Gas-phase structure of polymer ions: Tying together theoretical approaches and ion mobility spectrometry

An increasing number of studies take advantage of ion mobility spectrometry (IMS) coupled to mass spectrometry (IMS-MS) to investigate the spatial structure of gaseous ions. Synthetic polymers occupy a unique place in the field of IMS-MS. Indeed, due to their intrinsic dispersity, they offer a broad range of homologous ions with different lengths. To help rationalize experimental data, various theoretical approaches have been described. First, the study of trend lines is proposed to derive physicochemical and structural parameters. However, the evaluation of data fitting reflects the overall behavior of the ions without reflecting specific information on their conformation. Atomistic simulations constitute another approach that provide accurate information about the ion shape. The overall scope of this review is dedicated to the synergy between IMS-MS and theoretical approaches, including computational chemistry, demonstrating the essential role they play to fully understand/interpret IMS-MS data.

Automated summary

An increasing number of studies utilize ion mobility spectrometry coupled to mass spectrometry to investigate the spatial structure of gaseous ions. Synthetic polymers play a unique role in this field due to their dispersity, providing a wide range of homologous ions with different lengths. This review focuses on the synergy between IMS-MS and theoretical approaches, including computational chemistry, demonstrating their essential role in fully understanding and interpreting IMS-MS data.