Time of flight mass spectrometer

The critical aspect of this otherwise simple instrument is the need to produce the ions at an accurately known start time and position. These constraints generally limit TOF spectrometers to use pulsed ionization techniques, which include plasma and laser desorption (e.g., MALDI, matrix assisted laser desorption ionization). 

The resolution of TOF instruments is usually less than 20,000 because some variation in ion energy is unavoidable. Also, since the difference in arrival times at the detector can be less than 10 7 s, fast electronics are necessary for adequate resolution. On the positive side, the mass range of these instruments is unlimited, and, like quadrupoles, they have excellent sensitivity due to lack of resolving slits. Thus, the technique is most useful for large biomolecules. 

Because the instrument is operated at fixed magnetic field strength, extremely high field superconducting 

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Figure Bl.7.17. (a) Schematic diagram of a single acceleration zone time-of-flight mass spectrometer, (b) Schematic diagram showing the time focusing of ions with different initial velocities (and hence initial kinetic energies) onto the detector by the use of a reflecting ion mirror, (c) Wiley-McLaren type two stage acceleration zone time-of-flight mass spectrometer.

Time-of-flight mass spectrometers have been used as detectors in a wider variety of experiments tlian any other mass spectrometer. This is especially true of spectroscopic applications, many of which are discussed in this encyclopedia. Unlike the other instruments described in this chapter, the TOP mass spectrometer is usually used for one purpose, to acquire the mass spectrum of a compound. They caimot generally be used for the kinds of ion-molecule chemistry discussed in this chapter, or structural characterization experiments such as collision-induced dissociation. Plowever, they are easily used as detectors for spectroscopic applications such as multi-photoionization (for the spectroscopy of molecular excited states) [38], zero kinetic energy electron spectroscopy [39] (ZEKE, for the precise measurement of ionization energies) and comcidence measurements (such as photoelectron-photoion coincidence spectroscopy [40] for the measurement of ion fragmentation breakdown diagrams). 

Wiley W C and McLaren I H 1955 Time-of-flight mass spectrometer with improved resolution Rev. Sc/. Instrum. 26 1150-7... 

Karataev V I, Mamyrin B A and Shmikk D V 1972 New method for focusing ion bunches in time-of-flight mass spectrometers Sov. Phys.-Tech. Phys. 16 1177... 

Bergmann T, Martin T P and Schaber H 1989 High-resolution time-of-flight mass spectrometer Rev. Sol. Instrum. 60 792... 

The "time of flight" mass spectrometer has been used to confirm that this highly radioactive halogen behaves chemically very much like other halogens, particularly iodine. Astatine is said to be more metallic than iodine, and, like iodine, it probably accumulates in the thyroid gland. Workers at the Brookhaven National Laboratory have recently used reactive scattering in crossed molecular beams to identify and measure elementary reactions involving astatine. 

In Surface Analysis by Laser Ionization (SALI), a probe beam such as an ion beam, electron beam, or laser is directed onto a surfiice to remove a sample of material. An untuned, high-intensity laser beam passes parallel and close to but above the sur-fiice. The laser has sufficient intensity to induce a high degree of nonresonant, and hence nonselective, photoionization of the vaporized sample of material within the laser beam. The nonselectively ionized sample is then subjected to mass spectral analysis to determine the nature of the unknown species. SALI spectra accurately reflect the surface composition, and the use of time-of-flight mass spectrometers provides fast, efficient and extremely sensitive analysis. 

In Laser Ionization Mass Spectrometry (LIMS, also LAMMA, LAMMS, and LIMA), a vacuum-compatible solid sample is irradiated with short pulses ("10 ns) of ultraviolet laser light. The laser pulse vaporizes a microvolume of material, and a fraction of the vaporized species are ionized and accelerated into a time-of-flight mass spectrometer which measures the signal intensity of the mass-separated ions. The instrument acquires a complete mass spectrum, typically covering the range 0— 250 atomic mass units (amu), with each laser pulse. A survey analysis of the material is performed in this way. The relative intensities of the signals can be converted to concentrations with the use of appropriate standards, and quantitative or semi-quantitative analyses are possible with the use of such standards. 

Laser ionization mass spectrometry or laser microprobing (LIMS) is a microanalyt-ical technique used to rapidly characterize the elemental and, sometimes, molecular composition of materials. It is based on the ability of short high-power laser pulses (-10 ns) to produce ions from solids. The ions formed in these brief pulses are analyzed using a time-of-flight mass spectrometer. The quasi-simultaneous collection of all ion masses allows the survey analysis of unknown materials. The main applications of LIMS are in failure analysis, where chemical differences between a contaminated sample and a control need to be rapidly assessed. The ability to focus the laser beam to a diameter of approximately 1 mm permits the application of this technique to the characterization of small features, for example, in integrated circuits. The LIMS detection limits for many elements are close to 10 at/cm, which makes this technique considerably more sensitive than other survey microan-alytical techniques, such as Auger Electron Spectroscopy (AES) or Electron Probe Microanalysis (EPMA). Additionally, LIMS can be used to analyze insulating sam-... 

