Chemical profiling and marker characterization of Huangqin decoction prepared with three types of peony root by liquid chromatography with electrospray ionization mass spectrometry

Clarification of the quality and biological effect equivalence of traditional Chinese medicines containing multi‐origin species is essential to improve their current quality standards, and also is the core problem to clarify the origins of single herbs with multi‐species in Chinese formulas that will guarantee their clinical application. Huangqin decoction is the typical one of multi‐origin formulas frequently used in traditional Chinese medicine and Kampo medicine. An ultra high performance liquid chromatography with electrospray ionization–tandem mass spectrometry was developed for chemical profiling and marker quantification of Huangqin decoction prepared with two different original types of peony root, white and red peony root. Forty‐seven main peaks in chemical profiling of Huangqin decoction prepared with white and red peony root were identified: nine were from peony root, 20 from baical skullcap root, 17 from licorice root, and one from jujubae fruit. The markers characteristics of the respective types of peony root in Huangqin decoction differ from that in single herbs, especially in terms of monoterpenoids and hydrolysable tannins. Subsequently, 17 representative markers in Huangqin decoction prepared with three types of peony root and their chemical characteristics and content distribution were carried out.     

Comparison of the active components of Aster tataricus from different regions and related processed products by ultra‐high performance liquid chromatography with tandem mass spectrometry

We investigated crude Aster tataricus, vinegar‐processed Aster tataricus, honey‐processed Aster tataricus, and steamed Aster tataricus as a case study and developed a comprehensive strategy integrating quantitative analysis and chemical pattern recognition methods for the evaluation and differentiation of Aster tataricus from different regions, as well as related processed products. In the study, 15 batches of raw Aster tataricus collected from seven provinces were analyzed. A sensitive and rapid ultra‐high performance liquid chromatography with tandem mass spectrometry method for simultaneous determination of 15 compounds was established to evaluate the quality of raw and processed Aster tataricus. Furthermore, multivariate statistical techniques were applied to compare the differences among Aster tataricus samples. As a result, the herbs collected from seven provinces were divided into two categories, and chlorogenic acid was the most important component distinguishing between the regions. Moreover, all of the raw and processed samples were classified by partial least squares discriminant analysis based on the 15 analyzed compounds. Results showed that raw Aster tataricus, vinegar‐processed Aster tataricus, honey‐processed Aster tataricus, and steamed Aster tataricus were clustered in four different areas. Shionone, chlorogenic acid and kaempferol were the significant constituents differentiating the raw and differently processed Aster tataricus samples.     

Pseudotargeted screening and determination of constituents in Qishen granule based on compound biosynthetic correlation using UHPLC coupled with high‐resolution MS

Detection and determination of many known/unknown compounds in traditional Chinese medicines have always been challenging. To comprehensively identify compounds in Qishen granule, which is a widely prescribed herbal formula for treating chronic heart failure, a pseudotargeted screening method was proposed based on compound biosynthetic correlation using ultra high‐performance liquid chromatography coupled with high‐resolution mass spectrometry. Firstly, all possible compounds of Qishen granule were classified into nine types according to their core skeletons, and potential analogue molecular formulas were predicted according to core compound‐related biosynthetic correlations, such as methylation, hydroxylation, and glucosidation. Secondly, nine pseudocompound databases consisting of core compounds, deduced biosynthetic correlations, and predicted analogue molecular formulas were established. Then, compounds of interest were directly located by pseudotargeted screening of high resolution mass spectrometry data and further verified by target tandem mass spectrometry. As a result, 213 constituents were identified and 21 of them were determined as potential new compounds. This demonstrated that pseudotargeted screening based on compound biosynthetic correlations significantly facilitated the processing of extremely large information data and improved the efficiency of compound identification. This research provided essential data for exploration of effective substances in Qishen granule and enriched the methodology for comprehensive characterization of constituents in complex traditional Chinese medicines.     

Comprehensive separation of iridoid glycosides and triterpenoid saponins from Dipsacus asper with salt‐containing solvent by high‐speed countercurrent chromatography coupled with recycling mode

The roots of Dipsacus asper Wall as a commonly used traditional Chinese medicine are used for tonifying liver and kidney and strengthening bones and muscles. However, an effective separation strategy for comprehensive and rapid separation of the main active compounds from the roots of D. asper is nonexistent. This investigation provided an effective separation method based on AB‐8 macroporous resin column chromatography using different ratios of ethanol in water and two different modes of high‐speed countercurrent chromatography with salt‐containing solvent system for rapid enrichment and separation from the roots of D. asper. The macroporous resin column chromatography was performed on AB‐8 resin using ethanol in water ratios of 10, 30, 40, 50, and 80% as the optimized enrichment conditions for iridoid glycosides and triterpenoid saponins with different polarities. For high‐speed countercurrent chromatography separation, the conventional and recycling modes were combined together to develop a strategy for 12 compounds ( 1 – 12 ) from the enriched parts of 30, 40, and 80% ethanol, including six high‐polarity iridoid glycosides ( 1 – 6 ) using inorganic salt‐containing solvent system and six triterpenoid saponins ( 7 – 12 ). Recycling high‐speed countercurrent chromatography separation was successfully applied to separate two isomers ( 9 and 10 ) after 11 cycles.     

