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1.
Phytolacca acinosa is an herb for treatment of ascites and tumor. Two forms of P. acinosa, i.e. raw and vinegar‐processed herb, have been used in clinic. However, pharmacokinetic difference between the two forms of P. acinosa has not been fully understood. Herein, a comparative pharmacokinetic method based on liquid chromatography with tandem mass spectrometry was developed for quantification of six bioactive triterpenoids, including esculentoside H, esculentoside T, esculentoside A, esculentoside B, phytolaccagenic acid, and phytolaccagenin in rat plasma after oral administration of different forms of P. acinosa. Separation was performed on an Acquity BEH C18 column (1.7 µm, 2.1 mm × 50 mm). The method was validated over a linear range of 2.0–5000 ng/mL. Intraday and interday bias were within ±5%. Besides, all triterpenoids were stable in plasma during different storage conditions. The described method was successfully applied to a comparative pharmacokinetic study of raw and vinegar‐processed P. acinosa in rats. Notably, double peak phenomenon for six triterpenoids of P. acinosa was observed for the first time. AUC0→t and Cmax values of esculentoside H, esculentoside T, phytolaccagenic acid, and phytolaccagenin were significantly lower in vinegar‐processed group than that of raw group, indicating the oral bioavailability of the four triterpenoids was decreased after vinegar processing.  相似文献   

2.
Cyclocarya paliurus is a medicinal plant containing various bioactive components with significant health benefits. Cell cultures of C. paliurus have been used to produce these bioactive metabolites. A chemical fingerprint was obtained by high-performance liquid chromatography (HPLC) to monitor the synthesis of major triterpenoids in cultured C. paliurus cells and provide a reliable quality assessment for the cell strain screening. The determination of five triterpenoids, namely, maslinic acid, corosolic acid, betulinic acid, oleanic acid, and ursolic acid, was also performed. The HPLC method for the determination of triterpenoids in the cultured cells was accurate, stable, and reliable, and therefore suitable for chemical fingerprint analysis. Sixteen C. paliurus cell strains varied dramatically in their triterpenoid accumulations. The concentrations of the triterpenoids were 0.45–2.19 (maslinic acid), 0.92–5.34 (corosolic acid), 2.58–4.70 (betulinic acid), 4.07–12.47 (oleanic acid), and 12.64–40.98 (ursolic acid) mg/g. A high yield cell strain had a total triterpenoid concentration of 66.34?mg/g. Ten peaks in the HPLC chromatogram with reasonable height and high resolution were assigned as characteristic for fingerprint and analysis. A reference fingerprint was also obtained for cell strain assessment.  相似文献   

3.
The recent worldwide shortage of acetonitrile has prompted interest in alternative solvents for liquid chromatography/mass spectrometry (LC/MS). In this work, acetone was substituted for acetonitrile in the separation of a peptide mixture by reversed‐phase high‐performance liquid chromatography (RP‐HPLC) and in the positive electrospray ionization mass spectrometry (ESI‐MS) of individual peptides. On both C12 and C18 stationary phases, the substitution of acetone for acetonitrile as the organic component of the mobile phase did not alter the gradient elution order of a five‐peptide retention standard, but did increase peak width, shorten retention times, and increase peak tailing. Positive ESI mass spectra were obtained for angiotensin I, bradykinin, [Leu5]‐enkephalin, and somatostatin 14 dissolved in both acetonitrile/water/formic acid (25%/75%/0.1%) and acetone/water/formic acid (25%/75%/0.1%). Under optimized ESI‐MS conditions, the mass spectral response of [Leu5]‐enkephalin was increased two‐fold when the solvent contained acetone. The substitution of acetone for acetonitrile resulted in only slight changes in the responses of the remaining peptides. A higher capillary voltage was required for optimum response when acetone was used. Compared with acetonitrile/water/formic acid (50/50/0.1%), more interfering species below m/z = 140 were found in the ESI‐MS spectra of acetone/water/formic acid (50/50/0.1%). Copyright © 2009 John Wiley & Sons, Ltd.  相似文献   

