去皮炒附片炮制过程中酯型乌头碱动态变化规律的研究

Dynamic Changes of Ester-type Aconitine in the Processing of Peeled Fried Aconite

为揭示附子高温无水炮制的机理,研究不同炮制工艺有效成分转化的差异,以去皮炒附片为研究对象,通过与厂家合作的方式在实际生产过程中取样,测定采用HPLC法,以乙腈-四氢呋喃和乙酸铵冰乙酸水溶液作为流动相,梯度洗脱,对去皮炒附片6种酯型乌头碱在炮制过程中动态变化规律进行详细研究,结果表明,乌头碱和新乌头碱均在炒制2 min时内消失,次乌头碱则下降为原来的18.1%。3种单酯型乌头碱中,炒制2 min时苯甲酰次乌头原碱上升至最大值的48.5%,苯甲酰新乌头原碱上升至62.2%,苯甲酰乌头原碱上升至70.3%。炒制4 min时,三者分别上升至最大值的100%、96.1%和74.4%。总双酯型乌头碱在炒制2 min后仅剩12.2%,总单酯型乌头碱在2 min时上升至最大值的59.1%,4 min时上升至98.6%。总酯型乌头碱在2 min时下降为原来的54.8%,4 min时回升至79.1%,之后基本维持在79.1%~80.5%,10 min时再次下降为原来的78.0%。从测定结果可以看出,双酯型乌头碱到单酯型乌头碱的转化区间集中在炒制4 min内。存在单酯型乌头碱下降区间与双酯型乌头碱上升区间不一致现象,且总酯型乌头碱含量先下降后上升。推测可能由于双酯型乌头碱向单酯型乌头碱转化过程中存在中间体。

To reveal the mechanism of differences in the conversion of active （Chaofupian through the six kinds of high-temperature water-free processing of aconite and study the ingredients in different processing techniques, the peeled fried aconite ester-type aconitine, which were obtained from the peeled Chaofupian. The gradient elution was performed using acetonitrile-tetrahydrofuran and ammonium acetate aqueous acetic acid as the mobile phase. The results showed that aconitine （AC） and mesaconitine （MA） disappeared within two minutes of frying, and hypaconitine （HA） decreased to 18.1%. In the three monoester-type aconitine, 14-benzoylhypaconine （BHA） increased to 48.5% of the maximum value at 2 minutes of frying, 14-benzoylmesaconine （BMA） increased to 62.2%, and 14-benzoylaconine （BAC） rose to 70.3%. When frying for 4 minutes, they rose to 100%, 96.1% and 74.4% of the maximum, respectively. The total diester-type aconitine remained only 12.2% after 2 minutes of frying, the total monoester-type aconitine increased to 59.1% of the maximum value at 2 minutes, and rose to 98.6% at 4 minutes. The total ester-type aconitine decreased to 54.8% at 2 minutes, recovered to 79.1% at 4 minutes, and then remained at a level of 79.1% to 80.5%, and decreased again to 78.0% at 10 minutes. It could be seen from the measurement results that the conversion interval of the diester aconitine to the monoester aconitine is within 4 minutes of frying. There is inconsistency between the decrease range of the monoester aconitine and the rise range of the diester aconitine. The total ester aconitine content decrease first and then increase. It is speculated that there may be a reaction intermediate in the conversion of the diester aconitine to the monoester aconitine.