圆二色谱中的激子手性法在有机化学中的应用

激子手性法是圆二色谱领域内,近一、二十年内发展的一种测定有机化合物绝对构型的可靠方法。本文对其基本原理及规律作一简要介绍。并以邻二醇、共轭烯酮,共轭二烯及丙烯醇为例,介绍本法在测定绝对构型中的应用。此外,本法也可用于糖类的结构研究。     

轴手性双蒽醌的分子结构与电子圆二色谱的密度泛函研究

采用从头算密度泛函理论方法,计算了具有轴手性结构的3种双蒽醌分子的电子圆二色谱(ECD),分析了谱带的电子起源以及谱带与分子结构之间的关系.计算结果表明,由于在2,2′位置上的OH取代,导致2个蒽醌基平面之间的不同旋转二面角,使ECD谱具有不同的谱带特征,具有相反的ECD谱.计算的双蒽醌C的谱带形状特征与实验结果基本相符.     

高效液相色谱圆二色检测技术在手性化合物分析中的应用

对近年来高效液相色谱圆二色检测技术在手性化合物分析中的应用进展进行综述,简单介绍了高效液相色谱圆二色检测器的原理和特点,着重介绍了非手性色谱条件下圆二色检测技术在手性化合物对映体纯度测定、复杂基质中手性化合物分析以及在手性化合物绝对构型测定中的应用,并讨论了它的应用前景。     

秋水仙碱立体异构体电子结构及圆二色谱性质的理论研究

采用量子化学密度泛函理论(DFT)在B3LYP/6-311++G二水平上对秋水仙碱四个立体异构体分子几何构型进行了优化,在优化的基础上进行了振动圆二色谱(VCD),紫外-可见光谱(UV-Vis)和电子圆二色谱(ECD)研究.为模拟真实条件,以水为溶剂,计算其对分子电子结构和光谱性质的影响.研究结果表明:秋水仙碱四个立体...     

应用电子圆二色光谱方法确定手性金属配合物的绝对构型

与电子能级跃迁相关的电子圆二色(ECD)光谱因其研究对象宽泛,与涉及振动能级的振动圆二色(VCD)光谱互补,已成为应用于手性立体化学研究的集成手性光谱的主流表征手段。本文概述了确定手性金属配合物绝对构型的三种主要方法,详细介绍了ECD光谱法在确定手性金属配合物绝对构型中的应用,其中着重强调了激子手性方法,并对集成手性光谱学未来的发展趋势做出了展望。     

Gaussian软件在高校化学教学中的应用

介绍Gaussian软件在高校化学教学中的几种用途。提倡教师在教学过程中多使用能提高教学效果的软件。     

气相色谱-电子轰击源质谱法测定茶叶中氟虫腈残留量

建立了茶叶中氟虫腈残留量快速测定的气相色谱-电子轰击源质谱法。茶叶中的氟虫腈用正己烷-丙酮(7:3,V/V)混合液提取,经石墨化碳黑固相萃取小柱净化后,用正己烷-丙酮(9:1,V/V)混合液洗脱,浓缩定容后,用气相色谱-电子轰击源质谱法测定,外标法定量。结果表明,目标物质在0.001~0.040 mg/L范围内的线性关系良好;空白样品在0.002~0.010 mg/L范围三水平加标回收实验的平均回收率在96.6%~114.2%之间,相对标准偏差(n=6)为2.9%~4.4%;方法的定量限为0.001 mg/kg。该方法能满足茶叶中氟虫腈残留量0.002 mg/kg的检测要求。     

Gaussian软件在红外光谱学教学中的应用

探讨了Gaussian软件在红外光谱学教学中的具体应用,帮助学生在课堂上对分子的三维空间结构、振动光谱的理解、振动模式的指认与归属等方面有更加感性的认识,从而提高课堂趣味性,使得教学内容更为形象生动。     

含联萘基元的刚性环状齐聚物手性孔穴的振动圆二色谱研究

纳米尺度刚性环状齐聚物因其具有独特的孔穴结构,在基础与应用研究中引起了人们的广泛关注.当具有功能基团的分子骨架形成环状结构时,这种功能分子孔穴在分子识别及主-客体化学等方面具有广阔的应用前景.含有手性基团的手性大环分子具有特定的手性孔穴,在手性拆分、手性识别等方面引起了各国研究者的兴趣.     

Gaussian 03软件在染料化学教学中的应用

讨论了Gaussian 03在染整课程中的具体应用,尤其对结构的稳定性、振动频率、染料颜色和结构的关系、分子的电荷布局在化学反应中的应用进行具体介绍.这些应用极大的丰富了课堂教学内容,提高教学质量.     

Electronic Circular Dichroism-Circularly Polarized Raman (eCP-Raman): A New Form of Chiral Raman Spectroscopy

This Concept article summarizes recent work on the development of a new form of chiral Raman spectroscopy, e CP-Raman, which combines two spectroscopies: electronic circular dichroism (ECD) and circularly polarized Raman (CP-Raman). First, some puzzling observations while carrying out Raman optical activity (ROA) measurements of several transition metal complexes under resonance are described, as well as the search for the mechanisms responsible. Then an equation for quantifying the e CP-Raman contribution is presented, followed by several examples of how e CP-Raman influences the I_R−I_L spectra of achiral and chiral solvent molecules and of a number of chiral solutes under resonance. The conditions to extract resonance ROA, when the e CP-Raman contribution is minimized, are also discussed. Finally, we comment on the potential applications of e CP-Raman.     

