Capillary Electrophoresis/mass spectrometry The first report on coupling capillary electrophoresis with mass spectrometry was published in 1987.

Since then, it has become obvious that this hyphenated method will become a powerful and important tool in the analysis of large biopolymers, such as proteins, polypeptides and DNA species. In most of the applications reported to date, the capillary effluent is passed directly into an electrospray ionization device, and the products then enter a quadrupole mass filter for analysis. Continuous flow fast atom bombardment has also been used for ionization in some applications. Capillary electrophoresis/mass spectrometry is discussed in more detail in section 30B-4. Tandem mass spectrometry Another important hyphenated technique involves coupling one mass spectrometer to a second. In this method, the first spectrometer serves to isolate the molecular ions of various components of a mixture. These ions are then introduced one at a time into a second mass spectrometer, where they are fragmented to give a series of mass spectra, one for each molecular ion produced in the first spectrometer. This technique is called tandem mass spectrometry (often abbreviated as MS/MS). The first spectrometer in a tandem instrument is ordinarily equipped with a soft ionization source (often a chemical ionization source) so that its output is largely molecular ions. These ions then pass into the ion source for the second spectrometer. Most often this second ion source consist of a field free collision chamber through which helium is pumped. Collisions between the fast moving parent ions and helium atoms cause further fragmentation of the former to give numerous daughter ions is then scanned by the second spectrometer serves the same function as the chromatographic column in GC/MS or LC/MS in that it provides pure ionic species one by one for identification in the second spectrometer. To illustrated the power of this type of MS/MS, consider a hypothetical mixture of the isomers ABCD and BCDA, and other molecules such as UKL and UMN. To discriminate between the two isomers, a soft ionization source is used to produce predominantly singly charged molecular ions. The first spectrometer is then set to transmit ions with an m/z value corresponding to ABCD+ and BCDA+ (their m/z values are identical). Thus, the molecular ions of the isomers are separated from other components of the mixture. In the ionization chamber of the second spectrometer, collision fragmentation takes place to produce daughter ions such as AB+, CD+, BC+, DA+, and so forth. Because these fragments have unique mass-to-charge ratios, the identification of the two original isomers is possible in the second analyzer. The first spectrometer can then be set to transmit IJKL+ or IJMN+ ions, which in turn yield U+, JKL+, MN+, JMN+, and other characteristic ions that are also identified by the second analyzer. Figure 20-23 illustrates a practical application of this technique, which is sometimes called daughter-ion MS/MS. The analyte consist of two very different compounds that have identical wholenumber masses of 278. To discriminate between the two, the first