To explore the permeation mechanism of micro-molecule medicinal ingredients of water extract of tradition Chinese medicine(TCM) in membrane separation process. With phenolic acid components as the model solute, five phenolic acids with similar molecular weight and structure, namely gallic acid, protocatechuate acid, 4-hydroxybenzoic acid, 3-hydroxybenzoic acid and salicylic acid, were selected in the PES membrane separation experiments. With the relative flux and the transmission rate as indexes, the scanning electron microscopy(SEM) and the electrochemical impedance spectroscopy(EIS) were used to analyze the permeation mechanism of different phenolic acid components. The results showed phenolic acids with similar molecular weight had different permeation behaviors, with decreased relative flux and increased solute permeation with the increase of solute concentration. According to the permeation behavior analyzed by the molecular structure of solute, the transmission rate of phenolic acids increased with the increase of the number of hydroxyl, and the order of substituent positions of phenolic acids based on the permeation rate as follows: para-substituted > meta-substitution > ortho-substitution. Electrochemical impedance spectroscopy reflected the role of charge repulsion in the membrane process; that is to say, the greater the resistance is, the less the solute permeation is. Therefore, the permeation phenomenon of the phenolic acid components in the PES membrane is not only the result of simple sieving mechanisms, but also has the effects of steric hindrance and charge repulsion during the membrane process.
Drugs, Chinese Herbal/analysis* ; Hydroxybenzoates/isolation & purification* ; Medicine, Chinese Traditional ; Membranes, Artificial ; Molecular Structure ; Molecular Weight

There were significant differences in phenolic acid content between fresh and dried Salvia miltiorrhiza before and after drying. That is to say, the content of phenolic acid in S. miltiorrhiza significantly increased with the increase of dehydration during the drying process.In order to investigate the differences and transformation of free and bound phenolic acids before and after the drying process of S.miltiorrhiza, we studied hydrolysis method, hydrolysates and hydrolysis regularity of phenolic acids in S.miltiorrhiza. UPLC method was used to determine four main hydrolysates of bound phenolic acids, namely danshensu, caffeic acid dimer(SMND-309), caffeic acid, przewalskinic acid A(prolithosperic acid), and three main free phenolic acids in S.miltiorrhiza, namely rosmarinic acid, lithospermic acid, salvianolic acid B. The results of the acid-base hydrolysis experiment of salvianolic acid showed that the alkaline hydrolysis effect was significantly better than acid hydrolysis. The optimal alkaline hydrolysis condition was hydrolysis at 70 ℃ for 4 h with 2 mol·L~(-1) NaOH solution containing 1% ascorbic acid(Vit C). The hydrolysates of free phenolic acids were the same with the hydrolysates of bound phenolic acids. Fresh S.miltiorrhiza contains a low level of free phenolic acids and a high level of bound phenolic acids, which were exactly opposite to dried S.miltiorrhiza. It was suggested that a large amount of bound phenolic acids was accumulated during the growth of S.miltiorrhiza. These bound phenolic acids were coupled with polysaccharides on the cytoderm through ester bonds to form insoluble phenolic acids, which was not easy to be detected by conventional methods. However, during drying and dehydration processes, the bound phenolic acids were converted to a large amount of free phenolic acids under the action of the relevant enzyme.
Desiccation ; Hydroxybenzoates/analysis* ; Salvia miltiorrhiza/chemistry*

