ABSTRACT
ObjectiveBased on ultra performance liquid chromatography-quadrupole-time-of-flight mass spectrometry（UPLC-Q-TOF-MSE） technique， we identified qualitatively the metabolites of aristolochic acid（AAs） in rat in order to analyze the metabolic differences between water extract of Aristolochiae fructus（AFE） and Aristolochic acid Ⅰ（AAⅠ）. MethodSD rats were selected and administered AFE（110 g·kg-1·d-1） or AAⅠ（5 mg·kg-1·d-1） by oral for 5 days， respectively. Serum， urine and feces were collected after administration. Through sample pretreatment， ACQUITY UPLC BEH C18 column（2.1 mm×100 mm， 1.7 μm） was used with the mobile phase of 0.01% formic acid methanol（A）-0.01% formic acid water（B， containing 5 mmol·L-1 ammonium acetate） for gradient elution（0-1 min， 10%B； 1-7 min， 10%-75%B； 7-7.2 min， 75%-95%B； 7.2-10.2 min， 95%B； 10.2-10.3 min， 95%-10%B； 10.3-12 min， 10%B） at a flow rate of 0.3 mL·min-1. Positive ion mode of electrospray ionization（ESI+） was performed in the scanning range of m/z 100-1 200. In combination with UNIFI 1.9.4.053 system， the Pathway-MSE was used to qualitatively analyze and identify the AAs prototype and related metabolites in biological samples（serum， urine and feces）， and to compare the similarities and differences of metabolites in rats in the subacute toxicity test between AFE group and AAⅠ group. ResultCompared with AAⅠ group， 6， 10， 13 common metabolites and 14， 20， 30 unique metabolites were identified in biological samples（serum， urine and feces） of AFE group， respectively. Moreover， the main AAs components always followed the metabolic processes of demethylation， nitrate reduction and conjugation. Compared with common metabolites in AAⅠ group， prototype components of AAⅠ in serum and most metabolic derivatives of AAⅠ［AAⅠa， aristolochic lactam Ⅰ（ALⅠ）a， 7-OHALⅠ and its conjugated derivatives］ in biological samples were significantly increased in AFE group（P<0.05， P<0.01）， except that the metabolic amount of ALⅠ in feces of AFE group was remarkably lowed than that of AAⅠ group（P<0.01）. In addition， a variety of special ALⅠ efflux derivatives were also identified in the urine and feces of the AFE group. ConclusionAlthough major AAs components in AFE all show similar metabolic rules as AAⅠ components in vivo， the coexistence of multiple AAs components in Aristolochiae Fructus may affect the metabolism of AAⅠ， and achieve the attenuating effect by increasing the metabolic effection of AAⅠ and ALⅠ.
ABSTRACT
In this study, ultra performance liquid chromatography-quadrupole-time of flight mass spectrometer-MSE (UPLC-Q-TOF-MSE) combined with UNIFI analysis platform was used to rapidly analyze and identify the metabolites of hederagenins 3-O-α-L-rhamnosyl-(1→2)-[β-D-glucopyranosyl-(1→4)]-α-L-arabopyranoside (Pulsatilla saponin D) and oleanolic acid 3-O-α-L-rhamnosyl-(1→2)-[β-D-glucopyranosyl-(1→4)]-α-L-arabopyranoside (Pulsatilla saponin B7) and hederagenins 3-O-α-L-rhamnosyl-(1→2)-α-L-arabopyranoside (Pulsatilla saponin BD) in plasma and colonic tissue of normal and ulcerative colitis (UC) rats. The database and analysis methods were established based on the precise molecular weight of compounds, retention time, neutral loss and reported data, and then the final data were obtained by comparing with the blank control group, combining with the deviation and the cracking rule of the compound. The results showed that the glucoses, hydroxylation and dehydroxylation, methylation and demethylation, dehydrogenation, decarboxylation and hydrolysis of saponin D, B7 and BD occurred in the plasma and colon tissues of normal and UC model rats. This study will clarify the metabolic transformation of Pulsatilla saponins D, B7 and BD in rats, determine the prototype components and their metabolites that enter the body, and whether colon injury will affect their metabolism in vivo, so as to explore the possible anti-colitis effective components in the prototype or metabolites of Pulsatilla saponins D, B7 and BD. This experiment was approved by Animal Ethics Committee of Jiangxi Science and Technology Normal University (approval number: Y202227).