Sputter-Initiated Resonance Ionization Spectroscopy Surface Analysis by Resonant Ionization Spectroscopy Time-of-Flight Mass Spectrometer... 

SIMS using Time-of-Flight Mass Spectrometer Post Ionization SIMS... 

To minimize surface damage, static SIMS mass spectrometers should be as efficient as possible for detecting the total yield of secondary ions from a surface. Also, to be able to separate elemental from molecular species, and molecular species from each other, the mass resolution usually given as the mass m divided by the separable mass Am, should be very high. With this in mind, two types of mass spectrometer have been used - in early work mainly quadrupole mass filters and, more recently, time-of-flight mass spectrometers. 

Isotope shifts for most elements are small in comparison with the bandwidth of the pulsed lasers used in resonance ionization experiments, and thus all the isotopes of the analyte will be essentially resonant with the laser. In this case, isotopic analysis is achieved with a mass spectrometer. Time-of flight mass spectrometers are especially well-suited for isotopic analysis of ions produced by pulsed resonance ionization lasers, because all the ions are detected on each pulse. 

Fig. I. Experimental setup the clusters are emitted from the cluster condensation cell, passing as a particle beam through a differential pumping stage into the focus of a time-of-flight mass spectrometer, where they are ionized by a laser pulse.

After condensation, the clusters are transported by the He-flow through a nozzle and a differential pumping stage into a high vacuum chamber. For ionization of the clusters, we used excimer and dye laser pulses at various wavelengths. The ions were then mass analyzed by a time-of-flight mass spectrometer, having... 

Electrospray ionization mass spectrometry (ESI-MS) is an analytical method for mass determination of ionized molecules. It is a commonly used method for soft ionization of peptides and proteins in quadmpole, ion-trap, or time-of-flight mass spectrometers. The ionization is performed by application of a high voltage to a stream of liquid emitted from a capillaty. The highly charged droplets are shrunk and the resulting peptide or protein ions are sampled and separated by the mass spectrometer. 

The pulsed circuitry of the time-of-flight mass spectrometer is ideally suited for this type of operation, and both Hand and von Weyssenhoff (12, 13) and Lampe and Hess (25) have reported experiments using such an instrument with variable delay between the ionizing and withdrawal pulses to study secondary processes. 

Figure 3.10 Schematic of a quadrupole-time-of-flight mass spectrometer. From applications literature published by Micromass UK Ltd, Manchester, UK, and reproduced with permission.

Figure 5.45 Structures of (1) Bosentan (C27H29N5O6S [M + H]+ 552.1917) and three of its metabolites, formed by (2) oxidation (C27H29N5O7S [M + H]+ 568.1866), (3) demethylation (C26H27N5O6S [M- -H]+ 538.1760), and (4) demethylation-oxidation (C26H27N5O7S [M + M]+ 554.1709). Reprinted by permission of Elsevier Science from Exact mass measurement of product ions for the structural elucidation of drug metabolites with a tandem quadrupole orthogonal-acceleration time-of-flight mass spectrometer , by Hopfgartner, G., Chemushevich, I. V., Covey, T., Plomley, 1. B. and Bonner, R., Journal of the American Society for Mass Spectrometry, Vol. 10, pp. 1305-1314, Copyright 1999 by the American Society for Mass Spectrometry.

In general, the mass resolution required for most analyses is such that the singly charged isotope patterns of the detected ions are readily discernible. For applications involving molecular weights up to about 1500 Da, this can be provided by magnetic sector, quadrupole, and time-of-flight mass spectrometers. 

B magnetic sector E = electric sector Q = quadrupole mass filter ToF = time-of-flight mass spectrometer IT = ion trap FTICR = Fourier-transform ion-cyclotron resonance. 

Figure 6.15 Schematic design of a reflectron time-of-flight mass spectrometer...

An FIM may be modified so that the imaged atom chosen for analysis can be positioned over a small aperture in the phosphor-coated screen. If the electric field is raised to a sufficiently high value, material may be removed from the surface by field evaporation. The specimen is subjected to a high-voltage pulse, which causes a number of atoms on the specimen surface to field evaporate as positive ions. Only the atom that was imaged over the aperture (or probe hole ) passes into a time-of-flight mass spectrometer, all the other atoms being blocked off by the screen. The applied... 

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