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Although direct acetoxylation and cyclization of alkylamide have been extensively reported, investigation of the structural influence of directing groups on selectivity is limited. Pd-catalyzed 2-methoxyiminoacyl (MIA) assisted γ-acetoxylation of alkylamides has been developed. Further DFT studies have demonstrated that the directing groups have a significant influence on the reductive elimination step. The strong electron-donating effect of the OMe group in MIA leads to the preferential formation of a five-membered cyclopalladium (OAc-Pd-C) complex, which favors the acetoxylation pathway.

The 2-methoxyiminoacyl-mediated arylation of substituted phenylalanines has been examined. Selective monoarylation at the ortho position was achieved using pyridone ligands which decelerate the arylation process. Density functional theory (DFT) study of a continuous C-H arylation process that included the first and second arylation stage was performed. The computational result shows that the introduction of a pyridone ligand obviously disfavors the second arylation stage, which directly contributes to the selectivity between the mono/diarylated products. Furthermore, results of the kinetic isotope effect and a control experiment are agreed with DFT study.

The 2-methoxyiminoacyl-mediated arylation of substituted phenylalanines has been examined. Selective monoarylation at the

Interfacial engineering is an efficient strategy to develop electrocatalysts with excellent performance. By using this strategy, a novel Fe-doped urchin-like Ni2P/Ni3S2 (NPZFNS@C/NF) heterostructure with metal–organic frameworks (MOFs) as the precursor in-suit grows on nickel foam (NF) with abundant hetero-interfaces and carbon-coating is successfully constructed. Owing to the existence of hetero-interfaces and carbon coating, the unique surface electronic structure and d-band center of NPZFNS@C/NF are also obtained. Benefiting from the regulation of electronic structure and d-band center, the NPZFNS@C/NF electrode exhibits extremely high activity for oxygen evolution reaction (OER) and high activity for hydrogen evolution reaction (HER), which shows a very low overpotential of 141 mV at the current density of 10 mA cm−2 for OER and 129 mV for HER respectively in alkaline electrolyte. Furthermore, it also exhibits a small overpotential of 1.5 V for overall water splitting with NPZFNS@C/NF as both anode and cathode, which is lower than most of non-noble metal-based bifunctional electrocatalysts reported. Density functional theory (DFT) results further confirm that the hetero-interface with carbon coating can further optimize Gibbs free energies for both OER and HER processes. This design and constructure strategy provides a new avenue for overall water splitting.

An aerobic oxidative cyanation for the synthesis of α-aminonitriles was reported. The formation of C(sp3)-CN bonds was achieved under a metal-free condition by utilizing azobis(isobutyronitrile) as a sole organic cyanide source with the combination of pivalic acid and sodium acetate as additives.

Electrocatalytic Nitrogen Reduction Reaction (ECNRR) is a promising alternative NH3 production method relative to Haber-Bosch process. However, the ECNRR still suffers from rather low NH3 yield and selectivity (Faradaic efficiency (FE)) due to the poor catalytic activity of catalysts. Herein, benefiting from interface engineering, FeNi2S4/NiS hetero-interface electrocatalysts with unique electronic structures are successfully constructed, which the optimized catalyst can enhance the adsorption of N2 molecules meanwhile inhibit H atoms adsorption. Significantly, the NH3 yield and FE of FNS/CC-2 are reached to 128.398±1.32 μg h−1 cm−2 and 28.64 ± 0.18% which are higher than most of non-noble metal-based NRR electrocatalysts in alkaline electrolyte reported. Detailed experimental investigation and DFT calculations reveal that the enhanced electrocatalytic performance and selectivity of FeNi2S4/NiS towards N2 are attributed to the changes of the D-band center and electronic structure of electrocatalyst surface. The construction strategy of this NRR electrocatalyst provides a new avenue on electrocatalytic research.

Metal-organic frameworks (MOFs) have emerged as a promising electrode material for supercapacitors owing to their high porosity and a regular porous structure, however, the capacitance performance and/or ion conduction rate performance of most MOFs with poor electrical conductivity are greatly hindered. To increase the bulk electrical conductivity and the efficiency of MOFs, an effective method was proposed by interweaving organic conductive polymer polyaniline (PANI) and MOF crystals (ZIF-67) grown in situ. As a result, the highly conductive PANI that interlink the MOF particles (denoted as ZIF-67@PANI) increase the electron transfer between MOF particles while the effective porosity of the MOF is maintained, which greatly improves the electrical conductivity and capacitance of MOFs. Electrochemical studies indicates that the ZIF-67@PANI exhibits ultrahigh specific capacity of 1123.65 C g−1 at a current density of 1 A g−1 in a three-electrode system, superior rate capability (648.9 C g−1 at 10 A g−1 current density) and excellent cycling stability (92.3% capacity retention after 9000 cycles). Furthermore, a symmetrical supercapacitor device based on ZIF-67@PANI network exhibits ultrahigh energy density of 71.1 W h kg−1 at a power density of 504.72 W kg−1 at 1 A g−1 current density. The capacitance performance of ZIF-67@PANI-2 we report here is the best among the supercapacitor materials formed by MOFs and conductive polymers up to date, confirming the importance of hybrid materials on the nanoscale and the significance of in situ synthetic chemistry.

Carbonate weathering and the CO

Background Danggui (Radix Angelicae Sinensis) is an herb often used in Traditional Chinese medicine. It is used to promote blood flow and has been used in the treatment of myocardial ischemia-reperfusion injury in animal models. Angiotensin II (Ang II) has been shown to play important roles in mediating cardiovascular diseases, and may cause cardiac hypertrophy and apoptosis. This study aimed to investigate whether Danggui has protective effects on Ang II-induced apoptosis in H9c2 cardiomyoblast cells and study the mechanisms involved. Methods We evaluated the effect of Danggui on Ang II-induced apoptosis in an in vitro model. H9c2 cardiomyoblast cells were cultured in serum-free medium for 4 hr, then treated with Danggui (50, 100 μg/ml) 1 hr pre- or post-Ang II treatment. After a further 23 hr of culture, cells were harvested for analyses with assays for apoptosis markers and cell signaling pathways. Results Our results showed that Ang II induced upregulation of pro-apoptotic Bad, instability of the mitochondria membrane potential, cytochrome c release, caspase-9 and caspase-3 activation and cardiomyocyte apoptosis. Pre- or post-treatment with Danggui reversed all of the above Ang II-induced apoptotic effects in H9c2 cells. Furthermore, the JNK (SP600125) inhibitor completely blocked Danggui inhibition of caspase-3 activation in Ang II-treated H9c2 cells. Conclusions Our results showed that Danggui either pre-treatment or post-treatment highly attenuated the Ang II-induced apoptosis in cardiomyoblast cells. The findings demonstrated that the anti-apoptosis effect of Danggui is mediated by JNK and PI3k inhibitors. Electronic supplementary material The online version of this article (doi:10.1186/1472-6882-14-358) contains supplementary material, which is available to authorized users.