A <sup>15</sup>N labelling, FD and FAB study of ammonia loss from protonated arginine molecules

Zwinselman, J. J.; Nibbering, Nico M. M.; Greef, J. van der; Brauw, M.C. ten Noever de

doi:10.1002/oms.1210181206

Cited by 23 publications

(12 citation statements)

References 14 publications

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“…As the (gas-phase) proton affinity increases with the number of methyl groups added onto the terminal (-position) guanidino nitrogens [19], so is the detection sensitivity. Interest in understanding gas-phase fragmentation of protonated arginine derivatives has lasted for more than two decades [17][18][19][20]29]. With the use of a high performance mass spectrometer, this work reports many previously unreported fragmentation channels and products.…”

Section: Resultsmentioning

confidence: 98%

“…1. In early days when experimental data with <200 ppm accuracy and >10 4 resolving power was not available, two different isobaric fragmentation channels corresponding to the loss of either (C, H 3 , N, O) [17] or (C, O 2 , H) [32] remained unsolved for some years, until Shek et al performed an exquisite isotope labeling experiment where they postulated this fragment ion to be an aldehyde (structure II in Chart 2), a derivative of 1-butanal with a guanidino substituent at the Table 2 Common secondary fragmentation channels identified for the arginine homologues shown in Fig. 1.…”

Section: Loss Of Co and N˛hmentioning

confidence: 99%

“…In 1986, this method was first applied for finding the amino acid sequence information of peptides and proteins [14,15]. Several gas-phase fragmentation studies of arginine had been reported over the past two decades [16][17][18][19].…”

Section: Introductionmentioning

confidence: 99%

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Roadmap for fragmentation of protonated methylarginines in the gas phase

Sabu

Han

2015

International Journal of Mass Spectrometry

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Section: Resultsmentioning

confidence: 98%

Section: Loss Of Co and N˛hmentioning

confidence: 99%

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Roadmap for fragmentation of protonated methylarginines in the gas phase

Sabu

Han

2015

International Journal of Mass Spectrometry

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“…from the guanidino group. 21 Second, in conjunction with the guanidine loss, we considered only S N 2-type reactions (see later). 10 Finally, due to the very large number of possible conformers involved in such reaction pathways, we did not explore the whole routes, which would also include calculations on pre-fragmentation internal rotations and proton transfers.…”

Section: Fragmentation Reactions Of Protonated Argininementioning

confidence: 99%

Modeling of the gas‐phase ion chemistry of protonated arginine

2004

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Arginine is often involved at the C-terminus of peptides obtained from tryptic digests of proteins. The very basic guanidine group of the side-chain of arginine has a large effect on the backbone fragmentation of protonated peptides. Furthermore, arginine exhibits specific fragmentation reactions involving its side-chain. Various tautomerization states, conformers and side-chain dissociation channels of protonated arginine were studied using theoretical methods. The guanidine loss of protonated arginine is proved to be an S(N)2 substitution on the delta-carbon of the side-chain, starting from species containing the N(epsilon)H-C(+)(N(eta)H(2))(N(eta')H(2)) or -N(epsilon) (+)H(2)-C(N(eta)H)(N(eta')H(2)) moieties and leads to formation to either protonated guanidine or protonated proline. In the corresponding transition structures the proline moiety is protonated. Under low-energy collision conditions the extra proton transfers to the guanidine moiety, leading to the formation of C(+)(NH(2))(3). On the other hand, the lifetime of the fragmenting species under high-energy collision conditions is shorter, resulting in enhanced formation of protonated proline and its dissociation products. The first step of ammonia loss is the leaving of a preformed NH(3) from tautomers containing the -N(epsilon)H-C(N(eta)H(3) (+))(N(eta')H) or -N(epsilon)-C(N(eta)H(3) (+))(N(eta')H(2)) moieties. The resulting protonated carbodiimide group can be stabilized by intramolecular nucleophilic attack, leading to ring formation. Overall, reactions involved in the ammonia loss from protonated arginine can be considered as an S(N)1 substitution on the central zeta-carbon of the guanidine group.

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“…Interestingly, the formation mechanism of the m/z 130 fragment ion from protonated Arg is controversial, ie, the m/z 130 fragment ion corresponding to [Arg + H ‐ 45] + was suggested through 3 possible mechanisms as follows. Chait et al suggested the m/z 130 ion is [C 5 H 14 N 4 ] ·+ via the loss of the radical HCOO · from protonated Arg, while Zwinselman et al mentioned the m/z 130 ion is formed by CO and NH 3 loss from protonated Arg . Bouchonnet et al proposed that m/z 130 contained two signals, ie, [C 5 H 14 N 4 ] ·+ and [C 5 H 10 N 2 O 2 ] ·+ generated from protonated Arg through the loss of NH 3 + HN=CH · .…”

Section: Resultsmentioning

confidence: 99%

Gas‐phase intramolecular hydroxyl‐amino exchange of protonated arginine and verified by the synthetic intermediate compound

et al. 2018

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A new fragmentation process was proposed to interpret the characteristic product ion at m/z 130 of protonated arginine. The α-amino group was dissociated from protonated arginine and then combined with the (M + H-NH ) fragment to form an ion-neutral complex which further generated a hydroxyl-amino exchange intermediate compound through an ion-molecule reaction. This intermediate compound was synthesized from argininamide through a diazo reaction, and then the reaction mixture was analyzed using liquid chromatography combined with mass spectrometry (LC-MS). The collision-induced dissociation experiments under the same conditions revealed that this intermediate compound produced the characteristic product ion at m/z 130 as well as protonated arginine, and in addition, density functional theory calculations were performed to confirm simultaneous loss of NH and CO from this intermediate to give the m/z 130 ion.

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A ¹⁵N labelling, FD and FAB study of ammonia loss from protonated arginine molecules

Cited by 23 publications

References 14 publications

Roadmap for fragmentation of protonated methylarginines in the gas phase

Roadmap for fragmentation of protonated methylarginines in the gas phase

Modeling of the gas‐phase ion chemistry of protonated arginine

Gas‐phase intramolecular hydroxyl‐amino exchange of protonated arginine and verified by the synthetic intermediate compound

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A 15N labelling, FD and FAB study of ammonia loss from protonated arginine molecules

Cited by 23 publications

References 14 publications

Roadmap for fragmentation of protonated methylarginines in the gas phase

Roadmap for fragmentation of protonated methylarginines in the gas phase

Modeling of the gas‐phase ion chemistry of protonated arginine

Gas‐phase intramolecular hydroxyl‐amino exchange of protonated arginine and verified by the synthetic intermediate compound

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Product

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A ¹⁵N labelling, FD and FAB study of ammonia loss from protonated arginine molecules