4.
An anion‐exchange chromatography method combined solid phase extraction (SPE) was developed for the simultaneous analysis of glycolate acid (GL), monochloroacetic acid (MCA) and dichloroacetic acid (DCA) in synthetical betaine products. The analytes and unknown anionic impurities were well separated on a Metrosep A supp5 anion‐exchange column (150 mm×4 mm) with 2.0 mmol/L Na2CO3+2.0 mmol/L NaHCO3 solution as eluent. Suppressed conductivity detection was used. A strong cation exchange (SCX) solid phase extraction (SPE) cartridge was used to reduce the concentration of matrix betaine and a Cleanert IC‐Ag pretreatment cartridge was used to remove high Cl? concentration. The detection limits of GL, MCA and DCA were 0.09, 0.017 and 0.05 µg/L, respectively. The relative standard deviations (RSDs) of the retention times and peak areas were less than 0.09% and 0.49%, respectively. The recoveries of the three analytes were between 90.6% and 100.8%. The analytical results showed that GL and DCA were present in high concentration and no MCA was found when the proposed ion chromatography method was applied to three synthetical betaine samples. The proposed method is simple, sensitive and timesaving, and is also suitable for routine analysis in quality control of synthetical betaine products.  相似文献   

5.
Summer savory (Satureja hortensis L.) is most often used as a culinary herb, but it also has medicinal benefits. The extracts from control and irradiated savory were obtained by ultrasound extraction for 30 minutes in an ethanol — water (80:20, v/v) mixture. Polyphenolic compounds from savory were identified and characterized by high-performance liquid chromatography coupled with a photodiode array detector and mass spectrometer. The separation was performed using an Altima C18 column (100×3 mm, 3 μm) and as mobile phase two solvent mixture: A — acetonitrile and B — water-formic acid (99.9:0.1, v/v). Peaks were identified with authentic standards in accordance to retention time, UV spectra and molecular mass. It was identified as caffeic acid, rosmarinic acid, luteolin, naringenin and apigenin. A quantitative determination of polyphenolic compounds was performed applying the external standard method. Our study showed large quantitative differences between the control plant and the irradiated plant.   相似文献   

6.
A new method for the simultaneous determination of five transition metal ions in water and food by rapid high‐performance liquid chromatography was developed. The cobalt, nickel, copper, zinc and vanadium ions were pre‐column derivatized with 2‐(2‐quinolinylazo)‐4‐methyl‐1,3‐dihydroxidebenzene (QAMDHB) to form colored chelates, then the Co‐QAMDHB, Ni‐QAMDHB, Cu‐QAMDHB, Zn‐QAMDHB and V‐QAMDHB chelates were enriched by solid phase extraction with a C18 cartridge. The enrichment factor of 50 was achieved by eluting the retained chelates from the cartridge with tetrahydrofuran (THF). These chelates were separated on a ZORBAX Stable Bound rapid analysis column (4.6 × 50 mm, 1.8 um) with 68% methanol (containing 0.1% of acetic acid and 0.1% of CTMAB) as mobile phase at a flow rate of 2.0 mL/min and detected with a photodiode array detector from 450?600 nm. The Co‐QAMDHB, Ni‐QAMDHB, Cu‐QAMDHB, Zn‐QAMDHB and V‐QAMDHB chelates were separated completely within 2.0 min. The detection limits of cobalt, nickel, copper, zinc and vanadium are 2 ng/L, 1.5 ng/L, 2 ng/L, 3 ng/L, and 3 ng/L, respectively, in the original samples. This method was applied to the determination of the five transition metal ions in water and food samples with good results.  相似文献   

7.
A new method was employed to solid-phase extract ursolic acid from Ilex kudingcha C. J. Tseng using molecularly imprinted microspheres (MIMs) as the sorbent. Using a surface molecular imprinting technique, MIMs for ursolic acid were prepared with bonded beta-CD and acrylamide in combination based on functionalized poly(glycidyl methacrylate) microspheres (F-PGMA). Compared with non-MIMs (NIMs), MIMs showed high adsorption capacity, significant selectivity, and good site accessibility for ursolic acid. The maximum static adsorption capacities of the MIMs and NIMs for ursolic acid were 42.5 and 4.9 micromol/g, respectively. Chromatographic analysis shows that ursolic acid and oleanolic acid could be separated well when MIMs were used as the stationary phase of HPLC. The conditions of molecularly imprinted SPE (MISPE) of ursolic acid from the herb extract were optimized using different concentrations of ethanol solutions as loading, washing, and eluting solutions. The successful extraction of ursolic acid by MIMs provided a possible innovative approach to separate ursolic acid from herb.  相似文献   

