This review offers an introduction to the principles and generic applications of FT-ICR mass spectrometry, directed to readers with no prior experience with the technique. We are able to explain the fundamental FT-ICR phenomena from a simplified theoretical treatment of ion behavior in idealized magnetic and electric fields. The effects of trapping voltage, trap size and shape, and other nonidealities are manifested mainly as perturbations that preserve the idealized ion behavior modified by appropriate numerical correction factors. Topics include: effect of ion mass, charge, magnetic field, and trapping voltage on ion cyclotron frequency; excitation and detection of ICR signals; mass calibration; mass resolving power and mass accuracy; upper mass limit(s); dynamic range; detection limit, strategies for mass and energy selection for MSn; ion axialization, cooling, and remeasurement; and means for guiding externally formed ions into the ion trap. The relation of FT-ICR MS to other types of Fourier transform spectroscopy and to the Paul (quadrupole) ion trap is described. The article concludes with selected applications, an appendix listing accurate fundamental constants needed for ultrahigh-precision analysis, and an annotated list of selected reviews and primary source publications that describe in further detail various FT-ICR MS techniques and applications. © 1998 John Wiley & Sons, Inc., Mass Spec Rev 17, 1–35, 1998

Fourier transform ion cyclotron resonance mass spectrometry: A primer

Sustained off-resonance irradiation for collision-activated dissociation involving Fourier transform mass spectrometry. Collision-activated dissociation technique that emulates infrared multiphoton dissociation

The Electrospray Ionization (ESI) is a soft ionization technique extensively used for production of gas phase ions (without fragmentation) of thermally labile large supramolecules. In the present review we have described the development of Electrospray Ionization mass spectrometry (ESI-MS) during the last 25 years in the study of various properties of different types of biological molecules. There have been extensive studies on the mechanism of formation of charged gaseous species by the ESI. Several groups have investigated the origin and implications of the multiple charge states of proteins observed in the ESI-mass spectra of the proteins. The charged analytes produced by ESI can be fragmented by activating them in the gas-phase, and thus tandem mass spectrometry has been developed, which provides very important insights on the structural properties of the molecule. The review will highlight recent developments and emerging directions in this fascinating area of research.

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Electrospray Ionization Mass Spectrometry: A Technique to Access the Information beyond the Molecular Weight of the Analyte

Instrumentation, applications, and energy deposition in quadrupole ion-trap 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.

Collision-induced dissociations (CID) is demonstrated on a number of primary and secondary ions using a Nicolet prototype Fourier transform mass spectrometer (FT-MS). Like the triple quadrupole technique, CID using FT-MS is a relatively low energy and efficient process. The ability to study a wide range of ion-molecule reaction products is exemplified by results on proton-bound dimers and transition metal containing ionic species. Variation of collision energy by varying the RF irradiation level can provide information about product distributions as a function of energy as well as yield ion structural information. Like the triple quadrupole technique, no slits are employed and virtually all of the fragment ions formed by the CID process may be detected. Unlike all previous mass spectrometric techniques for studying CID, a tandem instrument is not required, and different experiments are performed by making software modifications rather than hardware modifications.

Collision-induced dissociation with Fourier transform mass spectrometry

Electron impact excitation of ions from organics: an alternative to collision induced dissociation

Collision-induced dissociation in a fourier-transform mass spectrometer

Laser ionization source for ion cyclotron resonance spectroscopy. Application to atomic metal ion chemistry

A pulsed laser has been used in conjunction with an ion cyclotron resonance spectrometer to generate and study the gas-phase ion-molecule reactions of Fe/sup +/ with simple carbonyl compounds and ethers. Oxidative addition reactions are observed, producing alkyl acyl, and alkoxide intermediates which undergo intramolecular rearrangement by a ..beta..-hydride shift mechanism. Decarbonylation reactions are observed with only a few small ketones. The main reaction channel is dehydrogenation for unbranched ketones and reductive elimination of methane for those branched at the ..cap alpha.. carbon. Reactions of Fe/sup +/ with diisopropyl ketone, cyclohexanone, cyclopentanone, and tetrahydrofuran suggest the existence of intermediate and stable ..pi..-ally complexes resulting from sequential ..beta..-hydride shifts.

B. S. Freiser

Papers

Collision-induced dissociation with Fourier transform mass spectrometry

Electron impact excitation of ions from organics: an alternative to collision induced dissociation

Collision-induced dissociation in a fourier-transform mass spectrometer

Laser ionization source for ion cyclotron resonance spectroscopy. Application to atomic metal ion chemistry

Gas-phase reactions of iron(1+) with ketones and ethers