IRMPD Spectroscopy of [PC (4:0/4:0) + M] (M = H, Na, K) and Corresponding CID Fragment Ions.

Glycerophospholipids (GPs) are highly abundant in eukaryotic cells and take part in numerous fundamental physiological processes such as molecular signaling. The GP composition of samples is often analyzed using mass spectrometry (MS), but identification of some structural features, for example, differentiation of stereospecific numbering () isomers by well-established tandem MS (MS) methods, is challenging. In particular, the formation of 1,3-dioxolane over 1,3-dioxane intermediates proposed to be responsible for the -selectivity of these tandem MS strategies has not been validated by spectroscopic methods.

Influence of protein ion charge state on 213 nm top-down UVPD.

Ultraviolet photodissociation (UVPD) is a powerful and rapidly developing method in top-down proteomics. Sequence coverages can exceed those obtained with collision- and electron-induced fragmentation methods. Because of the recent interest in UVPD, factors that influence protein fragmentation and sequence coverage are actively debated in the literature.

Relative Quantification of Phosphatidylcholine sn-Isomers Using Positive Doubly Charged Lipid-Metal Ion Complexes.

Phosphatidylcholines are the major phospholipid component of most eukaryotic cell membranes. Phosphatidylcholines have been shown to actively participate in regulatory and metabolic processes. Dysfunctional metabolic processes have been linked to human disease and can result in altered phosphatidylcholine structural features, such as permutation of fatty acid connectivity.

Selective phosphatidylcholine double bond fragmentation and localisation using Paternò-Büchi reactions and ultraviolet photodissociation.

The effect of double bond functionalisation for selective double bond localisation by ultraviolet photodissociation of phosphatidylcholines is investigated. Paternò-Büchi reactions in nanoESI emitter tips enable attachment of acetophenone to double bonds of unsaturated phosphatidylcholines after 100 s of 254 nm light irradiation with about 50-80% reaction yield. Functionalized phosphatidylcholines dissociate upon 266 nm irradiation yielding double bond selective fragment ions in contrast to results for ultraviolet photodissociation of unmodified lipids.

Effects of wavelength, fluence, and dose on fragmentation pathways and photoproduct ion yield in 213 nm and 266 nm ultraviolet photodissociation experiments.

Ultraviolet photodissociation tandem mass spectrometry is a powerful tool to investigate the structure of biomolecules, due to its ability to generate rich fragmentation patterns or bond selective cleavage, as a function of used laser wavelength, laser fluence, dose (number of accumulated laser pulses), and available chromophores. Herein, we report first results obtained with a newly developed two-wavelength (266 nm and 213 nm) ultraviolet photodissociation setup coupled to a Fourier-transform ion cyclotron resonance mass spectrometer. Photoproduct yields for protonated 3-iodo-l-tyrosine were up to ∼75%.