Evaluation of Various Silicon- and Boron-Containing Compounds for the Detection of Phosphorylation in Peptides via Gas-Phase Ion-Molecule Reactions

Abstract

Gas-phase ion-molecule reactions [IMR] of various boron- and silicon-containing neutrals were investigated as a potential route for detecting phosphorylation within peptides in the negative ion mode. Trimethyl borate (TMB), triethyl borate (TEB) and N,O- Bis(trimethylsilyl)acetamide (TMSA), unlike diethylmethoxyborane (DEMB), diisopropoxymethylborane [DiPMB] and chlorotrimethylsi- Lane (TMSCIL], reacted differently if a phosphate moiety was present and thus are suitable to detect phosphorylation. During multistage collision-induced dissociation experiments of the reaction products of IMR with TMB and TEB, the [LSsF - 4H + B]- ion formed a modified y2 fragment allowing the phosphorylation site to be assigned, unlike reaction products of DEMB and DiPMB which lost both the phos- phoric acid and the boron-containing moiety.

Identification of the Phenol Functionality in Deprotonated Monomeric and Dimeric Lignin Degradation Products via Tandem Mass Spectrometry Based on Ion–Molecule Reactions with Diethylmethoxyborane

“…However, most studies on functional group-specific ion-molecule reactions have focused on protonated analytes. Only in a few cases were deprotonated analytes examined [24][25][26][27][28], and to the best of our knowledge, no reagents have been developed for the identification of the phenol functionality. In this study, diethyl methoxyborane (DEMB) is explored as a reagent for the identification of the phenol functionality in deprotonated ligninrelated analytes.…”

Ion‐molecule reactions of mass‐selected ions

“…In addition, trimethyl‐ and triethylborane could be used for differentiation of positional isomers of phosphorylated carbohydrates. Another work by the same group compared the efficiency of various boron‐ and silicon‐containing species to identify phosphorylation in peptides via IMR (Piatkivskyi, Piatkivskyi, Ryzhov, et al, 2014). Again, IMR in the negative ion mode with trimethyl‐ and triethylborane followed by multi‐stage CID was shown to be useful in identifying the phiosphorylation site in peptides.…”

Determination of the compound class and functional groups in protonated analytes via diagnostic gas‐phase ion‐molecule reactions

“…Furthermore, an rf‐only quadrupole functions as a focusing reaction chamber and hence has a great ion transmission capability. However, the most powerful instruments for the study of these reactions are ion‐trapping instruments, such as Fourier‐transform ion cyclotron resonance (FT‐ICR) (Gao et al, 2003; Lanucara et al, 2014; Petzold et al, 2004; Watkins et al, 2004), linear quadrupole ion trap (LQIT) (Habicht et al, 2008, Habicht, Duan et al, 2011; Kong et al, 2018; Sheng, Williams, Tang, Riedeman et al, 2014) and three‐dimensional quadrupole ion trap (QIT) instruments (Piatkivskyi, Pyatkivskyy, Hurt, et al, 2014; Piatkivskyi, Pyatkivskyy, Ryzhov, 2014; Pyatkivskyy & Ryzhov, 2008; Song & Cooks, 2006). These instruments enable the execution of multiple stages of ion isolation followed by ion‐molecule reactions or dissociation reactions (MS n experiments), thus providing great flexibility and the ability to probe the structures of the ion‐molecule reaction product ions.…”

“…The first one was introduced by Gronert and co‐workers (Gronert, 1998, 2001, 2005). Its modified versions have been utilized by several research groups (Habicht et al, 2008; Piatkivskyi, Pyatkivskyy, Hurt et al, 2014; Piatkivskyi, Pyatkivskyy, Ryzhov, 2014; Sheng, Williams, Tang, Riedeman et al, 2014). The schematic of a commonly used external reagent manifold setup is provided in Figure 3A.…”