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Herein, rhodium(III)-catalyzed ß-C(sp2)–H alkenylation and alkylation of enamides are presented using readily accessible allylic alcohols by switching the reaction conditions. This tunable transformation has been applied to a wide range of substrates and typically proceeded with excellent regioselectivity and stereoselectivity as well as with good functional group tolerance. The catalytic system offers an efficient approach for synthesizing various functionalized enamides bearing N-(2Z,4E)-butadiene and (Z)-ß-C(sp2)–H alkylated enamides. In addition, mechanistic experiments suggest that Rh(III)-catalyzed C–H activation is not related to the critical step.

A straightforward cross-coupling of aryl thioether with aryl bromide with the aid of nickel salt, magnesium, and lithium chloride in tetrahydrofuran at ambient temperature was accomplished. The one-pot reactions proceeded efficiently via C–S bond cleavage to produce the desired biaryls in modest to good yields, avoiding the use of pregenerated or commercial organometallic reagents.

Aberrant lipid metabolism has recently been recognized as a new hallmark of malignancy, but the characteristics of fatty acid metabolism in breast cancer stem cells (BCSC) and potential interventions targeting this pathway remain to be addressed. Here, by using the in vitro BCSC models, mammosphere‐derived MCF‐7 cells and HMLE‐Twist‐ER cells, we found that the cells with stem cell‐like properties exhibited a very distinct profile of fatty acid metabolism compared with that of their parental cancer cells, characterized by increased lipogenesis, especially the activity of stearoyl‐CoA desaturase 1 (SCD1) responsible for the production of monounsaturated fatty acids, and augmented synthesis and utilization of the omega‐6 arachidonic acid (AA). Suppression of SCD1 activity by either enzyme inhibitors or small interfering RNA (siRNA) knockdown strikingly limited self‐renewal and growth of the BCSC, suggesting a key role for SCD1 in BCSC proliferation. Furthermore, elevated levels of SCD1 and other lipogenic enzymes were observed in human breast cancer tissues relative to the noncancer tissues from the same patients and correlated with the pathological grades. Interestingly, treatment of BCSC with omega‐3 fatty acids, eicosapentaenoic acid and docosahexaenoic acid, effectively downregulated the expression of the lipogenic enzymes and markedly suppressed BCSC self‐renewal and growth. Dietary supplementation of nude mice bearing BCSC‐derived tumors with omega‐3 fatty acids also significantly reduced their tumor load. These findings have demonstrated that increased lipogenesis is critical for self‐renewal and growth of BCSC, and that omega‐3 fatty acids are effective in targeting this pathway to exert their anticancer effect. Breast cancer stem cells (BCSC) have a distinct fatty acid profile due to the aberrant expressions of lipogenic enzymes (eg, FAS, SCD1, and FADS1/2), which are highly involved in sustaining their self‐renewal, and proliferative capabilities. Omega‐3 polyunsaturated fatty acids can effectively suppress the self‐renewal and growth of BCSC by downregulation of the lipogenic enzymes, especially SCD1.

The stereoselective β-C(sp2)–H arylation of various acyclic enamides with arylsilanes via Rh(III)-catalyzed cross-coupling reaction was illustrated. The methodology was characterized by extraordinary efficacy and stereoselectivity, a wide scope of substrates, good functional group tolerance, and the adoption of environmentally friendly arylsilanes. The utility of this present method was evidenced by the gram-scale synthesis and further elaboration of the product. In addition, Rh(III)-catalyzed C–H activation is considered to be the critical step in the reaction mechanism.

Herein we report a facile method for the synthesis of arylphosphonates via copper‐mediated the cross‐coupling reaction in the presence of 1, 10‐Phenanthroline and Ag2O. This method features a broad scope with respect to both the arylsilanes and H‐phosphonate diesters. Mechanistically, the reaction is proposed to involve oxidation by phosphinyl radical and reductive elimination process as the two key steps. With the optimized conditions established, various arylphosphonates were obtained up to 74% yield. This protocol is the first example of copper mediated the Ar−P bond formation of various arylsilanes with H‐phosphonates, and this novel methodology expands the applications of low cost and toxicity copper reagent in Ar−P bond construction. Copper‐mediatedcross‐coupling of various arylsilanes with H‐phosphonate diesters under mild conditions has been developed. This novel methodology expands the applications of copper reagent in Ar−P bond construction.

