o-Trityl phenoxy-imino vanadium (III) complexes: synthesis,characterization, and catalysis on ethylene (co)polymerization

Several phenoxy-imine ligands bearing o-trityl group in phenoxy moiety RN=CHArOH (Ar = C₆H₂(CPh₃)^tBu, R = 2,6-Me₂C₆H₃ ( L ₁ H ); 2,6-ⁱPr₂C₆H₃ ( L ₂ H ); 3,5-(CF₃)₂C₆H₃ ( L ₃ H ); 3,5-(OMe)₂C₆H₃ ( L ₄ H ); CHPh₂ ( L ₅ H ); CPh₃ ( L ₆ H )) were synthesized and characterized by¹H NMR and ¹³C NMR spectroscopy. The vanadium complexes based on these ligands LVCl₂(THF)₂ ( 1–6 ) were synthesized via conventional transmetalation reaction in moderate to high yields. Complexes 1–6 were fully characterized by FT-IR, elemental analyses and the molecular structures of 1 , 2 ·H₂O, (2 ·H₂O ) ₂ (μ-Cl) ₂ , 4 , and 5 were confirmed by X-ray crystallographic analysis in which the six-coordinated vanadium centers are in a typical octahedral geometry. Upon activation with Et₂AlCl in toluene, complexes 1–6 showed high activities in ethylene polymerization affording polymers with moderate molecular weight (5.9–11.8 × 10⁴ Da). Moreover, in hexane or CH₂Cl₂, 1–6 /Et₂AlCl exhibited enhanced activities. When activated with MAO or MMAO in toluene, these complexes showed relatively low activities but afforded polymers with ultra-high molecular weight (up to 3.30 × 10⁶ Da). 1–6 /Et₂AlCl also showed high activities in ethylene/1-hexene copolymerization at room temperature giving moderate molecular-weight polymers (6.5–11.4 × 10⁴ Da) with co-monomer incorporation being of 6.0 ~ 7.8%.     

The antidepressant effect of 4-hydroxybenzyl alcohol 2-naphthoate through monoaminergic,GABAergic system and BDNF signaling pathway

Abstract

Gastrodigenin, also known as 4-hydroxybenzyl alcohol (HBA), is one of the main components of Gastrodia elata, which is a perfect lead compound of natural products. In order to get new active compounds, we modified the structure of HBA through esterification with carboxylic acid, and got a series of derivatives in which 4-hydroxybenzyl alcohol 2-naphthoate (NHBA) showed stronger antidepressant activity than HBA. In this paper, we firstly evaluated the antidepressant activity of NHBA by tail suspension test (TST) and forced swimming test (FST). Then, we carried out the biochemical assay and western blot to determine its mechanism. The results displayed that NHBA could increase the content of serotonin, dopamine, norepinephrine, γ-aminobutyric acid, brain-derived neurotrophic factor (BDNF) and tropomyosin receptor kinase B (TrkB) in mice brain. It suggested that NHBA exhibited an antidepressant-like effect through monoaminergic system, GABAergic system and BDNF/TrkB signaling pathways.     

General Formation of Macro-/Mesoporous Nanoshells from Interfacial Assembly of Irregular Mesostructured Nanounits

Mesoporous core–shell nanostructures with controllable ultra-large open channels in their nanoshells are of great interest. However, soft template-directed cooperative assembly to mesoporous nanoshells with highly accessible pores larger than 30 nm, or even above 50 nm into macroporous range, remains a significant challenge. Herein we report a general approach for precisely tailored coating of hierarchically macro-/mesoporous polymer and carbon shells, possessing highly accessible radial channels with extremely wide pore size distribution from ca. 10 nm to ca. 200 nm, on diverse functional materials. This strategy creates opportunities to tailor the interfacial assembly of irregular mesostructured nanounits on core materials and generate various core–shell nanomaterials with controllable pore architectures. The obtained Fe,N-doped macro-/mesoporous carbon nanoshells show enhanced electrochemical performance for the oxygen reduction reaction in alkaline condition.     

