HPLC测定中药多成分总量溶度参数的实验研究

Experimental Study on Determination of Total Solubility Parameters of Chinese Traditional Medicine by High Performance Liquid Chromatography

目的:对HPLC测定中药多成分总量溶度参数的理论及实验进行研究。方法:采用高效液相色法对咖啡因、芦荟大黄素、大黄酸、大黄素和和大黄素甲醚进行检测,通过溶度参数理论与Hildebrand-Scatchard溶液溶解度的相关方程与高效液相色谱原理相互结合,对待测组分总量参数AT、BT、CT与相关指纹图谱参数平均保留时间a、b、c的关系等进行分析检测。结果:根据相关指纹图谱平均保留时间与总量表观溶度参数之间相关的函数表达和数学模型,根据高效液相色谱出峰时间结合相关公式(1)和(2)计算不同洗脱条件下的咖啡因溶度参数值分别为32.04J^1/2/cm^3/2、35.07J^1/2/cm^3/2、39.04J^1/2/cm^3/2、43.26J^1/2/cm^3/2、45.78J^1/2/cm^3/2、46.22J^1/2/cm^3/2。通过公式计算所得相关值分别为0.09256、0.14365、27.39、0.1533和0.16743。根据相关指纹图谱平均保留时间与大黄类组分的溶度参数之间相关的函数表达和数学模型,根据高效液相色谱出峰时间结合相关公式(1)和(2)计算不同洗脱条件下的芦荟大黄素溶度参数值分别为38.56J^1/2/cm^3/2、36.54J^1/2/cm^3/2、40.25J^1/2/cm^3/2、44.25J^1/2/cm^3/2、43.65J^1/2/cm^3/2、44.58J^1/2/cm^3/2,通过公式计算所得相关值分别为1.09584、0.5869、26.58、0.53647和0.12356;大黄酸溶度参数值分别为43.25J^1/2/cm^3/2、44.26J^1/2/cm^3/2、44.58J^1/2/cm^3/2、45.44J^1/2/cm^3/2、44.98J^1/2/cm^3/2、45.23J^1/2/cm^3/2,通过公式计算所得相关值分别为1.2569、0.5874、2.3689、0.5478和1.569;大黄素溶度参数值分别为44.73J^1/2/cm^3/2、42.16J^1/2/cm^3/2、47.69J^1/2/cm^3/2、43.21J^1/2/cm^3/2、44.78J^1/2/cm^3/2、43.26J^1/2/cm^3/2,通过公式计算所得相关值分别为0.57657、0.43256、0.44569、0.43225和0.44154;大黄素甲醚溶度参数值分别为42.16J^1/2/cm^3/2、47.56J^1/2/cm^3/2、46.21J^1/2/cm^3/2、44.38J^1/2/cm^3/2、47.56J^1/2/cm^3/2、44.23J^1/2/cm^3/2,通过公式计算所得相关值分别为0.44369、0.43212、0.44126、0.43256和0.44236。待测组分总量参数AT、BT、CT与相关指纹图谱参数平均保留时间a、b、c的关系拟合度较强,通过P值分析,各指数之间存在显著差异(P<0.01)。因此,结合相关中药多成分总量溶度参数理论及高效液相色谱能够对各指纹图谱参数平均值进行计算分析。结论:通过高效液相色谱指纹图谱与参数理论相结所得各组分模型能够对复杂的中药成分进行分析,同时能够在药效的监控、药理活性、相关组分的结合以及中药释放程度等方面进行定性定量分析。

Objective: The theory and experiment of HPLC determination of total solubility parameters of Chinese traditional medicine were studied. Methods: By high performance liquid chromatograph to caffeine,aloe emodin,rhein,emodin and emodin and methyl ether in the liquid phase detection,through the theory of solubility parameter and Hildebrand -Scatchard solution related equation and principle of high performance liquid chromatography (HPLC) combined with each other,treat total component parameter measurement AT,BT,CT and the related fingerprint parameters average retention time analysis the relationship between a,b,c and so on. Results: According to the fingerprint between apparent solubility parameter average retention time and amount of related function and a mathematical model,based on high performance liquid chromatographic peak time correlation formula (1) and (2) different elution conditions of caffeine solubility parameter values were 32.04 J^1/2 /cm^ 3/2 ,35.07 J^1/2 /cm^ 3/2 ,39.04 J^1/2 /cm^ 3/2 ,43.26 J^1/2 /cm^ 3/2 ,45.78 J^1/2 /cm^ 3/2 ,46.22 J^1/2 /cm^ 3/2 . The correlation values calculated by the formula were 0.09256,0.14365,27.39,0.1533 and 0.16743,respectively. According to the fingerprint average retention time and rhubarb components between the solubility parameter of the related function and a mathematical model,based on high performance liquid chromatographic peak time in combination with related formula (1) and (2) different elution conditions of aloe emodin solubility parameter values were 38.56 J^1/2 /cm^ 3/2 、36.54 J^1/2 /cm^ 3/2 、40.25 J^1/2 /cm^ 3/2 、44.25 J^1/2 /cm^ 3/2 、43.65 J^1/2 /cm^ 3/2 、44.58 J^1/2 /cm^ 3/2 . The correlation values calculated by the formula were 1.09584,0.5869,26.58,0.53647 and 0.12356,respectively. Rhubarb acid solubility parameter values were 43.25 J^1/2 /cm^ 3/2 ,44.26 J^1/2 /cm^ 3/2 ,44.58 J^1/2 /cm^ 3/2 ,45.44 J^1/2 /cm^ 3/2 ,44.98 J^1/2 /cm^ 3/2 ,45.23 J^1/2 /cm^ 3/2 ,respectively. The solubility parameters of emhutin were 44.73 J^1/2 /cm^ 3/2 、42.16 J^1/2 /cm^ 3/2 、47.69 J^1/2 /cm^ 3/2 、43.21 J^1/2 /cm^ 3/2 、44.78 J^1/2 /cm^ 3/2 、43.26 J^1/2 /cm^ 3/2 ,and 0.57657,0.43256,0.44569,0.43225,and 0.44154,respectively. The solubility parameters of emodin methyl ether were 42.16 J^1/2 /cm^ 3/2 、47.56 J^1/2 /cm^ 3/2 、46.21 J^1/2 /cm^ 3/2 、44.38 J^1/2 /cm^ 3/2 、47.56 J^1/2 /cm^ 3/2 、44.23 J^1/2 /cm^ 3/2 ,respectively. The relationship between the total parameters AT,BT,CT and the average retention time of the related fingerprint parameters a,b and c was strongly fitted. Through the P value analysis,there were significant differences among the indexes (P<0.01). Therefore,combined with the total solubility parameter theory of related TCM components and high performance liquid chromatography,the average values of fingerprint parameters can be calculated and analyzed. Conclusion: HPLC has a good application value in determining the solubility parameters of multiple components of traditional Chinese medicine and can lay a theoretical foundation for improving the application of single traditional Chinese medicine.