8.
A new, rapid, and efficient method for determining the fumagillin residues in honey was developed. The samples extracted were analyzed using LC/MS/MS. Chromatographic separation of fumagillin was performed in gradient mode on a C8 column (100 x 2.0 mm, 5 microm) at 40 degrees C. The mobile phase consisted of a mixture of 2 mM ammonium formate-0.01% formic acid solution and methanol; the flow rate was set to 0.2 mL/min. Under these conditions, it was possible to measure fumagillin and its isomers as a single peak. The sample preparation procedure used is based on the QuEChERS (quick, easy, cheap, effective, rugged, and safe) method, which is fast (approximately 30 min) and uses less organic solvent. The fumagillin was extracted with acetonitrile containing 0.1% formic acid, then purified using a solid-phase extraction method with an Oasis mixed-mode weak anion-exchange cartridge. The overall recovery of fumagillin ranged from 88.1 to 99.4%; the intra- and interassay CVs were <4.5% and <4.9%, respectively. The LOQ was 0.1 microg/kg. LC/MS/MS coupled with the QuEChERS method showed strong potential as a method for determining fumagillin residues in honey.  相似文献   

9.
A new HPLC coupled with evaporative light scattering detection method was established for the simultaneous determination of seven triterpenoids and triterpenoid saponins in Folium Ilicis Purpureae traditional Chinese medicinal herb derived from the leaf of Ilex purpurea, namely, 3-omicron-beta-D-glucopyranosyl (1-->2)-beta-D-[6-omicron-methyl-glucuronopyranosyl]-28-omicron-beta-D-glucopyranosyl oleanolic acid (SQ-1), pedunculoside (SQ-2), 23-hydroxytormentic acid 28-omicron-beta-D-glucopyranoside (SQ-3), 23-hydroxytormentic acid (SQ-4), rutundic acid (SQ-5), ilexoside B (SQ-6), and ursolic acid (SQ-7). The optimal chromatographic conditions were achieved on a C18 column with a linear gradient elution of mobile phase A: deionized water-isopropyl alcohol-THF-acetic acid (90:10:6:1, v/v) and B: methanol-isopropyl alcohol-THF-acetic acid (90:10:6:1, v/v) at the flow rate of 1.0 mL/min; temperature for drift tube was set at 98degreesC and nitrogen flow rate was 2.8 L/min. All calibration curves of the seven compounds showed good linear regression (r2 > 0.995) within test ranges. The developed method has good repeatability for quantitation of all analytes interested with overall intraday and interday variation of less than 4.1%. The LOD (S/N = 3) and LOQ (S/N = 10) were less than 0.13 and 0.26 microg/mL, respectively, for all analytes. The established method was successfully used to evaluate the quality of Folium Ilicis Purpureae samples of different collections.  相似文献   

10.
Four major triterpenoids (ganoderic acids C(2), B, K and H) in rat plasma after oral administration of G. lucidum extract were analyzed quantitatively by high-performance liquid chromatography (HPLC). Plasma samples taken from rats were acidified with hydrochloric acid and extracted with dichloromethane-ethyl acetate (90:10). The chromatographic separation was achieved on an Agilent Zorbax SB-C(18) column (250 x 4.6 mm, 5 microm) at 35 degrees C, with a linear gradient of acetonitrile and 0.03% aqueous phosphoric acid (v/v), at a flow rate of 1.0 mL/min. The four triterpenoids and internal standard (hydrocortisone) were detected at a wavelength 252 nm. All calibration curves showed good linearity (r(2) > 0.99) within test ranges. The relative deviation of this method was less than 10% for intra- and inter-day assays, and the accuracy ranged from 89 to 108%. The extract recovery for the four triterpenoids and internal standard ranged from 95 to 67%, and the QC samples were found to be stable according to the results of the stability study. This is the first report on determination of the major triterpenoids in rat plasma after oral administration of G. lucidum extract and the results provided a firm basis for clarifying the pharmacological effect of G. lucidum and evaluating the clinical applications of this medicinal fungus.  相似文献   

