Comparative analysis of chemical constituents in hawthorn leaves from different sources / 药学学报

We identified and analyzed the components and chemical constituents of hawthorn leaves of Crataegus pinnatifida Bge. (wild) and C. pinnatifida Bge. var major N. E. Br (cultivated) by using ultra high-performance liquid chromatography and quadrupole time-of-flight mass spectrometry (UHPLC-Q-TOF/MSE) combined with UNIFI data analysis platform and multivariate statistics. Fifty-eight chemical compounds were identified, including organic acids, flavonoids, triterpenoic acids, monoterpenes and sesquiterpenoids; among them, terpenoid content was the most abundant. Principal component analysis (PCA) and orthogonal partial least squares discriminant analysis (OPLS-DA) were used to identify the differential components of hawthorn leaves from two sources. The results show that there are differences in the chemical compositions of the two sources, including 24 flavonoids and terpenoids (including monoterpenoids, sesquiterpenoids and triterpenoid acids). The types of flavonoids (such as rutin, vitexin-2''-O-rhamnoside, isovitexin-2''-O-rhamnoside, hyperoside, quercetin-3-O-β-D-glucoside) and terpenoids (crataegolic acid, corosolic acid and ursolic acid) in C. pinnatifida were more varied than those found in C. pinnatifida Bge. var major N. E. Br, and their contents were relatively higher. This study provides a comprehensively analysis of the different chemical components of hawthorn leaves from two sources listed in the Chinese Pharmacopoeia, and provides a basis for the selection of raw materials and the potential development and utilization of hawthorn leaves.

Progress in research and development of Xanthoceras sorbifolia / 中国中药杂志

Xanthoceras sorbifolia, an excellent oil-rich woody species, has high comprehensive economic value in edible, medicinal, and ornamental fields. The chemical composition, pharmacological effect, and quality control of X. sorbifolia were introduced, and its development and application were reviewed in this study. As revealed by the previous research, the main chemical constituents of X. sorbifolia were triterpenoids, flavonoids, fatty acids, phenylpropanoids, steroids, phenolic acids, organic acids, etc. It possesses pharmacological effects, such as neuroprotection, bacteriostasis, anti-oxidation, anti-tumor, anti-inflammation, analgesia, anti-HIV, and anti-coagulation. X. sorbifolia is widely applied in medical, food, chemical industry, and other fields, and deserves in-depth research and development.

Terpenoids from leaves of Chinese hawthorn / 中国中药杂志

Fifteen compounds were isolated from the 70% EtOH extract of leaves of Chinese hawthorn(Crataegus pinnatifida var. major) by various purification steps, and their structures were determined as 2α,3α,12β,19α,-tetrahydroxyursan-13β,28-olide(1),euscaphic acid(2), tormentic acid(3), ursolic acid(4), pomolic acid(5), corosolic acid(6), maslinic acid(7), linalyl rutinoside(8),(Z)-3-hexenyl β-D-glucoside(9),(3S, 6S)-cis-linalool-3,7-oxide-β-D-glucopyranoside(10), pisumionoside(11), icariside B6(12), byzantionoside B(13),(6R,7E,9R)-9-Hydroxy-4,7-megastigmadien-3-one 9-O-β-D-glucopyranoside(14) and(6S,7E,9R)-6,9-dihydroxy-4,7-megastigmadien-3-one 9-O-β-D-glucopyranoside(15) mainly based on the mass spectrum(MS) and nuclear magnetic resonance(NMR) spectroscopic techniques, of which compound 1 was a new pentacyclic triterpene, and compounds 2, 5, 6, 8, 10, 13 and 15 were isolated form this plant for the first time.

