Department of Chemistry, Sogang University, Seoul, 04107, Korea.
College of Pharmacy, Kyung Hee University, Seoul, 02447, Korea.
J Am Soc Mass Spectrom. 2017 Jan;28(1):154-163. doi: 10.1007/s13361-016-1508-8. Epub 2016 Sep 29.
The present study demonstrates that one-step peptide backbone fragmentations can be achieved using the TEMPO [2-(2,2,6,6-tetramethyl piperidine-1-oxyl)]-assisted free radical-initiated peptide sequencing (FRIPS) mass spectrometry in a hybrid quadrupole time-of-flight (Q-TOF) mass spectrometer and a Q-Exactive Orbitrap instrument in positive ion mode, in contrast to two-step peptide fragmentation in an ion-trap mass spectrometer (reference Anal. Chem. 85, 7044-7051 (30)). In the hybrid Q-TOF and Q-Exactive instruments, higher collisional energies can be applied to the target peptides, compared with the low collisional energies applied by the ion-trap instrument. The higher energy deposition and the additional multiple collisions in the collision cell in both instruments appear to result in one-step peptide backbone dissociations in positive ion mode. This new finding clearly demonstrates that the TEMPO-assisted FRIPS approach is a very useful tool in peptide mass spectrometry research. Graphical Abstract ᅟ.
本研究表明，与离子阱质谱仪中的两步肽碎片化相比，在混合四极杆飞行时间（Q-TOF）质谱仪和正离子模式的 Q-Exactive Orbitrap 仪器中，TEMPO [2-(2,2,6,6-四甲基哌啶-1-氧代)]辅助的自由基引发肽测序（FRIPS）质谱可以实现一步肽骨架碎片化。在混合 Q-TOF 和 Q-Exactive 仪器中，与离子阱仪器施加的低碰撞能相比，可以向目标肽施加更高的碰撞能。这两种仪器中的碰撞室内更高的能量沉积和额外的多次碰撞似乎导致正离子模式下的一步肽骨架解离。这一新发现清楚地表明，TEMPO 辅助 FRIPS 方法是肽质谱研究中非常有用的工具。
