Mass spectrometer resolving power

Finally, an aspect that should not be left out of consideration is the off-line combination of LC with MS. A great advantage of on-line techniques is the integration of the evaluation systems used. In on-line LC-MS systems, identification of incompletely resolved peaks is easily and unambiguously accomplished, taking advantage of the mass spectrometer separation power. In contrast, with off-line LC-MS, complete resolution of the peaks is essential. Moreover, fraction collection. 

Probably the simplest mass spectrometer is the time-of-fiight (TOP) instrument [36]. Aside from magnetic deflection instruments, these were among the first mass spectrometers developed. The mass range is theoretically infinite, though in practice there are upper limits that are governed by electronics and ion source considerations. In chemical physics and physical chemistry, TOP instniments often are operated at lower resolving power than analytical instniments. Because of their simplicity, they have been used in many spectroscopic apparatus as detectors for electrons and ions. Many of these teclmiques are included as chapters unto themselves in this book, and they will only be briefly described here. 

The main function of the mass analyser is to separate (resolve) the ions formed in the ionisation source on the basis of their mass to charge ratios (m/z). The resolving power of a mass spectrometer is a measure of its ability to separate two ions of any defined mass difference. More precisely, the resolution (R) of a mass analyser is defined as its ability to separate the ion envelopes of two peaks of equal intensity, i.e. the ratio of the mass of a peak (M ) to the difference in mass between this peak and an adjacent higher mass peak (Af2), i.e. ... 

FTICR-MS is capable of powerful mixture analysis, due to its high mass range and ultrahigh mass resolving power. However, in many cases it is still desirable to couple a chromatographic interface to the mass spectrometer for sample purification, preconcentration, and mixture separation. In the example given above, DTMS under HRMS conditions provides the elementary composition. Apart from DTMS, PyGC-MS can be performed to preseparate the mixture of molecules and to obtain the MS spectrum of a purified unknown. Direct comparison with the pure reference compound remains the best approach to obtain final proof. 

Mass spectrometry is the only universal multielement method which allows the determination of all elements and their isotopes in both solids and liquids. Detection limits for virtually all elements are low. Mass spectrometry can be more easily applied than other spectroscopic techniques as an absolute method, because the analyte atoms produce the analytical signal themselves, and their amount is not deduced from emitted or absorbed radiation the spectra are simple compared to the line-rich spectra often found in optical emission spectrometry. The resolving power of conventional mass spectrometers is sufficient to separate all isotope signals, although expensive instruments and skill are required to eliminate interferences from molecules and polyatomic cluster ions. 

Resolution or resolving power is the ability of a mass spectrometer, and in particular of its analyzer system, to separate ions with different m/z ratios. An example of mass spectra obtained at different resolutions is reported in Figure 2.1 by increasing the resolution the peak shape becomes more and more narrow thus allowing the separation of ions with their m/z values differing in decimals (10 1—10 3). 

Resolving power decreases with increasing mass but spectrometers having a resolution of 1000, i.e. the ability to discriminate between m/z values of 1000 and 1001, or between 100 and 99.9, are adequate for many applications. Double-focusing instruments may be capable of resolutions of 20 000-50 000 or more. 

Orbital trapping mass spectrometers achieve resolutions of up to 105 and would be the next choice after ToF mass spectrometers if resolving powers above 104 are required. In addition to mass resolution, the selectivity of an MS can be critical to distinguish between co-eluting and not mass-resolved compounds. For example, typical triple-quad mass spectrometers usually cannot achieve better than unit-mass resolution. However, special operation modes like neutral loss scans and precursor ion scans can filter out compounds of interest even if neither LC separations nor MS scans would be sufficient to resolve these compounds (note that this is a filtering step). 

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