Clemens Schöpf Institut for Organic Chemistry and Biochemistry, Technical University of Darmstadt, Darmstadt, Germany.
Nitrochemie Aschau GmbH, Aschau am Inn, Germany.
Magn Reson Chem. 2021 May;59(5):577-586. doi: 10.1002/mrc.5003. Epub 2020 Feb 11.
Anisotropic samples of lyotropic liquid crystalline (LLC) phases of valine derived polyaryl acetylenes were employed as chiral alignment media for the measurement of residual dipolar couplings (RDCs) of 12 small, chiral, organic molecules. The quadrupolar splitting of the deuterium signal of CDCl can be adjusted by temperature and concentration changes from 0 to 350 Hz. The LLC phases showed excellent orienting properties for all analytes bearing various functional groups. The precise extraction of RDCs in the range of up to ±30 Hz from F2-coupled HSQC spectra was possible. Additionally, the chiral environment led to diastereomorphous interactions with the enantiomers of chiral analytes leading to two different sets of RDCs. This differential order effect was particularly pronounced with H-bond donors like alcohols and 2° amines.
各向异性的溶致液晶（LLC）相的缬氨酸衍生聚芳基乙炔被用作手性对齐介质，用于测量 12 个小的手性有机分子的残余偶极耦合（RDC）。CDCl 的氘信号的四极分裂可以通过温度和浓度变化从 0 调整到 350 Hz。 LLC 相显示出极好的取向性能，适用于带有各种官能团的所有分析物。可以从 F2 耦合 HSQC 谱中精确提取高达±30 Hz 的 RDC。此外，手性环境导致手性分析物的对映异构体之间的非对映异构相互作用，导致两组不同的 RDC。这种差分有序效应在手性氢键供体如醇和 2°胺中尤为明显。
