The Total-Ion-Current Trace

There are a number of features worthy of note in this figure. For example, there is a difference in retention times, determined by the two detectors, of ca. 0.32 min, and this reflects the fact that they are used in series, i.e. the column effluent passes through the UV detector on its way to the mass spectrometer. 

Secondly, the intensity of response for a certain compound from one type of detector is not necessarily the same as that obtained from the other detector. This should not be unexpected, since the two detectors are measuring quite different properties of the analyte, in this case UV absorption at a particular wavelength and how readily it is ionized and fragmented under the conditions employed. These properties are unrelated. 

The third feature is that of peak widths. One of the properties of an ideal detector, as described earlier in Chapter 1, is that it should not degrade the 

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Figure 5.27 Selective detection of lactolated peptides from a tryptic digest of / -lacto-globulins by LC-electrospray-MS-MS, showing (a) the total-ion-cnrrent trace in full-scan mode, and (b) the total-ion-current trace in neutral-loss-scanning mode. Figure from Selective detection of lactolated peptides in hydrolysates by liquid chromatography/ electrospray tandem mass spectrometry , by Molle, D., Morgan, F., BouhaUab, S. and Leonil, J., in Analytical Biochemistry, Volume 259, 152-161, Copyright 1998, Elsevier Science (USA), reproduced with permission from the publisher.

A reconstructed ion chromatogram is a plot showing the variation in intensity of an ion of a particular m/z ratio as a function of analysis time, while the total-ion-current trace shows the variation in the intensity of all ions being produced as a function of analysis time. Simplistically, the TIC will show an increase as a compound elutes from an HPLC column and is ionized. If an ion with a particular m/z value is found to be diagnostic of a compound or series of compounds of interest, then an RIC of this m/z will show where its intensity increases and, therefore, where a compound of interest may have eluted. The mass spectrum at this point can then be examined for further confirmation that it is of significance. 

Figure 2.2 shows the total ion current trace and a number of appropriate mass chromatograms obtained from the pyrolysis gas chromatography-mass spectrometry analysis of the polluted soil sample. The upper trace represents a part of the total ion current magnified eight times. The peak numbers correspond with the numbers mentioned in Table 2.1 and refer to the identified compounds. The identification was based on manual comparison of mass spectra and relative gas chromatographic retention times with literature data [34, 35] and with data of standards available. In some cases unknown compounds were tentatively identified on the basis of a priori interpretation of their mass spectra (labelled tentative in Table 2.1). 

Because no pretreatment of the samples was carried out, the peaks present in the total ion current trace reflect components generated by pyrolysis of primary compounds ( real pyrolysis products ) and components that are present as such in the sample and simply evaporate ( free products ). If desired these two types of products may be differentiated using wires with a Curie temperature of 358°C [36], It was demonstrated in separate analyses (not shown here) that most compounds were not generated by pyrolysis but were present as such in the sample and thermally extracted . Compounds 1-8 and 10-17, 27, 37, 38, 54 and 65 were only present in pyrolysis gas... 

Fig. 11.4 shows the total ion current trace and some mass chromatograms obtained by flash evaporation pyrolysis gas chromatography-mass spectrometric analysis of the polluted sediment sample. All compounds present in this complex mixture were not listed. A selection was made to exemplify several aspects of the screening approach. The peak number correspond with the numbers in Table 11.1. Identifications were based on the same criteria as mentioned above. Although several components were shown to be real pyrolysis products, all the compounds are present as such in the sample and resulted from simple thermal extraction from the wire. This was shown in separate analyses using ferromagnetic wires with a Curie temperature of 358°C. 

The APCI-RP-C 1 s - h - i I S ( / ) separation of this mixture consisted of the anionic nonylphenol derivatives besides synthetic by-products to the total ion current traces and selected mass traces as presented in Fig. 2.11.23. By-products from synthesis could be confirmed as... 

Sulfosuccinates, as presented with their general structural formula in Fig. 2.11.33, are applied as surfactants for personal hygiene because of their hypoallergenic features. The sodium salt of the sulfosuccinate blend with the formula ROOC-CH-(SC>3 )-CH2-COOR Na+ (R = CsH-iy) was examined by APCI-FIA-MS in the positive and negative modes. The addition of an excess of ammonium acetate under FIA-APCI-MS(+) conditions resulted in [M — NH4]+ ions with mlz 440 while [M — H] ions with mlz 421, however, were observed in the negative APCI-FIA-MS mode (Fig. 2.11.34(a)). Only one type of ion could be observed in this industrial blend by FIA-MS. This purity could also be confirmed by APCI-LC-MS(-), as shown in the total ion current trace (cf. Fig. 2.11.34(b)), which is presented in combination with the averaged mass spectrum under the signal in the inset of Fig. 2.11.34(b) [22],... 

These herbicides contain nitrogen and respond to both FID and AFID. However, the analysis of these compounds is complicated by their thermal instability. For example, the total ion current trace obtained from the GC-MS ofamethanolic solution of monolinuron shows four peaks (Fig. 9). The formation of these peaks is illustrated in Fig. 10. This thermal decomposition appears to be general for the substituted ureas and reaction of substituted phenyl isocyanates with higher alcohols also occurs. As certain substituted alkyl phenylcarbamates are used as pesticides in their own right, inert solvents such as ethyl acetate or hexane should always be used for injection. The mass spectra of the thermal... 

Sensitivity of Electron Capture Ionization. We have found that negative ion LC/MS provides substantial increases in sensitivity as compared with positive ion LC/MS during analysis of fluorinated pyridines such as dithiopyr 1. An example of such sensitivity enhancement is shown in Figure 2. The top panel illustrates the total ion current trace obtained from injection of increasing amounts of dithiopyr in the positive ion mode with discharge ionization. 

Figure 15 presents the total ion current trace obtained from negative ion LC/MS analysis of a rat fecal extract. 

Figure 5.40 Scanning electron micrographs of (a) a PPM filled capillary (100 p,m i.d., 360 p,m o.d.) and (b) a commercial 360 mm o.d. nanospray capillary with a 30t)um tip opening. A comparison of the robustness of the two nanospray devices after four hours of use is provided by the total ion current traces recorded over a 5 minutes period, (c) for the PPM device and (d) for the conventional nanospray tip. Reproduced from Lee, Rapid Commun. Mass Spectrom. 19, 2671 (2005), with permission of John Wiley Sons, Ltd.

Examination of the diethyl ether extract by liquid chromatography (LC) using a Cjg reverse phase gradient elution separation with atmospheric pressure chemical ionisation (APCI) in the positive mode gave the total ion current trace shown in Figure 8.3. The last three peaks showed ions of masses 538, 566 and 594 and are believed to relate to the presence of tellurium dithiocarbamates in the extract (ions +2H from ionised protonic solvent). These species were not detected by GC-MS. 

Figure 3. GC/MS analysis of a single bead, holding the indicated structure. Top the total ion current trace bottom the spectrum of the indicated peak reprinted from [11].

Mild up-front CID reduces the abundance of background ions, a distinct advantage for LC/MS or CE/MS where the contribution of background ions to the baseline noise in the total ion current trace is a serious problem. ... 

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