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外磁场诱导的振动旋光的双梳光活性光谱分析。

Dual-comb optical activity spectroscopy for the analysis of vibrational optical activity induced by external magnetic field.

机构信息

State Key Laboratory of Precision Spectroscopy, East China Normal University, Shanghai, 200062, China.

出版信息

Nat Commun. 2023 Feb 16;14(1):883. doi: 10.1038/s41467-023-36509-w.

Abstract

Optical activity (OA) spectroscopy is a powerful tool to characterize molecular chirality, explore the stereo-specific structure and study the solution-state conformation of biomolecules, which is widely utilized in the fields of molecular chirality, pharmaceutics and analytical chemistry. Due to the considerably weak effect, OA spectral analysis has high demands on measurement speed and sensitivity, especially for organic biomolecules. Moreover, gas-phase OA measurements require higher resolution to resolve Doppler-limited profiles. Here, we show the unmatched potential of dual-comb spectroscopy (DCS) in magnetic optical activity spectroscopy (MOAS) of gas-phase molecules with the resolution of hundred-MHz level and the high-speed measurement of sub-millisecond level. As a demonstration, we achieved the rapid, high-precision and high-resolution MOAS measurement of the nitrogen dioxide [Formula: see text]+[Formula: see text] band and the nitric oxide overtone band, which can be used to analyze fine structure of molecules. Besides, the preliminary demonstration of liquid-phase chiroptical activity (as weak as 10) has been achieved with several seconds of sampling time, which could become a routine approach enabling ultrafast dynamics analysis of chiral structural conformations.

摘要

旋光光谱学是一种强大的工具,用于表征分子手性,探索立体特异性结构,并研究生物分子在溶液状态下的构象,广泛应用于分子手性、制药学和分析化学领域。由于旋光效应相当微弱,旋光光谱分析对测量速度和灵敏度有很高的要求,特别是对于有机生物分子。此外,气相旋光测量需要更高的分辨率来分辨多普勒限制的轮廓。在这里,我们展示了双梳光谱学(DCS)在气相分子磁光活性光谱学(MOAS)中的无与伦比的潜力,其分辨率达到百兆赫兹级,亚毫秒级的高速测量。作为一个演示,我们实现了快速、高精度和高分辨率的二氧化氮 [Formula: see text]+[Formula: see text] 带和一氧化氮倍频带的 MOAS 测量,可用于分析分子的精细结构。此外,还初步展示了液相旋光活性(低至 10)的测量,其采样时间仅需几秒钟,这可能成为一种常规方法,实现手性结构构象的超快动力学分析。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/3666/9935641/54a548e6c88d/41467_2023_36509_Fig1_HTML.jpg

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