Characterization of Polylactides with Different Stereoregularity Using Electrospray Ionization Ion Mobility Mass Spectrometry

Abstract

We investigated the effect of stereoregularity on the gas-phase conformations of linear and cyclic polylactides (PLA) using electrospray ionization ion mobility mass spectrometry (ESI-IM-MS) combined with molecular dynamics simulations. IM-MS analysis of PLA ions shows intriguing difference between the collision cross section (ΩD) value of poly-L-lactide (PLLA) and poly-LD-lactide (PLDLA) ions with respect to their chain architecture and stereoregularity. In the singly sodiated linear PLA (l-PLA∙Na+) case, both l-PLLA and l-PLDLA up to 11mer have very similar ΩD values, but the ΩD values of l-PLLA are greater than that of l-PLDLA ions for larger ions. In the case of cyclic PLA (c-PLA), c-PLLA∙Na+ is more compact than c-PLDLA∙Na+ for short PLA ions. However, c-PLLA exhibits larger ΩD value than c-PLDLA for PLA ions longer than 13mer. The origin of difference in the ΩD values was investigated using theoretical investigation of PLAs in the gas phase. The gas-phase conformation of PLA ions is influenced by Na+-oxygen coordination and the weak intramolecular hydrogen bond interaction, which are more effectively formed in more flexible chains. Therefore, the less flexible PLLA has a larger ΩD value than PLDLA. However, for short c-PLA, concomitant maximization of both Na+-oxygen coordination and hydrogen bond interaction is difficult due to the constricted chain freedom, which makes the ΩD value of PLAs in this range show a different trend compared with other PLA ions. Our study facilitates the understanding of correlation between stereoregularity of PLAs and their structure, providing potential utility of IM-MS to characterize stereoisomers of polymers.

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Acknowledgments

This work was supported by Basic Research program (grant no. 2013R1A1A2008974 and grant no. 2012R1A2A2A01015148) through the National Research Foundation (NRF) of Korea funded by the Ministry of Science, ICT, and Future Planning (MSIP).

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Correspondence to Taihyun Chang or Hugh I. Kim.

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Kim, K., Lee, J.W., Chang, T. et al. Characterization of Polylactides with Different Stereoregularity Using Electrospray Ionization Ion Mobility Mass Spectrometry. J. Am. Soc. Mass Spectrom. 25, 1771–1779 (2014). https://doi.org/10.1007/s13361-014-0949-1

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Keywords

  • Ion mobility
  • Polylactide
  • Chiral polymer
  • Electrospray ionization