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Electrospray Ionization Mechanisms for Large Polyethylene Glycol Chains Studied Through Tandem Ion Mobility Spectrometry

  • Research Article
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Journal of The American Society for Mass Spectrometry

Abstract

Ion mobility mass spectrometry (IMS-MS) is used to investigate the abundance pattern, n z (m) of Poly-(ethyleneglycol) (PEG) electrosprayed from water/methanol as a function of mass and charge state. We examine n z (m) patterns from a diversity of solution cations, primarily dimethylammonium and triethylammonium. The ability of PEG chains to initially attach to various cations in the spraying chamber, and to retain them (or not) on entering the MS, provide valuable clues on the ionization mechanism. Single chains form in highly charged and extended shapes in most buffers. But the high initial charge they hold under atmospheric pressure is lost on transit to the vacuum system for large cations. In contrast, aggregates of two or more chains carry in all buffers at most the Rayleigh charge of a water drop of the same volume. This shows either that they form via Dole’s charge residue mechanism, or that highly charged and extended aggregates are ripped apart by Coulombic repulsion. IMS-IMS experiments in He confirm these findings, and provide new mechanistic insights on the stability of aggregates. When collisionally activated, initially globular dimers are stable. However, slightly nonglobular dimers projecting out a linear appendix are segregated into two monomeric chains. The breakup of a charged dimer is therefore a multi-step process, similar to the Fenn-Consta polymer extrusion mechanism. The highest activation barrier is associated to the first step, where a short chain segment carrying a single charge escapes (ion-evaporates) from a charged drop, leading then to gradual field extrusion of the whole chain out of the drop.

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Acknowledgments

The authors thank Applied Biosystems and SEADM for their loan of the IMS-MS facility, (http://www.eng.yale.edu/DMAMSfacility/), Yale’s W. M. Keck Center for hosting it, Bruce Thomson for his guidance on mass spectrometry and Q-Star MS issues, and Juan Fernández García (Yale) and Alejandro Casado (SEADM) for their key contributions to the data inversion routines. C.L. acknowledges the Ramon Areces Fellowship for its support. Following Yale University rules, J.F.M. declares that he has a personal interest in the company SEADM manufacturing the differential mobility analyzer used in this research.

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Authors and Affiliations

  1. Mechanical Engineering Department, Yale University, New Haven, CT, 06520, USA

    Carlos Larriba & Juan Fernandez de la Mora

  2. Department of Chemistry, Indiana University, Bloomington, IN, 55455, USA

    Carlos Larriba & David E. Clemmer

  3. SEADM, Parque Tecnológico de Boecillo, 47151 , Boecillo, , Valladolid, Spain

    Carlos Larriba

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  1. Carlos Larriba
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  2. Juan Fernandez de la Mora
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  3. David E. Clemmer
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Correspondence to Carlos Larriba.

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Larriba, C., de la Mora, J.F. & Clemmer, D.E. Electrospray Ionization Mechanisms for Large Polyethylene Glycol Chains Studied Through Tandem Ion Mobility Spectrometry. J. Am. Soc. Mass Spectrom. 25, 1332–1345 (2014). https://doi.org/10.1007/s13361-014-0885-0

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  • DOI: https://doi.org/10.1007/s13361-014-0885-0

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