Dang Qiankun, Xu Fuxing, Xie Xiaodong, Xu Chongsheng, Dai Xinhua, Fang Xiang, Ding Li, Ding Chuan-Fan
†Department of Chemistry and Laser Chemistry Institute, Fudan University, Shanghai 200433, China.
‡National Institute of Metrology, Beijing 100013, China.
Anal Chem. 2015 Jun 2;87(11):5561-7. doi: 10.1021/acs.analchem.5b00118. Epub 2015 May 12.
Collision-induced dissociation (CID) in linear ion traps is usually performed by applying a dipolar alternating current (AC) signal to one pair of electrodes, which results in ion excitation mainly in one direction. In this paper, we report simulation and experimental studies of the ion excitation in two coordinate directions by applying identical dipolar AC signals to two pairs of electrodes simultaneously. Theoretical analysis and simulation results demonstrate that the ion kinetic energy is higher than that using the conventional CID method. Experimental results show that more activation energy (as determined by the intensity ratio of the a4/b4 fragments from the CID of protonated leucine enkephalin) can be deposited into parent ions in this method. The dissociation rate constant in this method was about 3.8 times higher than that in the conventional method under the same experimental condition, at the Mathieu parameter qu (where u = x, y) value of 0.25. The ion fragmentation efficiency is also significantly improved. Compared with the conventional method, the smaller qu value can be used in this method to obtain the same internal energy deposited into ions. Consequently, the "low mass cut-off" is redeemed and more fragment ions can be detected. This excitation method can be implemented easily without changing any experimental parameters.
线性离子阱中的碰撞诱导解离(CID)通常是通过向一对电极施加偶极交流(AC)信号来实现的,这会导致离子主要在一个方向上被激发。在本文中,我们报告了通过同时向两对电极施加相同的偶极交流信号,对离子在两个坐标方向上的激发进行的模拟和实验研究。理论分析和模拟结果表明,离子动能高于使用传统CID方法时的动能。实验结果表明,用这种方法可以将更多的活化能(由质子化亮氨酸脑啡肽CID产生的a4/b4碎片的强度比确定)沉积到母离子中。在相同实验条件下,当马修参数qu(其中u = x, y)值为0.25时,这种方法的解离速率常数比传统方法高约3.8倍。离子碎片化效率也显著提高。与传统方法相比,这种方法可以使用更小的qu值来获得相同的沉积到离子中的内能。因此,“低质量截止”得到改善,可以检测到更多的碎片离子。这种激发方法无需改变任何实验参数即可轻松实现。