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Novel behavior of the chromatographic separation of linear and cyclic polymers


In various polymerization processes, the formation of a wide variety of chains, not only in length but also in chemical composition, broadly complicates comprehensive polymer characterization. In this communication, we compare different stationary and mobile phases for the analysis of complex polymer mixtures via size-exclusion chromatography-mass spectrometry (SEC-MS). To the best of our knowledge, we report novel chromatographic effects for the separation of linear and cyclic oligomers for polyesters (PE) and polyurethanes (PUR). A complete separation for the different structures was achieved for both polymer types with a single-solvent system (acetonitrile, ACN) and without extensive optimization. Additionally, cyclic species were found to show an inverse elution profile compared to their linear counterparts, suggesting distinct physical properties between species.

Novel chromatographic separation of cyclic and linear polymers.

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The authors thank Dr. Hartmut Nefzger and Dr. Stefan Wershofen of Bayer MaterialScience AG, Leverkusen, Germany, for providing the polymer samples. Research reported in this publication was supported by the National Center for Advancing Translational Sciences of the National Institutes of Health under Award Numbers 5UH3TR000491-04 and 3UH3TR000491-04S1. The content is solely the responsibility of the authors and does not necessarily represent the official views of the National Institutes of Health. The authors also acknowledge support for this work provided by the Vanderbilt University Center for Innovative Technologies, the Vanderbilt Institute for Chemical Biology, the Vanderbilt Institute for Integrative Biosystems Research and Education, and Vanderbilt University College of Arts and Science.

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Correspondence to John A. McLean or David M. Hercules.

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Montenegro-Burke, J.R., Bennett, J.M., McLean, J.A. et al. Novel behavior of the chromatographic separation of linear and cyclic polymers. Anal Bioanal Chem 408, 677–681 (2016).

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  • Cyclic and linear polymers
  • Polyurethanes
  • Polyesters
  • Size-exclusion chromatography
  • Electrospray mass spectrometry