手性锌卟啉对咪唑类客体的分子识别及圆二色光谱的研究

研究了手性α,α,α,β－四－[邻（叔丁氧羰L－酪氨酸）氨基苯基]卟啉 锌[α,α,α,β-ZnT(o-Boc)TyrTAPP](1)和手性α,α,α,β－四－[邻（叔 丁氧羰L－丙氨酸）氨基苯基]卟啉锌[α,α,α,β-ZnT(o-BocAla)TAPP](2)对 咪唑、2－甲基咪唑、N－甲基咪唑和2－乙基－4－甲基咪唑的分子识别行为,分别 求得主体（1）对咪唑类分子识别的缔合常数顺序为K（Im)>K(2-MeIm)>K(N-MeIm) >K(2-Et-4-MeIm),主体（2）对咪唑类分子识别的缔合常数顺序为K（2－MeIm)>K (Im)>K(2-Ek-4-MeIm)>K(N-MeIm),并用圆二色光谱（CD）研究了主体1和2对咪唑 在客体在CHCl3中分子识别的光谱行为,与热力学的结果做了比较。     

Conformation‐Specific Circular Dichroism Spectroscopy of Cold,Isolated Chiral Molecules

The CD spectroscopy of a chiral compound in solution yields an average CD value derived from all of the conformations of a chiral molecule. By contrast, CD spectroscopy of cold chiral molecules in the gas phase distinguishes specific conformers of a chiral molecule, but the weak CD effect has limited the practical application of this technique. Reported herein is the first resonant two‐photon ionization CD spectra of ephedrines in a supersonic jet using circularly polarized laser pulses, which were generated by synchronizing the oscillation of the photoelastic modulator with the laser firing. The spectra exhibited well‐resolved CD bands which were specific for the conformations and vibrational modes of each enantiomer. The CD signs and magnitudes of the jet‐cooled chiral molecules were very sensitive to their conformations and thus offered crucial information for determining the three‐dimensional structures of chiral species, as conducted in combination with quantum chemical calculations.     

Induced Circular Dichroism of Chiral Nematic Cellulose Films

Colloidal chiral nematic suspensions of cellulose were prepared from dissolving grade wood pulp. On evaporation of the water, the suspension dries down to give iridescent cellulose films. The optical properties of the films may be characterized by incorporating dyes in the films, and following the ordering of the dye molecules by measurement of induced circular dichroism (ICD). Structural changes to the films, such as decreasing the chiral nematic pitch by increasing the salt content and increasing the chiral nematic order through magnetic alignment, can be monitored by measuring the changes in ICD.     

Stereochemistry of the Reaction Intermediates of Prolinol Ether Catalyzed Reactions Characterized by Vibrational Circular Dichroism Spectroscopy

Spectroscopic characterizations of key reaction intermediates are often considered the final confirmation of a reaction mechanism. This proof-of-principle study showcases the application of vibrational circular dichroism (VCD) spectroscopy for the characterization of in situ generated reaction intermediates using the key intermediates of enamine catalysis of Jørgensen–Hayashi-type prolinol ether catalysts as model system. By comparison of experimental and computed spectra, the enamines are shown to preferentially adopt an anti-conformation with E-configured C=C bond. For the parent prolinol catalyst, the structure and stereochemistry of the oxazolidine side product is determined as well. This study thus demonstrates that VCD spectra can provide insights into structural preferences of organocatalysts that utilize a covalent activation mechanism. Thereby it outlines new fields of applications for VCD spectroscopy and finally adds the technique to the toolbox of physical organic chemistry for in-depth mechanistic studies.     

Gaussian软件在红外光谱教学中的应用——同位素效应

借助Gaussian软件探讨了同位素效应对分子特征官能团红外光谱的影响,帮助学生在课堂上认识同位素取代可能造成的红外特征吸收峰的光谱频移,并进一步促进学生在课后独立思考,发挥主观能动性,自行设计有效的同位素取代方案,利用软件工具将课堂知识应用于化合物组分的鉴别中。     

G‐Quadruplex Secondary Structure Obtained from Circular Dichroism Spectroscopy

A curated library of circular dichroism spectra of 23 G‐quadruplexes of known structure was built and analyzed. The goal of this study was to use this reference library to develop an algorithm to derive quantitative estimates of the secondary structure content of quadruplexes from their experimental CD spectra. Principal component analysis and singular value decomposition were used to characterize the reference spectral library. CD spectra were successfully fit to obtain estimates of the amounts of base steps in anti–anti, syn–anti or anti–syn conformations, in diagonal or lateral loops, or in other conformations. The results show that CD spectra of nucleic acids can be analyzed to obtain quantitative structural information about secondary structure content in an analogous way to methods used to analyze protein CD spectra.