Gas chromatographic-mass spectrometric fragmentation study of flavonoids as their trimethylsilyl derivatives: analysis of flavonoids, sugars, carboxylic and amino acids in model systems and in citrus fruits.
The fragmentation patterns and quantitation possibilities of three anthocyanidins (pelargonidin, cyanidin, malvidin), one flavonol (quercetin), two flavones (apigenin, luteolin) and two flavanones (naringenin, hesperetin) have been investigated as trimethylsilyl and as trimethylsilyl (oxime) derivatives by gas chromatography-mass spectrometry. Results proved that anthocyanidins and flavanones form trimethylsilyl (oximes), while flavonol and flavones provide simple trimethylsilyl derivatives. In all cases, characteristic fragments of high masses are formed proper for quantitation purposes. Hydrolysis conditions for naringin, hesperidin and rutin have been optimized, resulting in the quantitative release of naringenin, hesperetin and quercetin together with their corresponding saccharides. These basic studies made possible the identification and quantification of the flavonoid, carboxylic-/amino acid and sugar constituents of citrus fruit juices and albedos, without any extraction/enrichment procedure. In total 33 compounds have been determined in hydrolyzed samples, such as 2 flavonoids (naringenin and hesperetin), 6 phenolic acids (trimethoxybenzoic, 4-hydroxybenzoic, vanillic, quinic, chlorogenic and rosmarinic acids), 3 aliphatic carboxylic acids (levulinic, malic, citric acids), phosphoric acid, 4 amino acids (aspartic, glutamic acids, alanine, proline), 9 monosaccharides (xylose, arabinose, rhamnose, fucose, fructose, galactose, glucose, galacturonic acid, sedoheptulose), inositol, sugarphosphate, 5 disaccharides and tocopherol. Measurements were carried out as the trimethylsilyl (oxime) ether/ester derivatives of constituents, in the concentration range of 2 x 10(-3) to 49.9%. Identification level of samples varied between 26.4 and 77.5%, expressed in dry matter content of juices and albedos.
Füzfai
Zs
Z
Institute of Chemistry, Department of Analytical Chemistry, L. Eötvös University, Budapest 112, Hungary.
Molnár-Perl
I
I
D000596:Amino Acids / Q000032:analysis*; D002241:Carbohydrates / Q000032:analysis*; D002264:Carboxylic Acids / Q000032:analysis*; D002957:Citrus / Q000737:chemistry*; D005419:Flavonoids / Q000032:analysis*; D008401:Gas Chromatography-Mass Spectrometry / Q000379:methods*; D006868:Hydrolysis; D014297:Trimethylsilyl Compounds / Q000737:chemistry*
D000596:Amino Acids; D002241:Carbohydrates; D002264:Carboxylic Acids; D005419:Flavonoids; D014297:Trimethylsilyl Compounds