Chiral recognition by enantioselective liquid chromatography: Mechanisms and modern chiral stationary phases

An overview of the state-of-the-art in LC enantiomer separation is presented. This tutorial review is mainly focused on mechanisms of chiral recognition and enantiomer distinction of popular chiral selectors and corresponding chiral stationary phases including discussions of thermodynamics, additivity principle of binding increments, site-selective thermodynamics, extrathermodynamic approaches, methods employed for the investigation of dominating intermolecular interactions and complex structures such as spectroscopic methods (IR, NMR), X-ray diffraction and computational methods. Modern chiral stationary phases are discussed with particular focus on those that are commercially available and broadly used. It is attempted to provide the reader with vivid images of molecular recognition mechanisms of selected chiral selector–selectand pairs on basis of solid-state X-ray crystal structures and simulated computer models, respectively. Such snapshot images illustrated in this communication unfortunately cannot account for the molecular dynamics of the real world, but are supposed to be helpful for the understanding. The exploding number of papers about applications of various chiral stationary phases in numerous fields of enantiomer separations is not covered systematically.     

An optical cuvette for orientation of gelatinous media and measurements of their spectral-polarization characteristics

The design characteristics of the optical cuvette suggested here provide the possibility of accomplishing the uniaxial orientation of gels with retention of the constancy of their volume, which makes it possible to carry out highly accurate polarization measurements with commercial spectropolarimeters in directions parallel and perpendicular to the axis of orientation. Using as examples polyacrylamide gels containing biologically important molecules and membranes, the possibility of measuring absorption spectra, the linear dichroism, and the dispersion of optical rotation is demonstrated. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 66, No. 2, pp. 286–289, March–April, 1999.     

Nonexponential 1H spin–lattice relaxation and methyl group rotation in molecular solids

We report a quantitative measure of the nonexponential ¹H spin–lattice relaxation resulting from methyl group (CH₃) rotation in six polycrystalline van der Waals solids. We briefly review the subject in general to put the report in context. We then summarize several significant issues to consider when reporting ¹H or ¹⁹F spin–lattice relaxation measurements when the relaxation is resulting from the rotation of a CH₃ or CF₃ group in a molecular solid.     

Faraday Rotation of Overdense Magnetized Plasma

In this study, we investigate Faraday rotation of electromagnetic waves that are anomalously transmitted through an over‐dense magnetized plasma layer. Here, magnetized plasma indicates that the plasma layer is immersed in a uniform magnetic field. Firstly, normally opaque over‐dense magnetized plasma is shown to be transparent to obliquely incident electromagnetic waves. This high transparency can be achieved by providing conditions for resonant excitations of plasmonic modes. The resonant characteristics of the transmission coefficient of the considered structure are determined and discussed. The conditions under which the magnetized plasma behaves as a complete reflector are also obtained. Faraday rotation is shown to be enhanced under high transparency conditions. The reflected wave also exhibits Faraday rotation and is enhanced under total reflection conditions. (© 2015 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

从随机到取向--分子转动动力学的超快调控

分子取向物理是研究如何操控分子空间排列方向以及如何制备具有特定方向的分子。近十多年来,分子取向物理学取得巨大进展,人们通过各种技术对分子取向物理进行研究,使人们对分子取向的认识达到一个全新的高度。文章首先介绍了分子的量子态及其分布,转动量子态选择方法和分子的转动动力学,然后概述通过制备和调控转动态的相干布居来控制分子取向的方法。实验和理论表明,分子的不同转动态在相同激光条件作用下产生的转动波包不一样,从而导致分子的准直和取向程度随时间演化完全不一样。通过选择合适的转动量子态能够很好地提高分子取向程度。取向分子作为相互作用靶,为原子分子动力学、精密测量物理、立体化学反应和表面碰撞过程等提供了更加丰富多彩的研究内容。     

样品转动方式对中子全息成像结果的影响

在中子全息成像实验中, 为避免透射中子干扰, 入射中子束方向与样品-探测器方向不能在一条直线上, 同时采用探测器移动结合样品转动或仅样品转动的方式, 避免探测系统的大范围移动. 因此在样品的转动过程中, 入射中子束和探测器相对于样品的位置同时发生改变, 内源全息项和内探测器全息项作为变量被记录在同一幅全息图中, 并在重建过程中相互干扰. 本文对基于中子三轴谱仪和四圆谱仪的三种不同转动方式进行了中子全息记录和重建模拟研究, 并讨论其修正方法. 结果表明, 各转动方式都可以通过适当的方法消除或减轻相关影响, 而其中基于三轴谱仪的纯样品转动方式可以使用两个探测器记录的方式, 避开入射中子束方向与样品-探测器方向不能在一条直线上的限制, 得到完整的全息图, 同时通过数据处理能基本消除相对转动造成的干扰, 达到理想的重建结果, 在条件允许的情况下应予优先采用.     

Chloromethane–Water Adduct: Rotational Spectrum,Weak Hydrogen Bonds,and Internal Dynamics

The rotational spectra of four isotopologues of the 1:1 complex between chloromethane and water revealed the presence of only one rotamer in a pulsed jet expansion. The two subunits are linked through two weak hydrogen bonds, O? H???Cl (R_H???Cl=2.638(2) Å) and C? H???O (R_H???O=2.501(2) Å), forming a five‐membered ring. All transitions display the hyperfine structure due to the ³⁵Cl (or ³⁷Cl) nuclear quadrupole effects. Dynamical features in the spectrum are caused by two large‐amplitude motions. Each component line appears as an asymmetric doublet with a relative intensity ratio of 1:3. The splittings led to the determination of barrier to internal rotation of water around its symmetry axis, V₂=320(10) cm^?1. Finally, an unexpected small value of the inertial defect (?0.96 uŲ rather than ?3.22 uŲ) allowed the estimation of the barrier to the internal rotation of the CH₃ group, V₃≈8 cm^?1.     

Flow measurements inside a heated multiple rotating cavity with axial throughflow

This paper discusses experimental results from a multiple cavity test rig representative of a high pressure compressor internal air system. Measurements of the axial, tangential and radial velocity components are presented. These were made using a two component, laser doppler anemometry (LDA) system for a range of non-dimensional parameters representative of engine conditions (Re up to 4 × 10⁶ and Re_z up to 1.8 × 10⁵). Tests were carried out for two different sizes of annular gap between the (non-rotating) drive shaft and the disc bores.

The axial and radial velocities inside the cavities are virtually zero. The size of the annular gap between disc bore and shaft has a significant effect on the radial distribution of tangential velocity. For the narrow annular gap (d_h/b = 0.092), there is an increase of non-dimensional tangential velocity V/Ωr with radial location from V/Ωr < 1 at the lower radii to solid body rotation V/Ωr = 1 further into the cavity. For the wider annular gap (d_h/b = 0.164), there is a decrease from V/Ωr > 1 at the lower radii to solid body rotation further into the cavity. An analysis of the frequency spectrum obtained from the tangential velocity measurements is consistent with a flow structure in the r– plane consisting of pairs of contra rotating vortices.