Magnetic sector instruments

Magnetic sector instruments typically operate with ion sources held at a potential of between 6 and 10 kV. This results in ions with keV translational kinetic energies. The ion kinetic energy can be written as zt V = Ifur and thus the ion velocity is given by the relationship... 

Figure Bl.7.7. Summary of the other collision based experiments possible with magnetic sector instruments (a) collision-mduced dissociation ionization (CIDI) records the CID mass spectrum of the neutral fragments accompanying imimolecular dissociation (b) charge stripping (CS) of the incident ion beam can be observed (c) charge reversal (CR) requires the ESA polarity to be opposite that of the magnet (d) neutiiralization-reionization (NR) probes the stability of transient neutrals fonned when ions are neutralized by collisions in the first collision cell. Neutrals surviving to be collisionally reionized in the second cell are recorded as recovery ions in the NR mass spectrum.

The beam entering the ion chamber is suitable for both electron (El) and chemical (Cl) ionization, and either mode can be used (Figure 12.3). Mass analysis follows in the usual way, typically using quadruple or magnetic-sector instruments. 

Also in general terms, the TOF part of the hybrid is used mostly for MS/MS studies in which ions produced in the magnetic sector are collided with neutral gas molecules to induce decomposition (see Chapter 23). In this mode the instrument produces more highly resolved product ion spectra than can be attained in simple magnetic-sector instruments. 

A further important property of the two instruments concerns the nature of any ion sources used with them. Magnetic-sector instruments work best with a continuous ion beam produced with an electron ionization or chemical ionization source. Sources that produce pulses of ions, such as with laser desorption or radioactive (Californium) sources, are not compatible with the need for a continuous beam. However, these pulsed sources are ideal for the TOF analyzer because, in such a system, ions of all m/z values must begin their flight to the ion detector at the same instant in... 

There are other characteristics of quadrupoles that make them cheaper for attainment of certain objectives. For example, quadrupoles can easily scan a mass spectrum extremely quickly and are useful for following fast reactions. Moreover, the quadrupole does not operate at the high voltages used for magnetic sector instruments, so coupling to atmospheric-pressure inlet systems becomes that much easier because electrical arcing is much less of a problem. 

In an EW- of a B/E-linked scan using an electric/magnetic-sector instrument, a precursor ion is selected. In this case it is m, which might be a molecular ion but equally could be any fragment ion. All product ions (mj, m3, m4) from decomposition of m, in the first field-free region between the ion source and the ion collector are found, thereby giving connections mpm, m -m3, m -m4. 

An added consideration is that the TOF instruments are easily and quickly calibrated. As the mass range increases again (m/z 5,000-50,000), magnetic-sector instruments (with added electric sector) and ion cyclotron resonance instruments are very effective, but their prices tend to match the increases in resolving powers. At the top end of these ranges, masses of several million have been analyzed by using Fourier-transform ion cyclotron resonance (FTICR) instruments, but such measurements tend to be isolated rather than targets that can be achieved in everyday use. 

The appearance of the mass spectrum is closely similar to that provided by a magnetic-sector instrument. 

To examine metastable ions in electric/magnetic-sector instruments it is necessary to manipulate one or more of the electric or magnetic fields. 

Scanning techniques are carried out differently with such hybrid instruments as the triple quadrupole analyzer, the Q/TOF (quadrupole and time-of-flight), and double magnetic-sector instruments. 

Fig. 3.19. Basic set-up of a direct imaging magnetic sector instrument. The stigmatic secondary ion optics consists of an electrostatic analyzer (ESA) and a magnet sector field.

Fig. 3.20. Schematic d rawi ng of a Mattauch-Herzog magnetic-sector instrument with simultaneous mass detection.

Mass Spectrometry of Small Molecules Magnetic-Sector Instruments 409... 

Figure 1.1. Schematic of a double-focusing reverse geometry magnetic-sector instrument.

Electrostatic Analyzer In magnetic-sector instruments, an electrostatic sector can be incorporated either before or after the magnet to provide energy resolution and directional focusing of the ion beam. The resolution achievable in these double-focusing instruments is sufficient to separate ions having the same nominal mass (e.g., 28 Daltons) but with different chemical formula (e.g., N2 and CO). 

In magnetic-sector instruments, metastable ions are normally observed as small broad peaks. However, in GC/MS the analyst looks only at centrioded (processed) data thus, metastable peaks are not obvious and generally appear as part of the background. Metastable ions, when observed, can be used to link specific product and precursor ions. 

In the magnetic-sector instrument (Figure 1.1), gas phase ions produced in the ion source by one of several different methods are accelerated from near rest (thermal energy) through a potential gradient (commonly kV). These ions travel through a vacuum chamber into a magnetic field at a... 

Resolution Quadrupole instruments are not capable of achieving the high resolution that is common with double-focusing magnetic-sector instruments. In GC/MS analyses, a compromise is struck between sensitivity (ion transmission) and mass resolution. In the quadrupole instrument, the resolution is set to the lowest possible value commensurate with resolving peaks differing by 1 Dalton (unit resolution). 

The mass range requirement invariably means that FAB is used in conjunction with a magnetic sector instrument. Conventional detectors, such as the electron multiplier, are not efficient for the detection of large ions and the necessary sensitivity is often only obtained when devices such as the post-acceleration detector or array detector are used. Instruments capable of carrying out high-mass investigations on a routine basis are therefore costly and beyond the reach of many laboratories. 

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