Copper-Promoted Intramolecular Oxidative Dehydrogenation for Synthesizing Dihydroisocoumarins and Isocoumarins.

Isocoumarins and dihydroisocoumarins are important skeletons with a wide range of biological activities, such as anti-bacterial, anti-allergy, anti-fungal, anti-tumor, and anti-HIV properties. Herein, we demonstrated divergent syntheses of isocoumarins and 3,4-dihydroisocoumarins by intramolecular dehydrogenative cyclization of 2-(3-oxobutyl) benzoic acids. This transformation undergoes Csp3-H bonds and O-H bonds coupling in air using copper salt. The reactions may undergo free radical process.

Oxygen Vacancy Induced Boosted Visible-Light Driven Photocatalytic CO2 Reduction and Electrochemical Water Oxidation Over CuCo-ZIF@Fe2 O3 @CC Architecture.

Herein, the obtained Cu0.5 Co0.5 -ZIF@Fe2 O3 @CC-150 heterojunction (termed as Cu1- x Cox -ZFC-150) showed high hydrogen and oxygen evolution reaction (HER and OER) activities with low overpotential small Tafel slope. When employed to be the bifunctional anode and cathode, they only needed a cell voltage of 1.62 V. The composite also exhibited excellent photocatalytic performance on CO2 evolution into CO and CH4 . The enhanced OER kinetics and Z-scheme charge transfer model for photocatalytic property have been discussed based on the experiments and density functional theory (DFT) analysis. The optimized phase interfaces, abundant active sites, optional oxygen vacancy, and adjusted Gibbs free energy were beneficial for the fast electron/ion transport enhancing the water splitting performance.

MOFs assembled from C3 symmetric ligands: structure, iodine capture and role as bifunctional catalysts towards the oxidation-Knoevenagel cascade reaction.

Three new NiII/CoII-metal organic frameworks were self-assembled by the reaction of C3 symmetric 1,3,5-tribenzoic acid (H3BTC) and 2,4,6-tris(4-pyridyl)-1,3,5-triazine (4-TPT) ligands and NiII/CoII salts under solvothermal conditions. Isomorphous MOF1 and MOF2 exhibit a 3D pillar-layer framework based on binuclear M2(OH)(COO)2 units connected by tritopic BTC3- and 4-TPT ligands with a novel (3,5)-connected topology net. MOF3 displays a 3-fold interpenetrated 3D network exhibiting a (3,4)-connected topology net. The porous MOF3 can reversibly take up I2. The activated MOFs contain both Lewis acid (NiII center) and basic (uncoordinated pyridyl or carboxylic groups) sites, and act as bifunctional acid-base catalysts. The catalytic measurements demonstrate that the activated MOF3 exhibits good activities for benzyl alcohol oxidation and the Knoevenagel reaction and can be recycled and reused for at least four cycles without losing its structural integrity and high catalytic activity. Thus, the catalytic properties for the oxidation-Knoevenagel cascade reaction have also been studied.

Nanopore Formation and Structural Changes in Black Shale During the Initial Weathering Stage: A Longmaxi Formation Profile in Northwestern Hunan, China.

Understanding the controls on composition changes and porosity evolution in the critical zone of shale remains a major challenge. The aim of the present study is to develop a model of the changes in mineral compositions, chemical compositions and nanopore formation in shale during the initial weathering stage. To understand these processes, we selected a Silurian shale profile rich in pyrite and organic matter located in South China. Based on X-ray diffraction (XRD) and bulk elemental data, the variations in mineralogical and chemical compositions with depth were studied. To characterize the full pore size spectrum and to gain insight into the nature of secondary pores and their relationship with weathering, nuclear magnetic resonance (NMR) measurements and petrographic observations were combined with scanning electron microscopy (SEM) imaging. The results show that Al and K are enriched slightly, while Ca and Na are depleted in the upper part of the weathering profile. Si, Mn and Ti are relatively stable from the bottom to the top of the profile. Quartz, feldspar, mica, illite and chlorite are the main minerals in the parent rock, and they are relatively stable along the profile. The rock density gradually decreases from 2.6 g/cm³ to 2.1 g/cm³ from the bottom to the top, and the color of the shales changes from black to grayish yellow, but no secondary minerals are detected. The chemical weathering of black shale is dominated by the oxidation of pyrite and organic matter, giving rise to color variation and nanopore formation. The increase in interparticle pores at the nanometer-micron scale is initiated by the dissolution of easily weathered components such as organic matter and pyrite. The removal of clay minerals and tiny particles by groundwater seepage may be the main cause of porosity enhancement during the initial weathering stage. This study suggests that nanoporosity may play an important role in the process of fluid-rock interaction within black shale during the initial weathering stage.

Association between SCN1A polymorphism rs3812718 and valproic acid resistance in epilepsy children: a case-control study and meta-analysis.

Resistance to valproic acid (VPA), a first-line antiepileptic drug (AED), is occurring at an alarming rate, particularly in children. Signal nucleotide polymorphisms are considered crucial in this process. Therefore, we investigated whether the SCN1A polymorphism rs3812718 could be associated with VPA resistance. A total of 231 children with epilepsy who were solely administered VPA were enrolled. DNA was extracted from the peripheral blood samples and was genotyped by the Mass Array method. Furthermore, a meta-analysis was conducted between the drug responsive and resistant patients who were exposed to voltage-gated sodium channels. Results revealed that the TT genotype was associated with a higher risk of developing drug resistance (OR = 2.636, 95% CI 1.08-6.433, P = 0.033). After adjusting for the risk factors, a significant difference was still observed between the responsive and resistant groups (OR = 2.861, 95% CI 1.141-7.174, P = 0.025). Moreover, the recessive model was associated with a decreased drug resistance (OR = 0.402, 95% CI 0.167-0.968, P = 0.042) after correcting the risk factors. Meta-analysis of nine studies revealed similar results. In conclusion, our results proved that the rs3812718 TT genotype was associated with a high risk of developing drug resistance, and the recessive model could decrease the risk of VPA resistance.

Terpenoids with alpha-glucosidase inhibitory activity from the submerged culture of Inonotus obliquus.

Lanostane-type triterpenoids, inotolactones A and B, a drimane-type sesquiterpenoid, inotolactone C, and five known terpenoids 6ß-hydroxy-trans-dihydroconfertifolin, inotodiol, 3ß,22-dihydroxyanosta-7,9(11),24-triene, 3ß-hydroxycinnamolide, and 17-hydroxy-ent-atisan-19-oic acid, were isolated from the submerged culture of chaga mushroom, Inonotus obliquus. Their structures were characterized by spectroscopic methods, including MS and NMR (1D and 2D) spectroscopic techniques. Inotolactones A and B, examples of lanostane-type triterpenoids bearing α,ß-dimethyl, α,ß-unsaturated δ-lactone side chains, exhibited more potent alpha-glucosidase inhibitory activities than the positive control acarbose. This finding might be related to the anti-hyperglycemic properties of the fungus and to its popular role as a diabetes treatment. In addition, a drimane-type sesquiterpenoid and an atisane-type diterpenoid were isolated from I. obliquus.