ABSTRACT
ObjectiveIn order to explore the changes of chemical constituents in Plantaginis Semen before and after stir-frying， ultra-high performance liquid chromatography-quadrupole-time-of-flight mass spectrometry （UPLC-Q-TOF/MSE） was used to rapidly identify and semi-quantitatively analyze the differential components in Plantaginis Semen processed at different stir-frying time. MethodWaters ACQUITY UPLC BEH C18 column （2.1 mm×100 mm， 1.8 μm） was employed with the mobile phase of 0.1% formic acid aqueous solution （A）-acetonitrile （B） for gradient elution （0-1 min， 5%-10%B； 1-2 min， 10%-15%B； 2-10 min， 15%-20%B； 10-12 min， 20%-40%B； 12-13 min， 40%-100%B； 13-14 min， 100%-5%B； 14-15 min， 5%B）， the flow rate was 0.3 mL·min-1， the column temperature was 40 ℃， and the injection volume was 3 μL. Electrospray ionization （ESI） was applied for mass spectrometric analysis under positive and negative ion modes， and the scanning range was m/z 50-1 500. MarkerLynx 4.1 software was used to find the differential compounds， and the intensity of each ion peak in samples with different stir-frying time was compared to study the content variations of these compounds. ResultA total of 20 components with potential significant differences were found， among which 17 were identified and 3 were unknown， mainly including phenylethanoid glycosides， iridoid glycosides， alkaloids and others. After processing， the peak intensities of 7 compounds， such as sucrose， geniposidic acid， verbascoside and plantagoguanidinic acid A， in Plantaginis Semen decreased. The peak intensities of orobanchoside， dianthoside and plantain D increased first and then decreased during the stir-frying process. The peak intensities of 10 compounds （decaffeoylacteoside， calceolarioside A， isoacteoside， etc.） increased， and 9 of them were newly generated components. ConclusionThe content and composition of the chemical components in Plantaginis Semen changed significantly after stir-frying， which may be related to the reduction of laxative effect and the enhancement of antidiarrheal and diuretic activities of Plantaginis Semen after stir-frying.
ABSTRACT
Objective:In order to systematically clarify the chemical composition of Jiechangyan Qixiao granules， the main chemical components in this preparation were rapidly identified and assigned by ultra-performance liquid chromatography-quadrupole-time-of-flight mass spectrometry （UPLC-Q-TOF/MS<sup>E</sup>）. Method:ACQUITY UPLC BEH C<sub>18</sub> column （2.1 mm×100 mm， 1.8 μm） was employed for UPLC analysis with the mobile phase of 0.1% formic acid aqueous solution （A）-acetonitrile （B） for gradient elution （0-2 min， 5%B； 2-16 min， 5%-21%B； 16-30 min， 21%-95%B； 30-33 min， 95%B； 33-34 min， 95%-5%B； 34-37 min， 5%B）. The flow rate was 0.3 mL·min<sup>-1</sup>， the column temperature was 30 ℃， and the volume of sample injection was 2 μL. Electrospray ionization （ESI） was applied for scanning under positive and negative ion modes with the scanning range of <italic>m</italic>/<italic>z</italic> 60-1 200. MS<sup>E</sup> mode was used to collect mass spectral data. The ion peaks were identified by comparing with the information of control substances， literature references and self-built database. Result:A total of 102 chemical components were separated and identified in Jiechangyan Qixiao granules， including organic acids， flavonoids and its glycosides， triterpenes， phenylethanoid glycosides， tannins， iridoid glycosides and other components， among which flavonoids and its glycosides were from Drynariae Rhizoma and Crataegi Fructus， phenylethanoid glycosides and iridoid glycosides were from Plantaginis Semen， triterpenoids and tannins were from Crataegi Fructus and Chebulae Fructus. Among the identified chemical constituents， there were 28 from Drynariae Rhizoma， 31 from Plantaginis Semen， 53 from Chebulae Fructus and 58 ingredients from Crataegi Fructus. Conclusion:The established UPLC-Q-TOF/MS<sup>E</sup> can comprehensively and rapidly analyze the chemical constituents in Jiechangyan Qixiao granules， and preliminarily elucidates the chemical composition profile of this granules， which can lay a foundation for further research on the pharmacodynamic material basis and quality control of Jiechangyan Qixiao granules.
