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1.
本文利用环聚合分子动力学方法对C(1D)+H2反应开展了详细的理论研究. 计算中使用了最近构建的Zhang-Ma-Bian(ZMB)从头算势能面,该势能面对锥形交叉附近区域以及范德华区域均有精确的描述. 环聚合分子动力学计算得到的热反应速率常数与最新实验值吻合很好. 与前人计算结果比较,发现在?1A′电子基态的ZMB-a势能面上获得的反应速率常数远大于前人构建的RKHS势能面上的结果,这是由于ZMB势能面上的范德华鞍具有与之前势能面上的范德华阱完全不同的动态学作用,表明环聚合分子动力学方法能够处理范德华作用引起的势能面拓扑结构所导致的动态学效应. 本文还揭示了b1A′′电子激发态ZMB-b势能面以及量子效应对反应的重要性.  相似文献   
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Hu  Duo-Duo  Gao  Qian  Dai  Jing-Cheng  Cui  Ru  Li  Yuan-Bo  Li  Yuan-Ming  Zhou  Xiao-Guo  Bian  Kang-Jie  Wu  Bing-Bing  Zhang  Kai-Fan  Wang  Xi-Sheng  Li  Yan 《中国科学:化学(英文版)》2022,65(4):753-761
Science China Chemistry - A light-induced, nickel-catalyzed three-component arylsulfonation of 1,3-enynes in the absence of photocatalyst is reported. This methodology exhibited mild conditions,...  相似文献   
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Organic phosphorescence materials demonstrate potential optoelectronic applications due to their remarkably ultralong organic phosphorescence (UOP) lifetime and abundant optical characteristics prior to the fluorescence materials. For a better insight into the intrinsic relationship among regioisomeric molecules, crystalline interactions, and phosphorescence properties, three crystalline dicarbazol-9-yl pyrazine-based regioisomers with para-, meta-, and ortho-convergent substitutions (p-DCzP, m-DCzP, and o-DCzP) were designed and presented gradually increased UOP lifetimes prolonging from 63.14, 127.93 to 350.46 ms, respectively, due to the regioisomerism effect (RIE) which would be an effective strategy for better understanding of structure-property of UOP materials.  相似文献   
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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.  相似文献   
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A new asymmetric Salamo‐based ligand H2L was synthesized using 3‐tertbutyl‐salicylaldehyde and 6‐methoxy‐2‐[O‐(1‐ethyloxyamide)]‐oxime‐1‐phenol. By adjusting the ratio of the ligand H2L and Cu (II), Co (II), and Ni (II) ions, mononuclear, dinuclear, and trinuclear transition metal (II) complexes, [Cu(L)], [{Co(L)}2], and [{Ni(L)(CH3COO)(CH3CH2OH)}2Ni] with the ligand H2L possessing completely different coordination modes were obtained, respectively. The optical spectra of ligand H2L and its Cu (II), Co (II) and Ni (II) complexes were investigated. The Cu (II) complex is a mononuclear structure, and the Cu (II) atom is tetracoordinated to form a planar quadrilateral structure. The Co (II) complex is dinuclear, and the two Co (II) atoms are pentacoordinated and have coordination geometries of distorted triangular bipyramid. The Ni (II) complex is a trinuclear structure, and the terminal and central Ni (II) atoms are all hexacoordinated, forming distorted octahedral geometries. Furthermore, optical properties including UV–Vis, IR, and fluorescence of the Cu (II), Co (II), and Ni (II) complexes were investigated. Finally, the antibacterial activities of the Cu (II), Co (II), and Ni (II) complexes were explored. According to the experimental results, the inhibitory effect was found to be enhanced with increasing concentrations of the Cu (II), Co (II), and Ni (II) complexes.  相似文献   
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Huo Luo Xiao Ling Dan, a Chinese herbal formula consisting of 11 different herbs, has been used in folk medicine for the treatment of arthritis and other chronic inflammatory diseases. However, the chemical compositions of Huo Luo Xiao Ling Dan are not completely characterized. In the present study, an ultra high performance liquid chromatography coupled with electrospray ionization quadrupole time‐of‐flight mass spectrometry method in positive and negative ion modes was employed to identify biochemical constitutes in Huo Luo Xiao Ling Dan. As a result, a total of 76 compounds including alkaloids, monoterpene glycosides, iridoids, phenolic acids, and tanshinones, coumarins, lactones, flavones, and their glycosides, triterpenes, and triterpene saponins were characterized by comparing the retention time and mass spectrometry data with reference standards within 5 ppm error or by reference to the reference literature. These results would provide the basis for a further in vivo study of Huo Luo Xiao Ling Dan and information for potential new drug candidates for treating arthritis and other chronic inflammatory diseases.  相似文献   
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Estrone (E1), estradiols (α/β-E2), and estriol (E3) are four major metabolically active estrogens exerting strong biological activities at very low circulating concentrations. This paper reports a sensitive and efficient method with automated, on-line clean-up and detection to determine trace estrogens in a small volume of serum samples using liquid chromatography–electrospray ionization–tandem mass spectrometry directly, without off-line liquid–liquid or solid-phase extraction pretreatments. Serum aliquots (charcoal stripped fetal bovine serum, 100 μL) were spiked with four estrogen standards and their corresponding isotope-labeled internal standards, then bulk derivatized with 2-fluoro-1-methyl-pyridium p-toluenesulfonate (2-FMP) to establish the calibration curves and perform method validation. Calibration was established in the concentration ranges of 5–1000 pg mL−1, and demonstrated good linearity of R2 from 0.9944 to 0.9997 for the four derivatized estrogens. The lower detection limits obtained were 3–7 pg mL−1. Good accuracy and precision in the range of 86–112% and 2.3–11.9%, respectively, were observed for the quality control (QC) samples at low, medium, and high concentration levels. The stability tests showed that the derivatized serum samples were stable 8 h after derivatization at room temperature and at least to 48 h if stored at −20 °C. The method was applied to measure trace estrogens in real human and bovine serum samples, and three of four estrogen compounds studied were observed and quantified.  相似文献   
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