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Tandem mass spectrometry of poly(ethylene imine)s by electrospray ionization (ESI) and matrix-assisted laser desorption/ionization (MALDI).
J Mass Spectrom. 2012 Jan; 47(1):105-14.JM

Abstract

In this contribution, linear poly(ethylene imine) (PEI) polymers, which are of importance in gene delivery, are investigated in detail by using electrospray ionization-quadrupole-time of flight (ESI-Q-TOF) and matrix-assisted laser desorption/ionization-time of flight (MALDI-TOF) mass spectrometry (MS). The analyzed PEIs with different end groups were synthesized using the polymerization of substituted 2-oxazoline via a living cationic ring-opening polymerization (CROP) and a subsequent hydrolysis under acidic conditions. The main goal of this study was to identify linear PEI polymers in a detailed way to gain information about their fragmentation pathways. For this purpose, a detailed characterization of three different linear PEIs was performed by using ESI-Q-TOF and MALDI-TOF MS in combination with collision-induced dissociation (CID) experiments. In ESI-MS as well as MALDI-MS analysis, the obtained spectra of PEIs resulted in fitting mass distributions for the investigated PEIs. In the tandem MS analysis, a 1,2-hydride shift with a charge-remote rearrangement via a four-membered cyclic transition state, as well as charge-induced fragmentation reactions, was proposed as the main fragmentation mechanisms according to the obtained fragmentation products from the protonated parent peaks. In addition, heterolytic and homolytic cleavages were proposed as alternative fragmentation pathways. Moreover, a 1,4-hydrogen elimination was proposed to explain different fragmentation products obtained from the sodiated parent peaks.

Authors+Show Affiliations

Laboratory of Organic and Macromolecular Chemistry (IOMC), Friedrich-Schiller-Universität Jena, Humboldtstrasse 10, 07743 , Jena, Germany.No affiliation info availableNo affiliation info availableNo affiliation info availableNo affiliation info availableNo affiliation info availableNo affiliation info availableNo affiliation info available

Pub Type(s)

Journal Article

Language

eng

PubMed ID

22282096

Citation

Altuntaş, Esra, et al. "Tandem Mass Spectrometry of Poly(ethylene Imine)s By Electrospray Ionization (ESI) and Matrix-assisted Laser Desorption/ionization (MALDI)." Journal of Mass Spectrometry : JMS, vol. 47, no. 1, 2012, pp. 105-14.
Altuntaş E, Knop K, Tauhardt L, et al. Tandem mass spectrometry of poly(ethylene imine)s by electrospray ionization (ESI) and matrix-assisted laser desorption/ionization (MALDI). J Mass Spectrom. 2012;47(1):105-14.
Altuntaş, E., Knop, K., Tauhardt, L., Kempe, K., Crecelius, A. C., Jäger, M., Hager, M. D., & Schubert, U. S. (2012). Tandem mass spectrometry of poly(ethylene imine)s by electrospray ionization (ESI) and matrix-assisted laser desorption/ionization (MALDI). Journal of Mass Spectrometry : JMS, 47(1), 105-14. https://doi.org/10.1002/jms.2032
Altuntaş E, et al. Tandem Mass Spectrometry of Poly(ethylene Imine)s By Electrospray Ionization (ESI) and Matrix-assisted Laser Desorption/ionization (MALDI). J Mass Spectrom. 2012;47(1):105-14. PubMed PMID: 22282096.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Tandem mass spectrometry of poly(ethylene imine)s by electrospray ionization (ESI) and matrix-assisted laser desorption/ionization (MALDI). AU - Altuntaş,Esra, AU - Knop,Katrin, AU - Tauhardt,Lutz, AU - Kempe,Kristian, AU - Crecelius,Anna C, AU - Jäger,Michael, AU - Hager,Martin D, AU - Schubert,Ulrich S, PY - 2012/1/28/entrez PY - 2012/1/28/pubmed PY - 2012/3/22/medline SP - 105 EP - 14 JF - Journal of mass spectrometry : JMS JO - J Mass Spectrom VL - 47 IS - 1 N2 - In this contribution, linear poly(ethylene imine) (PEI) polymers, which are of importance in gene delivery, are investigated in detail by using electrospray ionization-quadrupole-time of flight (ESI-Q-TOF) and matrix-assisted laser desorption/ionization-time of flight (MALDI-TOF) mass spectrometry (MS). The analyzed PEIs with different end groups were synthesized using the polymerization of substituted 2-oxazoline via a living cationic ring-opening polymerization (CROP) and a subsequent hydrolysis under acidic conditions. The main goal of this study was to identify linear PEI polymers in a detailed way to gain information about their fragmentation pathways. For this purpose, a detailed characterization of three different linear PEIs was performed by using ESI-Q-TOF and MALDI-TOF MS in combination with collision-induced dissociation (CID) experiments. In ESI-MS as well as MALDI-MS analysis, the obtained spectra of PEIs resulted in fitting mass distributions for the investigated PEIs. In the tandem MS analysis, a 1,2-hydride shift with a charge-remote rearrangement via a four-membered cyclic transition state, as well as charge-induced fragmentation reactions, was proposed as the main fragmentation mechanisms according to the obtained fragmentation products from the protonated parent peaks. In addition, heterolytic and homolytic cleavages were proposed as alternative fragmentation pathways. Moreover, a 1,4-hydrogen elimination was proposed to explain different fragmentation products obtained from the sodiated parent peaks. SN - 1096-9888 UR - https://www.unboundmedicine.com/medline/citation/22282096/Tandem_mass_spectrometry_of_poly_ethylene_imine_s_by_electrospray_ionization__ESI__and_matrix_assisted_laser_desorption/ionization__MALDI__ L2 - https://doi.org/10.1002/jms.2032 DB - PRIME DP - Unbound Medicine ER -