We describe herein a regioselective palladium(II)-catalyzed intermolecular hydroarylation of unactivated aliphatic alkenes with electronically and sterically diverse (hetero)arylsilanes under redox-neutral conditions. A removable bidentate 8-aminoquinoline auxiliary was readily employed to dictate the regioselectivity, prevent β-hydride elimination, and facilitate protodepalladation. This silicon-based protocol features a broad substrate scope with excellent functional group compatibility and enables an expeditious route to a variety of γ-aryl butyric acid derivatives in good yields with exclusive anti-Markovnikov selectivity.

We report a chelation-assisted C–H arylation of various indoles with sterically and electronically diverse (hetero)arylsilanes enabled by cost-effective Cp*-free cobalt catalysis. Key to the success of this strategy is the judicious choice of copper(II) fluoride as a bifunctional sliane activator and catalyst reoxidant. This methodology features a broad substrate scope and good functional group compatibility. The synthetic versatility of this protocol has been highlighted by the gram-scale synthesis and late-stage diversification of biologically active molecules.

•Explore the use of PD-1 inhibitors in combination with nab-TP regimens in LA-NPC, which may offer patients near-term efficacy, long-term survival benefits, and a manageable safety profile.•To explore the relationship between PD-L1 expression level on the efficacy and prognosis of LA-NPC.•Exploring the optimal sequence for the use of immunotherapy in LA-NPC.

A catalyst and additive-free annulation of 2-pyridylacetates and ynals under molecular oxygen was the first developed, affording 3-acylated indolizines in good to excellent yields. Molecular oxygen was used as the source of the carbonyl oxygen atom in indolizines. This approach was compatible with a wide range of functional groups, and especially it has been successfully extended to unsaturated double bonds and triple bonds, which were difficult to prepare by previous methods in a single step.

The developed methodology describes an efficient Rh(III)-catalyzed oxidative C–H/C–H cross-coupling between acyclic enamides and heteroarenes. This cross dehydrogenative coupling (CDC) reaction offers advantages, including excellent regioselectivity and stereoselectivity, good functional group compatibility, and a broad substrate scope. Mechanistically, Rh(III)-catalyzed β–C(sp2)–H activation of acyclic enamides is proposed to be the critical step.

Herein, we report an efficient copper‐catalyzed aerobic Chan‐Lam type N‐arylation of various indoles and anilines with structurally diverse aryltrialkoxysilanes under mild conditions. This silicon‐based protocol enables the efficient C−N cross‐coupling of indoles and anilines with user‐friendly organosilicon reagents by employing inexpensive and nontoxic Cu(OAc)2, which is efficient and practical without the addition of other ligands, bases, and metal oxidants. This transformation is compatible with a wide range of substrates, and typically proceeds with high efficiency as well as with good functional group compatibility. A plausible mechanism involving the formation of Cu(III) species in the reaction was tentatively proposed. An efficient copper‐catalyzedaerobic Chan‐Lam type N‐arylation of indoles and anilines with structurally diverse aryltrialkoxysilanes under mild conditions is reported.

This study aimed to explore the effects of fluid hydration status on ultrasound muscle measurement in hemodialysis (HD) patients.

This method represents an efficient rhodium(III)-catalyzed o-C–H arylation of readily available benzimidate derivatives with diverse arylsilanes in water as a sustainable solvent, enabling the straightforward synthesis of potentially useful biphenyl-2-carbonitrile derivatives. This silicon-based protocol employs benzimidates as both an efficacious directing group and the source of a nitrile group.

Nanoporous Anodic Aluminum Oxide (AAO), its average diameters of porous were 50 nm, was obtained by two-step electrochemical anodization aluminum process. Highly ordered luminescence arrays formed by filling AAO nanopores with quercetin molecules has been studied by fluorescent spectroscopy in this work. AAO showed stronger adsorption capability of quercetin than Al3+-quercetin complex. The mechanism may be physical and chemical adsorption all together. Meanwhile, red shift of the maximum fluorescence peak of quercetin in AAO was observed. The molecular assemblies in the nanopore array are highly ordered and the fluorescence polarization dependence indicates a preferred molecular orientation along the pore axis. This maybe explains the mechanism of molecular luminescence depending on its environment.

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