FT-ICR

FT-ICR is derived from earlier work of E. O. Lawrence on ion cyclotron resonance in the 1930s [37]. Its further development using image current 

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In the other types of mass spectrometer discussed in this chapter, ions are detected by having them hit a detector such as an electron multiplier. In early ICR instruments, the same approach was taken, but FT-ICR uses a very different teclmique. If an RF potential is applied to the excitation plates of the trapping cell (figure B 1.7.18(b)) equal to the cyclotron frequency of a particular ion m/z ratio, resonant excitation of the ion trajectories takes place (without changing the cyclotron frequency). The result is ion trajectories of higher... 

In many respects, the applications of FT-ICR are similar to those of the quadmpole ion trap, as they are both trapping instmments. The major difference is in the ion motion inside the trapping cell and the wavefomi detection. In recent... 

As with the quadmpole ion trap, ions with a particular m/z ratio can be selected and stored in tlie FT-ICR cell by the resonant ejection of all other ions. Once isolated, the ions can be stored for variable periods of time (even hours) and allowed to react with neutral reagents that are introduced into the trapping cell. In this maimer, the products of bi-molecular reactions can be monitored and, if done as a fiinction of trapping time, it is possible to derive rate constants for the reactions [47]. Collision-induced dissociation can also be perfomied in the FT-ICR cell by tlie isolation and subsequent excitation of the cyclotron frequency of the ions. The extra translational kinetic energy of the ion packet results in energetic collisions between the ions and background... 

Comisarow M B and Marshall A G 1996 Early development of Fourier transform ion cyclotron resonance (FT-ICR) spectroscopy J. Mass Spectrom. 31 581-5... 

This volume eontains exeellent diseussions of the various methods for studying ion-moleeule reaotions in the gas phase, ineluding high pressure mass speotrometry, ion eyelotron resonanee speotrosoopy (and FT-ICR) and seleeted ion flow tube mass speotrometry. 

The reactivity of size-selected transition-metal cluster ions has been studied witli various types of mass spectrometric teclmiques [1 ]. Fourier-transfonn ion cyclotron resonance (FT-ICR) is a particularly powerful teclmique in which a cluster ion can be stored and cooled before experimentation. Thus, multiple reaction steps can be followed in FT-ICR, in addition to its high sensitivity and mass resolution. Many chemical reaction studies of transition-metal clusters witli simple reactants and hydrocarbons have been carried out using FT-ICR [49, 58]. 

Alford J M, Williams P E, Trevor D E and Smalley R E 1986 Metal oluster ion oyolotron resonanoe oombining supersonio metal oluster beam teohnology with FT-ICR Int J. Mass Spectrom. Ion Process. 72 33... 

Alford J M, Weiss F D, Laaksonen R T and Smalley R E 1986 Dissociative chemisorption of H2 on niobium cluster ions. A supersonic cluster beam FT-ICR experiment J. Rhys. Chem. 90 4480... 

Instruments are available that can perform MS/MS type experiments using a single analyzer. These instruments trap and manipulate ions in a trapping cell, which also serves as the mass analyzer. The ion trap and fourier transform ion cyclotron resonance (FT-ICR) mass spectrometers are examples. 

Tandem quadrupole and magnetic-sector mass spectrometers as well as FT-ICR and ion trap instruments have been employed in MS/MS experiments involving precursor/product/neutral relationships. Fragmentation can be the result of a metastable decomposition or collision-induced dissociation (CID). The purpose of this type of instrumentation is to identify, qualitatively or quantitatively, specific compounds contained in complex mixtures. This method provides high sensitivity and high specificity. The instrumentation commonly applied in GC/MS is discussed under the MS/MS Instrumentation heading, which appears earlier in this chapter. 

The kinetics study [38] utilized a Fourier transform-ion cyclotron resonance (FT-ICR) mass spectrometer to measure the pathway branching ratios. The ability to eject selected masses and the extremely high mass resolution of this technique ensured that the observed CD3CH2 was in fact a primary product of the reaction. Temporal profiles from this reaction are shown in Fig. 1. Noticeably absent from the mass spectrum are the cations C2D2H3 and... 

Easterling, M.L., Mize, T.H., and Amster, I. J., Routine part-per-million mass accuracy for high-mass ions space-charge effects in MALDI FT-ICR, Anal. Chem., 71, 624, 1999. 

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

When laser-ablated Ni atoms were reacted with CS2 during cocondensation in excess argon, the C-bonded Ni( /-CS2) and side-on bonded Ni(//2-CS)S complexes were formed on annealing, whereas the inserted SNiCS was formed on photolysis. All species were characterized by IR spectroscopy and DFT calculations.2466 The reaction of low-valent [Ni(CO)J (x=2, 3) with CS2 has been studied by FT-ICR spectroscopy.2467... 

Frahm, J.L., Howard, B.E., Heber, S., Muddiman, D.C. (2006). Accessible proteomics space and its implications for peak capacity for zero-, one-, and two-dimensional separations coupled with FT-ICR and TOF mass spectrometry. J. Mass Spectrom. 41, 281-288. 

With the FT-ICR mass spectrometer it is possible to obtain high mass accuracy (about 1-5 ppm calibrated externally, 0.5-1-0 ppm if calibrated internally here an external calibration has been carried out using a tune mix containing compounds with m/z from... 

FT-ICR and the Orbitrap belong to this group. In these analyzers the m/z values of the ions are not directly measured, but they are obtained by Fourier transform treatment of the signal (Figure 2.12). 

The Orbitrap allows very high resolution to be achieved (the resolving power in commercial instruments is 100000, rivalling that of FT-ICR instruments) and routine mass measurement accuracies less than 2 ppm. It finds applications in many fields, such as biology, proteomics, food chemistry and cultural heritage. 

In FT-ICR mass spectrometers, ion isolation and detection occur in the same region. In fact all ions coming from the source are simultaneously excited applying a RF pulse of a... 

The main feature of this analyzer is its extremely high resolution. However, owing to the difficulty of operation and its very high cost, the FT-ICR analyzer cannot be used for routine purposes. 

Various analyzers have been used to analyze phenolic compounds. The choice of the MS analyzer is influenced by the main objective of the study. The triple quadrupole (QqQ) has been used to quantify, applying multiple reaction monitoring experiments, whereas the ion trap has been used for both identification and structure elucidation of phenolic compounds. Moreover, time-of-flight (TOF) and Fourier-transform ion cyclotron resonance (FT-ICR) are mainly recommended for studies focused on obtaining accurate mass measurements with errors below 5 ppm and sub-ppm errors, respectively (Werner and others 2008). Nowadays, hybrid equipment also exists, including different ionization sources with different analyzers, for instance electrospray or atmospheric pressure chemical ionization with triple quadrupole and time-of-flight (Waridel and others 2001). 

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