Fragmentation of arginine- and lysine-containing dipeptides cationized by Cu+ and Cu2+

Lavanant, Hélène; Hoppilliard, Y.

doi:10.1255/ejms.248

Cited by 20 publications

(10 citation statements)

References 30 publications

(49 reference statements)

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“…The most intense product is [a 7 + Cr − 2H] 2+ , which is the loss of both CO and H 2 O from the precursor. This has also been reported by Lavanant and Hoppilliard from studies involving Cu + and Cu 2+ ‐cationized arginine‐ and lysine‐containing dipeptides.…”

Section: Resultssupporting

confidence: 89%

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Effects of transition metal ion coordination on the collision‐induced dissociation of polyalanines

2011

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Transition metal-polyalanine complexes were analyzed in a high-capacity quadrupole ion trap after electrospray ionization. Polyalanines have no polar amino acid side chains to coordinate metal ions, thus allowing the effects metal ion interaction with the peptide backbone to be explored. Positive mode mass spectra produced from peptides mixed with salts of the first row transition metals Cr(III), Fe(II), Fe(III), Co(II), Ni(II), Cu(I), and Cu(II) yield singly and doubly charged metallated ions. These precursor ions undergo collision-induced dissociation (CID) to give almost exclusively metallated N-terminal product ions whose types and relative abundances depend on the identity of the transition metal. For example, Cr(III)-cationized peptides yield CID spectra that are complex and have several neutral losses, whereas Fe(III)-cationized peptides dissociate to give intense non-metallated products. The addition of Cu(II) shows the most promise for sequencing. Spectra obtained from the CID of singly and doubly charged Cu-heptaalanine ions, [M + Cu - H](+) and [M + Cu](2+) , are complimentary and together provide cleavage at every residue and no neutral losses. (This contrasts with [M + H](+) of heptaalanine, where CID does not provide backbone ions to sequence the first three residues.) Transition metal cationization produces abundant metallated a-ions by CID, unlike protonated peptides that produce primarily b- and y-ions. The prominence of metallated a-ions is interesting because they do not always form from b-ions. Tandem mass spectrometry on metallated (Met = metal) a- and b-ions indicate that [b(n) + Met - H](2+) lose CO to form [a(n) + Met - H](2+), mimicking protonated structures. In contrast, [a(n) + Met - H](2+) eliminate an amino acid residue to form [a(n-1) + Met - H](2+), which may be useful in sequencing.

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Section: Resultssupporting

confidence: 89%

“…The exact mechanism is unclear and may vary depending on the nature of the transition metal. Transition metal ions can coordinate at electron pairs on heteroatoms such as oxygen . Therefore, metal ion coordination at carbonyl oxygen along the peptide backbone may lead to cleavage of C–C bonds alpha to the carbonyl.…”

Section: Resultsmentioning

confidence: 99%

Effects of transition metal ion coordination on the collision‐induced dissociation of polyalanines

2011

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“…Although the doubly charged [CuA C H T U N G T R E N N U N G (H 2 O)] 2 + ion has been recently characterized as a stable complex by means of charge-stripping experiments, [29] the failure to detect it here points to a reduction process, as already observed before for copper under electrospray conditions. [30][31][32][33][34][35] Interaction between copper(II) ions and uracil gives rise to different types of ions, the structure of which clearly depends on the cone voltage applied. At low DP values (Figure 1), two pairs of peaks are associated with copper/uracil interaction: 1) peaks at m/z 285.9 and 287.9, which correspond to [Cu- www.chemphyschem.org through a reduction process, as already observed before under electrospray conditions.…”

Section: Resultsmentioning

confidence: 99%

“…Interaction of doubly charged metal cations with organic ligands L often results in the detection in electrospray spectra of a series of doubly charged [ML n ] 2 + complexes (n ! 1), [9,30,32,[36][37][38][39][40][41][42] but the smallest species [ML] 2 + (n = 1) is often not observed, especially for metals having a high second ionization potential, such as copper [30,32,36] and lead. [9,39,40] Consistently, in the case of the Cu 2 + /uracil system, no [CuA C H T U N G T R E N N U N G (uracil)] 2 + ions are observed, nor we do detect higher homologues, and this suggests that the source conditions are likely not mild enough to allow the production of multiply charged complexes.…”

