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Pentafluorobenzylpyridinium: new thermometer ion for characterizing the ions produced by collisional activation during tandem mass spectrometry

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Abstract

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.

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Acknowledgements

The authors acknowledge Prof. Naoki Asao of Shinshu University for the synthesis of CF3-BnPy+ and F5-BnPy+. The syntheses of CF3-BnPy+ and F5-BnPy+ were conducted at Shinshu University, supported by the Advanced Research Infrastructure for Materials and Nanotechnology in Japan (ARIM)” of the Ministry of Education, Culture, Sports, Science, and Technology (MEXT). Proposal Number: JPMXP1222SH-031. Molecular structure computations were performed at the Research Center for Computational Science in Okazaki, Japan (project nos. 23-IMS-C066 and 22-IMS-C074). This work was supported by JSPS KAKENHI (grant number 23H01996).

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  1. National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba, 305-8568, Japan

    Daiki Asakawa & Kazumi Saikusa

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  1. Daiki Asakawa
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Correspondence to Daiki Asakawa.

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Asakawa, D., Saikusa, K. Pentafluorobenzylpyridinium: new thermometer ion for characterizing the ions produced by collisional activation during tandem mass spectrometry. ANAL. SCI. 39, 2031–2039 (2023). https://doi.org/10.1007/s44211-023-00419-0

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