Transition metal ions: charge carriers that mediate the electron capture dissociation pathways of peptides.

Electron capture dissociation (ECD) of model peptides adducted with first row divalent transition metal ions, including Mn(2+), Fe(2+), Co(2+), Ni(2+), Cu(2+), and Zn(2+), were investigated. Model peptides with general sequence of ZGGGXGGGZ were used as probes to unveil the ECD mechanism of metalated peptides, where X is either V or W; and Z is either R or N. Peptides metalated with different divalent transition metal ions were found to generate different ECD tandem mass spectra.

Formation of peptide radical cations (m+·) in electron capture dissociation of peptides adducted with group IIB metal ions.

Peptides adducted with different divalent Group IIB metal ions (Zn(2+), Cd(2+), and Hg(2+)) were found to give very different ECD mass spectra. ECD of Zn(2+) adducted peptides gave series of c-/z-type fragment ions with and without metal ions. ECD of Cd(2+) and Hg(2+) adducted model peptides gave mostly a-type fragment ions with M(+•) and fragment ions corresponding to losses of neutral side chain from M(+•).

Natural structural motifs that suppress peptide ion fragmentation after electron capture.

Series of doubly and triply protonated diarginated peptide molecules with different number of glutamic acid (E) and asparagine (N) residues were analyzed under ECD conditions. ECD spectra of doubly-protonated peptides show a strong dependence on the number of E and N residues. Both the backbone cleavages and hydrogen radical (H*) loss from the charge-reduced precursor ions ([M+2H](+*)) were suppressed as the number of E and N residues increases.

Electron transfer dissociation with supplemental activation to differentiate aspartic and isoaspartic residues in doubly charged peptide cations.

Electron-transfer dissociation (ETD) with supplemental activation of the doubly charged deamidated tryptic digested peptide ions allows differentiation of isoaspartic acid and aspartic acid residues using the c + 57 or z*-57 peaks. The diagnostic peak clearly localizes and characterizes the isoaspartic acid residue. Supplemental activation in ETD of the doubly charged peptide ions involves resonant excitation of the charge reduced precursor radical cations and leads to further dissociation, including extra backbone cleavages and secondary fragmentation.

A mechanistic study of the electron capture dissociation of oligonucleotides.

Electron capture dissociation (ECD) of a series of custom-synthesized oligonucleotide pentamers was performed in a Fourier-transform mass spectrometer with a conventional filament-type electron gun. Dissociation of oligonucleotide ions by electron capture generates primarily w/d-type and z/a-type ions with and without the loss of a nucleobase fragment ions. Minor yields of radical [z/a + H].