荧光淬灭和加强理论公式合理性的热力学分析

通过荧光法在不同温度下研究了3种第三代头孢新药: 盐酸头孢吡肟、头孢匹胺和头孢唑肟钠与人血清白蛋白(HSA)和牛血清白蛋白(BSA)的作用, 分别应用荧光淬灭和荧光加强理论公式计算了它们的结合常数等, 进而分别计算了它们的热力学函数. 因对应于不同的理论公式得出的K_A值并不完全相同, 由此得到它们相应的热力学参数也有所不同. 本文对这些热力学数据的差异进行了分析比较, 结果表明: 基于荧光加强理论公式(4)获得的热力学数据显示更为合理. 因而我们建议, 即使在研究受体-底物的荧光淬灭反应时, 采用荧光加强理论公式(4)可以获得更符合实际的结果.     

A biochemometrics strategy combining quantitative determination,bioactivity evaluation and relationship analysis for identification of analgesic alkaloids of raw and vinegar‐processed Corydalis turtschaninovii

A biochemometrics strategy combining quantitative determination, bioactivity evaluation, and relationship analysis was proposed for identification of analgesic components of herbs. First, a robust liquid chromatography tandem mass spectrometry method was developed for simultaneous determination of nine major alkaloids in crude and vinegar‐processed Corydalis turtschaninovii. Nine alkaloids were separated on a BEH C₁₈ column with a mobile phase consisting of acetonitrile and water spiked with 0.1% formic acid and then detected by multiple reactions monitoring in the positive ion mode. Nitidine chloride was employed as the internal standard. The method displayed good linearity and the precisions of intra‐day and inter‐day were all within 3.0%. The recovery rates of each alkaloid ranged from 97.1 to 102.9%. The method was successfully applied for quantitative analysis of nine alkaloids in ten batches of crude and vinegar‐processed Corydalis turtschaninovii. Second, the analgesic effects of crude and vinegar‐processed Corydalis turtschaninovii were evaluated in mice. Third, principle component analysis, canonical correlation analysis, and partial least squares regression were used to analysis the relationship between the contents of nine major alkaloids and the analgesic effect of different crude and vinegar‐processed samples. Tetrahydropalmatine, coptisine, and dehydrocorydaline have a close positive correlation with the analgesic effect.     

中药质量控制的研究策略和色谱技术

综述了色谱技术作为现代高效分离分析技术在中药药效物质基础研究和中药质量控制中的重要作用。提出中药药效物质组学研究策略,以实现中药药效物质基础与作用机理研究的一体化,进而从深层次揭示和全面控制中药的内在质量。论述结果表明,现代色谱及其联用技术是中药质量研究的重要技术平台之一。     

固定化脂质体色谱研究中药复方的细胞膜通透性成分及其质量控制

提出了固定化脂质体色谱(immobilized liposome chromatography,ILC)研究中药复方的细胞膜通透性成分及其质量控制的方法。以当归补血汤及其组分为例,考察了它们在ILC色谱柱上的分离效果;当归补血汤水提取液和75％乙醇提取液在ILC色谱柱上各有8个保留峰,当归水提取液、甲醇提取液和75％乙醇提取液在ILC色谱柱上分别有3、6、9个保留峰,黄芪水提取液、甲醇提取液和75％乙醇提取液在ILC色谱柱上各有7个保留峰;建立了当归补血汤及其组分中阿魏酸和蒿本内酯的定量分析方法,当归补血汤水提取液和75％乙醇提取液中阿魏酸的含量分别为0．0743％和0．0688％,蒿本内酯的含量分别为0．0472％和0．457％,当归水提取液和75％乙醇提取液中阿魏酸的含量分别为0．0694％和0．0691％,蒿本内酯的含量分别为0．0781％和0．455％。     

中药复杂组效关系的变结构神经网络辨识方法

针对中药复杂组效关系的辨识问题,研究了变结构多层前馈神经网络,推导出一种新型的变结构网络学习算法,成功地应用于中药川芎药效活性预测计算.该方法从一个规模较小的网络出发,当网络无法达到预定的学习精度时,自动增加隐含层神经元个数,并在原有学习结果的基础上确定新的网络参数,自适应地确定前馈神经网络结构,可用于处理复杂化学模式信息.计算机仿真实验结果表明,该方法能有效地确定多层前馈神经网络的最佳结构,提高网络学习效率和函数逼近精度,解决复杂非线性函数映射关系准确建模问题.