11.
A sensitive LC/MS/MS assay for determining zidovudine (ZDV) and lamivudine (3TC) in human plasma was validated to support antiretroviral pharmacology research programs. After addition of stable labeled isotopic zidovudine (ZDV‐IS) and lamivudine (3TC‐IS) as internal standard, a solid‐phase extraction was performed with an Oasis HLB 1 cm3 cartridge, with recoveries of 92.3% for ZDV and 93.9% for 3TC. A Phenomonex Synergi Hydro‐RP (2.0 × 150 mm) reversed‐phase analytical column was utilized for chromatographic separation. The mobile phase consisted of an aqueous solution of 15% acetonitrile and 0.1% acetic acid. Detection was accomplished by ESI/MS/MS in the positive ion mode, monitoring 268/127, 271/130, 230/112 and 233/115 transitions, for ZDV, ZDV‐IS, 3TC and 3TC‐IS, respectively. The method was linear from 1 to 3000 ng/mL with a minimum quantifiable limit of 1 ng/mL when 100 μL of plasma was analyzed. Validation results demonstrated high accuracy (≤8.3% deviation) and high precision (≤10% CV) for the quality control samples. The method was also shown to be specific and reproducible. The value of the high sensitivity was demonstrated by quantitation of approximately 100 existing samples that had ZDV below the limit of quantitation using a previously validated, less sensitive HPLC‐UV method utilized in the laboratory. Copyright © 2011 John Wiley & Sons, Ltd.  相似文献   

12.
A simple, rapid and sensitive ultra‐performance liquid chromatography–tandem mass spectrometry (UPLC‐MS/MS) method has been developed and validated for the determination of alosetron (ALO) in human plasma. The assay method involved solid‐phase extraction of ALO and ALO 13C‐d3 as internal standard (IS) on a LichroSep DVB‐HL (30 mg, 1 cm3) cartridge. The chromatography was performed on an Acquity UPLC BEH C18 (50 × 2.1 mm, 1.7 µm) column using acetonitrile and 2.0 mm ammonium formate, pH 3.0 adjusted with 0.1% formic acid (80:20, v/v) as the mobile phase in an isocratic mode. For quantitative analysis, the multiple reaction monitoring transitions studied were m/z 295.1/201.0 for ALO and m/z 299.1/205.1 for IS in the positive ionization mode. The method was validated over a concentration range of 0.01–10.0 ng/mL for ALO. Post‐column infusion experiment showed no positive or negative peaks in the elution range of the analyte and IS after injection of extracted blank plasma. The extent of ion‐suppression/enhancement, expressed as IS‐normalized matrix factor, varied from 0.96 to 1.04. The assay recovery was within 97–103% for ALO and IS. The method was successfully applied to support a bioequivalence study of 1.0 mg alosetron tablets in 28 healthy Indian male and female subjects. Copyright © 2015 John Wiley & Sons, Ltd.  相似文献   

13.
A reliable and sensitive ultra‐performance liquid chromatography/quadrupole time‐of‐flight mass spectrometry (UPLC/Q‐TOF‐MS) method has been optimized and established for analysis of protostane triterpenoids in a commonly used traditional Chinese herbal medicine Alisma orientalis (Sam.) Juzep. The separation of crude extract of A. orientalis was achieved on a Waters ACQUITY HSS T3 column (100 mm × 2.1 mm, 1.8 µm) eluting with 0.1% (v/v) formic acid/acetonitrile. A total of 20 protostane triterpenoids including 19 known compounds and a new one were well separated within 7 min. The collision‐induced dissociation (CID) tandem mass spectrometric (MS/MS) fragmentation patterns of protostane triterpenoids was firstly reported in this study. The hydrogen rearrangement at the C‐23‐OH leads to dissociation of the bond between C‐23 and C‐24 in the protostane triterpenoid skeleton during the CID process. This dissociation was the characteristic CID fragmentation pathway of this class of triterpenoids, and was useful for further differentiation of some positional isomers which contain an acetyl unit on the C‐23 or C‐24 position. The identities of isolated compounds were identified by comparing their retention times and CID fragmentation behaviors with those of reference standards or tentatively assigned by matching the empirical molecular formulae with those reported in the literature. It is concluded that this newly established UPLC/Q‐TOF‐MS method is a powerful approach for structural elucidation of protostane triterpenoids isolated from A. orientalis. Copyright © 2010 John Wiley & Sons, Ltd.  相似文献   

