In this study, pentafluorobenzylpyridinium (F5-BnPy+), which has the highest dissociation energy among the reported benzylpyridinium thermometer ion, is proposed to characterize the internal energy distributions of ions activated by higher energy collisional dissociation (HCD) and ion-trap collision-induced dissociation (CID) during tandem mass spectrometry. The dissociation threshold energies of F5-BnPy+ was determined using quantum chemistry calculations at the CCSD(T)/6-311++G(d,p)//M06-2X-D3/6-311++G(d,p) level of theory, and the appearance energies for ion dissociation in HCD and ion-trap CID were estimated using Rice-Ramsperger-Kassel-Marcus theory. The main differences between HCD and ion-trap CID are the collision energies used and the timescales of collisional activation. For both HCD and ion-trap CID, the average internal energy of the ions increased with increasing collision energy. In contrast, the average value for the internal energy of the ions activated by ion-trap CID was lower than that of ions activated by HCD, probably because of the smaller collisional energy and longer activation time of the ion-trap CID experiments. The reported method will aid in the determination of the optimum tandem mass spectrometry parameters for the analysis of small molecules such as metabolites.

中文翻译：

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五氟苄基吡啶鎓：新型温度计离子，用于表征串联质谱分析过程中碰撞激活产生的离子。

在本研究中，五氟苄基吡啶鎓（F5-BnPy+）在已报道的苄基吡啶鎓温度计离子中具有最高的解离能，被提议用来表征由高能碰撞解离（HCD）和离子阱碰撞诱导激活的离子的内能分布。串联质谱分析期间的解离 (CID)。F5-BnPy+ 的解离阈值能量是使用 CCSD(T)/6-311++G(d,p)//M06-2X-D3/6-311++G(d,p) 上的量子化学计算确定的）理论水平，并使用 Rice-Ramsperger-Kassel-Marcus 理论估计了 HCD 和离子阱 CID 中离子解离的表观能量。HCD 和离子阱 CID 之间的主要区别在于所使用的碰撞能量和碰撞激活的时间尺度。对于 HCD 和离子阱 CID，离子的平均内能随着碰撞能量的增加而增加。相反，离子阱 CID 激活的离子的内能平均值低于 HCD 激活的离子，这可能是因为离子阱 CID 实验的碰撞能量较小且激活时间较长。所报道的方法将有助于确定用于分析代谢物等小分子的最佳串联质谱参数。