Section: Resultsmentioning

confidence: 99%

Unimolecular Reactivity of Uracil–Cu²⁺ Complexes in the Gas Phase

et al. 2006

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The gas-phase interaction of copper(II) ions with uracil are studied by means of mass spectrometry and B3LYP/6-311+G(2df,2p)//B3LYP/6-31G(d) calculations. Positive-ion electrospray spectra show that the reaction of uracil with copper(II) gives rise to singly charged species, whereby the [Cu(uracil--H)](+) complex is the most intense ion in the spectra at low concentration. Mass spectrometry/mass spectrometry (MS/MS) experiments show that the loss of HNCO and NCO are the dominant fragmentation processes, accompanied by a minor loss of CO. A systematic study of the spectra obtained with different labeled species, namely, 2-(13)C- (m/z 175), 2-(13)C,1,3-(15)N(2)- (m/z 177) and 3-(15)N-uracil (m/z 175), concludes unambiguously that both the loss of HNCO and NCO involve exclusively C2 and N3, whereas only C4 is involved in the loss of CO. Suitable mechanisms for these fragmentation processes are proposed through a theoretical survey of the corresponding potential energy surface. In these mechanisms, pi complexes, which lie high in energy with respect to the global minimum, play a significant role in the loss of NCO; this explains why both products, HNCO and NCO involve the same atoms of the ring.

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“…31 The MS 3 CID spectra of b þ nÀ1 ions display abundant loss of water and form a n -1 þ ions by loss of CO (Fig. 8).…”

Section: Hexapeptide Estersmentioning

confidence: 99%

Differentiation of three pairs of positional isomers of hybrid peptides with repeats of phenylalanine‐β³‐h‐valine/β³‐h‐valine‐phenylalanine by electrospray ionization tandem mass spectrometry

Ramesh¹,

Reddy²,

Srinivas³

et al. 2007

Rapid Comm Mass Spectrometry

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Electrospray ionization ion trap mass spectrometry has been used to distinguish three pairs of positional isomers of a new series of N-blocked hybrid peptides derived from repeats of phenylalanine(D)-beta3-h-valine/beta3-h-valine-phenylalanine(D) (FbetaV/betaVF) non-natural amino acids. MSn of protonated isomeric peptides produces characteristic fragmentation involving the peptide backbone, the Boc group and the side chain. FbetaV-peptides can be distinguished from betaVF-peptides by the loss of R-OH from [M+H-Boc+H]+, which is either of relatively low abundance or totally absent for the latter peptides. In contrast, betaVF-peptides show abundant Mannich base characteristic ions by the elimination of ammonia, and imine due to a retro-Mannich cleavage. This fragmentation is absent for FbetaV-peptides. When beta-valine is at the C-terminus, abundant b+(n-1) ions are produced. This is ascribed to the probable formation of a stable diketopiperazine structure, and this has been supported by the loss of H2O and CO in the CID spectra of b+(n-1) ions. The hybrid dipeptide acids have also been distinguished in negative ion mass spectrometry.

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Fragmentation of arginine- and lysine-containing dipeptides cationized by Cu+ and Cu2+

Cited by 20 publications

References 30 publications

Effects of transition metal ion coordination on the collision‐induced dissociation of polyalanines

Effects of transition metal ion coordination on the collision‐induced dissociation of polyalanines

Unimolecular Reactivity of Uracil–Cu²⁺ Complexes in the Gas Phase

Differentiation of three pairs of positional isomers of hybrid peptides with repeats of phenylalanine‐β³‐h‐valine/β³‐h‐valine‐phenylalanine by electrospray ionization tandem mass spectrometry

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Fragmentation of arginine- and lysine-containing dipeptides cationized by Cu+ and Cu2+

Cited by 20 publications

References 30 publications

Effects of transition metal ion coordination on the collision‐induced dissociation of polyalanines

Effects of transition metal ion coordination on the collision‐induced dissociation of polyalanines

Unimolecular Reactivity of Uracil–Cu2+ Complexes in the Gas Phase

Differentiation of three pairs of positional isomers of hybrid peptides with repeats of phenylalanine‐β3‐h‐valine/β3‐h‐valine‐phenylalanine by electrospray ionization tandem mass spectrometry

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Unimolecular Reactivity of Uracil–Cu²⁺ Complexes in the Gas Phase

Differentiation of three pairs of positional isomers of hybrid peptides with repeats of phenylalanine‐β³‐h‐valine/β³‐h‐valine‐phenylalanine by electrospray ionization tandem mass spectrometry