ABSTRACT
Gandou decoction (GDD), a well-known traditional Chinese medicine (TCM) formula, has been widely used for decades to treat Wilson's disease (WD) in China due to its remarkable clinical effects. However, the chemical constituents of GDD still remain unclear because of their complexity. In this work, a reliable and sensitive strategy based on ultra-performance liquid chromatography coupled with quadrupole time-of-flight tandem mass spectrometry (UPLC-Q-TOF-MSE) and UNIFI informatics platform was applied to investigate the chemical components in GDD. In total, 96 compounds including anthraqui-nones, alkaloids, protostane triterpenoids, flavonoids, triterpenoid saponins, tannins, curcuminoids, etc, were identified or tentatively characterized from GDD by comparing their retention time, accurate mass within 5 ppm error and MSE fragmentation patterns. Among them, eleven compounds were confirmed unambiguously with reference standards. Representative compounds in different chemical structure types were analyzed in fragmentation patterns and characteristic ions. Moreover, to better understand the chemical contribution of individual herbs to the whole decoction, the corresponding each herb in GDD was also detected. This study developed a rapid method for characterizing the chemical constitu-ents in GDD, which could not only be used for chemical standardization and quality control, but also be helpful for further research of GDD in vivo.
ABSTRACT
Objective:To identify the quality differential markers of different processed products of Glycyrrhiza uralensis dry roots and rhizomes. Method:Ultra-high performance liquid chromatography-quadrupole time-of-flight mass spectrometry (UPLC-Q-TOF-MSE) was used to collect high-precision mass-charge ratio and ion response strength information of the components in G. uralensis dry roots and rhizomes before and after processing by negative ion mode. The data set collected after pretreatment was analyzed with principal component analysis (PCA) and orthogonal partial least squares-discriminant analysis (OPLS-DA) to quickly search the differential components in different processed products of G. uralensis dry roots and rhizomes. Differential components were identified according to the relative molecular weight, fragment ion, mass spectrum database and related literature information, then the migration of components before and after processing was studied. Result:A total of 10 quality differential markers were searched from raw products, roasted products and honey-roasted products of G. uralensis dry roots and rhizomes, mainly derivatives of liquiritin and glycyrrhizic acid. Among them, the contents of 6''-O-acetylliquiritin apioside, 6''-O-acetylliquiritin apioside isomer, 6''-O-acetylliquiritin, formononetin and 11-deoxo-18β-glycyrrhetic acid were the highest in the raw products, the contents of 6''-O-acetylisoliquiritin apioside, 6''-O-acetylisoliquiritin, isoliquiritin and glycyrrhetic acid 3-O-glucuronide were the highest in the roasted products, the content of liquiritin was the lowest in the honey-roasted products. Conclusion:There are some chemical differences among the three products. This study can provide material basis for the quality control and pharmacodynamic research of processed products of G. uralensis dry roots and rhizomes.