To study the non-flavonoids chemical constituents in water extract of Spatholobi Caulis. Some purification and analysis techniques like silica gel, D101-macroporous adsorptive resins, and Sephadex LH-20 column chromatographies as well as reversed phase high-performance liquid chromatography were used to isolate and analyze the phenolic acid esters and other type compounds from Spatholobi Caulis integrally. The structures of these compounds were identified by spectroscopic techniques such as nuclear magnetic resonance and high resolution mass spectrometries. Twenty-seven compounds, including phenolic acid, coumarin, lignan, terpene, alkaloid, and steroid compounds, were isolated from ethyl acetate and n-butanol fractions in water extract of Spatholobi Caulis, and they were identified as β-sitosterol(1), feruli acid methyl ester(2), syringaresinol(3),(+)-medioresinol(4),(+)-epipinoresinol(5), p-acetylphenol(6), bolusanthin Ⅳ(7), evofolin B(8), salicylic acid(9), trans-p-hydroxy-cinnamic acid(10), abscisic acid(11), m-hydroxyphenol(12), C-veratroylglycol(13), p-hydroquinone(14), 8,9-dihydroxymegastigma-4,6-dien-3-one(15), p-hydroxybenzoic acid(16), 6,9-dihydroxymegastigma-4,7-dien-3-one(17), protocatechuic acid(18), protocatechuic acid methyl ester(19), 5,7-dihydroxycoumarin(20), isolariciresinol(21), nicotinic acid(22), daucosterol(23),(+)-pinoresinol(24), stigmasterol(25), allantoin(26) and koaburaside(27), respectively. Furthermore, compounds 2-15, 19-22, 24 and 26 were isolated from genus Spatholobus for the first time.
Drugs, Chinese Herbal/analysis* ; Esters/analysis* ; Fabaceae/chemistry* ; Hydroxybenzoates/analysis* ; Mass Spectrometry ; Phytochemicals/analysis*

Ten batches of Angelica sinensis from three producing areas( Tuoxiang,Minxian and Weiyuan of Gansu province) were selected as the research objects,and processed into raw A. sinensis,A. sinensis with alcohol,and A. sinensis with soil respectively through the standard processing methods. Ultra-high performance liquid chromatography( UPLC) was used to establish fingerprint for three processed products of A. sinensis,and determine the contents of 9 phenolic acids and phthalide compounds. The similarity was analyzed with Similarity Evaluation System for Chromatographic Fingerprint of Traditional Chinese Medicine,which showed that the chromatographic peaks of the same processed samples of A. sinensis were basically similar,with all similarities greater than 0. 950. The difference between different processed products and their control spectra was not obvious,with all similarities also higher than 0. 950.On the basis of using principal component analysis( PCA) and OPLS-DA to seek the difference components between groups,the improved distance coefficient method can be used to effectively distinguish the three processed products of A. sinensis by fingerprint similarity. At the same time,the determination method of nine phenolic acids and phthalide in A. sinensis was established by UPLC,and the comparison between different processed products was carried out. The results showed that the content of various components was changed as compared with the raw A. sinensis. The contents of coniferyl ferulate and ligustilide in the A. sinensis with alcohol were increased significantly,and the content of coniferyl ferulate was obviously increased in A. sinensis with soil. The method established in this paper can effectively distinguish different processed products of A. sinensis and determine the content of the main components in them.
4-Butyrolactone ; analogs & derivatives ; analysis ; Angelica sinensis ; chemistry ; Benzofurans ; analysis ; Chromatography, High Pressure Liquid ; Coumaric Acids ; analysis ; Drugs, Chinese Herbal ; analysis ; Hydroxybenzoates ; analysis ; Medicine, Chinese Traditional ; Principal Component Analysis

The study aims to qualitatively and quantitatively analyze phenolic acids and flavonoids in Artemisiae Argyi Folium cultivated in Qichun(Qiai) for the quality control of this genuine regional herbs. UPLC-LTQ-Orbitrap-MS was used for rapid separation and structural identification of the constituents. Samples were separated on an UPLC column(2. 1 mm×100 mm,1. 8 μm) by gradient elution using 0. 1% formic acid and acetonitrile as mobile phases at a flow rate of 0. 4 m L·min-1. By UPLC-LTQ-Orbitrap-MS,16 compounds including phenolic acids and flavonoids were identified by comparison with reference standards or literature data. For quantitative analysis,12 identified compounds were simultaneously determined by UPLC-DAD at wavelengths of 330 nm. The method was validated with respect to linearity,precision,repeatability,stability and recovery. The contents of these compounds were found to differ significantly between the samples from Qichun and other areas. This strategy was novel,effective and straightforward,which provided a potential approach for holistic quality control of Qiai.
Artemisia ; chemistry ; Chromatography, High Pressure Liquid ; Drugs, Chinese Herbal ; analysis ; Flavonoids ; analysis ; Hydroxybenzoates ; analysis ; Mass Spectrometry ; Phytochemicals ; analysis ; Plant Leaves ; chemistry

