Laboratoire de Chimie Physique Moléculaire, École Polytechnique Fédérale de Lausanne, EPFL SB ISIC LCPM, Station 6, CH-1015 Lausanne, Switzerland.
Faraday Discuss. 2019 Jul 18;217(0):114-125. doi: 10.1039/c8fd00180d.
Double-resonance spectroscopic schemes in combination with cryogenic ion traps are the go-to techniques when isomer-specific high-resolution spectra are required for analysis of molecular ions. Their limitation lies in the requirement for well-resolved, isomer-specific absorption bands as well as in the potentially time-consuming steps to identify each isomer. We present an alternative approach where isomeric species are readily separated using ion mobility spectrometry (IMS) and selected prior to cryogenic spectroscopic analysis. To date, most IMS approaches suffer from relatively low resolution, however, recent technological developments in the field of travelling-wave ion mobility using structures for lossless ion manipulation (SLIM) permit the use of extremely long drift paths, which greatly enhances the resolution. We demonstrate the power of combining this type of ultra-high resolution IMS with cryogenic vibrational spectroscopy by comparing mobility-resolved IR spectra of a disaccharide to those acquired using IR-IR double resonance. This new approach is especially promising for the investigation of larger molecules where spectral congestion interferes with double resonance techniques.
当需要分析分子离子的具有异构体特异性的高分辨率光谱时,双共振光谱方案与低温离子阱相结合是首选技术。其局限性在于需要分辨率良好且具有异构体特异性的吸收带,以及可能需要耗时的步骤来鉴定每种异构体。我们提出了一种替代方法,其中使用离子淌度谱(IMS)可以轻松分离异构体,并在低温光谱分析之前进行选择。迄今为止,大多数 IMS 方法的分辨率相对较低,但是,最近在使用无损离子操控结构的行波离子淌度(SLIM)领域中的技术发展使得可以使用非常长的漂移路径,这极大地提高了分辨率。我们通过比较二糖的迁移率分辨 IR 光谱与使用 IR-IR 双共振获得的光谱,证明了将这种类型的超高分辨率 IMS 与低温振动光谱相结合的强大功能。对于研究光谱拥挤会干扰双共振技术的较大分子,这种新方法尤其有前途。