14.
气相色谱法同时测定玉米中12种三嗪类除草剂的残留量   总被引:6,自引:0,他引:6  
张敬波  姜文凤  董振霖  赵守成  卫锋 《色谱》2006,24(6):648-651
建立了气相色谱-氮磷检测器同时检测玉米中12种三嗪类除草剂(西玛通、西玛津、阿特拉津、扑灭津、特丁通、特丁津、环丙津、西草净、扑草净、特丁净、甲氧丙净、环嗪酮)残留量的方法。玉米样品用乙腈萃取,强阳离子交换(SCX)固相萃取柱净化后,用DB-5弹性石英毛细管柱(30 m×0.25 mm i.d.×0.25 μm)分离样品,氮磷检测器测定。12种三嗪类除草剂在0.01~2.0 mg/L范围内线性关系关系良好,相关系数均大于0.998;最低检测限为0.01 mg/kg;添加回收率为84.0%~106.8%;相对标准偏差为0.9%~4.7%。  相似文献   

15.
A multi‐analyte screening method for the quantification of 50 acidic/neutral drugs in human plasma based on on‐line solid‐phase extraction (SPE)–HPLC with photodiode array detection (DAD) was developed, validated and applied for clinical investigation. Acetone and methanol for protein precipitation, three different SPE materials (two electro‐neutral, one strong anion‐exchange, one weak cation‐exchange) for on‐line extraction, five HPLC‐columns [one C18 (GeminiNX), two phenyl‐hexyl (Gemini C6‐Phenyl, Kinetex Phenyl‐Hexyl) and two pentafluorophenyl (LunaPFP(2), KinetexPFP)] for analytical separation were tested. For sample pre‐treatment, acetone in the ratio 1:2 (plasma:acetone) showed a better baseline and fewer matrix peaks in the chromatogram than methanol. Only the strong anion‐exchanger SPE cartridge (StrataX‐A, pH 6) allowed the extraction of salicylic acid. Analytical separation was carried out on a Gemini C6‐Phenyl column (150 × 4.6 mm, 3 µm) using gradient elution with acetonitrile–water 90:10 (v/v) and phosphate buffer (pH 2.3). Linear calibration curves with correlation coefficients r ≥ 0.9950/0.9910 were obtained for 46/four analytes. Additionally, this method allows the quantification of 23 analytes for therapeutic drug monitoring. Limits of quantitation ranged from 0.1 (amobarbital) to 23 mg/L (salicylic acid). Inter‐/intra‐day precisions of quality control samples (low/high) were better than 13% and accuracy (bias) ranged from ?14 to 10%. A computer‐assisted database was created for automated detection of 223 analytes of toxicological interests. Four cases of multi‐drug intoxications are presented. Copyright © 2015 John Wiley & Sons, Ltd.  相似文献   

16.
Ursane-type pentacyclic triterpenoids exert various biological effects, including anticancer and anti-inflammatory activities. We previously reported that ursolic acid, corosolic acid, and asiatic acid interfered with the intracellular trafficking and glycosylation of intercellular adhesion molecule-1 (ICAM-1) in human lung adenocarcinoma A549 cells stimulated with the pro-inflammatory cytokine interleukin-1α. However, the structure–activity relationship of ursane-type pentacyclic triterpenoids remains unclear. In the present study, the biological activities of seven ursane-type pentacyclic triterpenoids (β-boswellic acid, uvaol, madecassic acid, 3-O-acetyl-11-keto-β-boswellic acid, ursolic acid, corosolic acid, and asiatic acid) were investigated. We revealed that the inhibitory activities of ursane-type pentacyclic triterpenoids on the cell surface expression and glycosylation of ICAM-1 and α-glucosidase activity were influenced by the number of hydroxy groups and/or the presence and position of a carboxyl group. We also showed that β-boswellic acid interfered with ICAM-1 glycosylation in a different manner from other ursane-type pentacyclic triterpenoids.  相似文献   

