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首页> 外文期刊>Chemistry: A European journal >Photocatalytic Redox Reactions for In-Source Peptide Fragmentation
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Photocatalytic Redox Reactions for In-Source Peptide Fragmentation

机译：内源肽片段的光催化氧化还原反应

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摘要

In-source photocatalytic redox reactions based on a photosensitive target plate have been developed to realize peptide fragmentation during laser desorption ionization. Sample peptides and glucose are simply deposited on a spot of sintered TiO2 nanoparticles. With the irradiation of UV laser on TiO2 electrons are excited from the valence to the conduction band, leaving oxidative holes and reductive electrons to drive various in-source redox reactions. Glucose, working here as a hole scavenger and conductor, can favor both on-surface reduction and long distance in-plume oxidation, therefore inducing peptide fragmentation. C-alpha-C backbone cleavage was observed to generate a,x fragment decay, while the N-C-alpha, bond cleavage was also sometimes obtained to induce c,z fragmentation, but was rather weaker. The former dissociation is believed to originate from oxidative routes induced by the valence band holes, based on the oxidation of nitrogen atom at the peptide backbone, including hydrogen-radical abstraction and electron transfer. In contrast, the latter dissociation is supposed to be the result of reductive processes by the conduction band electrons, which are then rather similar to electron capture dissociation in tandem mass spectrometry.
机译：已经开发了基于光敏靶板的源内光催化氧化还原反应，以在激光解吸电离过程中实现肽片段化。样品肽和葡萄糖仅沉积在烧结的TiO2纳米颗粒的斑点上。在TiO2上用紫外线激光照射时，电子从化合价激发到导带，留下氧化空穴和还原电子，以驱动各种源内氧化还原反应。葡萄糖在这里起着空穴清除剂和导体的作用，既有利于表面还原，又有利于长距离的管内氧化，因此可诱导肽片段化。观察到C-alpha-C主链裂解产生a，x片段衰变，而有时也获得N-C-alpha，键裂解以诱导c，z断裂，但较弱。据信前一种解离是由价带孔诱导的氧化途径引起的，该氧化途径基于肽主链上的氮原子的氧化，包括氢自由基提取和电子转移。相反，后者的解离被认为是由导带电子进行的还原过程的结果，这与串联质谱法中的电子捕获解离非常相似。

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