The quantitative LC/ESI/SRM results for cabergoline on the TSQ Quantum at unit resolution are summarized in Figures 24 and in Table 1. The LLOQ observed for cabergoline was 50 fg on column (5 L injection of 10 pg/mL) which gave a S/N ratio of 23 (Figure 2). Bioanalytical methods for the pharmacokinetic analysis of cabergoline ideally require detection limits of 12 pg/mL in plasma. This is easily accomplished on the TSQ Quantum since an LLOQ of 50 fg on column represents only 5% (50 L) of a 1 mL plasma sample containing 1 pg of cabergoline. By extrapolation, it is clear that extremely sensitive limits of detection (down to the low pg/mL level for cabergoline) can be achieved with small plasma sample volumes.

A significant advantage of using smaller plasma volumes is that it lends itself to improved pharmacokinetic analyses, as replicate and other large samples-per-subject study designs would not be limited by the plasma volume requirements of the assay. The ability to easily attain such low detection limits on the TSQ Quantum with complex plasma samples also negates the need to develop highly selective sample enrichment procedures to minimize matrix interferences and to maximize the amount of analyte injected on the column.^[67] The method used here is in marked contrast to a previous method for cabergoline developed on the older generation TSQ 7000 triple quadrupole mass spectrometer, which reported an LLOQ value of 1.86 pg/mL (S/N ratio of 1813.1). However, this LLOQ actually represents ~900 fg of cabergoline on column^[6] rather than the 50 fg on column reported here. Furthermore, in order to acquire an accurate, reproducible LLOQ for cabergoline on the TSQ 7000, the assay required use of a 1-mL plasma sample, a complex extraction procedure including a five-fol
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