Sensitivity mass analyzers

For rapid scanning of GC output and to maximize sensitivity, mass analyzers are normally operated in selected ion mode, where only a few pre-selected ions are monitored at any one time. Electron ionization at 70 eV is normal although increased response has been observed in some systems using helium carrier gas when operated at lower ionization energies (10-20 eV). There is a growing interest in the use of negative ion chemical ionization as this technique is very sensitive to certain halocarbons, notably those containing bromine or iodine. 

AMS is used to determine highly accurate isotopic ratios of U and Pu in nuclear reactor fuels and environmental samples. AMS combines a highly specific particle accelerator with highly sensitive mass analyzers to remove molecular isobaric interferences and achieve detection limits of single atoms. Figure 20.13 shows a diagram of the Vienna Environmental Research Accelerator s MS setup for analyzing heavy isotopes. 

The Z-spray inlet causes ions and neutrals to follow different paths after they have been formed from the electrically charged spray produced from a narrow inlet tube. The ions can be drawn into a mass analyzer after most of the solvent has evaporated away. The inlet derives its name from the Z-shaped trajectory taken by the ions, which ensures that there is little buildup of products on the narrow skimmer entrance into the mass spectrometer analyzer region. Consequently, in contrast to a conventional electrospray source, the skimmer does not need to be cleaned frequently and the sensitivity and performance of the instrument remain constant for long periods of time. 

The main advantages of the ms/ms systems are related to the sensitivity and selectivity they provide. Two mass analyzers in tandem significantly enhance selectivity. Thus samples in very complex matrices can be characterized quickly with Htde or no sample clean-up. Direct introduction of samples such as coca leaves or urine into an ms or even a gc/lc/ms system requires a clean-up step that is not needed in tandem mass spectrometry (28,29). Adding the sensitivity of the electron multiplier to this type of selectivity makes ms/ms a powerhil analytical tool, indeed. It should be noted that introduction of very complex materials increases the frequency of ion source cleaning compared to single-stage instmments where sample clean-up is done first. 

Reliable analytical methods are available for determination of many volatile nitrosamines at concentrations of 0.1 to 10 ppb in a variety of environmental and biological samples. Most methods employ distillation, extraction, an optional cleanup step, concentration, and final separation by gas chromatography (GC). Use of the highly specific Thermal Energy Analyzer (TEA) as a GC detector affords simplification of sample handling and cleanup without sacrifice of selectivity or sensitivity. Mass spectrometry (MS) is usually employed to confirm the identity of nitrosamines. Utilization of the mass spectrometer s capability to provide quantitative data affords additional confirmatory evidence and quantitative confirmation should be a required criterion of environmental sample analysis. Artifactual formation of nitrosamines continues to be a problem, especially at low levels (0.1 to 1 ppb), and precautions must be taken, such as addition of sulfamic acid or other nitrosation inhibitors. The efficacy of measures for prevention of artifactual nitrosamine formation should be evaluated in each type of sample examined. 

In the case of carbamate insecticides, both ESI and APCI can be used. However, in this study, the sensitivity of APCI was 3-5-fold less than that of ESI. In this case, the Z-spray configuration was used with APCI, which gives a lower efficiency of ions reaching the mass analyzer than is achieved with other instrumental configurations. 

The last sample preparation method for IMS is the transfer of a tissue section onto the PVDF membrane. Proteins in the section can be transferred onto the PVDF membrane and then analyzed on the membrane. The advantage of this method is that the enzyme can be digested for MS" measurement, because the information on protein localization in the organization is fixed on the membrane.5,20 This technique can denature, reduce, and digest the proteins in the tissue section efficiently and remove the salt from the tissue. This increases the efficiency with which biological molecules are ionized, making it possible to obtain sensitive mass imaging spectra. 

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... 

One reason for lower sensitivity is the lack of flexibility to optimize the positions of the sprayers on the MUX interface another may be the lower electrospray desolvation efficiency on the MUX. The longer total cycle time on a MUX interface with a quadrupole MS in comparison to a single sprayer interface adds another concern. Assuming typical chromatographic peak widths appeared on average at 15 sec, 17 data points could be easily detected across the peak for each transition with a total cycle time of 0.88 sec on a conventional single sprayer set-up. With the MUX, only 12 data points could be detected across the same peak even with a total cycle time of 1.24 sec because of the introduction of additional interspray time on top of dwell time. Hence, when MUX is used with a quadrupole mass analyzer, it is important to consider dwell time and chromatographic peak width... 

F. Hillenkamp, E. Unsold, R. Kaufmann, and R. Nitsche. A High-Sensitivity Laser Microprobe Mass Analyzer. Appl. Phys., 8(1975) 341-348. 

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