Instrumentation time-of-flight

All four scan modes can be implemented with magnetic sector- and quadrupole-based true or hybrid tandem instruments. Time-of-flight (TOF) and tandem-in-time devices are also suitable for product scan experiments, but they are unable to perform the other three scans. 

Regarding MS instruments, time-of-flight detectors provide elevated mass resolution and accuracy over a broad mass of range, and thus help structural elucidation of nontargeted compounds based on accurate mass measurements and isotopic patterns. Triple quadrupole instmments are particularly well suited for targeted analysis and provide excellent sensitive and selectivity by performing tandem MS/MS analysis [71]. 

The following table provides a cursory list of selected parameters approximating varions standalone SIMS instrument capabilities (available commercially or otherwise), along with areas these are most commonly applied, and any additional comments. The omission of specific instruments is in no way reflective of their capabilities or otherwise. These are listed in the order of Quadrupole-based SIMS instruments. Magnetic Sector-based SIMS instruments, Time-of-Flight-based SIMS instruments, and a Hybrid instrument These instruments are listed alphabetically within each sub-gronp. Additional information can be acqnired from the respective vendors (see Section A.8.12). 

In the simplest fomi, reflects the time of flight of the ions from the ion source to the detector. This time is proportional to the square root of the mass, i.e., as the masses of the ions increase, they become closer together in flight time. This is a limiting parameter when considering the mass resolution of the TOP instrument. 

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). 

Guilhaus M 1995 Principles and instrumentation in time-of-flight mass spectrometry physical and instrumental concepts J. Mass Spectrom. 30 1519-32... 

Hybrid Magnetic-Sector Time-of-Flight (Sector/TOF) Instruments... 

The AutoSpec -TOF hybrid mass spectrometer combines the advantages of a magnetic/electric-sector instrument with those of time-of-flight to give a versatile instrument capable of MS or MS/MS at high or low resolution. 

The term Q/TOF is used to describe a type of hybrid mass spectrometer system in which a quadrupole analyzer (Q) is used in conjunction with a time-of-flight analyzer (TOP). The use of two analyzers together (hybridized) provides distinct advantages that cannot be achieved by either analyzer individually. In the Q/TOF, the quadrupole is used in one of two modes to select the ions to be examined, and the TOF analyzer measures the actual mass spectrum. Hexapole assemblies are also used to help collimate the ion beams. The hybrid orthogonal Q/TOF instrument is illustrated in Figure 23.1. 

A brief description of this hybrid system appears in Chapter 20. For further information on the quadrupole or TOF instruments, see Chapters 25 and 26, Quadrupole Ion Optics and Time-of-Flight Ion Optics. ... 

Other types of mass spectrometer may use point, array, or both types of collector. The time-of-flight (TOF) instrument uses a special multichannel plate collector an ion trap can record ion arrivals either sequentially in time or all at once a Fourier-transform ion cyclotron resonance (FTICR) instrument can record ion arrivals in either time or frequency domains which are interconvertible (by the Fourier-transform technique). 

Another form of array is called a microchannel plate detector. A time-of-flight (TOP) mass spectrometer collects ions sequentially in time and can use a point detector, but increasingly, the TOP instrument uses a microchannel plate, most particularly in an orthogonal TOP mode. Because the arrays and microchannel plates are both essentially arrays or assemblies of small electron multipliers, there may be confusion over their roles. This chapter illustrates the differences between the two arrays. 

Commercial mass analyzers are based almost entirely on quadrupoles, magnetic sectors (with or without an added electric sector for high-resolution work), and time-of-flight (TOE) configurations or a combination of these. There are also ion traps and ion cyclotron resonance instruments. These are discussed as single use and combined (hybrid) use. 

Almost any type of analyzer could be used to separate isotopes, so their ratios of abundances can be measured. In practice, the type of analyzer employed will depend on the resolution needed to differentiate among a range of isotopes. When the isotopes are locked into multielement ions, it becomes difficult to separate all of the possible isotopes. For example, an ion of composition CgHijOj will actually consist of many compositions if all of the isotopes ( C, C, H, H, 0, O, and 0) are considered. To resolve all of these isotopic compositions before measurement of their abundances is difficult. For low-molecular-mass ions (HjO, COj) or for atomic ions (Ca, Cl), the problems are not so severe. Therefore, most accurate isotope ratio measurements are made on low-molecular-mass species, and resolution of these even with simple analyzers is not difficult. The most widely used analyzers are based on magnets, quadrupoles, ion traps, and time-of-flight instruments. 

Electrospray can be used with sector, time-of-flight, and quadrupole instruments. The technique has been used extensively to couple liquid chromatographs to mass spectrometers. 

Once inside the hot plasma, which is at a temperature of about 8000 K and contains large numbers of energetic electrons and ions, the sample molecules are broken down into their constituent elements, which appear as ions. The ions are transported into a mass analyzer such as a quadrupole or a time-of-flight instrument for measurement of m/z values and ion abundances. 

If samples are introduced batchwise, then each one enters the flame as a plug, and the elements are measured transiently. If more than one m/z ration must be examined, the analyzer needs to be a quadrupole or time-of-flight instrument. 

---