Mass analyzer resolution

Performance Parameters. Since the detector is often involved in the separation of isobars, normal mass analyzer resolution and mass accuracy do not really apply. The mass spectrometric resolution would be determined by the magnetic and electric sectors. Only atomic species are analyzed, so that sets the upper m/z... 

Table 1 Common polyatomic ion interferences with the mass analyzer resolution necessary to resolve them from the analyte of interest...

Positive ions are obtained from a sample by placing it in contact with the filament, which can be done by directing a gas or vapor over the hot filament but usually the sample is placed directly onto a cold filament, which is then inserted into the instrument and heated. The positive ions are accelerated from the filament by a negative electrode and then passed into a mass analyzer, where their m/z values are measured (Figure 7.1). The use of a suppressor grid in the ion source assembly reduces background ion effects to a very low level. Many types of mass analyzer could be used, but since very high resolutions are normally not needed and the masses involved are quite low, the mass analyzer can be a simple quadrupole. 

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. 

Rapid scanning mass spectrometers providing unit resolution are routinely used as chroaatographic detectors. Ion separation is accomplished using either a magnetic sector, quadrupole filter or ion trap device. Ions can also be separated by time-of-flight or ion cyclotron resonance mass analyzers but these devices are not widely used with chromatograidiic inlets and will not be discussed here [20]. 

Once the ions are formed in the ion source, they are accelerated towards the mass analyzer where separation according to their m/z ratio occurs. Before describing the main analyzers, it is better to consider one feature common to all of them the resolution. 

For high-throughput analysis, it is important to increase the specihcity of each bioanalytical method. The enhancement of chromatographic resolution presents various limitations. Better selectivity can be obtained with TOF mass analyzers that routinely provide more than 5000 resolution (full width at half-mass or FWHM). The enhanced selectivity of a TOF MS is very attractive for problems such as matrix suppression and metabolite interference. In one report of quantitative analysis using SRM, TOF appeared less sensitive than triple quadrupole methods but exhibited comparable dynamic range with acceptable precision and accuracy.102... 

MS equipment is evaluated on several performance metrics. Mass accuracy, mass resolution, and mass range are standard parameters frequently assessed to determine the suitability of an instrument. Mass accuracy is defined as the extent to which a mass analyzer reflects true m/z values and is measured in atomic mass units (amu), parts per million (ppm), or percent accuracy. 

Mass resolution describes the capability of an MS to distinguish ions with different m/z values. It is defined by the M/AM equation in which M is the m/z ratio of a mass peak and AM is the full width of a peak at half its maximum height. The mass resolution of an instrument often correlates with its accuracy. Mass range indicates the m/z range at which the mass analyzer best functions. For example, quadrupole mass analyzers exhibit a mass range of up to 4000 m/z, while the mass ranges of TOF extend up to 100,000. The operating principles of common MS instruments are discussed below. 

The orbitrap is the most recently invented mass analyzer. Like with the QIT, ions are trapped and stored in a potential well. However, instead of ejecting the ions for external detection the frequency of the trapped oscillationg ions is measured. This method provides substantially better resolution and mass accuracy in normal operation. 

Resolution (or resolving power) plays an important role in mass spectrometry for applications requiring the characterization of very similar chemical species. The ability to detect and accurately measure the m/z ratio of a particular ion depends directly on the resolving power of the mass analyzer. For example, if a sample contains two isobaric compounds (i.e., having the same nominal molecular mass but different elemental formulae) the difference in the exact masses of the molecular ions will be much less than 1 m/z unit. Any mass analyzer possessing a nominal resolving power (e.g., RP< 1000) will register only one peak in the mass spectrum of such a binary mixture. Attempts to measure the... 

One important characteristic of the mass analyzers used in GC is that they do not offer high resolution 0.1-1 Da resolution in the mass range of 10-800 is sufficient. 

Typical quadrupoles transmit ions with mass-to-charge ratios ranging from 1-300 or greater with a mass-dependent resolution of twice the mass. More sophisticated instmments can achieve m/z of 4000 with comparable resolution. The suitability of a quadrupole mass analyzer depends in large part on the duty cycle... 

Fig. 2. Schematic diagram of a high resolution He time-of-flight spectrometer. N-nozzle beam source, SI, 2-skimmers, Al-5 - apertures, T - sample, G - gas doser, CMA - Auger Spectrometer, IG - ion gun, L - LEED, C -magnetically suspended pseudorandom chopper, QMA-detector, quadrupole mass analyzer with channeltron.

With the advent of linear quadrupole analyzers the full width at half maximum (FWHM) definition of resolution became widespread especially among instruments manufacturers. It is also commonly used for time-of-flight and quadrupole ion trap mass analyzers. With Gaussian peak shapes, the ratio of / fwhm to Rio% is 1.8. The practical consequences of resolution for a pair of peaks at different m/z are illustrated below (Fig. 3.17). 

It is certainly desirable to have at least sufficient resolution to resolve isotopic patterns to their nominal mass contributions. However, not every mass analyzer is capable of doing so with any ion it can pass through. Such conditions often occur when ions of several thousand u are being analyzed by quadrupole, time-of-flight or quadrupole ion trap analyzers, and hence it is useful to know about the changes in spectral appearance and their effect on peak width and detected mass. [42]... 

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