Mass resolution, determination

Qualitatively, the spark source mass spectrum is relatively simple and easy to interpret. Most instrumentation has been designed to operate with a mass resolution Al/dM of about 1500. For example, at mass M= 60 a difference of 0.04 amu can be resolved. This is sufficient for the separation of most hydrocarbons from metals of the same nominal mass and for precise mass determinations to identify most species. Each exposure, as described earlier and shown in Figure 2, covers the mass range from Be to U, with the elemental isotopic patterns clearly resolved for positive identification. 

In practice image quality is also reduced by use of high mass resolution and energy offset. Often, therefore, mass interference cannot he avoided. Determination of element distributions is possible by use of image processing tools for classification of mappings of different masses [3.53]. 

Quadrupoles are low-resolution MS instruments frequently used for molecular weight determination. QMS provides unit-mass resolution, sufficient dynamic range, good quantitation capabilities, and easy sample introduction without severe vacuum restrictions. The limited mass range (up to 4000 Da) generally does not pose problems in polymer/additive analysis. Some limitations of QMS in polymer research are ... 

The mass resolution at the sample surface is usually determined primarily by the detector resolution. 

Figure 4. Peak assignment of spherical silsesquioxanes and homo-silsesquioxanes obtained from CH3SiX3 the accurate masses were determined by means of high resolution TOF-SIMS (the O-atoms located on the edges of the polyhedra are not shown).

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. 

The first few decades of space exploration went by without any MS better than m/Am 4 because understanding the solar wind flow, its density, its pressure, or its temperature did not require mass resolution. Not until 1984 did a space MS fly with a resolution of about 10 [10], and it was 1994 before that increased to 100 [11], Suddenly for the first time, the solar wind isotopes of carbon, oxygen, magnesium, silicon, and iron were known, and the models could be tested. Even then, space MS had difficulty measuring rare isotopes, so that it wasn t until 2005 that solar wind samples were returned to Earth inside ultra-pure silicon wafers (the ill-fated Genesis mission [12]) to determine the important triple ratios of ieO 170 lsO. 

In tandem MS mode, because the product ions are recorded with the same TOF mass analyzers as in full scan mode, the same high resolution and mass accuracy is obtained. Isolation of the precursor ion can be performed either at unit mass resolution or at 2-3 m/z units for multiply charged ions. Accurate mass measurements of the elemental composition of product ions greatly facilitate spectra interpretation and the main applications are peptide analysis and metabolite identification using electrospray iomzation [68]. In TOF mass analyzers accurate mass determination can be affected by various parameters such as (i) ion intensities, (ii) room temperature or (iii) detector dead time. Interestingly, the mass spectrum can be recalibrated post-acquisition using the mass of a known ion (lock mass). The lock mass can be a cluster ion in full scan mode or the residual precursor ion in the product ion mode. For LC-MS analysis a dual spray (LockSpray) source has been described, which allows the continuous introduction of a reference analyte into the mass spectrometer for improved accurate mass measurements [69]. The versatile precursor ion scan, another specific feature of the triple quadrupole, is maintained in the QqTOF instrument. However, in pre-... 

FT-ICR mass spectrometers take advantage of ion-cyclotron resonance to select and detect ions. This analyzer can be used with both ESI and MALDI interfaces. Their particular advantages are their sensitivity, extreme mass resolution, and mass accuracy. The latter allows for the determination of the empirical formulae of compounds under 1000 Da. As far as we know, this analyzer has not been applied to flavonoids. 

A time-of-flight spectrometer can be used as a mass analyzer, an ion kinetic energy analyzer, and an ion reaction time analyzer. We will consider here only what factors affect the resolution of the system in mass analysis.74 The same consideration can easily be extended to find the resolution in other analyses. There are at least two kinds of mass resolution. One refers to the ability of the system to separate two ion species of nearly equal masses in the same mass spectrum. This is related to the sharpness of the mass lines, or the full width at half maximum (FWHM) of the mass lines. The other refers to the ability of the system to distinguish two ion species of nearly identical masses, but not necessarily in the same mass spectrum. This latter mass resolution is related to the sharpness of reference points in the mass lines such as the onset flight times of the ion species, and the overall long-term stability of the system. This latter resolution determined also how accurately the instrument can measure the mass of ion species. Although this latter resolution is more closely related to ion kinetic energy analysis and is as important as the former one, we will consider here only the former kind, or the conventional kind, of mass resolution. 

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