Building 2D classification models and 3D CoMSIA models on small-molecule inhibitors of both wild-type and T790M/L858R double-mutant EGFR

Molecular Diversity - Epidermal growth factor receptor (EGFR) has received widespread attention because it is an important target for anticancer drug design. Mutations in the EGFR, especially the...     

One-pot synthesis of peony-like Bi2S3/BiVO4(040) with high photocatalytic activity for glyphosate degradation under visible light irradiation

In this work, samples consisting of BiVO₄ with exposed (040) facets coupled with Bi₂S₃ (Bi₂S₃/BiVO₄) were prepared through a one-pot hydrothermal method, using ethylenediaminetetraacetic acid as directing agent and L-cysteine as sulfur source and soft template. X-ray diffraction, field emission scanning electron microscopy, and high-resolution transmission electron microscopy measurements indicated that the Bi₂S₃ content had a significant influence on the growth of (040) and (121) facets as well as on the morphology of the Bi₂S₃/BiVO₄ samples. When the Bi₂S₃ content reached 1 mmol, the Bi₂S₃/BiVO₄ samples exhibited a peony-like morphology. The results of transient photocurrent tests and electrochemical impedance spectroscopy measurements confirmed that a more effective charge separation and a faster interfacial charge transfer occurred in Bi₂S₃/BiVO₄ than BiVO₄. The enhanced photocatalytic activity of the Bi₂S₃/BiVO₄ samples could be attributed to the improved absorption capability in the visible light region and the enhanced electron-hole pair separation efficiency due to the formation of the Bi₂S₃/BiVO₄ heterostructure. In addition, the Bi₂S₃/BiVO₄ samples showed relative stability and reusability. The simple method presented in this work could be used to fabricate composite photocatalysts with high activity for different applications, such as photocatalytic degradation of organic pollutants, photocatalytic splitting of water, and photocatalytic reduction of carbon dioxide.     

A bioactive new protostane-type triterpenoid from Alisma plantago-aquatica subsp. orientale (Sam.) Sam.

A new protostane-type triterpenoid, 5β,29-dihydroxy alisol A (1) was isolated from Alisma plantago-aquatica subsp. orientale (Sam.) Sam. as well as 12-deoxyphorbol-13α-pentadecanoate (2). We first report the presence of compound 2 in the genus Alisma. Their structures were established on the basis of 1D and 2D NMR, and HRESIMS spectroscopic analyses. All the isolated compounds were assayed for their inhibitory effects against human carboxylesterase 2 (HCE-2). Compounds 1 and 2 displayed inhibitory activities against HCE-2 with IC₅₀ values of 29.2 and 4.6 μM, respectively. The interaction mechanisms of HCE-2 with compounds 1 and 2 were investigated by molecular docking, respectively.     

Stereodivergent Desymmetrization of Simple Dicarboxylates via Branch-Selective Pd/Cu Catalyzed Allylic Substitution

Asymmetric desymmetrization has been demonstrated to be a powerful strategy for building stereocenters in asymmetric synthesis. Herein, a Pd/Cu catalyzed asymmetric desymmetrization reaction with a simple geminal dicarboxylate is reported. A wide scope of imino esters bearing an aryl or heteroaromatic group were compatible with this bimetallic catalytic system. The reactions proceeded smoothly, giving the desired products in good yields with high to excellent regio-, diastereo-, and enantioselectivity (up to 20 : 1 branched:linear, >20 : 1 dr, >99 % ee). Notably, the reaction favored branched selectivity, which is unusual for the Pd-catalyzed allylic alkylation reaction. In addition, the standard product could be easily transformed to other valuable molecules such as chiral allylic alcohols, carbamates, and organic boron compounds. Furthermore, DFT calculations were conducted to explain the origin of the branched selectivity.     

Nb(iPrNPMe2)3Fe–PMe3: A potential high reactivity heterobimetallic catalyst for acetylene cycloadditions

Alkynes cycloaddition reactions are powerful tools for constructing cyclic molecules with optimal atom efficiency, but these reactions cannot proceed at ambient temperature without transition-metal catalysts. In this work, a heterobimetallic complex featuring an Nb–Fe triple bond, Nb(ⁱPrNPMe₂)₃Fe–PMe₃, has been evaluated as the potential catalyst for acetylene cycloaddition, using density functional theory. The calculated results show that the singlet-state (i.e. ground-state) Nb(ⁱPrNPMe₂)₃Fe–PMe₃ can be applied to benzene synthesis, but is not suitable for cyclobutadiene. Benzene can be obtained easily at room temperature and is the unique product on the singlet potential surface. The irradiation of infrared-red light can drive the excitation of singlet Nb(ⁱPrNPMe₂)₃Fe–PMe₃ to its triplet state. Both benzene and cyclobutadiene can be formed on the triplet reaction potential surface due to their low energy barriers. Therefore, Nb(ⁱPrNPMe₂)₃Fe–PMe₃ is a potential high reactivity heterobimetallic catalyst for the cyclotrimerization of alkynes. In the reaction process, the catalytic active site of Nb(ⁱPrNPMe₂)₃Fe–PMe₃ moves from niobium to iron.     

