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通过基质辅助激光解吸电离飞行时间/飞行时间串联质谱法对由癸二酸和4-氨基-1-丁醇合成的聚(酯酰胺)进行结构表征。

Structural characterization of synthetic poly(ester amide) from sebacic acid and 4-amino-1-butanol by matrix-assisted laser desorption ionization time-of-flight/time-of-flight tandem mass spectrometry.

作者信息

Rizzarelli Paola, Puglisi Concetto

机构信息

Institute of Chemistry and Technology of Polymers, National Council of Research, V. le A. Doria 6, 95125 Catania, Italy.

出版信息

Rapid Commun Mass Spectrom. 2008;22(6):739-54. doi: 10.1002/rcm.3417.

Abstract

Matrix-assisted laser desorption/ionization time-of-flight/time-of-flight tandem mass spectrometry (MALDI-TOF/TOF-MS/MS) was employed to analyze a poly(ester amide) sample (PEA-Bu) from the melt condensation of sebacic acid and 4-amino-1-butanol. In particular, we investigated the fragmentation pathways, the ester/amide bond sequences and the structure of species derived from side reactions during the synthesis. MALDI-TOF/TOF-MS/MS analysis was performed on cyclic species and linear oligomers terminated by dicarboxyl groups, carboxyl and hydroxyl groups and diamino alcohol groups. The sodium adducts of these oligomers were selected as precursor ions. Different end groups do not influence the fragmentation of sodiated poly(ester amide) oligomers and similar series of product ions were observed in the MALDI-TOF/TOF-MS/MS spectra. According to the structures of the most abundant product ions identified, the main cleavages proceed through a beta-hydrogen-transfer rearrangement, leading to the selective scission of the --O--CH2-- bonds. Abundant product ions originating from --CH2--CH2-- (beta-gamma) bond cleavage in the sebacate moiety were also detected. Their formation should be promoted by the presence of an alpha,beta-unsaturated ester or amide end group. MALDI-TOF/TOF-MS/MS provided structural information concerning the ester/amide sequences in the polymer chains. In the MALDI-TOF/TOF-MS/MS spectra acquired, using argon as the collision gas, of cyclic species and linear oligomers terminated by diamino alcohol groups, product ions in the low-mass range, undetected in the mass spectra acquired using air as the collision gas, 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) sample. Furthermore, MALDI-TOF/TOF-MS/MS provided useful information to clarify the structures of precursor ions derived from side reactions during the synthesis.

摘要

采用基质辅助激光解吸/电离飞行时间/飞行时间串联质谱法(MALDI-TOF/TOF-MS/MS)对癸二酸与4-氨基-1-丁醇熔融缩聚得到的聚(酯酰胺)样品(PEA-Bu)进行分析。特别地,我们研究了合成过程中的裂解途径、酯/酰胺键序列以及副反应衍生物种的结构。对由二羧基、羧基和羟基以及二氨基醇基团封端的环状物种和线性低聚物进行了MALDI-TOF/TOF-MS/MS分析。选择这些低聚物的钠加合物作为前体离子。不同的端基不影响钠化聚(酯酰胺)低聚物的裂解,并且在MALDI-TOF/TOF-MS/MS谱图中观察到了类似系列的产物离子。根据鉴定出的最丰富产物离子的结构,主要裂解通过β-氢转移重排进行,导致--O--CH2--键的选择性断裂。还检测到了源自癸二酸酯部分中--CH2--CH2--(β-γ)键裂解的丰富产物离子。α,β-不饱和酯或酰胺端基的存在应会促进它们的形成。MALDI-TOF/TOF-MS/MS提供了有关聚合物链中酯/酰胺序列的结构信息。在以氩气作为碰撞气体采集的环状物种和由二氨基醇基团封端的线性低聚物的MALDI-TOF/TOF-MS/MS谱图中,在以空气作为碰撞气体采集的质谱图中未检测到的低质量范围内的产物离子被证明具有诊断价值,并且使得确定聚(酯酰胺)样品中酯键和酰胺键的无规序列成为可能。此外,MALDI-TOF/TOF-MS/MS提供了有用信息,以阐明合成过程中副反应衍生的前体离子的结构。

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