Optical Activity from Asymmetric Transition Metal Atoms

The preparation and resolution of asymmetric organometallic compounds of the transition series with four different ligands on the metal atom are described. Some of the optically active complexes retain their configuration, while others undergo racemization in solution. Their properties and reactions are discussed. Centers of asymmetry at transition metal atoms can also be detected on the basis of the magnetic nonequivalence of diastereotopic groups. Information about the configurational stability of such compounds can be obtained by investigation of the temperature dependence of the nuclear magnetic resonance spectra.     

物质的绝对构型与旋光性的关系

对物质的绝对构型与旋光方向关系的有关理论进行了简单介绍。     

胆色素类化合物光学活性及其立体化学研究进展

本文综述了20 年来胆色素光学活性及其立体化学的研究进展, 着重讨论了分子内和分子间相互作用对色素构象的选择性及其光活性的影响。对研究前景进行了展望。     

Observation of Paramagnetic Raman Optical Activity of Nitrogen Dioxide

Raman optical activity (ROA) detects the intensity difference between right and left circularly polarized scattered light, and thus brings about enhanced information about the molecules under investigation. The difference is quite small and the technique is mostly constrained to the condensed phase. For NO₂ in the presence of a static magnetic field, however, the ROA signal with high ROA/Raman intensity ratio was observed. The signal is so strong owing to molecular paramagnetism and a pre‐resonance signal enhancement. The spectral shape was explained on the basis of the Fermi golden rule and rotational wave functions expanded to a spherical top basis. The results indicate that the technique can be immediately used to obtain information about molecular properties, such as polarizability components. It also has a potential to detect other paramagnetic gases and discriminate among them.     

光学活性和手性光谱的溯源和发展

概述了19世纪以来光学活性和手性光谱的发现和发展,着重对旋光色散(ORD)、电子圆二色(ECD)和振动圆二色(VCD)光谱的发展背景和基本原理作出介绍。其中特别提及华人科学家徐光宪和徐云洁在手性光谱发展历程中的杰出贡献。     

新型偶氮化合物的合成及其光学性质

以咔唑和苯酚为原料,经重氮和偶合反应合成了一种新型偶氮化合物--N-对(4-羟基苯偶氮基)苯基-3,6-二(叔丁基)咔唑(4),其结构经1H NMR和13C NMR表征.4的 UV和固体荧光光谱研究结果表明,4具有较好的光学活性.     

含偶氮苯光学活性侧基聚合物研究进展

综述了含偶氮苯光学活性侧基聚合物近年来的发展概况 ,介绍了多种聚合体系的类型。由于偶氮苯光于活性侧基的存在 ,使得这些聚合物具有光致变色性、非线性光学活性、光学各向异性等光学性能 ,在光信息存储材料、非线性光学材料、液晶材料、光电子器件、生物分子活性光调控、纳米技术等诸多领域都有广泛的应用。     

Solution Structure of Mannobioses Unravelled by Means of Raman Optical Activity

Structural analysis of carbohydrates is a complicated endeavour, due to the complexity and diversity of the samples at hand. Herein, we apply a combined computational and experimental approach, employing molecular dynamics (MD) and density functional theory (DFT) calculations together with NMR and Raman optical activity (ROA) measurements, in the structural study of three mannobiose disaccharides, consisting of two mannoses with varying glycosidic linkages. The disaccharide structures make up the scaffold of high mannose glycans and are therefore important targets for structural analysis. Based on the MD population analysis and NMR, the major conformers of each mannobiose were identified and used as input for DFT analysis. By systematically varying the solvent models used to describe water interacting with the molecules and applying overlap integral analysis to the resulting calculational ROA spectra, we found that a full quantum mechanical/molecular mechanical approach is required for an optimal calculation of the ROA parameters. Subsequent normal mode analysis of the predicted vibrational modes was attempted in order to identify possible marker bands for glycosidic linkages. However, the normal mode vibrations of the mannobioses are completely delocalised, presumably due to conformational flexibility in these compounds, rendering the identification of isolated marker bands unfeasible.     

Raman Optical Activity of Glucose and Sorbose in Extended Wavenumber Range

Raman optical activity (ROA) is pursued as a promising method for structural analyses of sugars in aqueous solutions. In the present study, experimental Raman and ROA spectra of glucose and sorbose obtained in an extended range (50–4000 cm⁻¹) are interpreted using molecular dynamics and density functional theory, with the emphasis on CH stretching modes. A reasonable theoretical basis for spectral interpretation was obtained already at the harmonic level. Anharmonic corrections led to minor shifts of band positions (up to 25 cm⁻¹) below 2000 cm⁻¹, while the CH stretching bands shifted more, by ∼180 cm⁻¹, and better reproduced the experiment. However, the anharmonicities could be included on a relatively low approximation level only, and they did not always improve the harmonic band shapes. The dependence on the structure and conformation shows that the CH stretching ROA spectral pattern is a sensitive marker useful in saccharide structure studies.     

