Theoretical prediction of the optical rotation of chiral molecules in ordered media: A computational study of (R a )-1,3-dimethylallene, (2R )-2-methyloxirane, and (2R )-N-methyloxaziridine

2015 ◽  
Vol 115 (14) ◽  
pp. 900-906
Author(s):  
Maria C. Caputo ◽  
Stefano Pelloni ◽  
Paolo Lazzeretti
2021 ◽  
Vol 93 (13) ◽  
pp. 5403-5411
Author(s):  
Dang-Bao-An Tran ◽  
Katherine M. Manfred ◽  
Robert Peverall ◽  
Grant A. D. Ritchie

2020 ◽  
Author(s):  
Marc Hamilton Garner ◽  
Clemence Corminboeuf

<div><div><div><p>Helical frontier molecular orbitals (MOs) appear in disubstituted allenes and even-n cumulenes. Chiral molecules are optically active, but while these molecules are single-handed chiral, π-orbitals of both helicities are present. Here we computationally examine whether the optical activity of chiral cumulenes is controlled by the axial chirality or the helicity of the electronic structure. We exploit hyperconjugation with alkyl, silaalkyl, and germaalkyl substituents to adjust the MO helicity without altering the axial chirality. For the same axial chirality, we observe an inversion of the helical MOs contribution to the electronic transitions and a change of sign in the electronic circular dichroism and optical rotation dispersion spectra. While the magnitude of the chiroptical response also increases, it is similar to that of chiral cumulenes without helical π-orbitals. Overall, Helical π-orbitals correlate with the big chiroptical response in cumulenes, but are not a prerequisite for it.</p></div></div></div>


2016 ◽  
Vol 41 (17) ◽  
pp. 4032 ◽  
Author(s):  
Xiaodong Qiu ◽  
Linguo Xie ◽  
Xiong Liu ◽  
Lan Luo ◽  
Zhiyou Zhang ◽  
...  

CNS Spectrums ◽  
2002 ◽  
Vol 7 (S1) ◽  
pp. 8-13 ◽  
Author(s):  
Joseph Gal

ABSTRACTSingle-isomer drugs are of great importance in modern therapeutics. In this article, the basics of the underlying phenomenon are explained. Some molecules are chiral, ie, their mirror image is not superposable on the original. The most common element producing molecular chirality is a chiral center, typically a carbon atom carrying four different groups. The mirror-image molecules are termed enantiomers, but the less specific terms stereoisomers and isomers are also used. A substance consisting of only one of the two enantiomers is a single enantiomer or single isomer, and the 1:1 mixture of the enantiomers is the racemic mixture or racemate. A graphical convention that conveys the three-dimensional aspects of chiral molecules drawn in two dimensions, as well as two nongraphical conventions, based on optical rotation and configuration, are used to identify enantiomers. Optical rotation is a physical property of single enantiomers and involves rotation of the plane of plane-polarized light, each pure enantiomer rotating with equal magnitude but in the opposite direction (dextro and levo). Configuration is the actual arrangement in space of the atoms of chiral molecules. Two systems of indicating configuration are in use. One employs D and L to denote the respective enantiomers, and is applicable only to α-amino acids and carbohydrates. The other is a universal system using R and S as descriptors for the two possible arrangements, respectively, of the atoms around the chiral center. Interest in chiral drugs stems from the frequently observed biological differences between enantiomers. Such enantioselectivity is the result of different interactions of the drug enantiomers with target receptors that are themselves chiral and single-enantiomeric.


Sensors ◽  
2018 ◽  
Vol 18 (11) ◽  
pp. 3788 ◽  
Author(s):  
Yang Xu ◽  
Lixuan Shi ◽  
Tian Guan ◽  
Suyi Zhong ◽  
Xuesi Zhou ◽  
...  

We propose a self-referential fast detection scheme for a frequency domain weak measurement system for the detection of enantiomeric impurities in chiral molecules. In a transmissive weak measurement system, the optical rotation (OR) is used to modify the pre-selected polarization state and the post-selection polarization state. We obtained the sum and difference of the optical rotations produced by the sample and the standard by rotating the quarter wave plate in the system. Then, we estimate the ratio of chiral molecules to enantiomeric impurities using the ratio of the central wavelength shifts caused by the addition and subtraction states described above. In this paper, our system has an optical resolution of 1.88 × 10−5°. At the same time, we completed the detection of the ratio of the two substances in the mixture of L-proline and D-proline in different proportions, which proved that our system can quickly detect the content of enantiomeric impurities in chiral molecules.


2016 ◽  
Vol 18 (35) ◽  
pp. 24506-24510 ◽  
Author(s):  
Muhammad Ali Hashmi ◽  
Sarah K. Andreassend ◽  
Robert A. Keyzers ◽  
Matthias Lein

Despite advances in electronic structure theory the theoretical prediction of spectroscopic properties remains a computational challenge.


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