Integrated evaluation of malonyl ginsenosides, amino acids and polysaccharides in fresh and processed ginseng

•Malonyl-ginsenosides in ginseng products were characterized by LC–Q-TOF/MS.•Twelve malonyl ginsenosides were rapidly screened by the characterized ions.•Contents of 17 amino acids and polysaccharides in ginseng products were determined.•Arginine, glutamic acid, and aspartic acid were abundant in ginseng products.•Optimal time for the accumulation of ingredients was suggested to be 5–6 years. Many analytical methods have been developed to characterize ginsenosides in ginseng. Relatively less attention has been paid to the malonyl ginsenosides, amino acids and polysaccharides in various processing ginsengs. In this study, malonyl ginsenosides were characterized by LC–Q-TOF/MS. In positive mode, the most abundant ions at m/z 425.38 were observed corresponding to the protopanoxadiol-type ginsenosides. A rich diagnostic ion at 835.48 was shown representing the malonyl ginsenosides with at least two glucosides. Twelve malonyl ginsenosides were rapidly screened using 835.48–835.49 to restructure ion chromatograms. In negative mode, besides the high deprotonated ion, a neutral loss of 44Da (CO2) was found. High-energy collision-induced dissociation at 50V produced the most abundant product ion [M−H-malonyl]− by a neutral loss of 86Da. Determination of 17 common amino acids was performed on an automatic amino acid analyzer. Arginine, glutamic acid, and aspartic acid were abundant. The contents of amino acids were 9.1% in fresh ginseng and 3.1% in black ginseng. Phenol-sulfuric acid method was applied to analysis of polysaccharides. The contents of polysaccharides were 29.1% in fresh ginseng and 11.1% in black ginseng. The optimal growth age for the accumulation of constituents was supposed to be 5–6 years. In conclusion, the contents of malonyl ginsenosides, amino acids, and polysaccharides, based on decreasing order, ranked as follows: fresh ginseng>frozen ginseng>white ginseng>stoved ginseng>red ginseng>black ginseng. Processing should be paid more attention for the quality control of ginseng products.