• Mass Spectrometry Letters
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• v.2 no.1
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• pp.8-11
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• 2011

Two types of glycerolipids [monoacylglycerols (MAG) and cyclitols] were isolated by reversed phase high-performance liquid chromatography from the methanol extracts of a marine sponge, and analyzed by fast atom bombardment mass spectrometry (FAB-MS) in positive-ion mode. FAB mass spectra of these compounds yielded protonated molecules $[M + H]^+$ and abundant sodiated molecules $[M + Na]^+$ from a mixture of 3-nitrobenzyl alcohol and NaI. The structures of these compounds were elucidated by FAB-collisional-induced dissociation (CID)-tandem mass spectrometry. We carried out collision-indused dissociation (CID) of these lipids in B/E-linked scan mode. The CID B/E-linked scan of $[M + H]^+$ and $[M + Na]^+$ precursor ions resulted in the formation of numerous characteristic product ions through a series of dissociative processes. The product ions formed by charge-remote fragmentation (CRF) provided important information for the identification of the acyl chain structure substituted at the glycerol backbone. Some of the product the ions were diagnostic for the presence of a glycerol backbone or acyl chain structure.

• Mass Spectrometry Letters
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• v.12 no.2
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• pp.41-46
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• 2021

Collision-induced dissociation (CID) and higher-energy collisional dissociation (HCD) are the widely used fragmentation technique in mass spectrometry-based proteomics studies. Understanding the fragmentation pattern from the tandem mass spectra using statistical methods helps to implement efficient spectrum analysis algorithms. The study characterizes the frequency of occurrence of multi-charged fragment ions and their neutral loss events of doubly and triply charged peptides in the CID and HCD spectrum. The dependency of the length of the fragment ion on the occurrence of multi-charged fragment ion is characterized here. Study shows that the singly charged fragment ions are generally dominated in the doubly charged peptide spectrum. However, as the length of the product ion increases, the frequency of occurrence of charge 2 fragment ions increases. The y- ions have more tendencies to generate charge 2 fragment ions than b- ions, both in CID and HCD spectrum. The frequency of occurrence of charge 2 fragment ion peaks is prominent upon the dissociation of the triply charged peptides. For triply charged peptides, product ion of higher length occurred in multiple charge states in CID spectrum. The neutral loss peaks mostly exist in charge 2 states in the triply charged peptide spectrum. The b-ions peaks are observed in much less frequency than y-ions in HCD spectrum as the length of the fragment increases. Isotopic peaks are occurred in charge 2 state both in doubly and triply charged peptide's HCD spectrum.

• Mass Spectrometry Letters
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• v.12 no.4
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• pp.131-136
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• 2021

Collision-induced dissociation of peptides involves a series of proton-transfer reactions in the activated peptide. To describe the kinetics of energy-variable dissociation, we considered the heat capacity of the peptide and the Marcus-theory-type proton-transfer rate. The peptide ion was activated to the high internal energy states by collision with a target gas in the collision cell. The mobile proton in the activated peptide then migrated from the most stable site to the amide oxygen and subsequently to the amide nitrogen (N-protonated) of the peptide bond to be broken. The N-protonated intermediate proceeded to the product-like complex that dissociated to products. Previous studies have suggested that the proton-transfer equilibria in the activated peptide affect the dissociation kinetics. To take the extent of collisional activation into account, we assumed a soft-sphere collision model, where the relative collision energy was fully available to the internal excitation of a collision complex. In addition, we employed a Marcus-theory-type rate equation to account for the proton-transfer equilibria. Herein, we present results from the integrated thermochemical approach using a tryptic peptide of ubiquitin.