Liquid chromatography with atmospheric pressure chemical ionization and electrospray ionization mass spectrometry of flavonoids with triple-quadrupole and ion-trap instruments.
With 15 flavonoids as test compounds, the analytical performance of four modes of LC-MS, multiple MS (MSn) and tandem MS operation (atmospheric pressure chemical ionization (APCI), electrospray ionization, positive and negative ionization) was compared for two mass spectrometers, a triple-quadrupole and an ion-trap instrument. Two organic modifiers, methanol and acetonitrile, and two buffers, ammonium acetate and ammonium formate, were used. In general, the use of APCI in the negative ion mode gave the best response, with the signal intensities and the mass-spectral characteristics not differing significantly between the two instruments. The best results were obtained when methanol-ammonium formate (pH 4.0) was used as LC eluent. Under optimum conditions full-scan limits of detection of 0.1-30 mg/l were achieved in the negative APCI mode. Here it needs to be emphasized that up to 2-order response differences were found both between analytes and between modes of ionization. This implies that one should be very cautious when interpreting data on the screening of real-life samples. The main fragmentations observed in the MSn spectra on the ion-trap, or the tandem MS spectra on the triple-quadrupole were generally the same. The advantage of the former approach is the added possibility to ascertain precursor-->product ion relationships.
de Rijke
Eva
E
Department of Analytical Chemistry and Applied Spectroscopy, Free University, De Boelelaan 1083, 1081 HV Amsterdam, The Netherlands.
Zappey
Herman
H
Ariese
Freek
F
Gooijer
Cees
C
Brinkman
Udo A Th
UA
D001274:Atmospheric Pressure; D002853:Chromatography, Liquid / Q000379:methods*; D005419:Flavonoids / Q000032:analysis*; D012680:Sensitivity and Specificity; D021241:Spectrometry, Mass, Electrospray Ionization / Q000295:instrumentation / Q000379:methods*; D013056:Spectrophotometry, Ultraviolet
D005419:Flavonoids