Two new sensitive and selective LC-MS methods have been developed for the quantification of the total coenzyme Q(10) concentration in human blood serum. The sensitivity of the methods is based on the very efficient formation of the radical anions of CoQ(10)[M(-)[radical dot]] by negative atmospheric pressure ionisation, APCI(-). The mass detection of the [M(-)[radical dot]] ions, m/z= 862.6, was performed either in selective ion monitoring (SIM) or in MS(2) mode (m/z= 862.6 [rightward arrow]m/z= 847.6) using an LCQ-deca ion-trap mass spectrometer. Two standard serum samples with medium (0.73 [micro sign]g ml(-1)) and high (1.96 [micro sign]g ml(-1)) total CoQ(10) concentrations were analysed by LC-APCI(-)-SIM and LC-APCI(-)-MS(2) and the results compared with a HPLC literature procedure with electrochemical detection (ECD). Both the LC-MS methods were shown to be more selective and with comparable or better sensitivity than the HPLC-ECD method. The LC-MS-SIM and LC-MS(2) chromatograms of the medium concentration sample showed CoQ(10) signal to noise ratios of 25 and 625, respectively. In addition, a simple and fast serum pre-treatment procedure was developed, in which the serum CoQ(10)H(2) content was quantitatively oxidised quantitatively to CoQ(10) in less than 15 min by 1,4-benzoquinone.

The bis tetrabutylammonium salt of the solar cell dye, L(2)Ru(NCS)(2), ((Bu(4)N(+))(2) [Ru(dcbpyH)(2)(NCS)(2)](2-)), was oxidized electrochemically in both dimethylformamide and acetonitrile. Four different ruthenium complexes were identified by LC-UV/Vis-MS during the electrochemical oxidation process in dimethylformamide. The formation of the four complexes may be explained by a competition between a solvent-independent route with the formation of the intermediate complex L(2)Ru(NCS)(CN) and the final oxidation product L(2)Ru(CN)(2) and a solvent-dependent route, which proceeds through the intermediate complex L(2)Ru(NCS)(DMF)(+) to the final product L(2)Ru(CN)(DMF)(+). In acetonitrile the solvent-dependent mechanism is dominant and only the oxidation products L(2)Ru(NCS)(ACN)(+) and L(2)Ru(CN)(ACN)(+) were identified.

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