Qin Si-Yong, He Jin-Hao, Zhao You, Yang Yan-Ling, Zhang Ai-Qing, Lei Xinxiang
Hubei Engineering Technology Research Centre of Energy Polymer Materials, School of Chemistry and Materials Science, South-Central Minzu University, Wuhan 430074, China.
Key Laboratory of Analytical Chemistry of the State Ethnic Affairs Commission, School of Chemistry and Materials Science, South-Central Minzu University, Wuhan 430074, China.
Anal Chem. 2023 Dec 5;95(48):17759-17765. doi: 10.1021/acs.analchem.3c03777. Epub 2023 Nov 23.
Multiple independent sets of residual dipolar couplings (RDCs) acquired by relying on different alignment media show the great potential for de novo structure determination of organic compounds. However, this methodology is severely compromised by the limited availability of multialignment media. In this work, an engineering strategy was developed to program the oligopeptide amphiphiles (OPAs) to create different peptide liquid crystal (LC) media for the acquisition of independent sets of RDCs. With no need for de novo design on peptide sequences, the molecular alignment can be simply modulated by varying the length of the hydrophobic tails within OPAs. Relying on these programmed peptide LC media, five independent sets of RDCs were extracted in a highly efficient and accurate manner. Because of the similar bulk composition of OPAs, this approach offers the significant advantage in circumventing the possible incompatibilities of analytes with one or several different alignment media, therefore avoiding the analysis complication. Notably, these peptide LC media show enantiodifferentiating properties, and the enantiodiscriminating capabilities could also be optimized through the programmed strategy. Furthermore, we show that these media are compatible with different polar solvents, allowing the possible de novo structure elucidation of organic compounds with varied polarities and solubilities.
通过依赖不同的取向介质获得的多组独立的剩余偶极耦合（RDC）显示出用于有机化合物从头结构测定的巨大潜力。然而，这种方法因多取向介质的可用性有限而受到严重影响。在这项工作中，开发了一种工程策略来对寡肽两亲物（OPA）进行编程，以创建不同的肽液晶（LC）介质，用于获取独立的RDC集。无需对肽序列进行从头设计，分子取向可以通过改变OPA中疏水尾的长度来简单调节。依靠这些编程的肽LC介质，以高效且准确的方式提取了五组独立的RDC。由于OPA的整体组成相似，这种方法在规避分析物与一种或几种不同取向介质可能存在的不相容性方面具有显著优势，从而避免了分析复杂性。值得注意的是，这些肽LC介质表现出对映体区分特性，并且对映体区分能力也可以通过编程策略进行优化。此外，我们表明这些介质与不同的极性溶剂兼容，从而有可能对具有不同极性和溶解性的有机化合物进行从头结构解析。
