基于UPLC/Q-TOF-MS分析附子半夏配伍相反的物质基础

UPLC/Q-TOF-MS Based Chemical Profiling Approach to Evaluate Chemical Composition of Augmentation Toxicity in Combination of Radix Aconiti and Pinellia Praeparata

利用超高效液相色谱-飞行时间质谱联用技术(UPLC/Q-TOF-MS)分析附子半夏药对配伍相反的物质基础,从化学成分层次阐释其配伍相反机制.基于UPLC/Q-TOF-MS建立附子半夏药对配伍后生物碱类成分的化学指纹图谱,通过主成分分析法和正交偏最小二乘判别法分析药对配伍在合煎过程中的生物碱类成分的含量变化,找出差异变化显著的化学成分.结果表明正离子模式时附子半夏药对合煎液中次乌头碱,中乌头碱,乌头碱,去氧乌头碱,10-OH-中乌头碱,10-OH-乌头碱等的含量明显增高,而中乌头原碱,去乙酸中乌头原碱,去乙酸次乌头原碱,苯甲酰乌头原碱,苯甲酰次乌头原碱,10-OH-苯甲酰中乌头原碱等含量降低.附子半夏药对配伍应用时双酯型二萜生物碱的含量明显增高,而单酯型二萜生物碱的含量明显降低,这可能是附子半夏药对配伍相反作用的物质基础.

In the present UPLC/Q-TOF-MS study, an ultra performance liquid chromatography coupled with time-of-fight mass spectrometry （UPLC/Q-TOFMS） based chemical profiling approach was used to evaluate chemical constitution between co-decoction and mixed decoction of radix aconiti and pinellia pra- eparata. Two different kinds of decoctions, namely radix aconiti and pinellia praeparata co-decoction： wa- ter extract of mixed two herbs, and radix aconiti and pinellia praeparata mixed decoction： mixed water ex- tract of each individual herbs, were prepared. Batches of these two kinds of decoction samples were sub- jected to UPLC/Q-TOF-MS analysis, the datasets of tR-m/z pairs, ion intensities and sample codes were processed with orthogonal partial least squared discriminant analysis （OPLS-DA） to holistically compare the difference between these two kinds of decoction samples. The results of positive ion mode showed significant difference between two kinds of decoction samples, the content of hypaconitine, mesaconitine, aco-nitine, deoxyaconitine, lO-OH-mesaconitine, lO-OH-aconitine increased, while the content of mesaconine, dehydrated benzoylmesaconine, dehydrated benzoylhypaconine, benzoylaconine, benzoylhypaconine, l O- OH-benzoylmesaconine decreased in samples of co-decoction of radix aconiti and pinellia praeparata. The content of diester-diterpenoid alkaloids increased, while the content of monoester-diterpenoid alkaloids decreased, which may be basis of chemical composition in combination of radix aconiti andpinelliapraeparata.