Revealing and comparing different excited-state intramolecular proton transfer processes for 3-(4-dimethylamino-phenyl)-1-(4-fluoro-2-hydroxy-phenyl)-propenone and 3-(4-dimethylamino-phenyl)-1-(4-fluoro-2-hydroxy-phenyl)-3-hydroxy-propenon

Two novel 2′-hydroxychalcone derivatives (i.e., M1 and M2) are explored in this work. We mainly focus on investigating the effects of photoexcitation on hydrogen bonds and on the excited-state intramolecular proton transfer (ESIPT) process. On the basis of calculations of electrostatic potential surface and intramolecular interactions, we verify the formation of hydrogen bond O1 H2···O3 in both S₀ and S₁ states. Exploring the ultraviolet–visible spectra in the liquid phase, our simulated results reappear in the experimental phenomenon. Analyzing molecular geometry and infrared stretching vibrational spectra, we confirm O1 H2···O3 is strengthened for both M1 and M2 in the S₁ state. We further confirm that charge redistribution facilitates ESIPT tendency. Constructing potential energy curves, we find the ultrafast ESIPT behavior for M1, which is because of the deficiency of side hydroxyl moiety comparing with M2. This work makes a reasonable affiliation of the ESIPT mechanism for M1 and M2. We wish this paper could facilitate understanding these two novel systems and promote their applications.     

大尺寸工程模型试验中的相似材料配比试验研究

大型物理模型试验是研究复杂工程问题的重要方法，如何快速、准确地确定相似材料配比是试验中至关重要的一环.为降低试验成本、简化试验步骤、充分调用原料性能，采用河砂、水泥和石膏这三种最普通的原料，以骨胶比(河砂与水泥石膏的质量比)和水膏比(水泥与石膏的质量比)为变量，进行了45组对比试验，对相似材料的物理及动、静力学参数进行了研究.获得了以河砂、水泥和石膏为原料配制的相似材料各物理量的变化区间；探讨了骨胶比和水膏比对相似材料各物理量的控制作用，并对比了其敏感性；基于多元线性回归分析建立了各因素与物理量间的定量关系，得到的拟合公式能较好地描述相似材料的性质.     

Numerical Evaluation of a Two-Loop Diagram in the Cutoff Regularization

The sunset diagram of λφ4 theory is evaluated numerically in cutoff scheme and a nonzero finite term(in accordance with dimensional regularization (DR) result) is found in contrast to published calculations. This findingdramatically reduces the critical couplings for symmetry breaking in the two-loop effective potential discussed in ourprevious work.     

An Efficient Selective Oxidation of Alcohols with Potassium Permanganate Adsorbed on Aluminum Silicate under Solvent-free Conditions and Shaking

A new procedure for the selective oxidation of alcohols to the corresponding aldehydes and ketones with potassium permanganate supported on aluminum silicate at room temperature under solvent-free conditions and shaking is reported.     

浅析中国铝锭产能迅速扩充的原因

文章阐述了我国铝锭产能迅速扩充的原因。     

光束发散度对紫外写入光纤光栅的影响

用傅里叶衍射光学分析了准分子激光束发散度对于光纤光栅制备的影响，发现光束发散角使光纤光栅的布拉格波长发生改变，相位版后干涉场沿光纤轴向和径向不均匀，对制备30dB高反射率光纤光栅造成困难。实验结果与理论分析基本一致，相对于理想平行光束情况，会聚光束使得光纤光栅布拉格波长出现在短波一边，发射光束使得光纤光栅布拉格波长出现在长波一边。     

碳钢膏剂无孔渗硅工艺的研究

本研究用膏剂法进行无孔渗硅研究,透射电镜、电子探针和M351腐蚀仪分析证实:获得了致密、无孔隙、具有良好耐磨性和耐腐蚀性的渗硅层,并分析了渗硅层形成机理及表层疏松层以及内部孔隙成因。