Tailoring Morphology of PVDF-HFP Membrane via One-step Reactive Vapor Induced Phase Separation for Efficient Oil-Water Separation

Poly(vinylidene fluoride-co-hexafluoropropylene)(PVDF-HFP) receives increasing attention in membrane separation field based on its advantages such as high mechanical strength, thermal and chemical stability. However, controlling the microporous structure is still challenging.In this work, we attempted to tailor the morphology of PVDF-HFP membrane via a one-step reactive vapor induced phase separation method.Namely, PVDF-HFP was dissolved in a volatile solvent and then was cast in an ammonia water vapor atmosphere. After complete evaporation of solvent, membranes with adjustable porous structure were prepared, and the microstructures of the membranes were analyzed by scanning electron microscopy, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy and X-ray diffraction characterizations. Based on the results, a mechanism of dehydrofluorination induced cross-linking of PVDF-HFP has been suggested to understand the morphology tailoring.To our knowledge, this is the first report of one-step reactive vapor induced phase separation strategy to tailor morphology of PVDF-HFP membrane. In addition, the membranes prepared in the ammonia water vapor exhibited enhanced mechanical strength and achieved satisfactory separation efficiency for water-in-oil emulsions, suggesting promising potential.     

Octahedral Chiral‐at‐Metal Iridium Catalysts: Versatile Chiral Lewis Acids for Asymmetric Conjugate Additions

Octahedral iridium(III) complexes containing two bidentate cyclometalating 5‐tert‐butyl‐2‐phenylbenzoxazole ( IrO ) or 5‐tert‐butyl‐2‐phenylbenzothiazole ( IrS ) ligands in addition to two labile acetonitrile ligands are demonstrated to constitute a highly versatile class of asymmetric Lewis acid catalysts. These complexes feature the metal center as the exclusive source of chirality and serve as effective asymmetric catalysts (0.5–5.0 mol % catalyst loading) for a variety of reactions with α,β‐unsaturated carbonyl compounds, namely Friedel–Crafts alkylations (94–99 % ee), Michael additions with CH‐acidic compounds (81–97 % ee), and a variety of cycloadditions (92–99 % ee with high d.r.). Mechanistic investigations and crystal structures of an iridium‐coordinated substrates and iridium‐coordinated products are consistent with a mechanistic picture in which the α,β‐unsaturated carbonyl compounds are activated by two‐point binding (bidentate coordination) to the chiral Lewis acid.     

A New Carotane Sesquiterpenoid Derivative with Antifungal Activity from Gymnopus sp. 0612-9

Chemistry of Natural Compounds - A new carotane sesquiterpenoid, methyl gymnabloate (1), was isolated from the fermentation broth of the wild macrofungus Gymnopus sp. 0612-9. Its structure was...     

表面喷砂对有机玻璃沿面闪络性能影响

绝缘子表面粗糙处理是提升其沿面闪络性能的重要途径,表面粗糙化处理方式不当,极易带来表面结构不均匀,难以获得稳定耐压性能的绝缘材料。为提升绝缘子表面粗糙处理的均匀性,本文利用表面喷砂技术对圆柱形有机玻璃(PMMA)绝缘子进行了粗糙化处理研究,以球形二氧化硅(SiO2)颗粒为工作介质,研究了不同喷砂粒径、氢氟酸后处理等因素对绝缘材料表面形貌和组分的影响,并利用短脉冲高压测试平台对喷砂处理前后有机玻璃绝缘子样品进行了真空沿面闪络性能测试。研究结果表明,喷砂处理在有机玻璃表面形成了较为均匀的凹坑,HF酸能够有效去除表面残留的SiO2颗粒,具有表面喷砂粗糙结构的绝缘子沿面闪络电压得到了稳定提升,相较于未处理的绝缘子闪络电压提升了约80%。     

Stereoselectivity and nonmigratory insertion mechanism of dimethylacetylene dicarboxylate into metallocene-hydride of Cp2M(L)H [Cp = η5-C5H5; M = Nb,V; L = CO,P (OMe)3]: A DFT study

The insertion of an alkyne into transition metal–hydrogen bonds is a key elementary step in catalytic polymerization and hydrogenation processes. It was found that a (Z)- or (E)-type alkyenyl complex can be formed through trans/cis stereospecific processes. In this work, the reaction mechanism of Cp₂M(L)H [Cp = η⁵-C₅H₅; M = Nb, V; L = CO, P (OMe)₃] with dimethylacetylene dicarboxylate (DMAD), and the factors influencing the stereoselectivity have been investigated based on density functional theory calculations. The calculated results show that all of the reactions are exothermic. For L = CO, the Z-isomer product forms first even at low temperatures because of the low Gibbs free energy barrier (ΔG^#). Then the Z-pro converts to E-pro , while for L = P (OMe)₃, the exclusive product is the E-isomer. For different metal centers, the reaction mechanisms of the Cp₂M(CO)H + DMAD (M = Nb and V) reaction are similar, while their products are different at room temperature. For M = Nb, because the energy barrier of the isomerization from Z-pro to E-pro is low and the relative free energies of Z-pro and E-pro are almost equal, both Z-pro and E-pro can be obtained. While for the Cp₂V(CO)H + DMAD reaction, only the Z-pro can be obtained under mild conditions, E-pro can be obtained only at high temperatures. For the Cp₂M(CO)H+DMAD(M=V and Nb) reactions, the formation of E-isomer products proceeds via two five-membered ring transition states. The calculated results provide an reasonable explanation for the experimental results and predict a new insertion reaction.