To construct a quality management model for the whole industry chain of compound Danshen Tablets,and quality control system for all key links in the production of compound Danshen Tablets. In this paper,with salvianolic acid B as internal reference substance,three batches of mix standards were prepared,and three sets of relative correlation factors between salvianolic acid B and other phenolic acids were calculated in parallel. Finally,the correlation factors are obtained on average. The quality transfer process was studied by optimizing the concentration of Salvia miltiorrhiza extract. The results showed that RSD among three sets of relative correlation factors ranged between 1. 7%-4. 1%,with no significant difference between the quantitative result of two methods. In addition,the quality transfer study showed that with the rise of the concentration temperature,the content of phenolic acid components changed,which had a significant effect on the salvianolic acid B at more than 80 ℃. It was suggested to rationally control the concentration temperature during the industrial production. The results of this study provide a methodology for the establishment of the quality control system for the whole industry chain of compound Danshen Tablets,and quality control methods for the improvement of the quality of medicinal materials and finished medicine products.
Chromatography, High Pressure Liquid ; Drugs, Chinese Herbal ; chemistry ; Hydroxybenzoates ; analysis ; Quality Control ; Salvia miltiorrhiza ; chemistry ; Tablets

Artemisiae Argyi Folium,the dried leaves of Artemisia argyi,has been widely used in traditional Chinese and folk medicines for a long time. Qiai is one of the top-geoherb of Artemisiae Argyi Folium. Trying to investigate dynamic changes of chemical components of Qiai in different harvest periods and explore the optimum harvest time of Qiai,in this study,the contents of total flavonoids and total phenolic acids of 36 batches of Qiai collected in 6 different harvest periods were analyzed by ultraviolet-visible spectrophotometry. Furthermore,an HPLC method was applied for simultaneous determination of eight bioactive compounds including six phenolic acids( 5-caffeoylquinic acid,3-caffeoylquinic acid,4-caffeoylquinic acid,3,4-di-O-caffeoylquinic acid,3,5-di-O-caffeoylquinic acid and 4,5-di-O-caffeoylquinic acid) and two flavonoids( jaceosidin and eupatilin) in Qiai samples. The quantitative results indicated that there were some differences in the contents of total flavonoids,total phenolic acids and bioactive compounds of Qiai samples in different harvest periods. The dynamic changes of total flavonoids and total phenolic acids of Qiai in different harvest periods were consistent. The contents of total flavonoids and total phenolic acids of Qiai samples were higher in the third harvest period( around the Dragon Boat Festival),which is basically consistent with the traditional harvest periods. This present study can provide the basis for determining the suitable harvest time of Qiai,and might be useful for the quality evaluation of this herbal medicine.
Artemisia/chemistry* ; Chromatography, High Pressure Liquid ; Drugs, Chinese Herbal/chemistry* ; Flavonoids/analysis* ; Hydroxybenzoates/analysis* ; Plant Leaves/chemistry* ; Spectrophotometry, Ultraviolet ; Time Factors