Non-alkaloid constituents of Hymenocallis littoralis / 中国中药杂志

Perennial herb Hymenocallis littoralis(Amaryllidaceae) boasts anti-tumor, anti-virus, and anti-inflammatory activities. As the representative constituents, alkaloids have attracted much attention, whereas the non-alkaloid constituents have been rarely reported. Therefore, this study investigated the non-alkaloid constituents of H. littoralis and their contribution to the various pharmacological activities of the herb. Thirteen non-alkaloid compounds were isolated from the 95% ethanol extract of dried whole plant of H. littoralis after a series of chromatographic separation steps and spectral analysis, and they were identified as 5,7-dihydroxy-6,8-dimethoxy-2-hydroxymethyl-4H-chromoen-4-one(1), undulatoside A(2),(2S)-7,4'-dihydroxyflavane(3), naringenin(4), 4',7-hydroxy-8-methylflavanone(5), 8-methylnaringenin(6), 8-demethylfarrerol(7), 6-methyl-aromadendrin(8), 4',5,7-trihydroxy-8-methylflavanone(9), syzalterin(10), 6-methylapigenin(11), isoliquiritigenin(12), and undatuside C(13) based on the spectroscopic data analysis. Among them, compound 1 was a new chromone derivative, and compounds 2 and 4-13 were isolated form this plant for the first time.

Four new dammarane-type triterpenoid saponins from Gynostemma longipes C.Y.Wu / 药学学报

Dammarane-type triterpenoid saponins are regarded as the main active constituents of Gynostemma longipes C.Y.Wu. By using MCI and silica gel column chromatography, as well as preparative HPLC, we isolated four new dammarane-type triterpenoid saponins from the polar saponin fraction of G. longipes C.Y.Wu. Their structures were determined by comprehensive analyses of NMR and MS data and identified as (20S)-3β,20,21-trihydroxydammar-19-oxo-24-ene-3-O-{[α-L-rhamnopyranosyl(1→2)]-[β-D-xylopyranosyl(1→3)]-α-L-arabinopyranosyl}-21-O-β-D-glucopyranosyl(1→6)-β-D-glucopyranoside (1), (20S)-3β,20,21-trihydroxydammar-24-ene-19-oxo-3-O-[α-L-rhamnopyranosyl(1→2)]-[β-D-xylopyranosyl(1→3)]-α-L-arabinopyranosyl-21-O-α-L-rhamnopyranosyl(1→6)-β-D-glucopyranoside (2), (20S)-3β,19,20,21-terahydroxydammar-24-ene-3-O-{[α-L-rhamnopyranosyl(1→2)]-[β-D-xylopyranosyl(1→3)]-α-L-arabinopyranosyl}-21-O-[β-D-glucopyranosyl(1→6)]-β-D-glucopyranoside (3), (20S)-3β,20,21-trihydroxydammar-24-ene-3-O-{[α-L-rhamnopyranosyl(1→2)]-[β-D-glucopyranosyl(1→3)]-β-D-glucopyranosyl}-21-O-[β-D-glucopyranosyl(1→6)]-β-D-glucopyranoside (4). Compounds 1-4 are new dammarane-type triterpenoid saponins which contain five glycosyl residues.

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.

Evaluation of cultivated and wild Herba Epimedii using UHPLC-PDA-Q-TOF/MSE / 药学学报

Qualitative and relatively quantitative methods were used to study the quality of cultivated Epimedium sagittatum (Sieb. et Zucc.) Maxim., Epimedium myrianthum Stearn, and Epimedium pubescens Maxim by ultra high-performance liquid chromatography coupled with photo-diode array and quadrupole time-of-flight mass spectrometry (UHPLC-PDA-Q-TOF/MSE). Thirty-two compounds in cultivated and wild samples of E. sagittatum, E. myrianthum and E. pubescens were identified using UHPLC-Q-TOF/MSE combined with the UNIFI data analysis platform. Principal component analysis (PCA) was used to compare the cultivated and wild samples of these three species. The results show that the chemical compositions of cultivated samples were consistent with the corresponding wild samples. UHPLC-PDA was used to determine the relative content of 12 flavonoids as well as total flavonoids in all samples. The results show that the relative chemical content of these flavonoids in cultivated and wild samples is similar and the quality of cultivated Epimedium is more stable. These qualitative and relatively quantitative methods using UHPLC-PDA-Q-TOF/MSE combined with the UNIFI data analysis platform and PCA can be used to study the quality of cultivated Herba Epimedii. This research provides a scientific basis for the cultivation and rational development and utilization of Epimedium medicinal materials.

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.

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.

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.

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.

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.

