Qualitative analysis of Gynostemma longipes for medicinal usage / 中国中药杂志

The Qinling-Daba Mountains area is the main producing areas of Gynostemma longipes for medicinal usage, and samples of wild whole plants in Pingli, Shaanxi Province and Qingchuan, Sichuan Province were collected. The ultra-high performance liquid chromatography coupled with quadrupole time-of-flight mass spectrometry(UHPLC-Q-TOF-MS~E) was used to profile the chemical compositions and analyze the similarities and differences of G. longipes samples in these areas. Based on the accurate molecular weight and fragment information obtained from Q-TOF-MS~E, the structures of the main components were identified by combining with the mass spectra, chromatographic behaviors of reference standards and related literatures. The results showed that the components of wild G. longipes from different places among Qinling-Daba Mountains area were similar. Forty-five chemical components were identified in the whole plant of G. longipes from Pingli, Shaanxi Province, including 43 triterpenoid saponins and 2 flavonoids which contain all main peaks in its fingerprint. The main components are dammarane-type triterpenoid saponins, such asgypenoside ⅩLⅨ, gypenoside A and its malonylated product of glycosyl.

Change of icariin content in five Epimedium species by heating process / 中国中药杂志

The change of icariin( ICA) content in thirty-three samples of five Epimedium species listed in the Chinese Pharmacopoeia( 2015 edition),including E. brevicornu,E. sagittatum,E. pubescens,E. koreanum,and E. wushanense has been investigated in this study. The results indicated that the optimized process procedure was baking at 150 ℃ for 30 min,and 3'''-carbonyl-2″-β-L-quinovosyl icariin( CQICA) could not be translated into ICA and ICA could be converted under this heating process condition. ICA increased remarkably after the heating process by 1-3 times in E. brevicornu,E. wushanense and E. koreanum,and increased lightly in E. brevicornum and E. pubescens,while ICA slightly increased or decreased in E. sagittatum and E. wushanense.

Difference of alkaloid components between old stems and tender stems of Gelsemium elegans / 中国中药杂志

This study aimed to comprehensively assess the difference of alkaloid components between old stems and tender stems of Gelsemium elegans by using ultra high-performance liquid chromatography coupled with photo-diode array and quadrupole time-of-flight mass spectrometry( UPLC-Q-TOF/MS~E) and high-performance liquid chromatography coupled with UV detector( HPLC-UV). Firstly,the different components in old stems and tender stems were analyzed by UHPLC-Q-TOF/MSEcombined with principal component analysis( PCA) and orthogonal partial least squares discriminant analysis( OPLS-DA),respectively. As a result,17 major different components were found. At the same time,the distribution of these alkaloids in old stems and tender stems was determined,and the alkaloids with higher polarity are relatively higher in the tender stems,while the old stems are in the opposite case. In addition,three main components in the G. elegans were quantified by HPLC-UV. The results showed that the contents of koumine and humantenmine in old stems were higher than those in tender stems,and the content of gelsemine in tender stems was relatively high. This study systematically evaluated the differences of alkaloids between the old stems and tender stems of G. elegans,and quantified the main three alkaloids. It laid the foundation of the safe and effective application of G. elegans.

Changes and mechanisms of terrestroside B and terrestrosin K in stir-frying Tribuli Fructus / 中国中药杂志

The contents of terrestroside B and terrestrosin K in Tribuli Fructus with different degree of stir-frying were determined by high performance liquid chromatography with evaporative light-scattering detector( HPLC-ELSD). The results showed that the contents of terrestroside B and terrestrosin K were increased at first and then decreased,and both of them had the highest content at the best time of heating. The results of simulated processing of Tribulus Terrestris saponins showed that when the processing time kept constant,the contents of terrestroside B and terrestrosin K were decreased gradually with the increase of processing temperature from 180 ℃ to240 ℃. At a certain temperature,the content of terrestrosin K was increased first and then decreased with the prolongation of processing time,and reached the highest level at 5 min. However,the content of terrestroside B was increased first and then decreased with the increase of processing time only at 180 ℃,and reached the highest level at 10 min. When the processing temperature was controlled at200,220 and 240 ℃ respectively,the content of terrestroside B was decreased gradually with the increase of processing time. The simulated processing products of tribuluside A,terrestroside B and terrestrosin K were qualitatively characterized by ultra-performance liquid chromatography-time of flight mass spectrometry( UPLC-TOF/MS). It was proved that tribuluside A and terrestrosin Ⅰ containing C-22-OH were dehydroxylated in the processing of Tribuli Fructus and transformed respectively into terrestroside B and terrestrosin K containing C-20-C-22 double bond. As a result,the contents of terrestroside B and terrestrosin K were increased. The sugar chains at C-3 and C-26 positions of terrestroside B and terrestrosin K could be deglycosylated and converted into monosaccharide chain saponins and short sugar chain saponins,so the contents of terrestroside B and terrestrosin K were reduced. The study provides reference for further revealing the processing principle of Tribuli Fructus.

