An expeditious and high-yield formal synthesis of hirsutene using Rh(I)-catalyzed [(5+2)+1] cycloaddition

An expeditious and high-yield formal synthesis of hirsutene has been achieved. This synthesis features Rh(I)-catalyzed [(5+2)+1] cycloaddition to construct a bicyclic cyclooctenone, which can be efficiently transformed to bicyclic diketone, an advanced intermediate for racemic and asymmetric syntheses of hirsutene.     

One single standard substance for the determination of multiple anthraquinone derivatives in rhubarb using high-performance liquid chromatography-diode array detection

Due to the complexity of the chemical constitution of traditional Chinese medicines (TCMs), now there is a trend to establish methods, using multi-components analysis, for the effective quality control of TCMs. However, the limited availability of multiple reference substances hinders the wide popularization for routine quality control of TCMs. Using an easily available single component contained in the analyte as an internal standard to determine multiple analogues should be a practical option. In this study, we selected rhubarb rhizome as an example, and used emodin, the easily available active component, as the external standard to determine directly the content of emodin in rhubarb, and the same component as the internal standard to simultaneously determine the other six anthraquinones in rhubarb. Compared with the results obtained using the external standard method, this alternative method was found to have no statistically significant differences in our laboratory as verified by the F-test (p = 95%, n = 6). However, due to weak robustness caused by the fluctuation of relative response factors in different laboratories, such a method can only serve as a practical measure to solve the lack of so many chemical standard substances when relative response factors have been determined. This alternative method can then be used without reference substances. Once the corresponding chemical standards are available and are acceptable as well as cost-effective, then the external standard method for the simultaneous determination of multiple components (SDMC) in TCMs will prevail.     

Metal ion complexation in acetonitrile by di-ionized calix[4]arenes bearing two dansyl fluorophores

The influence of metal cations (Li⁺, Na⁺, K⁺, Rb⁺, Cs⁺, Mg²⁺, Ca²⁺, Sr²⁺, Ba²⁺, Ag⁺, Cd²⁺, Co²⁺, Fe²⁺, Hg²⁺, Mn²⁺, Pb²⁺, Zn²⁺ and Fe³⁺) on the spectroscopic properties of two dansyl (1-dimethylaminonaphthalene-5-sulfonyl) groups linked to the lower rims of a series of three, structurally related, di-ionized calix[4]arenes was investigated by means of absorption and emission spectrophotometry. Di(tetramethylammonium) salts of the di-ionized ligands, (TMA)₂L1, (TMA)₂L2 and (TMA)₂L3, which differ in having zero, two and four tert-butyl groups, respectively, on the upper rim of the calix[4]arene scaffold were utilized for the spectrofluorimetric titration experiments in acetonitrile. On complexation by alkaline earth metal cations, both the absorption and emission spectra undergo marked red shifts and quenching of the dansyl fluorescence. These effects are weaker with alkali metal cations. Transition metal cations interact strongly with the ligands. In particular, Fe³⁺, Hg²⁺ and Pb²⁺ cause greater than 97% quenching of the dansyl fluorescence in the di-ionized ligands.     

Osher Flux with Entropy Fix for Two-Dimensional Euler Equations

We compare in this paper the properties of Osher flux with O-variant and P-variant (Osher-O flux and Osher-P flux) in finite volume methods for the two-dimensional Euler equations and propose an entropy fix technique to improve their robustness. We consider both first-order and second-order reconstructions. For inviscid hypersonic flow past a circular cylinder, we observe different problems for different schemes: a first-order Osher-O scheme on quadrangular grids yields a carbuncle shock, while a first-order Osher-P scheme results in a dislocation shock for high Mach number cases. In addition, a second-order Osher scheme can also yield a carbuncle shock or be unstable. To improve the robustness of these schemes we propose an entropy fix technique, and then present numerical results to show the effectiveness of the proposed method. In addition, the influence of grid aspects ratio, relative shock position to the grid and Mach number on shock stability are tested. Viscous heating problem and double Mach reflection problem are simulated to test the influence of the entropy fix on contact resolution and boundary layer resolution.     

抽运-检测型非线性磁光旋转铷原子磁力仪的研究

报道了一种抽运-检测型的非线性磁光旋转铷原子磁力仪.其原理是线偏振光通过处于外磁场环境中被极化的原子介质后,由于原子对线偏振光中左、右圆偏成分不同的吸收和色散,导致光的偏振方向会产生与磁场相关的转动.分析了该磁力仪的工作原理,并测试了它对不同磁场大小的响应.测试结果表明,磁力仪测量范围为100—100000 nT,极限灵敏度为0.2 p T/Hz~(1/2),磁场分辨率为0.1 p T.进一步研究了不同磁场下原子系综极化态的横向弛豫时间,讨论了原子磁力仪高磁场采样率的获得方法.本文的原子磁力仪在5000—100000 n T的磁场测量范围内磁场采样率可实现1—1000 Hz范围内可调,能够测量低频的微弱交变磁场.本文的研究内容为大磁场测量范围、高灵敏度、高磁场采样率的原子磁力仪研制提供了重要参考.     

胍类抗菌聚合物的构建及应用

抗菌与大众生活密切相关,药物或基因的有效传送对于现代医疗来说是个不可或缺的手段,而含胍聚合物在这两个方向都有其独特的性能,如胍类聚合物的杀菌方式是通过非特异性（静电）相互作用来实现的,从生物进化的角度来看,细菌很难对其产生抗药性. 其次,胍基与细胞膜磷脂中的磷酸根“牢固”的双氢键相互作用,使其在药物或基因的转运方面表现优秀. 同时,含胍聚合物对哺乳动物细胞相应低的或无毒性也为其应用扫清了障碍. 因此,本文基于现有的文献资料,归纳了含胍聚合物的构建方式和方法、综述了其在微生物抑制、药物或基因转运领域的应用.