ABSTRACT
Objective:To quickly analyze and identify the differential chemical compositions of Aurantii Fructus Immaturus before and after stir-frying with bran and chemical compositions of wheat bran after processing by ultra-high performance liquid chromatography-quadrupole time-of-flight mass spectrometry （UPLC-Q-TOF-MSE） combined with UNIFI database screening method. Method:ACQUITY UPLC BEH C18 column （2.1 mm×100 mm， 1.7 µm） was used for chromatographic separation with 0.1% formic acid solution （A）-acetonitrile （B） as the mobile phase for gradient elution （0-11 min， 98%-70%B； 11-15 min， 70%-55%B； 15-16 min， 55%-35%B； 16-20 min， 35%-5%B； 20-20.5 min， 5%-98%B； 20.5-22 min， 98%B） at the flow rate of 0.3 mL·min-1 and the injection volume of 2 µL. The analytes were determined in positive ion mode with electrospray ionization （ESI） and data collection range of m/z 50-1 500. Principal component analysis （PCA） and orthogonal partial least squares discriminant analysis （OPLS-DA） were used to find the component differences between raw and processed products of Aurantii Fructus Immaturus， and the chemical compositions of wheat bran after processing were determined. Result:There were 64 compounds in raw products， 58 compounds in bran-fried products， and 18 compounds in wheat bran.There were 19 different components between raw and processed products of Aurantii Fructus Immaturus， mainly volatile oil， flavonoids， phenolic acid， coumarins and saponins. Conclusion:Based on the analysis of these different components before and after stir-frying with bran and the chemical compositions carried by wheat bran， the stir-frying with bran can alleviate the intensity of Aurantii Fructus Immaturus， which proves the necessity of stir-frying with bran for the processing technology of this herb， and provides a comprehensive experimental basis for research on processing mechanism of Aurantii Fructus Immaturus.
ABSTRACT
To identify major bioactive components and metabolites of Gandou decoction (GDD) in urine of normal and copper-laden rats, an integrative approach that ultra-performance liquid chromatography quadrupole time-of-flight tandem mass spectrometry (UPLC-Q-TOF-MSE) coupled with xenometabolomics analytical platform was established. Mass spectral data information about retention time, accurate m/z and ionic strength of rat urine samples was performed under positive and negative ion modes. Unsupervised principal components analysis (PCA) and supervised orthogonal partial least-squared discriminant analysis (OPLS-DA) were used to reveal the differential ions. As a result, a total of 77 compounds including 45 prototypes and 32 metabolites in urine were detected. Results indicated that anthraquinones, alkaloids and tetracyclic triterpenoids and flavonoids were the main chemical components of GDD in rat urine; the main metabolic pathways of these compounds in rat urine mainly include hydroxyl, methylation, sulfating, glucuronidation, and so on. UPLC-QTOF-MSE coupled with xenometabolomics analytical platform is fast and efficient so that facilitates authentication of the material basis of Chinese herb compound in vivo, can also be used as an effective tool for ascertaining trace bioactive components in vivo. The animal experiments were approved by the Experimental Animal Ethics Committee of Anhui University of Chinese Medicine (No. 2019025).
ABSTRACT
Boswellia serrata is a widely used herb in Indian systems of medicine and is well known for its potential medicinal properties. A chromatographic method was developed for the analysis and quantification of six boswellic acid marker compounds, i.e., keto boswellic acid (1), 3-O-Acetyl 11-keto β-boswellic acid (2), ɑ-Boswellic acid (3), β-Boswellic acid (4), 3-O-Acetyl-ɑ-boswellic acid (5) and 3-O-Acetyl-β-boswellic acid (6) in commercial herbal products containing B. serrata as an ingredient. Combining UPLC with Q-Tof-MS/MS makes the better identification of secondary metabolites and adulterants in the herbal formulations containing B. serrata in rapid time using fragmentation approach than the traditional approaches. In this study quantification of boswellic acids with UPLC-PDA method was performed as per the pharmacopeia guidelines. Furthermore, minor phytochemical constituents were identified and characterized with the help of LC-Q-Tof-MS/MS fragmentation data and various isoforms of boswellic acids and tirucallic acids in B. serrata oleo-gum-resin extract were identified.
