Liquid Chromatography with electrochemical detection (LC-ECD) systems by means of a variety of voltammetric reactions have been developed as a sensitive, selective, and accurate method for determining bioactive compounds in plasma. Capillary LC-ECD (CLC-ECD) utilizing voltammetric oxidation on a glassy carbon electrode was applicable to determine attomole levels of flavonoids that have antioxidant activities. A boron-doped diamond (BDD) electrode was used to provide sensitive CLC-ECD for determining femtomole levels of polymethoxyflavones (PMFs) that were difficult to be oxidized on a carbon electrode. Voltammetric acid sensing by the means of reducing 3,5-di-
tert-butyl-1,2-benzoquinone (DBBQ) was applied to determine electro-inactive acid compounds, such valproic acid and free fatty acids (FFAs), and thus enabling one to detect valproic acid and FFAs without derivatization by HPLC-ECD. Moreover, voltammetric base sensing by the means of oxidizing trolox was applied to determine theophylline in plasma. In conclusion, the present HPLC-ECD systems characterized by sensitivity and selectivity are powerful analytical methods for determining plasma bioactive compounds using a small blood sample (about 10 μL). Additionally, the present HPLC-ECD systems are useful to examine concentration-time profiles of bioactive compounds and determine pharmacokinetic parameters in rat and/or human blood.
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