Fourier Transform-Ion Cyclotron Resonance Mass Spectrometry

5 Fourier-Transform Ion-Cyclotron Resonance Mass Spectrometry 

The basis for FTMS is ion-cyclotron motion. A simple experimental sequence in FTMS is composed of four events quench, ion formation, excitation and ion detection. Ions are created in or injected into a cubic cell where they are held by an electric trapping potential and a constant magnetic field B. Each ion assumes 

The ability to selectively excite a particular ion (or group of ions) by irradiating the cell with the appropriate radiofrequencies provides a level of flexibility unparalleled in any other mass spectrometer. The amplitude and duration of the applied RF pulse determine the ultimate radius of the ion trajectories. Thus, by simply turning on the appropriate radiofrequency, ions of a single m/z may be ejected from the cyclotron. In this way, a gas-phase separation of analyte from matrix is achieved. At a fixed radius of the ion trajectories the signal is proportional to the number of orbiting ions. Quantitation therefore requires precise RF control. 

The FTMS instrument operates in a very different fashion from most other types of mass spectrometers. With FTMS, the principal functions of ionisation, mass analysis and ion detection occur in the same space 

Fast screening techniques, such as temperature-resolved in-source filament pyrolysis and laser-assisted pyrolysis, benefit from the high cycle time and mass accuracy of FUCR-MS [214]. An additional advantage of FUCR-MS in the study of pyrolysis processes is that MS can be readily used for structural identification of desorption and pyrolysis products. 

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Vartanian V H, Anderson J S and Laude D A 1995 Advances in trapped ion cells for Fourier transform ion cyclotron resonance mass spectrometry Mass Spec. Rev. 41 1-19... 

Jensen P.K., Pasa-Tolic L., Anderson G. A., Horner J. A., Lipton M.S., Bruce J.E., and Smith R.D., Probing proteomes using capillary isolectric focusing-elec-trospray ionization Fourier transform ion cyclotron resonance mass spectrometry, Anal. Chem. 71, 2076, 1999. 

B. Asamoto (ed.), FT-ICR/MS Applications of Fourier Transform Ion Cyclotron Resonance Mass Spectrometry, VCH Publishers, New York, NY (1991). 

Fourier transform ion cyclotron resonance mass spectrometry... 

CsFeo.72Agi.28Te2,1053 and Cs2Ag2ZrTe4. The latter has a structure that comprises 2D slabs of Ag- and Zr-centered tetrahedral separated by Cs+ cations.1054 Gas-phase silver chalcogenide ions of the type [Ag2 i E ] (E = S, Se, Te) with < 14 have been investigated by laser-ablation Fourier transform ion cyclotron resonance mass spectrometry.1055... 

Wunschel, D. S. Fox, K. F. Bruce, J. E. Muddiman, D. C. Smith, R. D. Analysis of double-stranded polymerase chain reaction products from the Bacillus cereus group by electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry. Rapid Comm. Mass Spectrom 1996,10, 29-35. 

Leinweber, F.C., Schmid, D.G., Lubda, D., Wiesmuller, K., Jung, G., Tallarek, U. (2003). Silica-based monoliths for rapid peptide screening by capillary hquid chromatography hyphenated with electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry. Rapid Commun. Mass. Spectrom. 17, 1180-1188. 

Kalkhof, S. et al. (2005a) Chemical cross-linking and high-performance fourier transform ion cyclotron resonance mass spectrometry for protein interaction analysis Application to a calmodulin/target peptide complex. Anal. Chem. 77, 495-503. 

Multiple mass analyzers exist that can perform tandem mass spectrometry. Some use a tandem-in-space configuration, such as the triple quadrupole mass analyzers illustrated (Fig.3.9). Others use a tandem-in-time configuration and include instruments such as ion-traps (ITMS) and Fourier transform ion cyclotron resonance mass spectrometry (FTICRMS or FTMS). A triple quadrupole mass spectrometer can only perform the tandem process once for an isolated precursor ion (e.g., MS/MS), but trapping or tandem-in-time instruments can perform repetitive tandem mass spectrometry (MS ), thus adding n 1 degrees of structural characterization and elucidation. When an ion-trap is combined with HPLC and photodiode array detection, the net result is a profiling tool that is a powerful tool for both metabolite profiling and metabolite identification. 

Resolutions in the range of 10,000 to 20,000 are achievable with modem time-of-flight mass spectrometry (TOFMS). Fourier transform ion cyclotron resonance mass spectrometry (FTICRMS) is more costly but capable of resolutions exceeding 100,000. Resolutions exceeding 10,000 can provide low to sub parts-per-million mass accuracies. One ppm is equivalent to a mass accuracy of 0.001 for a molecular weight of 1,000 Da. 

