone-medium dose group, zingerone-high dose group, pcDNA group, pcDNA-FBXW7 group, and zingerone-high dose group +si-NC group, zingerone-high dose +si-FBXW7 group. Cell proliferation inhibition was detected by methyl thiazolyl tetrazolium (MTT) method, cell migration and invasion were detected by Transwell assays, and the expression of F-box with 7 tandem WD40 (FBXW7) mRNA and protein were detected by Western blot and real-time(RT-qPCR). Results Compared with control group, the proliferation, migration and invasion of A549 cells in the zingerone-low, medium and high dose groups were significantly reduced (P＜0.05), the expression of FBXW7 mRNA and protein were significantly increased (P＜0.05). Compared with the pcDNA group, the proliferation, migration and invasion of A549 cells in the pcDNA-FBXW7 group were significantly reduced (P＜0.05). Compared with the Zingerone-high-dose+si-NC group, the cell proliferation, migration and invasion ability of A549 in the Zingerone-high-dose+si-FBXW7 group was significantly increased (P＜0.05). Conclusions Zerumbone reduces proliferation, migration and invasion of non-small cell lung cancer cells, and the underlying mechanism is related to the up-regulation of FBXW7 expression.

In this study, we characterized the intratumoral expression of IL-17 and CD8+ TILs in gastric adenocarcinoma patients after resection and determined the correlation between the survival probability of gastric adenocarcinoma patients and the expression of IL-17 in tumor. Expression of IL-17 and CD8 was assessed by immunohistochemistry, and the prognostic effects of intratumoral IL-17 expression and CD8+ TILs were evaluated by Cox regression and Kaplan-Meier analysis. Immunohistochemical detection revealed the presence of IL-17 and CD8+ cells in gastric adenocarcinoma tissue samples (90.6%, 174 out of 192 patients and 96.9%, 186 out of 192 patients, respectively). We have also found that intratumoral IL-17 expression was significantly correlated with age (p=0.004) and that the number of CD8+ TILs was significantly correlated with UICC staging (p=0.012) and the depth of tumor invasion (p=0.022). The five-year overall survival probability among patients intratumorally expressing higher levels of IL-17 was significantly better than those expressing lower levels of IL-17 (p=0.036). Multivariate Cox proportional hazard analyses revealed that intratumoral IL-17 expression (HR: 0.521; 95% CI: 0.329-0.823; p=0.005) was an independent factor affecting the five-year overall survival probability. We conclude that low levels of intratumoral IL-17 expression may indicate poor prognosis in gastric adenocarcinoma patients.

The safety problem caused by lithium dendrite of lithium metal anode and the rapid capacity decay problem caused by the shuttle effect of polysulfide and polyselenide during the charge and discharge of selenium disulfide cathode limit the application of lithium selenium disulfide batteries significantly. Here, a fibrous ATFG-COF, containing rich carbonyl and amino functional groups, was applied as the separator coating layer. Density Functional Theory (DFT) theoretical calculations and experimental results showed that the abundant carbonyl group in ATFG-COF had a positive effect on lithium ions, and the amino group formed hydrogen bonds with bis ((trifluoromethyl) sulfonyl) azanide anionics (TFSI−), which fixed TFSI− in the channel, so as to improve the transfer number of lithium ions and narrow the channels. Therefore, ATFG-COF fiber coating can not only form a rapid and uniform lithium-ion flow on the lithium anode to inhibit the growth of lithium dendrites, but also effectively screen polysulfide and polyselenide ions to suppress the shuttle effect. The Li-SeS2 cell with ATFG-COF/polypropylene (ATFG-COF/PP) separator exhibited good cycle stability at 0.5 C and maintained a specific capacity of 509 mAh/g after 200 cycles. Our work provides insights into the design of dual-function separators with high-performance batteries. [ABSTRACT FROM AUTHOR]

Due to the extremely high bond energy of N≡N (∼941 kJ/mol), the traditional Haber-Bosch process of ammonia synthesis is known as an energy-intensive and high CO 2 -emission industry. In this paper, a cascade N 2 reduction process with dielectric barrier discharge (DBD) plasma oxidation and electrocatalytic reduction as an alternative route is first proposed. N 2 is oxidized to be reactive nitrogen species (RNS) by nonthermal plasma, which would then be absorbed by KOH solution and electroreduced to NH 4 + . It is found that the production of NO x is a function of discharge length, discharge power, and gas flow rate. Afterward, the cobalt catalyst is used in the process of electrocatalytic reduction of ammonia, which shows high selectivity (Faradic efficiency (FE) above 90%) and high yield of ammonia (45.45 mg/h). Finally, the cascade plasma oxidation and electrocatalytic reduction for ammonia synthesis is performed. Also, the performance of the reaction system is evaluated. It is worth mentioning that a stable and sustainable ammonia production efficiency of 16.21 mg/h is achieved, and 22.16% of NO x obtained by air activation is converted into NH 4 + . This work provides a demonstration for further industrial application of ammonia production with DBD plasma oxidation and electrocatalytic reduction techniques.