This present study aims to establish a UPLC method for simultaneously determining eleven components such as new chlorogenic acid,chlorogenic acid,caffeic acid,cryptochlorogenic acid,artichoke,isochlorogenic acid A,isochlorogenic acid B,isochlorogenic acid C,rutin,hibisin and loganin in Lonicerae Japonicae Flos,Lonicerae Japonicae Caulis and leaves of Lonicera japonica and comparing the differences in the contents of phenolic acids,flavonoids and iridoid glycosides of Lonicerae Japonicae Flos,Lonicerae Japonicae Caulis and leaves of Lonicera japonica.The method was carried out on an ACQUITY UPLC BEH C18column(2.1 mm×100 mm,1.7 μm) by a gradient elution using acetonitrile and 0.1% phosphoric acid.The flow rate was 0.3 mL·min-1.The column temperature was maintained at 30 ℃.The sample room temperature was 8 ℃.The wavelength was set at 326 nm for new chlorogenic acid,chlorogenic acid,caffeic acid,cryptochlorogenic acid,artichoke,isochlorogenic acid A,isochlorogenic acid B and isochlorogenic acid C,352 nm for rutin and lignin,and 238 nm for loganin.The injection volume was 1 μL.The eleven components has good resolution and was separated to baseline.Each component had a wide linear range and a good linear relationship(r≥0.999 6),the average recovery rate(n=9) was 98.96%,100.7%,97.24%,97.06%,99.53%,96.78%,98.12%,95.20%,95.12%,100.2%,98.61%and with RSD was 2.5%,1.4%,1.9%,2.1%,1.7%,1.9%,1.6%,2.0%,1.4%,2.2%,2.0%,respectively.Based on the results of the content determination,the chemometric methods such as cluster analysis and principal component analysis were used to compare the Lonicerae Japonicae Flos,Lonicerae Japonicae Caulis and leaves of Lonicera japonica.The results showed that Lonicerae Japonicae Flos and leaves of Lonicera japonica were similar in the chemical constituents,but both showed chemical constituents difference compored to Lonicerae Japonicae Caulis.The established multi-component quantitative analysis method can provide a reference for the quality control of Lonicerae Japonicae Flos,Lonicerae Japonicae Caulis and leaves of Lonicera japonica.
Chromatography, High Pressure Liquid ; Drugs, Chinese Herbal ; chemistry ; Flavonoids ; analysis ; Flowers ; chemistry ; Hydroxybenzoates ; analysis ; Iridoid Glycosides ; analysis ; Lonicera ; chemistry ; Phytochemicals ; analysis ; Plant Leaves ; chemistry ; Quality Control

A quick HPLC-ESI-MS/MS method was established for simultaneous determination of three chemical compositions in Usnea, including usnic acid, diffractaic acid, and ramalic acid. The separation was performed on a chromatographic column of Agilent ZORBAX SB-C, (4.6 mm x 250 mm, 5 µm), and the mobile phase was methanol (0.05% formic acid)-0.05% formic acid solution (4 mmol ammonium acetate), with an isocratic elution at a flow rate of 0.8 ml · min⁻¹. Multiple reaction monitoring scanning mode (MRM) was performed combined with the ion switching technology in positive and negative ion switching mode to apply for the quantitative determination. The calibration curves for the above three compounds were linear in corresponding injection amount. Their average recoveries were 95.0%-105.1%, with RSDs of 1.1%-5.2%. The method was simple, rapid, accurate with high repeatability, which could provide a reference for overcalling evaluation the quality of Usnea.
Chromatography, High Pressure Liquid ; methods ; Hydroxybenzoates ; analysis ; Spectrometry, Mass, Electrospray Ionization ; methods ; Tandem Mass Spectrometry ; methods ; Usnea ; chemistry

To provide a scientific basis for the selection of the appropriate drying method for Mentha Haplocalyx Herba (MHH), determine 2 monoterpenes, 4 phenolic acids and 5 flavonoids in MHH by GC-MS and UPLC-TQ-MS methods, and investigate the effects of the drying methods on the changes in contents of these analytes. The qualities of products obtained with different drying methods were evaluated by the multivariate statistical method of Technique for Order Preference by Similarity to Ideal Solution (TOPSIS). Results showed that the drying methods had the greatest impact on menthol, caffeic acid, and rosemary acid, which were followed by chlorogenic acid and diosmetin-7-O-glucoside. The contents in these analytes processed with hot-air-drying method were higher than those with microwave-drying and infrared-drying methods at the same temperatures. The contents in these analytes processed under low temperature (40-45 °C) were higher than those under higher temperature (60-70 °C). Above all, the contents in phenolic acids processed with microwave fixation (exposed under microwave at 100 °C for several minutes) were obviously higher than those of not being processed, showing an inhibition of some enzymes in samples after fixation. The TOPSIS evaluation showed that the variable temperature drying method of 'Hot-Air 45-60 °C' was the most suitable approach for the primary drying processing of MHH. The results could provide the scientific basis for the selection of appropriate drying method for MHH, and helpful reference for the primary drying proces of herbs containing volatile chemical components.
Desiccation ; methods ; Flavonoids ; analysis ; Hydroxybenzoates ; analysis ; Mentha ; chemistry ; Monoterpenes ; analysis