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Matrix-assisted laser desorption ionization time-of-flight/time-of-flight tandem mass spectra of biodegradable polybutylenesuccinate.
Rapid Commun Mass Spectrom. 2013 Oct 15; 27(19):2213-25.RC

Abstract

RATIONALE

Matrix-Assisted Laser Desorption/Ionization Time-Of-Flight/Time-Of-Flight Tandem Mass Spectrometry (MALDI-TOF MS/MS) was employed to analyze five poly(butylene succinate) (PBSu) oligomers and to investigate their fragmentation pathways.

METHODS

MALDI-TOF MS/MS analysis was performed on cyclic and linear oligomers terminated by dicarboxyl groups, carboxyl and hydroxyl groups, hydroxyl and olefin groups, and dihydroxyl groups. The sodium adduct ions of these oligomers were selected as precursor ions. Experiments were carried out with and without argon as the collision gas.

RESULTS

A β-hydrogen transfer rearrangement, leading to the selective cleavage of the -O-CH2- bonds, and cleavage of the -CH2-CO- bonds, the ester bonds, and the -CH2-CH2- bonds in the diol moiety were observed. Two fragmentation mechanisms, correlated to the end-group structure of the precursor ions, were also proposed. The detection of cyclic anhydrides was related to the presence of succinic acid terminal groups. The formation of microcyclic oligoesters probably occurred via an intramolecular transesterification mechanism involving a hydroxyl end group.

CONCLUSIONS

A β-hydrogen transfer rearrangement has been proposed as the main fragmentation mechanism occurring in PBSu without using the collision gas. Cleavages of almost all types of bonds take place in the MALDI CID experiments. According to the structures of the most abundant product ions, six fragmentation pathways have been proposed when using argon as the collision gas. Two fragmentation mechanisms were suggested as being correlated to the end-group structure of the precursor ions.

Authors+Show Affiliations

Istituto di Chimica e Tecnologia dei Polimeri-Consiglio Nazionale delle Ricerche, Catania, Italy. paola.rizzarelli@cnr.it

Pub Type(s)

Journal Article
Research Support, Non-U.S. Gov't

Language

eng

PubMed ID

23996395

Citation

Rizzarelli, Paola. "Matrix-assisted Laser Desorption Ionization Time-of-flight/time-of-flight Tandem Mass Spectra of Biodegradable Polybutylenesuccinate." Rapid Communications in Mass Spectrometry : RCM, vol. 27, no. 19, 2013, pp. 2213-25.
Rizzarelli P. Matrix-assisted laser desorption ionization time-of-flight/time-of-flight tandem mass spectra of biodegradable polybutylenesuccinate. Rapid Commun Mass Spectrom. 2013;27(19):2213-25.
Rizzarelli, P. (2013). Matrix-assisted laser desorption ionization time-of-flight/time-of-flight tandem mass spectra of biodegradable polybutylenesuccinate. Rapid Communications in Mass Spectrometry : RCM, 27(19), 2213-25. https://doi.org/10.1002/rcm.6669
Rizzarelli P. Matrix-assisted Laser Desorption Ionization Time-of-flight/time-of-flight Tandem Mass Spectra of Biodegradable Polybutylenesuccinate. Rapid Commun Mass Spectrom. 2013 Oct 15;27(19):2213-25. PubMed PMID: 23996395.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Matrix-assisted laser desorption ionization time-of-flight/time-of-flight tandem mass spectra of biodegradable polybutylenesuccinate. A1 - Rizzarelli,Paola, PY - 2013/05/03/received PY - 2013/06/21/revised PY - 2013/06/25/accepted PY - 2013/9/3/entrez PY - 2013/9/3/pubmed PY - 2014/2/25/medline SP - 2213 EP - 25 JF - Rapid communications in mass spectrometry : RCM JO - Rapid Commun Mass Spectrom VL - 27 IS - 19 N2 - RATIONALE: Matrix-Assisted Laser Desorption/Ionization Time-Of-Flight/Time-Of-Flight Tandem Mass Spectrometry (MALDI-TOF MS/MS) was employed to analyze five poly(butylene succinate) (PBSu) oligomers and to investigate their fragmentation pathways. METHODS: MALDI-TOF MS/MS analysis was performed on cyclic and linear oligomers terminated by dicarboxyl groups, carboxyl and hydroxyl groups, hydroxyl and olefin groups, and dihydroxyl groups. The sodium adduct ions of these oligomers were selected as precursor ions. Experiments were carried out with and without argon as the collision gas. RESULTS: A β-hydrogen transfer rearrangement, leading to the selective cleavage of the -O-CH2- bonds, and cleavage of the -CH2-CO- bonds, the ester bonds, and the -CH2-CH2- bonds in the diol moiety were observed. Two fragmentation mechanisms, correlated to the end-group structure of the precursor ions, were also proposed. The detection of cyclic anhydrides was related to the presence of succinic acid terminal groups. The formation of microcyclic oligoesters probably occurred via an intramolecular transesterification mechanism involving a hydroxyl end group. CONCLUSIONS: A β-hydrogen transfer rearrangement has been proposed as the main fragmentation mechanism occurring in PBSu without using the collision gas. Cleavages of almost all types of bonds take place in the MALDI CID experiments. According to the structures of the most abundant product ions, six fragmentation pathways have been proposed when using argon as the collision gas. Two fragmentation mechanisms were suggested as being correlated to the end-group structure of the precursor ions. SN - 1097-0231 UR - https://www.unboundmedicine.com/medline/citation/23996395/Matrix_assisted_laser_desorption_ionization_time_of_flight/time_of_flight_tandem_mass_spectra_of_biodegradable_polybutylenesuccinate_ L2 - https://doi.org/10.1002/rcm.6669 DB - PRIME DP - Unbound Medicine ER -