Bromine isotopic signature facilitates de novo sequencing of peptides in free-radical-initiated peptide sequencing (FRIPS) mass spectrometry.
Bromine isotopic signature facilitates de novo sequencing of peptides in free-radical-initiated peptide sequencing (FRIPS) mass spectrometry.
复制标题
溴同位素特征有助于自由基引发肽测序 (FRIPS) 质谱法中肽的从头测序。
DOI：
10.1002/jms.3539
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发表时间：
2015
期刊：
影响因子：
--
通讯作者：
H. Oh
中科院分区：
文献类型：
--
作者：
Jungjoo Nam;Hyuksu Kwon;Inae Jang;Aeran Jeon;Jingyu Moon;Sun Young Lee;Dukjin Kang;S. Han;Bongjin Moon;H. Oh
我们最近表明，自由基引发的肽测序质谱（FRIPS MS）的显着的热化学稳定性（2，2，6，6-四甲基哌啶-1-基）氧基（克里思）的辅助下，是另一个有吸引力的自由基驱动的肽碎片MS工具。在o-TEMPO-Bz-C（O）-肽中克里思部分的苄基碳和氧之间的键的容易均裂断裂以及在·Bz-C（O）-肽中产生的苄基自由基物质的高反应性是导致广泛的自由基驱动的肽骨架断裂的关键因素。在本研究中，我们证明了溴掺入苯环，即o-TEMPO-Bz（Br）-C（O）-肽，允许通过独特的溴双重同位素特征明确区分N-末端肽片段和C-末端片段。此外，溴取代不改变o-TEMPO-Bz-C（O）-肽的整体自由基驱动的肽骨架解离途径。从实践的角度来看，溴同位素签名的存在下，在N-末端肽片段的TEMPO辅助FRIPS MS代表了一个有用的和成本效益的机会从头肽测序。
We recently showed that free-radical-initiated peptide sequencing mass spectrometry (FRIPS MS) assisted by the remarkable thermochemical stability of (2,2,6,6-tetramethyl-piperidin-1-yl)oxyl (TEMPO) is another attractive radical-driven peptide fragmentation MS tool. Facile homolytic cleavage of the bond between the benzylic carbon and the oxygen of the TEMPO moiety in o-TEMPO-Bz-C(O)-peptide and the high reactivity of the benzylic radical species generated in •Bz-C(O)-peptide are key elements leading to extensive radical-driven peptide backbone fragmentation. In the present study, we demonstrate that the incorporation of bromine into the benzene ring, i.e. o-TEMPO-Bz(Br)-C(O)-peptide, allows unambiguous distinction of the N-terminal peptide fragments from the C-terminal fragments through the unique bromine doublet isotopic signature. Furthermore, bromine substitution does not alter the overall radical-driven peptide backbone dissociation pathways of o-TEMPO-Bz-C(O)-peptide. From a practical perspective, the presence of the bromine isotopic signature in the N-terminal peptide fragments in TEMPO-assisted FRIPS MS represents a useful and cost-effective opportunity for de novo peptide sequencing.
影响因子：
2.9
作者：
Perkins, DN;Pappin, DJC;Cottrell, JS
通讯作者：
Cottrell, JS