Chiral DMAP‐N‐oxides as Acyl Transfer Catalysts: Design,Synthesis, and Application in Asymmetric Steglich Rearrangement

A DMAP‐N‐oxide, featuring an α‐amino acid as the chiral source, was developed, synthesized and applied in asymmetric Steglich rearrangement. A series of O‐acylated azlactones afforded C‐acylated azlactones possessing a quaternary stereocenter in high yields (up to 97 % yield) and excellent enantioselectivities (up to 97 % ee). Compared to the widespread use of pyridine nitrogen, which serves as the nucleophilic site in the asymmetric acyl transfer reaction, we discovered that chiral DMAP‐N‐oxides, in which the oxygen now acts as the nucleophilic site, are efficient acyl transfer catalysts. Our finding might open a new door for the development of chiral DMAP‐N‐oxides for asymmetric acyl transfer reactions.     

Four new dammarane-type triterpenes derivatives from hydrolyzate of total Gynostemma pentaphyllum saponins and their bioactivities

Phytochemical investigation of hydrolysate of total G. pentaphyllum saponins led to the isolation of four novel triterpenes, Gypensapogenin U (1), Gypensapogenin V (2), Gypensapogenin W (3) and Gypensapogenin X (4). The structures of these compounds were identified by 1D, 2D-NMR and HR-ESI-MS evidences. Additionally, the protective activity of these new compounds against cardiomyocytes injury induced by H₂O₂ and their cytotoxic activity against t-HSC/Cl-6 cells were evaluated.     

Lab-in-cell based on spontaneous amino-yne click polymerization

Unnatural reaction in the living cells is a powerful tool for biological research. However, the polymerization inside cells is rarely reported. In this work, a lab-in-cell is illustrated based on our developed spontaneous amino-yne click polymerization. Carbonyl group activated terminal diyne can spontaneously polymerize with tetraphenylethene(TPE)-containing primary diamine inside cells, and polymer with weight-average molecular weight of 7,300 was yielded. By utilizing this in vivo amino-yne click polymerization and taking advantage of the aggregation-induced emission feature of TPE, a "turn-on" cell imaging was realized,and in-situ killing of cells was also acquired by destroying the structures of actin and tubulin, which cannot be realized by preprepared polymer. This strategy provides a useful platform and holds great promise in biochemistry and therapy applications.     

常用制冷工质稠密流体的黏度推算方法

本文通过关联无量纲化剩余黏度与对比密度的关系,提出了一种推算常用制冷工质稠密流体黏度的维里型黏度状态方程.应用该方程只需已知该工质的临界参数、分子量和偏心因子即可完成计算,使得迁移性质的计算在热力学面上和平衡性质的计算保持了完整的一致性.本文通过上述方法计算了9种常用制冷工质的液相黏度,与实验数据比较显示,总平均偏差为2.36%,最大偏差为27.6%.     

Effects of degree correlation on the controllability of networks

In this paper, we investigate the effects of degree correlation on the controllability of undirected networks with different degree-mixing patterns based on simulation analysis. Considering random pinning, max-degree pinning and mix-degree pinning, some relevance factors on controllability such as the control gain and the number of pinned nodes are discussed in detail. It is found that disassortative mixing enhances the network controllability contrast to assortative mixing, to which the network controllability is sensible. Furthermore, too large or too low value of the feedback gain can reduce the controllability. From the viewpoint of practical application, mix-degree pinning strategy is suggested in assortative network, while in disassortative network, max-degree pinning scheme is better than random pinning.     

Spin accumulation in coupled quantum dots with ferromagnetic and superconducting electrodes

We theoretically investigate the spin accumulation in two parallel coupled quantum dots (QDs) with ferromagnetic and superconducting electrodes. Due to the ferromagnetic lead, the spin accumulation appears on the resonance of Andreev reflection. The spin accumulation in each of the two QDs can be controlled by the gate voltage. The sign of the spin accumulation is also controllable by tuning the bias. Furthermore, tuning the magnetic flux can exchange the amplitude of the spin accumulation in the two QDs. The Aharonov-Bohm oscillation effects also provides a way to control the spin accumulation of each QD.     

Half analytical method with application to the high order Laue zone effects in monoclinic and triclinic crystals

The simulation of the high order Laue zone (HOLZ) diffractions of monoclinic and triclinic crystals is a very complicated problem. The conventional multislice (MS) method suffers from the problem of infinity of the phase grating size. To avoid the difficulty of the infinity, Chen et al. arranged the phase grating plane along the ab plane of the crystal lattice. In this paper we introduce a new method which allows the incident and exit wavefunction planes perpendicular to the zone axis without the difficulty of infinity. We name the method half analytical method. The results calculated by half analytical method are in good agreement with those calculated by the conventional MS method.     

Zrn Pdm(n+m≤5)混合团簇的密度泛函研究

在相对论有效原子实势(RECP)近似和密度泛函(B3LYP)方法基础上,优化计算了ZrnPdm(n + m≤5) 混合团簇的结构、团簇基态的平均结合能、离解能、最高占据轨道与最低空轨道之间的能级间隙。结果表明,ZrnPdm(n+m≤5)混合团簇成员存在多种异构体,且易于形成密堆积结构;Zr原子与团簇结合得更为紧密,团簇稳定性随Zr数目的增大而增加,在钯中掺入锆可以大大提高合金的稳定性;锆钯混合团簇易得电子,得电子的能力高于纯锆团簇,在钯中掺入锆可以提高合金的化学活性。     

m面GaN平面内结构和光学各向异性研究

采用金属有机物化学气相淀积方法在铝酸锂LiAlO₂衬底上外延生长m面GaN薄膜.X射线衍射测量的结果表明所得薄膜具有较理想的m面晶体取向,并对其各向异性的应变进行了计算,摇摆曲线的测量发现样品存在明显的面内结构各向异性.采用偏振光致发光研究材料的面内光学各向异性,发现随着偏振角度的改变,发光峰的峰位和强度均有明显变化,并用对称性破缺导致价带子带劈裂的理论对结果进行了解释. 关键词： m面GaN 结构各向异性 偏振光致发光     

MOCVD生长中载气H2对N掺杂ZnO性质的影响

采用MOCVD方法在石英衬底上生长ZnO。实验使用二乙基锌(DEZn)为锌源,N2O作为氧和氮源,H2作为载气。采用PL和Raman光谱方法对ZnO样品进行表征,结果表明H2的加入大幅度减少薄膜中碳的掺入,明显改善了薄膜的光学质量。采用N2O离化技术,可以进一步提高其带边峰的强度,抑制带内发光。XRD测量表明,生长的ZnO薄膜具有c轴择优取向。目前生长高质量N掺杂的p型ZnO薄膜是很困难的,而H2作为载气的加入明显改善了ZnO薄膜的光学性质,在生长过程中加入H2将为获得高质量N掺杂的p型ZnO薄膜提供一种途径。