Symmetry Breaking in Chiral Ionic Liquids Evidenced by Vibrational Optical Activity

Ionic liquids (ILs) are receiving increasing interest for their use in synthetic laboratories and industry. Being composed of charged entities, they show a complex and widely unexplored dynamic behavior. Chiral ionic liquids (CILs) have a high potential as solvents for use in asymmetric synthesis. Chiroptical methods, owing to their sensitivity towards molecular conformation, offer unique possibilities to study the structure of these chiral ionic liquids. Raman optical activity proved particularly useful to study ionic liquids composed of amino acids and the achiral 1‐ethyl‐3‐methylimidazolium counterion. We could substantiate, supported by selected theoretical methods, that the achiral counterion adopts an overall chiral conformation in the presence of chiral amino acid ions. These findings suggest that in the design of chiral ionic liquids for asymmetric synthesis, the structure of the achiral counter ion also has to be carefully considered.     

Gold Nanowire Chiral Ultrathin Films with Ultrastrong and Broadband Optical Activity

An ultrastrong and broadband chiroptical response is key but remains challenging for many device applications. A simple and cost‐effective bottom‐up method is introduced to fabricate large‐area long‐range ordered chiral ultrathin films with the Langmuir–Schaeffer technique using gold nanowires as building blocks. Significantly, as‐prepared ultrathin films display giant optical activity across a broad wavelength range covering visible and near infrared regions with an anisotropic factor of up to 0.285, which is the record value for bottom‐up techniques. Detailed experimental result and theoretical analysis disclose that such remarkable optical activity originates from birefringence and dichroism of the well‐aligned Au nanowire layers in the ultrathin films. The universality of this facile strategy for constructing chiral ultrathin films is further demonstrated with many other one‐dimensional nanomaterials.     

Investigation of Structural,Optical and Antibacterial Activity of ZnS Nanoparticles

Zinc sulfide (ZnS) nanoparticles have been successfully prepared by sol–gel precipitation method. The successful formation of cubic structure is ensured by XRD analysis and Debye Scherrer’s equation is used to determine the crystallite size which was found to be 36 nm for ZnS sample annealed at 200 °C. Surface morphology was studied using HRSEM as well as HRTEM and lattice parameters of the samples were obtained from SAED pattern which was found to have close resemblance to values attained from XRD pattern. Further elemental mapping of ZnS nanoparticles is confirmed by EDX studies. Further Kubelka Munk function was employed to estimate the band gap value which was seen lying within 3.58 to 3.64 eV. Further the antibacterial activity of ZnS is investigated and it is found to be an antibacterial agent of Escherichia coli and staphylococcus aurous, further it can be employed as an antimicrobial agent for prohibiting implant linked infections.

     

Tunable Nonlinear Optical Property and Photocatalytic Activity on Luminescent Chiral Lanthanide Chains

Five chiral (P2₁) isostructural lanthanide coordination complexes Ln(pic)₃ [pic=picolinic acid, Ln=La ( 1 ), Gd ( 2 ), Nd ( 3 ), Sm ( 4 ) and Eu ( 5 )] have been hydrothermally generated, featuring one dimensional right‐handed 2₁ helical chains constructed from LnN₃O₆ of square antiprism geometry and N,O‐chelated pic^? groups, in which 3 , 4 and 5 have been reported, but we explore undiscovered properties of their own systematically. In special, 1 undergoes an abnormal transformation of symmetry as the temperature cooling to 100 K. TG‐DSC studies demonstrated that all isologues have good thermal stability with the decomposition temperature up to 400°C. Then, UV‐Vis‐NIR transmission spectroscopy measurements indicated that they possess a short‐wavelength absorption edge onset at 377 nm, corresponding to the optical band gap of 3.29 eV. Meanwhile, powder second harmonic generation (SHG) measurements revealed that the SHG intensity of 1 , 2 , 4 and 5 may be about 1.2, 2.0, 0.9 and 0.75 times that of KH₂PO₄, respectively. Interestingly, 1 and 3 exhibit efficient photocatalytic degradation for MB (Methylene Blue) upon UV‐light irradiation. Moreover, both 1 and 2 show strong blue luminescence.