Wan Jin-Yi, Fan Yong, Yu Qing-Tao, Ge Ya-Zhong, Yan Chen-Pu, Alolga Raphael N, Li Ping, Ma Zhong-Hua, Qi Lian-Wen
State Key Laboratory of Natural Medicines, China Pharmaceutical University, No. 24 Tongjia Lane, Nanjing 210009, China; School of Pharmacy, Jiangsu University, 301 Xuefu Road, Zhenjiang 212013, China.
State Key Laboratory of Natural Medicines, China Pharmaceutical University, No. 24 Tongjia Lane, Nanjing 210009, China.
J Pharm Biomed Anal. 2015 Mar 25;107:89-97. doi: 10.1016/j.jpba.2014.11.014. Epub 2014 Dec 19.
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 44 Da (CO2) was found. High-energy collision-induced dissociation at 50 V produced the most abundant product ion M-H-malonyl by a neutral loss of 86 Da. 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.
人们已经开发了许多分析方法来表征人参中的人参皂苷。相对而言，各种加工人参中的丙二酰人参皂苷、氨基酸和多糖受到的关注较少。在本研究中，丙二酰人参皂苷通过液相色谱-四极杆-飞行时间质谱（LC-Q-TOF/MS）进行表征。在正模式下，观察到质荷比（m/z）为425.38处最丰富的离子，对应于原人参二醇型人参皂苷。显示出一个丰富的诊断离子835.48，代表具有至少两个糖苷的丙二酰人参皂苷。使用835.48 - 835.49快速筛选出12种丙二酰人参皂苷以重构离子色谱图。在负模式下，除了高去质子化离子外，还发现有44 Da（CO₂）的中性丢失。在50 V下进行高能碰撞诱导解离产生最丰富的产物离子M - H - 丙二酰，伴有86 Da的中性丢失。使用自动氨基酸分析仪测定17种常见氨基酸。精氨酸、谷氨酸和天冬氨酸含量丰富。鲜人参中氨基酸含量为9.1%，黑参中为3.1%。采用苯酚-硫酸法分析多糖。鲜人参中多糖含量为29.1%，黑参中为11.1%。推测成分积累的最佳生长年龄为5 - 6年。总之，丙二酰人参皂苷、氨基酸和多糖的含量按降序排列如下：鲜人参＞冻人参＞白参＞烤参＞红参＞黑参。对于人参产品的质量控制，应更加关注加工过程。
