Stochasticity of poly(2-oxazoline) oligomer hydrolysis determined by tandem mass spectrometry.
Stochasticity of poly(2-oxazoline) oligomer hydrolysis determined by tandem mass spectrometry.
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DOI：
10.1039/d2py00437b
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发表时间：
2022-07-19
影响因子：
4.6
通讯作者：
O'Connor, Peter B.
中科院分区：
文献类型：
--
作者：
Morgan, Tomos E.;Floyd, Thomas G.;Marzullo, Bryan P.;Wootton, Christopher A.;Barrow, Mark P.;Bristow, Anthony W. T.;Perrier, Sebastien;O'Connor, Peter B.
了解合成聚合物结构的修饰对于其准确合成和潜在应用是必要的。在这项贡献中，产生了一系列部分水解的聚（2-恶唑啉）物质，形成聚[（2-聚恶唑啉）-co-（乙烯亚胺）]（P（EtOx-co-EI））共聚物； EI是Ox的水解产物。本体质谱 (MS) 测量可准确测量 EI 含量。对共聚物样品中 EI 含量的串联质谱分析确定了共聚物内每种单体的分布，并且对应于理论上模拟的随机分布。聚合物的 EI 分布受末端选择的影响，在 OH 末端观察到永久水解事件。在分析的聚合物长度（大约 25 聚体）上没有观察到邻近基团效应，这表明之前观察到的邻近基团效应需要更大的聚合物链。尽管对于随机聚合物分布明显有用，但该方法可应用于包含非特异性修饰的许多系统，以确定它们是跨肽、蛋白质、聚合物和核酸的定向位置还是随机位置。串联质谱可用于更好地了解合成聚合物结构的修饰位点，提供更完整的化学知识，这对于其准确合成和潜在应用是必需的。
Understanding modification of synthetic polymer structures is necessary for their accurate synthesis and potential applications. In this contribution, a series of partially hydrolyzed poly(2-oxazoline) species were produced forming poly[(2-polyoxazoline)-co-(ethylenimine)] (P(EtOx-co-EI)) copolymers; EI being the hydrolyzed product of Ox. Bulk mass spectrometry (MS) measurements accurately measured the EI content. Tandem mass spectrometry analysis of the EI content in the copolymer samples determined the distribution of each monomer within the copolymer and corresponded to a theoretically modelled random distribution. The EI distribution across the polymers was shown to be effected by the choice of terminus, with a permanent hydrolysis event observed at an OH terminus. A neighbouring group effect wasn't observed at the polymer length analysed (approximately 25-mer species), suggesting that previously observed neighbouring group effects require a larger polymer chain. Although clearly useful for random polymer distribution this approach may be applied to many systems containing non-specific modifications to determine if they are directed or random locations across peptides, proteins, polymers, and nucleic acids. Tandem mass spectrometry can be used to better understand modification sites of synthetic polymer structures providing more complete chemical knowledge which is necessary for their accurate synthesis and potential applications.
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DOI：
10.1002/rcm.7525
发表时间：
2016-04-15
期刊：
Rapid communications in mass spectrometry : RCM
影响因子：
--
作者：
Fouquet T;Nakamura S;Sato H
通讯作者：
Sato H
影响因子：
6
作者：
Atuntas, Esra;Weber, Christine;Schubert, Ulrich S.
通讯作者：
Schubert, Ulrich S.
影响因子：
7.4
作者：
KENDRICK, E
通讯作者：
KENDRICK, E
影响因子：
1.4
作者：
HEAP, BR
通讯作者：
HEAP, BR
影响因子：
2.3
作者：
Altuntas, Esra;Knop, Katrin;Schubert, Ulrich S.
通讯作者：
Schubert, Ulrich S.