New electrophilic addition of α-diazoesters with ketones for enantioselective C-N bond formation

α-Diazoesters were discovered to be good electrophiles in a catalytic asymmetric α-functionalization of ketones for the first time. This reaction also provided a direct and efficient method for C-N bond formation with excellent yields (up to 98%) and enantioselectivities (up to 99% ee) under mild conditions. The application of the electrophilicity of α-diazoesters opens up a novel way to access the diversity of diazo chemistry.     

稳态托卡马克堆中的自举电流

在稳态托卡马克堆的燃烧阶段,当感应电流下降后,新经典输运产生的自举电流便成为维持稳定电流的最好手段。本文根据α粒子新经典自举电流的最新结果,计算了感应电流消失阶段,稳态堆中α粒子、电子和离子的自举电流。     

数值模型内力影响面分析的机动法

本文提出并证明了普遍适用于以广义位移为独立变量的各种数值模型的内力影响面分析的机动算法原理。这一原理把内力影响面分析归结为求解在一个等价荷载作用下的结构位移场,并给出了得到等价荷载的方法。用本文方法得到的是结构某一点的内力的影响面,而且对数值模型来说,是精确解。作为本文原理的应用,用机动法分析了采用有限条模型的薄板的内力影响面,并给出了若干数值例子。     

Analysis and demonstration of PID algorithm based on arranging the transient process for adaptive optics

The fastness and robustness of a control algorithm are highly important in the performance of adaptive optics systems. The proportional-integral-derivative control with arranging the transient process, which is designed using a tracking differentiator, is applied into an adaptive optics system. This control algorithm greatly improves the dynamic properties of the control system. To identify the underlying reasons for these improvements, the influence of the control algorithm is theoretically discussed. The control algorithm is verified by a simple adaptive optics system for tip/tilt correction. The experimental results demonstrate that the control algorithm is fast and robust.     

Application of TA–MS combined with PulseTA for characterization of materials

The thermal behavior of the anticancer drug-irinotecan was measured by Thermogravimetry–Differential thermal analysis (TG–DTA) to explore the application of TG–DTA in nanomedicine firstly. The TG–DTA result showed that the irinotecan was oxidized completely before 700 °C. When irinotecan was loaded onto nanosized mesoporous silica spheres, the loading capacity for irinotecan measured by TG–DTA was about 9.11% in the irinotecan/mesoporous SiO₂ composite, similar to the typical UV–Vis spectra results (10.5%), which showed that TG–DTA characterization provided an alternative method to determine the drug loading amount on inorganic carriers. Secondly, Thermogravimetry–Differential scanning calorimetry–Mass Spectrometry coupling techniques (TG–DSC–MS) were used to characterize the hydrogen adsorption temperature and capacity of TiCr_1.2 (V-Fe)_0.6 alloy. The MS result showed that the released region of hydrogen was 250–500 °C, which was consistent with the TG–DSC results. Lastly, TA–MS combined with pulse thermal analysis (PulseTA) were used for a simultaneous characterizing study in the changes of mass, determination and quantitative calibration of the evolved nitrogen formed during the thermal decomposition of the InN powder. The results showed that relative error of this method between measured value and theoretical value was 2.67% for the quantitative calibration of evolved N₂. It shows that TA–MS combined with PulseTA techniques offer a good tool for the quantification of the evolved nitrogen in the InN powder.     

新型龙胆酸衍生物的合成及其抑制酪氨酸酶活性研究

为发现新型的美白活性化合物,以龙胆酸甲酯、卤代烃和α-羟基酸乙酯为原料,合成了10个未见文献报道的2-羟基-5-烷(H)氧基苯甲酸酯类衍生物(3a,3b和6a～6h),其结构经1H NMR,IR,MS和HRMS确认.初步生物活性测试结果表明6a,6b,6e和6f具有较强的抑制酪氨酸酶活性,进一步药理实验表明经取代改造后的6a～6h,其毒性和光学毒性都相对龙胆酸甲酯和氢醌更低.     

Cross-Coupling of Diarylborinic Acids and Anhydrides with Arylhalides Catalyzed by a Phosphite/N-Heterocyclic Carbene Co-supported Palladium Catalyst System

A highly efficient cross-coupling of diarylborinic acids and anhydrides with aryl chlorides and bromides has been effected by using a palladium catalyst system co-supported by a strong σ-donor N-heterocyclic carbene (NHC), N,N'-bis(2,6-diisopropylphenyl) imidazol-2-ylidene, and a strong π-acceptor phosphite, triphenylphosphite, in tert-BuOH in the present of K(3)PO(4)·3H(2)O. Unsymmetrical biaryls with a variety of functional groups could be obtained in good to excellent yields using as low as 0.01, 0.2-0.5, and 1 mol % palladium loadings for aryl bromides and activated and deactivated aryl chlorides, respectively, under mild conditions. A ligand synergy between the σ-donor NHC and the π-acceptor phosphite in the Pd/NHC/P(OPh)(3) catalytic system has been proposed to be responsible for the high efficacy to arylchlorides in the cross-coupling. A scalable and economical process has therefore been developed for synthesis of Sartan biphenyl from the Pd/NHC/P(OPh)(3) catalyzed cross-coupling of di(4-methylphenyl)borinic acid with 2-chlorobenzonitrile.     

截断非傍轴双曲余弦-高斯光束的远场特性

基于瑞利-索末菲衍射积分公式,推导出截断非傍轴双曲余弦-高斯光束在自由空间传输的解析表示式,分析了一些特例,并引入非傍轴范畴的桶中功率概念,用以描述非傍轴光束的远场光束质量。结果表明:截断非傍轴双曲余弦-高斯光束的光强和桶中功率不仅与束腰宽度与波长之比、偏心参数及截断参数有关,而且桶中功率还与桶的尺寸有关。在一定的范围内,较大的束腰宽度与波长之比, 截断参数和较小的偏心参数使光束有更好的聚焦特性,表现出更好的光束质量。     

集成光学器件对光纤陀螺稳定性影响的研究

通过对集成光学器件调制特性的研究分析,指出了其调制特性影响光纤陀螺稳定性的主要原因,研究并设计了对集成光学器件调制度不稳定性进行实时跟踪补偿的方法,并对设计方案进行了实验,得到较好的实验效果,提高了光纤陀螺的稳定性.     

2-氨基吡啶金属配合物对羧酸酯水解的催化作用

 合成了2-氨基吡啶(2-AP)为配体的Zn(2-AP)2(OAc)2,Ni(2-AP)2(OAc)2和Cu(2-AP)2(OAc)2三种金属配合物,并将其用于催化2-吡啶甲酸对硝基苯酚酯(PNPP)和乙酸对硝基苯酚酯(PNPA)的水解反应. 研究了金属配合物催化PNPP水解的动力学,提出了可能的催化机理. 结果表明,Zn(2-AP)2(OAc)2和Ni(2-AP)2(OAc)2金属配合物对PNPP水解反应有显著的催化作用,且Ni(2-AP)2(OAc)2的催化活性大于Zn(2-AP)2(OAc)2,而对PNPA无催化活性. Cu(2-AP)2(OAc)2对PNPP和PNPA均无催化活性. 这可能源自底物本身的特性以及配合物结构的差异. 同时,实验结果也说明合成的Zn(2-AP)2-(OAc)2和Ni(2-AP)2(OAc)2是水解金属酶的良好模型.