J. S. Sampson, A. M. Hawkridge, and D. C. Muddiman. Generation and Detection of Multiply-Charged Peptides and Proteins by Matrix-Assisted Laser Desorption Electrospray Ionization (MALDESI) Fourier Transform Ion Cyclotron Resonance Mass Spectrometry. J. Am. Soc. Mass Spectrom., 17(2006) 1712-1716. 

A. G. Marshall. Milestones in Fourier Transform Ion Cyclotron Resonance Mass Spectrometry Technique Development. Int. J. Mass Spectrom., 200(2000) 331-356. 

S. D.-H. Shi, C. L. Hendrickson, and A. G. Marshall. Counting Individual Sulfur Atoms in a Protein by Ultrahighresolution Fourier Transform Ion Cyclotron Resonance Mass Spectrometry Experimental Resolution of Isotopic Fine Structure in Proteins. Proc. Natl. Acad. Sci. U.S.A., 95(1998) 11532-11537. 

M. E. Belov, M. V. Gorshkov, H. R. Udseth, G. A. Anderson, and R. D. Smith. Zeptomole-Sensitivity Electrospray Ionization-Fourier Transform Ion Cyclotron Resonance Mass Spectrometry of Proteins. Anal. Chem., 72(2000) 2271-2279. 

M. Ramstrom, I. Ivonin, A. Johansson, H. Askmark, K. E. Markides, R. Zubarev, P. Hakansson, S.-M. Aquilonius, and J. Bergquist. Cerebrospinal Fluid Protein Patterns in Neurodegenerative Disease Revealed by Liquid Chromatography Fourier Transform Ion Cyclotron Resonance Mass Spectrometry. Proteomics, 4(2004) 4010-4018. 

Z. Wu, R.P. Rodgers and A.G. Marshall, Characterization of vegetable oils Detailed compositional fingerprints derived from electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry, J. Agric. Food Chem., 52 (2004) 5322-5328. 

Octadecyl sulfate sodium salt (Ci8H37-0-S03 Na+) was examined by laser desorption (LD) Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) in the negative mode resulting in [M - H] ions. Little fragmentation was observed under these conditions [28]. 

Severs J.C., Hofstadler S.A., Zhao Z., Senh R.T., and Smith R.D. (1996), The interface of capillary electrophoresis with high performance Fourier transform ion cyclotron resonance mass spectrometry for biomolecule characterization, Electrophoresis 17(12) 1808-1817. 

Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR) is a very high-resolution mass spectral method (105 to 106, with mass accuracy better than 1 ppm), which allows separation and empirical formula measurement of potentially thousands of metabolites without chromatic separation. 

The development of mass spectrometric techniques, such as fast atom bombardment mass spectrometry (FAB-MS), ° ° Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS), ° and tandem mass spectrometry (MS"), ° allowed enantiodiscrimination of chiral ion-dipole complexes the gas phase. These techniques and others will be illustrated in detail in the next Section 3. 

Fourier transform ion cyclotron resonance mass spectrometry (FTIC-MS), 172-173... 

Fourier Transform Ion Cyclotron Resonance Mass Spectrometry Analytical Applications 1st ed. Asamoto, B., editor John Wiley Sons New York, 1991. 

Hughey, C.A. Hendrickson, C.L. Rodgers, R.P. Marshall, A.G. Elemental Composition Analysis of Processed and Unprocessed Diesel Fuel by Electrospray Ionization Fourier Transform Ion Cyclotron Resonance Mass Spectrometry. Energy Fuels 2001,15. 1186-1193. 

The matrix isolation and spectroscopic characterization of m- and p-benzynes and their derivatives have been reported. Fourier transform ion cyclotron resonance mass spectrometry has been employed to investigate the reactivity of w-benzyne biradical with a pyridinium charge site in the 5-position. The chemical properties of w-benzyne in the gas phase differ from those of the monoradical and... 

Studies of gas-phase S"n2 reactions at sp carbon have been made by Fourier transform ion cyclotron resonance mass spectrometry (FTlCRMS) and complemented by both semiempirical and ab initio MO calculations. The particular processes of interest involved intramolecular reactions in which neutral nucleophiles displace neutral leaving groups within cationic substrates, e.g. A-(2-piperidinoethyl)-2,4,6-triphenylpyridinium cation (59), in which the piperidino moiety is the nucleophile and 2,4,6-triphenylpyridine (60) is the leaving group. No evidence has been obtained for any intermolecular gas-phase 5) 2 reaction involving a pyridine moiety as a leaving group. The quantum mechanical treatments account for the intramolecular preference. 

Marshall, A. G. Hendrickson, C. L. Jackson, G. S. Fourier transform ion cyclotron resonance mass spectrometry a primer. Mass Spectrom. Rev. 

Zampronio, C.G. Giannakopulos, A.E. Zeller, M. Bitziou, E. Macpherson, J.V. Derrick, P.J. Production and properties of nanoelectrospray emitters used in fourier transform ion cyclotron resonance mass spectrometry implications for determination of association constants for noncovalent complexes. Anal. Chem. 2004, 76, 5172-5179. 

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