CH908, Problem set 7, Tandem Mass Spectrometry 1. In a quadrupole ion trap, a m/z 660 ion is fragmented, with the instrument running at a qz of 0.3. What is the low mass cut off for the MS/MS data? LMCO = qz* precursor mass, so (0.3*660) = 198 Da 2. In the pharmaceutical industry, triple quadrupole mass spectrometers are used extensively for quality control and measurement of pharmacokinetics. The most common experiment used is called “Selected Reaction Monitoring”. Explain this experiment and why it’s useful for the pharmaceutical industry. One ion (one m/z region) is isolated (usually using a quadrupole) from a sample stream (usually an LC or GC effluent) and fragmented. The intensity of one fragment ion peak is then plotted over time to yield a selected ion chromatogram. 3. For peptides, what kind of ion series is most dominant for the following fragmentation methods: a) CAD, b) ECD/ETD, c) UVPD, d) IRMPD. Define these acronyms. a) collisionally activated dissociation - same as collision induced dissociation - generates the b/y ion series. b) electron capture dissociation or electron transfer dissociation generates c/z• ion series from peptides. c) ultraviolet photodissociation. Generates the a/x ion series, and some b/y ions. d) infrared multiphoton dissociation. Generates b/y ions, just like CAD. 4. In ECD and ETD, the bond n-terminal to proline is not cleaved. Why? The n-cα that is usually cleaved is within the ring, so it would require two bond cleavages to observe a mass change.