ABSTRACT
In this paper, an approach was applied for separation and identification of oligosaccharides in Morinda officinalis How by Ultra performance liquid chromatography/quadrupole time-of-flight mass spectrometry (UPLC-Q-TOF-MS) with collision energy. The separation was carried out on an ACQUITY UPLC BEH Amide C₁₈(2.1mm×100 mm，1.7 μm) with gradient elution using acetonitrile(A) and water(B) containing 0.1% ammonia as mobile phase at a flow rate of 0.2 mL·min⁻¹. The column temperature was maintained at 40 °C. The information of accurate mass and characteristic fragment ion were acquired by MSE in ESI negative mode in low and high collision energy. The chemical structures and formula of oligosaccharides were obtained and identified by the software of UNIFI and Masslynx 4.1 based on the accurate mass, fragment ions, neutral losses, mass error, reference substance, isotope information, the intensity of fragments, and retention time. A total of 19 inulin oligosaccharide structures were identified including D(+)-sucrose, 1-kestose, nystose, 1F-fructofuranosyl nystose and other inulin oligosaccharides (DP 5-18). This research provided important information about the inulin oligosaccharides in M. officinalis. The results would provide scientific basis for innovative utilization of M. officinalis.
ABSTRACT
Objective To establish a UPLC-Q-TOF-MSE fingerprint of Yiqi Fumai Injection (YQFM) for providing reference for visual, easy and overall control of its quality. Methods The chromatographic separation was performed on a Waters Acquity UPLC HSS T3 (100 mm × 2.1 mm, 1.8 μm) column with the mobile phase consisting of acetonitrile and 0.1% formic acid for gradient elution. The flow rate was 0.3 mL/min, and the column temperature was 30 ℃. The capillary voltage was set at 2.5 kV. The nebulization gas was set to 800 L/h at 400 ℃, and the source temperature was 100 ℃. The BPC obtained with negative ion ESI mass spectra were selected for the fingerprint analysis. Similarity evaluation was used to evaluate the quality of YQFM from different batches. Based on the intensities of the ions for common peaks, HCA and PCA were performed using SPSS 19.0 and Simca-P software. Results The UPLC-Q-TOF-MSE fingerprint of YQFM was established by using 28 batches of sample and 18 common peaks were found, of which 15 mutual peaks from Ginseng Radix et Rhizoma rubra, three mutual peaks from Ophiopogonis Radix. Compared with the reference substances and references, 16 of the common peaks were identified and the similarity of 28 batches samples were over 0.970. 28 batches of YQFM could be divided into four grades when the sum of squared Euclidean distance is 5-10 in the result of HCA; PCA got seven principal components through dimension reduction and accumulative contribution rate reached 84.989%. By fitting the load factor model of the first principal component, ten markers greatly impacting on the quality were found. The comprehensive evaluation function of YQFM in different batches was constructed according to the principal component score. Among 28 batches of YQFM, the comprehensive score of S28 was the best, closely followed by S22, S11 and S9, while S14 and S13 was the worst. Conclusion The utilization of UPLC-Q-TOF-MSE fingerprint coupled with chemical pattern recognition could objectively and effectively assess the quality of YQFM, can provide a more comprehensive reference for the quality control of YQFM.
ABSTRACT
OBJECTIVE: To identify rapidly the chemical constituents in Tanreqing injection and Tanreqing capsules by ultra-performance liquid chromatography with quadrupole-time-of-flight mass spectrometry (UPLC/Q-TOF-MSE). METHODS: The separation was performed on a Waters Acquity UPLC BEH C18 column (1.0 mm × 100 mm, 1.7 μm) with acetonitrile-0.1% formic acid as mobile phase in gradient elution. ESI ion source was employed in negative ion mode. The differences of chemical compositions between the two preparations and the sources of these compounds were illustrated based on their retention time, accurate mass measurements and the mass fragments by comparison with those in the literature or database and the reference standards. RESULTS: A total of 111 compounds including 13 unknown components were identified or tentatively characterized. Among these compounds, 14 were derived from Scutellariae Radix (SR) intermediate, 36 were from Bear Bile Powder(BBP) intermediate, 7 were from Caprae Hircus Cornu(CHC) intermediate, 34 were from Lonicerae japonicae Flos(LJF) intermediate and 22 were from Forsythiae Fructus(FF) intermediate. Moreover, quinic acid and rutin were simultaneously detected in LJF and FF intermediates, 28 constituents were unambiguously confirmed by their reference standards. However, 71 compounds were observed both in injection and capsules, while 24 compounds were only found in Tanreqing injection and 16 compounds only in the capsules. CONCLUSION: The differences of chemical constituents between Tanreqing injection and capsules are effectively characterized by UPLC/Q-TOF-MSE method, which will facilitate the quality control of the two preparations.
