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Sequence determination in aliphatic poly(ester amide)s by matrix‐assisted laser desorption/ionization time‐of‐flight and time‐of‐flight/time‐of‐flight tandem mass spectrometry
Author(s) -
Rizzarelli Paola,
Puglisi Concetto,
Montaudo Giorgio
Publication year - 2005
Publication title -
rapid communications in mass spectrometry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.528
H-Index - 136
eISSN - 1097-0231
pISSN - 0951-4198
DOI - 10.1002/rcm.2075
Subject(s) - chemistry , amide , mass spectrometry , tandem mass spectrometry , time of flight mass spectrometry , mass spectrum , sebacic acid , fragmentation (computing) , matrix assisted laser desorption/ionization , ion , desorption , matrix isolation , ionization , analytical chemistry (journal) , polymer chemistry , molecule , chromatography , organic chemistry , adsorption , computer science , operating system
Abstract Poly(ester amide)s from dimethyl sebacate or sebacic acid and 2‐aminoethanol or 4‐amino‐1‐butanol were characterized by post‐source decay matrix‐assisted laser desorption/ionization time‐of‐flight (PSD‐MALDI‐TOF) and time‐of‐flight/time‐of‐flight tandem mass spectrometry (MALDI‐TOF/TOF‐MS/MS). Sodiated oligomers were selected as precursor ions for dissociation studies. PSD analysis was performed on dimethyl sebacate, dicarboxylic, carboxylic and amino alcohol, and diamino alcohol terminated oligomers. PSD‐MALDI‐TOF mass spectra yielded information on the fragmentation mechanisms of the poly(ester amide) chains, showing that the main cleavages proceed through a β ‐hydrogen transfer rearrangement. MALDI‐TOF/TOF‐MS/MS provided structural information concerning ester/amide sequences in the polymer chains. As expected, together with the ions appearing in the PSD‐MALDI mass spectrum, several new abundant fragment ions in the low‐mass range are present in MALDI‐TOF/TOF‐MS/MS spectra. These new product ions proved to be diagnostic and made it possible to establish the presence of random sequences of ester and amide bonds in the poly(ester amide)s samples. Copyright © 2005 John Wiley & Sons, Ltd.