Comparative analysis on chemical constituents in Bupleurum chinense,B. marginatum,B. marginatum var. stenophyllum and B. smithii var. parvifolium / 中国中药杂志

UPLC-Q-TOF-MS was used to analyze the chemical differences in Bupleurum. chinense,B. marginatum,B. marginatum var. stenophyllum and B. smithii var. parvifolium. Chromatographic separation was carried out on an Acquity HSS T3 C_(18) column( 2. 1 mm ×100 mm,1. 8 μm,Waters) with the mobile phase composed of 0. 1% formic acid in water-acetonitrile in the gradient elution. A hybrid quadrupole time-of-flight tandem mass spectrometry( Q-TOF-MS~E) was used for mass spectrometric analysis. Finally,25 peaks were identified based on their exact mass data and fragmentation characteristics. B.chinense,B.marginatum,B. marginatum var. stenophyllum and B. smithii var. parvifolium were obviously clustered into 3 types through processing by principal component analysis( PCA). There was almost no difference between B. chinense and B. marginatum. However,the compounds existed in B. chinense were different from those in B. marginatum var. stenophyllum,and B. smithii var. parvifolium.

Metabolism of saponins from traditional Chinese medicines: a review / 药学学报

Saponins are important components in traditional Chinese medicine (TCM) with significant biological activities, which could be divided into triterpenoid saponins and steroidal saponins according to structures of the aglycone skeletons. This article reviews the in vivo metabolic pathways of some typical natural saponins such as ginsenosides, licorice saponins, saikosaponins, timosaponins and diosgenin glycosides. Saponins often show poor absorbance after oral administration. The in vivo metabolism of saponins generally contain two steps. These compounds usually undergo hydrolysis in stomach and gut. Then they are absorbed into blood and metabolized in liver. The secondary glycosides and the aglycones produced in gastrointestinal tract often show higher bioavailability and better bioactivity, while downstream metabolites in liver are mainly produced by phase I metabolism. Clarification of the in vivo metabolism of bioactive saponins is helpful for the understanding of the effective ingredients in TCM, as well as the discovery of new drugs from natural products.

A rapid method for chemical fingerprint analysis of Pan Panax notoginseng powders by ultra performance liquid chromatography coupled with quadrupole time-of-flight mass spectrometry / 中国天然药物

A method coupling ultra-performance liquid chromatography (UPLC) with quadrupole time-of-flight mass spectrometer (Qtof MS) using the electrospray ionization (ESI) source was developed for the identification of the major saponins from Panax notoginseng powder (PNP). Ten different PNP samples were analyzed and evaluated for their quality by similarity evaluation and principle component analysis (PCA). Based on the accurate mass, summarized characteristic fragmentation behaviors, retention times of different types of saponins, related botanical biogenesis, and reported chromatographic behavior of saponins, fifty-one common peaks were effectively separated and identified, including 28 protopanaxadiol saponins and 18 protopanaxatriol saponins. Simultaneously, 15 significant discrepancy compounds were identified from the disqualified PNP samples. The established UPLC/Qtof MS fingerprint method was successfully applied for profiling and identifying the major saponins of PNP, providing a fast quality evaluation tool for distinguishing the authentic PNP and the adulterated products.

