High mass

OF High-Molecular-Weight Samples 1. Definition of High Mass 

Ten years ago, it was easy to give a working definition of high mass. At that time, most mass spectrometers had a mass range of less than 1000 at 

There are three main reasons for this choice. Firstly, it becomes more and more difficult to obtain recordable, molecular-ion signals from un-derivatized carbohydrates as their M, increases significantly above 3000. Secondly, the mass spectrometers that have been used in all high-mass-carbofiydrate studies published at the time of writing this article are not capable of very sensitive analysis above —3800 mass units (see later). Thirdly, at masses 4000, it is usually not practicable to work at the resolution necessary for adjacent peaks to appear as separate signals in the spectrum. To do so would require that the source and collector slits be narrowed to such a degree that there would be an unacceptable loss in sensitivity. Thus, spectra acquired at mass 4000 are usually composed of unresolved clusters. 

Operation of the high-field ZAB spectrometer at 7-kV accelerating voltage extends the mass range to nearly 3800 without a significant loss in sensitivity. Above that point, there is a steady decline in sensitivity. When V is lessened 

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Laser desorption methods are particularly useful for substances of high mass such as natural and synthetic polymers. Glycosides, proteins, large peptides, enzymes, paints, ceramics, bone, and large... 

On the other hand, there are some ionization techniques that are very useful, particularly at very high mass, but produce ions only in pulses. For these sources, the ion extraction field can be left on continuously. Two prominent examples are Californium radionuclide and laser desorption ionization. In the former, nuclear disintegration occurs within a very short time frame to give a... 

Peak matching can be done on quadrupole and magnetic-sector mass spectrometers, but only the latter, particularly as double-focusing instruments, have sufficiently high resolution for the technique to be useful at high mass. 

The techniques described thus far cope well with samples up to 10 kDa. Molecular mass determinations on peptides can be used to identify modifications occurring after the protein has been assembled according to its DNA code (post-translation), to map a protein structure, or simply to confirm the composition of a peptide. For samples with molecular masses in excess of 10 kDa, the sensitivity of FAB is quite low, and such analyses are far from routine. Two new developments have extended the scope of mass spectrometry even further to the analysis of peptides and proteins of high mass. 

When multicharged ions are formed, the simple rule of thumb used widely in mass spectrometry that m/z = m because, usually, z = 1 no longer applies for z > 1 then m/z < m, and the apparent mass of an ion is much smaller than its true mass. Accurate mass measurement is much easier at low mass than at high, and the small m/z values, corresponding to high mass with multiple charges, yield accurate values for the high mass. 

For very high mass, when sensitivity is frequently critical, the reflectron is not used and lower resolution is accepted. 

After acceleration through an electric field, ions pass (drift) along a straight length of analyzer under vacuum and reach a detector after a time that depends on the square root of their m/z values. The mass spectrum is a record of the abundances of ions and the times (converted to m/z) they have taken to traverse the analyzer. TOP mass spectrometry is valuable for its fast response time, especially for substances of high mass that have been ionized or selected in pulses. 

Delayed Proton and Neutron Decays. By means of a variety of nuclear reactions, as weh as the spontaneous fission of synthetic nucHdes, large numbers of isotopes of some elements have been produced. For example, whereas the only stable isotope of Cs (Z = 55) is Cs (JV = 78), ah of the Cs isotopes from Cs where 77 = 59 and = 0.57 s, to Cs where N = 93 and = 0.13 s, have been observed. At the low mass end of this series, the last proton is only loosely bound, and at the high mass end, the last neutron is only loosely bound. 

Leveque s approximation Concentration BL is thin. Assume velocity profile is linear. High mass velocity. Fits liquid data well. 

High mass-transfer rates in both vapor and hquid phases. Close approach to eqiiilihriiim. Adiabatic contact assures phase eqiiilihriiim, Only moderate mass-transfer rate in liquid phase, zero in sohd. Slow approach to equilibrium achieved in brief contact time. Included impurities cannot diffuse out of solid. Sohd phase must be remelted and refrozen to allow phase equilibrium. 

High mass resolution techniques are used to separate peaks at the same nominal mass by the very small mass differences between them. As an example, a combination of Si and H to form the molecular ion Si H , severely degrades the detection limit of phosphorous ( P) in a silicon sample. The exact mass of phosphorous ( P) is 31.9738 amu while the real masses of the interfering Si H and Si H2 molecules are 31.9816 amu and 31.9921 amu, respectively. Figure 8 shows a mass... 

SiiH2 are completely separated from the peak. Quadrupole instruments are not usually capable of such high mass resolution. 

Figures High mass resoiution mass spectrum obtained from a phosphorus-doped amorphous silicon hydride thin film using a magnetic sector ion microanalyzer. The peak is well separated from the hydride iirterferences.

The choice of mass spectrometer for a particular analysis depends on the namre of the sample and the desired results. For low detection limits, high mass resolution, or stigmatic imaging, a magnetic sector-based instrument should be used. The analysis of dielectric materials (in many cases) or a need for ultrahigh depth resolution requires the use of a quadrupole instrument. 

Figure 3.5 shows the positive SSIMS spectrum from a silicon wafer, illustrating both the allocation of peaks and potential isobaric problems. SSIMS reveals many impurities on the surface, particularly hydrocarbons, for which it is especially sensitive. The spectrum also demonstrates reduction of isobaric interference by high-mass resolution. For reasons discussed in Sect. 3.1.3, the peak heights cannot be taken to be directly proportional to the concentrations on the surface, and standards must be used to quantify trace elements. 

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