ABSTRACT
Objective: To rapidly identify the chemical constituents of Paeonia delavayi var. lutea roots by ultra-high performance liquid coupled with quadrupole time-of-flight mass spectrometry (UPLC-Q-TOF-MSE) and UNIFI informatics platform. Methods: Time-dependent MSE data-acquistion mode was applied to acquire mass spectrometric data, and then the chemical constituents were identified by automatic identification and artificial identification. Results: Totally 57 compounds were identified, including monoterpene glycosides, phenolic acids, tannins, paeonols, and triterpenes. Conclusion: UPLC-Q-TOF-MSE combined with UNIFI database could be used to rapidly and comprehensively characterize the chemical constituents of P. delavayi var. lutea roots. This study provides a reference for quality control of P. delavayi var. lutea roots and clarifying the material basis of its efficacy.
ABSTRACT
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.
ABSTRACT
This study was to identify the chemical constituents of Schisandra propinqua, one herbal medicine of Yi nationality in China by using ultra performance liquid chromatography-quadrupole-time of flight-mass spectrometry (UPLC-Q-TOF/MSE). Acetonitrile- water containing 0.1% formic acid was used as the mobile phase for gradient elution. Data were collected under ESI negative mode and ESI positive mode, and then screened and verified by the software of UNIFI and Masslynx4.1. Based on the accurate mass, fragment ions, neutral losses, mass error, retention time, reference substance, isotope information, the intensity of fragments, as well as the previous reports, the known compounds were validated and identified. The chemical structures of the unknown components were identified according to exact molecular weight, MS fragment, chromatographic retention behavior, and characteristic fragments of known congener compounds. A total of 68 chemical components were identified from S. propinqua, including 3 flavonoids, 10 flavanols, 34 lignans compounds (including 20 dibenzocyclooctene lignans), 4 triterpenoids, 17 organic acid and other compounds. 37 compounds of them were found in S. propinqua for the first time, and one potential compound needed to be identified.
ABSTRACT
Diagnostic ions filter method was used to rapidly detect and identify the phenolic compounds in Rheum palmatum based on ultra performance liquid chromatography coupled with quadrupole time-of-flight mass spectrometry (UPLC-Q-TOF/MSE). The representative authentic standards of phenolic compounds, including gallic acid, (+)-catechin, (－)-epicatechin, (－)-epicatechin-3-O-gallate and procyanidin B2, were subjected to analysis by UPLC-Q-TOF/MSE system with negative ion mode. Fragmentation patterns of each standard were summarized based on assigned fragment ions. The prominent product ions were selected as diagnostic ions. Subsequently, diagnostic ions filter was employed to rapidly recognize analogous skeletons. Combined with retention time, accurate mass, characteristic fragments and previous literature data, the structures of the filtered compounds were identified or tentatively characterized. A total 63 phenolic compounds (36 phenolic acid derivatives, 8 flavonoid derivatives and 19 tennis derivatives) in R. palmatum were identified, including 6 potential new compounds. The method of diagnostic ions filter could rapidly detect and identify phenolic compounds in R. palmatum This study provides a method for rapid detection of phenolic compounds in R. palmatum and is expected to complete the material basis of rhubarb.