Techniques and strategies for characterization and isolation 01 chemical components of traditional chinese medicines / 国际药学研究杂志

The chemical composition of traditional Chinese medicine (TCM) is the material base for its prevention and treatment of disease. Characterization, analysis and isolation of chemical constituents, important fields of modern research on TCM, however, are still a great challenge due to the complexity. In recent years, considerable progress has been made in these fields with the application of new chromatographic packing materials and methods, analysis technologies represented by LC-MS and the associated databases and softwares. Here, the advancement of methods and strategies used in the research on the chemical constituents of TCM is briefly reviewed.

Qualitative analysis of chemical constituents in Si-Wu Decoction based on TCM component database / 药学学报

In order to clarify the chemical constituents of Si-Wu Decoction rapidly and holistically, we analyzed the ethanol extract of Si-Wu Decoction by UPLC/Q-TOF-MSE and UNIFI which based on traditional Chinese medicine database, the probable structures of 113 compounds were identified. The results show that this method can rapidly and effectively characterize the chemical compounds of Si-Wu Decoction and provide a new solution for identification of components from complex TCM extract.

Study on steroidal saponins from Dioscorea zingiberensis and their platelet aggregation activities / 中国中药杂志

Using the absorbent resin, silica gel and ODS column chromatography as well as semi-preparative HPLC, ten compounds were isolated from 70% ethanol extract of tubers of Dioscorea zingiberensis C. H. Wright, and their structures were elucidated as trigoneoside XIIIa (1), parvifloside (2), trigoneoside IVa (3), deltoside (4), protobioside (5), lilioglycoside k (6), zingiberensis newsaponin I (7), deltonin (8), prosapogenin A of dioscin (9), and trillin (10) on the basis of NMR and MS spectral data analysis. Among these compounds, 1, 3, 5 and 6 were isolated from this plant for the first time. In the screening test on platelet aggregation, compounds 7 and 8 exhibited induction effect on platelet aggregation, while compound 9 exhibited significant inhibitory effect on platelet aggregation in vitro.

Original plant identification of Dai nationality herb "Daibaijie" / 中国中药杂志

<p><b>OBJECTIVE</b>To identify the original plant of "Daibaijie", commonly used Dai herb.</p><p><b>METHOD</b>The literature review, morphology and anatomy, pharmacognosy, molecular biology, chemistry were used to analysis.</p><p><b>RESULT</b>Daibaijie's historical scientific name, Dregea sinensis Hemsl., was mistakenly given "Daibaijie" and D. sinensis have significant differences from the distribution, morphology and anatomy, pharmacognosy, molecular biology and chemical composition. "Daibaijie" matches with the characteristics of Marsdenia tenacissima (Roxb.) Moon in Flora of China in English.</p><p><b>CONCLUSION</b>Daibaijie's original plant is M. tenacissima (Roxb.) Moon. The description and illustration of M. tenacissima (Roxb.) Moon in Flora of China in China are wrong. The illustration of M. tenacissima in Flora of China in English is wrong too.</p>

Chemical constituents from processed rhizomes of Panax notoginseng / 中国中药杂志

To investigate the chemical constituents of the processed rhizomes of Panax notoginseng, their 70% ethanol extract was chromatographed on macroporous resin (SP825), silica gel, RP-C18 and semi-preparative HPLC to afford compounds 1-23. On the basis of physicochemical properties and spectral data analysis, their structures were identified to be 6'-O-Acetylginsenoside Rh1 (1), ginsenoside RK3 (2), ginsenoside Rh4 (3), 20S-ginsenoside Rg3 (4), ginsenoside Rk1 (5), 20R-ginsenoside Rg3 (6), ginsenoside Rg5 (7), ginsenoside F2 (8), 20S-ginsenoside Rh1 (9), 20R-ginsenoside Rh1 (10), gypenoside X VII (11), notoginsenoside Fa, (12), ginsenoside Ra3 (13), ginsenoside Rg1 (14), ginsenoside Re (15), notoginsenoside R2 (16), ginsenoside Rg2 (17), notoginsenoside R1 (18), ginsenoside Rd (19), ginsenoside Rb1 (20), notoginsenoside D (21), notoginsenoside R4 (22) and ginsenoside Rb2 (23), respectively. Among them, compound 1 was isolated from P. notoginseng for the first time, and compounds 4, 6, 8 and 11 were isolated from the processed P. notoginseng for the first time. According to the fingerprint profiles of raw and processed P. notoginseng, the putative chemical conversion pathways of panoxatriol and panoxadiol compounds in the processing procedure was deduced, and the results revealed the main reactions to be dehydration and glycosyl hydrolysis.

