Instrumentation, applications, and energy deposition in quadrupole ion-trap tandem mass spectrometry

This tutorial presents the most common ion activation techniques employed in tandem mass spectrometry. In-source fragmentation and metastable ion decompositions, as well as the general theory of unimolecular dissociations of ions, are initially discussed. This is followed by tandem mass spectrometry, which implies that the activation of ions is distinct from the ionization step, and that the precursor and product ions are both characterized independently by their mass/charge ratios. In collision-induced dissociation (CID), activation of the selected ions occurs by collision(s) with neutral gas molecules in a collision cell. This experiment can be done at high (keV) collision energies, using tandem sector and time-of-flight instruments, or at low (eV range) energies, in tandem quadrupole and ion trapping instruments. It can be performed using either single or multiple collisions with a selected gas and each of these factors influences the distribution of internal energy that the activated ion will possess. While CID remains the most common ion activation technique employed in analytical laboratories today, several new methods have become increasingly useful for specific applications. More recent techniques are examined and their differences, advantages and disadvantages are described in comparison with CID. Collisional activation upon impact of precursor ions on solid surfaces, surface-induced dissociation (SID), is gaining importance as an alternative to gas targets and has been implemented in several different types of mass spectrometers. Furthermore, unique fragmentation mechanisms of multiply-charged species can be studied by electron-capture dissociation (ECD). The ECD technique has been recognized as an efficient means to study non-covalent interactions and to gain sequence information in proteomics applications. Trapping instruments, such as quadrupole ion traps and Fourier transform ion cyclotron resonance instruments, are particularly useful for the photoactivation of ions, specifically for fragmentation of precursor ions by infrared multiphoton dissociation (IRMPD). IRMPD is a non-selective activation method and usually yields rich fragmentation spectra. Lastly, blackbody infrared radiative dissociation is presented with a focus on determining activation energies and other important parameters for the characterization of fragmentation pathways. The individual methods are presented so as to facilitate the understanding of each mechanism of activation and their particular advantages and representative applications.

http://aether.cmi.ua.ac.be/artikels/MB_31643.pdf

Ion activation methods for tandem mass spectrometry.

The most commonly used activation method in the tandem mass spectrometry (MS) of peptides and proteins is energetic collisions with a neutral target gas. The overall process of collisional activation followed by fragmentation of the ion is commonly referred to as collision-induced dissociation (CID). The structural information that results from CID of a peptide or protein ion is highly dependent on the conditions used to effect CID. These include, for example, the relative translational energy of the ion and target, the nature of the target, the number of collisions that is likely to take place, and the observation window of the apparatus. This chapter summarizes the key experimental parameters in the CID of peptide and protein ions, as well as the conditions that tend to prevail in the most commonly employed tandem mass spectrometers.

Collision-induced dissociation (CID) of peptides and proteins.

https://link.springer.com/content/pdf/10.1016/1044-0305(92)85001-Z.pdf

Principles of collisional activation in analytical mass spectrometry.

summary
N2 fixation is an extremely O2-sensitive process. N2-fixing bacteria (diazotrophys) have therefore evolved a variety of strategies by which they maintain an active nitrogenase in the presence of atmospheric O2 and, in some cases, of O2 generated photosynthetically. In this review, the effects of O2 on nitrogenase activity and synthesis are described, as are the mechanisms by which diazotrophs limit O2damage to nitrogenase. These mechanisms are classified as behavioural strategies, physical barriers or physiological and biochemical strategies. Individual diazotrophs frequently empoly a combination of these. In addition, the particular problems faced by the O2-evolving cyanobacteria are discussed.

Reconciling the incompatible: N2 fixation And O2

The MM-ZAB-2F double-focussing mass spectrometer and mike spectrometer

Doubly charged molecular ions of methane

Comparison of photo-excitation of ions and collisional excitation using gases

Using nitrobenzene as an example, various ways in which a contemporary mass spectrometer can be utilized to yield a wealth of information about the compound studied are reviewed. Applying a variety of different techniques and procedures, in addition to the conventional low resolution mass spectrum, the following nitrobenzene spectra have been obtained: collision induced dissociation mass spectrum, mass analysed ion kinetic energy spectra, collision induced dissociation mass analysed ion kinetic energy spectra, spectra obtained at constant B/E, spectra obtained at constant B2/E, high voltage scans of metastable ion fragmentation processes, consecutive fragmentations in different field free regions, charge exchange mass spectra, charge stripping mass spectra, doubly charged ion mass spectra, chemical ionization mass spectra, negative ion mass spectra, negative ion mass analysed ion kinetic energy spectra, negative ion mass analysed ion kinetic energy collision induced dissociation spectra, charge inversion spectra, etc. The complementary types of information available from the above studies are discussed to show the unique versatility of mass spectrometry as a technique for the examination of organic compounds.

John H. Beynon

Papers

The MM-ZAB-2F double-focussing mass spectrometer and mike spectrometer

Doubly charged molecular ions of methane

Comparison of photo-excitation of ions and collisional excitation using gases

The modern mass spectrometer—a complete chemical laboratory

Photodissociation of mass-selected ions investigated using a modified ZAB—2F spectrometer