ABSTRACT
In order to clarify the chemical constituents in Yangxue Qingnao granule, we established a rapid ultra-performance liquid chromatography/orthogonal acceleration time-of-flight mass spectrometry (UPLCQ- TOF/MSE) method. According to the high resolution MS spectra data, fragmentation ion information and retention time, 142 peaks were identified or tentatively presumed by comparison with reference standards data and literature reports. The herbal sources of these peaks were assigned. The results implied that phenolic acids, alkaloids, anthraquinones, phthalides, monoterpene glycosides were included in the main components of Yangxue Qingnao granule. The method is rapid for systematically elucidation of the constituents of Yangxue Qingnao granule and the results would facilitate the quality control of Yangxue Qingnao granule for safe and efficacious use.
ABSTRACT
Objective: To analyze the chemical differences in the fruits of Tritulus terrestris from different areas in the domestic and explore the potential chemical markers between the fruits and whole plants of T. terrestris. Methods: Chromatographic separation was carried out on the Acquity HSS T3 C18 column (100 mm×2.1 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 MSE) was used for mass spectrometric analysis. The obtained datasets were processed by principal component analysis (PCA) and orthogonal partial least squares discriminant analysis (OPLS-DA). Finally, the structures of chemical markers between fruits and whole plants were identified based on their exact mass data and fragmentation characteristics. Results: There was almost no difference in fruits of T. terrestris from different areas of China. However, the compounds existed in the fruits were different from those in the whole plants of T. terrestris. Eventually 12 chemical markers between fruits and whole plants of T. terrestris were identified online including nine chemical markers mainly distributed in the fruits and three chemical markers mainly distributed in the whole plants. Conclusion: This study could provide the guidance for the utilization of resource and treatments of T. terrestris in clinic by comparative analysis on chemical constituents in the different parts of T. terrestris from different areas.
ABSTRACT
Objective: A rapid and specific ultra performance liquid chromatography (UPLC) method was established for simultaneous analysis on six compounds and fingerprint analysis on Polygalae Radix to evaluate the herb quality from different habitats in China. Methods: The UPLC method was carried out by gradient elution with acetonitrile-formic acid water (0.1%). The flow rate was 0.4 mL/min. The detection wavelength was at 320 nm. The fingerprint chromatograms and the contents of six compounds including sibiricose A5, sibiricose A6, sibiricaxanthone B, glomeratose A, polygalaxanthone III, and 3,6'-disinapoyl sucrose in 24 batches of Polygalae Radix were analyzed. The common peaks were identified by ultra performance liquid chromatography tandem with time-of-flight mass spectrometry with MSE data-acquistion mode (UPLC-Q-TOF-MSE). Results: There was a difference in contents of six compounds, especially for the content of 3,6'-disinapoyl sucrose and sibiricose A6. Thirty-seven peaks were selected as the common peaks, of which 33 peaks were identified, and the similarities of 24 batches were between 0.756 and 0.997. Based on the results of quantification and fingerprint analysis, a certain difference between samples from different habitats was further proven. Conclusion: The validated UPLC quantitative analysis and fingerprint methods are successfully used in the quality control of Polygalae Radix.
ABSTRACT
Objective: To establish a method to fast identify the chemical constituents in the fruits of Schisandra sphenanthera and Schisandra chinensis by ultra performance liquid chromatography tandem with time-of-fight mass spectrometry with MSE data-acquistion mode (UFLC-Q-TOF-MSE) and provide the basis for high throughput characterization and distinction of the two two samples of Schisandra Michx by analyzing the remarkably different chemical components in the fruits between S. sphenanthera and S. chinensis. Methods: To rapidly identify the main chemical constituents in the fruits between S. sphenanthera and S. chinensis by using time-dependent scan mode, and combine with orthogonal partial least squares discriminant analysis (OPLS-DA) method to acquire significantly different constituents in the two samples of Schisandra Michx. Results: A total of 33 compounds were identified including 27 dibenzocyclooctene lignans. The differences of chemical compounds between the two sample groups could be obviously observed through the method of OPLS-DA in positive mode. There were 15 chemical ingredients of lignanes with significant differences identified in the two sample groups by comparison with retention time and mass spectra. Conclusion: The present study provides the basis for rapidly qualitative analysis of constituents and quantity control of the fruits in S. sphenanthera and S. chinensis.