目的 分析黄柏在不同温度下进行模拟炮制后, 不同炮制品中主要化学成分的变化情况, 为解析黄柏不同炮制品的科学内涵提供参考依据。方法 采用高效液相色谱法检测黄柏不同炮制品中生物碱类成分小檗碱、小檗红碱、黄柏碱、药根碱、巴马汀和柠檬苦素类成分黄柏内酯、黄柏酮。生物碱类成分检测的色谱条件为Ecosil C₁₈色谱柱(250 mm×4.6 mm, 5 μm);流动相:乙腈-0.1%磷酸水(50:50)(每100 mL 0.1%磷酸水加十二烷基硫酸钠0.4 g);检测波长:284 nm;体积流量:1 mL/min;柱温:35 ℃;进样量:3 μL。柠檬苦素类成分检测的色谱条件为Ecosil C₁₈色谱柱(250 mm×4.6 mm, 5 μm);流动相:乙腈-水-磷酸(45:55:0.2);检测波长:210 nm;体积流量:1 mL/min;柱温:35 ℃;进样量:10 μL。结果 直接烘制品、水润烘制品、酒润烘制品、盐水润烘制品在最佳炮制温度160 ℃下, 总生物碱的质量分数分别为3.009 6%、2.993 1%、3.989 6%、4.537 9%, 其中酒润烘制品和盐水润烘制品均较生品3.528 2%高, 提示黄柏经辅料炮制后有利于生物碱类成分的溶出, 且增加溶出率的是辅料盐和酒, 而非水。当炮制温度达到160 ℃以上时, 在相应炮制温度下的直接烘制品和水润烘制品中柠檬苦素类成分质量分数未见明显差异, 酒润烘制品和盐水润烘制品随着温度的升高其质量分数相差较大, 提示水对黄柏炮制过程中的柠檬苦素类成分基本没有影响, 酒、盐炮制具有影响。结论 黄柏经炮制后生物碱类和柠檬苦素类成分会发生量变和质变, 辅料和温度对其成分的变化有直接的影响, 本研究可为黄柏炮制后药性发生改变与其化学成分的变化具有相关性提供参考和依据。

Objective To study the variation of the main components in Phellodendri Cortex processed with different methods and temperature, and to provide scientific references for processing principle. Methods The contents of alkaloids (berberine, berberrubine, phellodendrine, jatrorrhizine, and palmatine) and limonoids (obaculactone and obacunone) from different processed products were determined by HPLC method. Alkaloids determination were carried out on an Ecosil C₁₈ column (250 mm × 4.6 mm, 5 μm) with acetonitrile-0.1% phosphoric acid water (50:50) (added 0.4 g SDS to 0.1% phosphoric acid water per 100 mL) as mobile phase. The detection wavelength was 284 nm and injection volume was 3 μL at the flow rate of 1.0 mL/min. The column temperature was set for 35 ℃. An Ecosil C₁₈ column (250 mm × 4.6 mm, 5 μm) was used for determination of limonoids. Mobile phase was consisted of acetonitrile-water-phosphoric acid (45:55:0.2), and it was monitored at a wavelength of 210 nm. The column temperature was 35 ℃, and the injection volume was 10 μL at a flow rate of 1.0 mL/min. Results At the optimal temperature 160 ℃, the total alkaloids in Phellodendri Cortex direct drying product, processed products with water, rice-wine, and salt-water were 3.009 6%, 2.993 1%, 3.989 6%, and 4.537 9%, respectively. Contents of the total alkaloids in processed products with rice-wine and salt-water were above that of raw product with 3.528 2%. It was suggested that it was rice-wine and salt-water, not water which improved dissolution of total alkaloids in Phellodendri Cortex. When the temperature is above 160 ℃, the total contents of limonoids in processed products with water and direct drying products were similar, but the processed products with rice-wine and salt-water were large difference with the increase of temperature. It was also suggested that it was accessories rice-wine and salt-water, not water which improved dissolution of the total contents of limonoids in Phellodendri Cortex. Conclusion After procession, alkaloids and limonoids have qualitative and quantitative change, and the accessories and temperature have directly influence on the change of their contents. It would provide reference and basis to the correlation between the properties change and the chemical components variation from Phellodendri Cortex after processing.

国家自然科学基金资助项目(81274083)