17.
A liquid chromatography–tandem mass spectrometric (LC/MS/MS) method was developed for the determination of an atypical antipsychotic drug, lurasidone, in rat plasma. The method involves the addition of acetonitrile and ziprasidone (internal standard) solution to plasma samples, followed by centrifugation. An aliquot of the supernatant was diluted with water and directly injected into the LC/MS/MS system. The separations were performed on a column packed with octadecylsilica (5 μm, 2.0 × 50 mm) with 0.1% formic acid and 0.1% formic acid in acetonitrile as mobile phase and the detection was performed using tandem mass spectrometry by multiple‐reaction monitoring via an electrospray ionization source. The standard curve was linear (r = 0.9982) over the concentration range 0.002–1 μg/mL. The intra‐ and inter‐assay precisions were 1.7 and 8.6%, respectively. The accuracy range was from 90.3 to 101.8%. The lower limit of quantification was 2.0 ng/mL using 50 μL of rat plasma sample. The developed analytical method was successfully applied to the pharmacokinetic study of lurasidone in rats. Copyright © 2011 John Wiley & Sons, Ltd.  相似文献   

18.
The isolation and identification of fifteen crystalline components from the whole herb of Clinopodium umbrosum (Bieb.) C. Koch (Labiatae) are described. Their structures were determined on the basis of spectral evidence and chemical transformation. These compounds include five steroids (α-spinasterone, β-sitosterol, stigmasterol, α-spinasterol, and α-spinasteryl-3-O-β-glucopyranoside), four triterpenoids (3β-hydroxyurs-11-en-28,13-olide, betulinic acid, oleanolic acid, ursolic acid), four flavonoids (luteolin, luteolin-7-O-β-glucopyranoside, apigenin-7-O-β-glucuronide, and apigenin-7-O-β-methylglucuronate), and two lignolic acids [3-(3,4-dihydroxyphenyl)- lactic acid and rosmarinic acid].  相似文献   

19.
A simple and specific analytical method for the quantitative determination of five cucurbitane-type triterpenoids isolated from the fruit of Momordica charantia is developed. The triterpenoids present in the fruits of Momordica charantia are separated with an acetonitrile (0.1% acetic acid)-water (0.1% acetic acid)-methanol (0.1% acetic acid) gradient at a flow rate of 0.5 mL/min. The high-performance liquid chromatography separation was performed on a Phenomenex C18 reversed-phase column. By using an evaporative light scattering detector, the main triterpenoids of Momordica charantia could be detected at levels as low as 10 microg/mL. The method was validated for precision, repeatability, and accuracy. The relative standard deviation was between 0.6-4.4%. The method was sensitive, quick, and accurate for the determination of main triterpenes and saponins in Momordica charantia, and can be used for quality control of Momordica charantia and its related dietary supplements.  相似文献   

20.
α‐Amyrin margarate ( 1 ), moretenyl margarate ( 2 ) and moretenyl palmitate ( 3 ), three triterpenoid fatty acid esters, have been isolated from the acetone extract of the small twigs of Viburnum odoratissimum in addition to the three known compounds, α‐amyrin palmitate ( 4 ), ursolic acid ( 7 ) and vibsanin‐K ( 8 ). The structures of compounds 1–3 were elucidated based on extensive spectroscopic analysis and alkaline hydrolysis. Preliminary pharmacological studies revealed that vibsanin‐K and ursolic acid exhibited significant cytotoxicity against human gastric (NUGC) and oral epidermoid (HONE‐1) tumor cells at a concentration of 50 μg/mL while compounds 1–3 were inactive.  相似文献   

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