Chromatographic fingerprint analysis of Toosendan Fructus by HPLC-CAD coupled with chemometrics methods / 药学学报

A new method was developed for the chromatographic fingerprint analysis of Toosendan Fructus by HPLC coupled with the charged aerosol detector (CAD) in the present study. Samples were well separated on an Agilent ZOBAX SB C18 column (4.6 mm×250 mm, 5 μm) by gradient elution using acetonitrile and water containing 0.1% formic acid (v/v) at the flow rate of 1.0 mL·min-1. The column temperature was 30℃ and the injection volume was 5 μL. The nitrogen inlet pressure of the charged aerosol detector (CAD) was 35 psi, and the nebulizer chamber temperature was 35℃. In addition, the method of the chromatographic fingerprints combined with multivariate statistical analysis was effective and reasonable lead to an accurate classification of 20 batches of samples from different locations. The results showed that 28 common peaks were observed in the fingerprint and the samples were classified into three clusters. The established method was well validated, and showed high precision, good repeatability, and satisfactory stability. It may serve in the quality control and evaluation of Toosendan Fructus.

Determination of three saponins in rhizoma and fibrous root of Trillium tschonoskii and Trillium kamtschaticum / 中国中药杂志

To compare the differences of main components between in rhizoma and fibrous root of Trillium tschonoskii and T. kamtschaticum, a simple, accurate and reliable high performance liquid chromatography coupled with the charged aerosol detector (HPLC-CAD) method was developed and then successfully applied for simultaneous quantitative analysis of three compounds, including polyphyllin Ⅶ (T1),pennogenin 3-O-α-L-rhamnopyranosyl-(1→2) [α-L-rhamnopyranosyl-(1→4)]-β-D-glucopyranoside (T2),polyphyllin Ⅵ (T3), in 16 batches of rhizome and 14 batches of fibrous root. The analytes were well separated from other constituents on TSK gel ODS (4.6 mm×250 mm, 5 μm) with acetonitrile-water (43∶57) at a flow rate of 1.0 mL•min⁻¹. The injection volume was 20 μL. The nitrogen inlet pressure for the CAD system was 35 psi and the nebulizer chamber temperature was 35 ℃.The method was validated for linearity (r>0.999 0), intra and inter-day precision (0.29%-3.0%), repeatability (0.45%-1.4%), stability (1.9%-2.6%), recovery (100.1%-100.2%, 1.2%-1.8%), limits of detection (0.002 g•L⁻¹), and limits of quantification (0.005 g•L⁻¹).The obtained datasets were processed by principal component analysis (PCA) and it showed that there was almost no difference in rhizoma of T. tschonoskii and T. kamtschaticum from different areas of China. However, the 3 major compounds existed in rhizoma were different from those in fibrous root of T. tschonoskii and T. kamtschaticum.

Analysis of chemical markers in sulfur-fumigated Anemarrhenae Rhizoma / 中国中药杂志

Sulfur-containing Anemarrhenae Rhizoma decoction pieces were prepared by using sulfur-fumigating procedure. The difference components before and after sulfur fumigation in Anemarrhenae Rhizoma were analyzed and on-line identified by UPLC-Q-TOF-MSE combined with UNIFI informatics platform, principal component analysis (PCA) and orthogonal partial least squares discriminant analysis (OPLS-DA) respectively. As a result, 16 major differences components were identified, and among them, 9 components were mainly from sulfur-fumigated samples. The main chemical markers in sulfur-fumigated Anemarrhenae Rhizoma were identified as the sulfite derivatives newly produced after sulfur-fumigating. Meanwhile, UPLC-Q-TOF-MSE was used to find the main chemical marker anemarrhena saponin BⅡ sulfite (m/z 983). By using this method, a rapid screening method for sulfur-fumigated Anemarrhenae Rhizoma was established. This was a convenient and accurate detection method for sulfur dioxide residue, and it can be used as an effective assistant method to control the quality of Anemarrhenae Rhizoma. At the same time, it was the first time to identify sulfited derivatives of steroidal saponins, and screen the sulfur-fumigated Anemarrhenae Rhizoma.

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.

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.

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.

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>

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.