Analysis and identification of chemical constituents in Siwu decoction by UPLC-Q-TOF-MS(E) / 中国中药杂志

This research analyzed the chemical constituents of Siwu decoction by UPLC-Q-TOF-MS(E). Base on the data of mass and related-literatures, 43 peaks were profiled and 25 compounds, which contain 8 monoterpene glycosides from Paeonia lactiflora and 13 phthalides from Rhizoma chuanxiong and Radix angelica sinensis mainly, were identified in both positive and negative mode respectively. Meanwhile, chemical constituents of water extract and 60% ethanol extract of Siwu decoction were compared by the principal constituent analysis with MarkerLynx software, which provides the basis for the active ingredients of Siwu decoction.

Advances in the study of derivatization of ginsenosides and their anti-tumor structure-activity relationship / 药学学报

Ginsenosides, belonging to a group of saponins with triterpenoid dammarane skeleton, show a variety of pharmacological effects. Among them, some ginsenoside derivatives, which can be produced by acidic and alkaline hydrolysis, biotransformation and steamed process from the major ginsenosides in ginseng plant, perform stronger activities than the major primeval ginsenosides on inhibiting growth or metastasis of tumor, inducing apoptosis and differentiation of tumor and reversing multidrug resistance of tumor. Therefore ginsenoside derivatives are promising as antitumor active compounds and drugs. In this review, the derivatization methods, ginsenoside derivatives and their anti-tumor structure-activity relationship have been summarized for providing useful information for the research and development of novel antitumor drugs.

Identification of chemical constituents in qiliqiangxin capsule by UPLC-Q-TOF/MS(E) / 药学学报

In order to clarify the chemical constituents in Qiliqiangxin capsule, a rapid ultra-performance liquid chromatography/orthogonal acceleration time-of-flight mass spectrometry (UPLC-Q-TOF/MS(E)) method was established. Forty peaks were identified on line using this method. The herbal sources of these peaks were assigned. The results implied that triterpenoid saponins, flavonoid glycosides, C21-steroids and phenolic acids were included in the main components of Qiliqiangxin capsule. The method is simple and rapid for elucidation of the constituents of Qiliqiangxin capsule and the results are useful for the quality control of Qiliqiangxin capsule.

Two new furostanol saponins from the rhizomes of Anemarrhena asphodeloides / 药学学报

<p><b>AIM</b>To investigate the chemical constituents of the rhizomes of Anemarrhena asphodeloides Bunge.</p><p><b>METHODS</b>The compounds were separated by means of solvent extraction, chromatography on absorbent resin SP825 and silica gel C18 repeatedly, and their structures were elucidated on the basis of chemical methods and spectral analyses (FAB-MS, 1H NMR, 13C NMR, 1H-1H COSY).</p><p><b>RESULTS</b>Six steroidal saponins were isolated from the rhizomes of Anemarrhena asphodeloides Bunge. They were identified as (25S)-26-O-beta-D-glucopyranosyl-22-hydroxy-5beta-furostane-2beta, 3beta, 26-triol-3-O-beta-D-glucopyranosyl-(1 --> 2)-beta-D-galactopyranoside (timosaponin N, 1), timosaponin E1 (2), (25S)-26-O-beta-D-glucopyranosyl-22-methoxy-5beta-furostane-2beta, 3beta, 26-triol-3-O-beta-D-glucopyranosyl-(1 --> 2)-beta-D-galactopyranoside (timosaponin O, 3) , timosaponin E2 (4), (25R) -26-O-beta-D-glucopyranosyl-22-hydroxy-5alpha-furostane-2alpha, 3beta, 26-triol-3-O-beta-D-glucopyranosyl-(1 --> 2)-[beta-D-xylpyranosyl-(1 --> 3)]-beta-D-glucopyranosyl-(1 --> 4)-beta-D-galactopyranoside (purpureagitosid, 5) and marcogenin-3-O-beta-D-glucopyranosyl-(1 --> 2)-beta-D-galactopyranoside (6).</p><p><b>CONCLUSION</b>Compound 1 and compound 3 are new compounds, and compound 5 was isolated from the rhizomes of Anemarrhena asphodeloides Bunge for the first time.</p>

Preliminary study on hematopoietic constituents of si-wu-tang / 中国中药杂志

<p><b>OBJECTIVE</b>To make preliminary study on the chemical foundation of hematopoietic effect of si-wu-tang.</p><p><b>METHOD</b>Si-wu-tang was fractionated by using precipitation method with ethanol and liquid-liquid extraction. Activity was investigated on radiated mice as model of blood deficiency.</p><p><b>RESULT</b>At first si-wu-tang was separated into three fractions, fraction A, B and C. Activity study showed that fraction B and C could raise the amount of peripheral white blood cell in radiated mice. Then fraction B and C were respectively further separated into fraction B1, B2, B3 and fraction C1, C2, C3. Activity study showed that fraction C2, C3 and B3 could raise the amount of peripheral white blood cell in radiated mice. Furthermore, effect of fraction C1, C2, C3, B and paeoniflorin on hematopoietic progenitor cell in bone marrow of radiated mice were investigated. Fraction C2, C3, B and paeoniflorin could promote the proliferation of hematopoietic progenitor cell in bone marrow of radiated mice.</p><p><b>CONCLUSION</b>Fraction C2, C3, B and paeoniflorin are responsible for hematopoietic activity of si-wu-tang.</p>

Investigation of constituents in siwu tang fractions by chromatographic and ESI-MS methods / 中国中药杂志

<p><b>OBJECTIVE</b>In order to discuss the chemical foundation of hematopoietic effect of Siwu Tang, three fractions of different polarities (C1, C2 and C3) were prepared from Siwu Tang and the characteristics of these fractions' constituents were investigated.</p><p><b>METHOD</b>Fraction C1, C2 and C3 of Siwu Tang and corresponding fractions of Siwu Tang's four ingredient drugs were analyzed and compared, synthetically using the three methods of high-performance thin layer chromatography (HPTLC), high-performance liquid chromatography (HPLC) and direct infusion electrospray ionization mass spectrometry (ESI-MS).</p><p><b>RESULT</b>Fraction C1 of Siwu Tang contained various types of compounds, including ferulic acid, paeoniflorin and supposedly ligustilide, etc. Saccharide content in fraction C1 was very little. The major constituents in fraction C2 of Siwu Tang were paeoniflorin, monosaccaride and disaccharide. The major constituents in fraction C3 of Siwu Tang were monosaccaride and disaccharide.</p><p><b>CONCLUSION</b>With synthetical chromatographic and direct infusion ESI-MS methods, abundant information on composition of fractions of traditional Chinese medicine formulas can be obtained. The results gained with different methods can be compared with each other and corroborate each other, so that the obtained information can be more comprehensive and more definite than that gained with single method. The results of this study are important as references for the discussion of the chemical foundation of hematopoietic effect of Siwu Tang.</p>

Investigations on the molecular mechanisms of saponins from Anemarrhena asphodeloides Bunge using oligonucleotide microarrays / 药学学报

<p><b>AIM</b>To investigate the molecular mechanisms of saponins from the rhizome of Anemarrhena asphodeloides Bunge.</p><p><b>METHODS</b>Oligonucleotide microarrays consisting of 87 probes representing 87 human cardiovascular disease-related genes were constructed. Effects of saponins on gene expression in human umbilical vein endothelial cells were analyzed by comparing hybridization of Cy 5-labeled cDNAs from saponins-treated human umbilical vein endothelial cells and Cy 3-labeled cDNAs from untreated human umbilical vein endothelial cells.</p><p><b>RESULTS</b>The results indicate that angiotensinogen gene, alpha 2A-adrenoceptor gene and endothelin-converting enzyme 1 gene were downregulated 2.8, 1.9 and 3.1 folds respectively after human umbilical vein endothelial cells were incubated in medium containing 80 mg.L-1 saponins.</p><p><b>CONCLUSION</b>These results suggest that saponins may have beneficial effect on cardiovascular diseases by modulating the function of vein endothial cells and microarray can be used to investigate the biological action of extracts from traditional Chinese medicine.</p>