Unbiased metabolite profiling by liquid chromatography-quadrupole time-of-flight mass spectrometry and multivariate data analysis for herbal authentication: classification of seven Lonicera species flower buds.

Plant-based medicines become increasingly popular over the world. Authentication of herbal raw materials is important to ensure their safety and efficacy. Some herbs belonging to closely related species but differing in medicinal properties are difficult to be identified because of similar morphological and microscopic characteristics.

Characterization and identification of steroidal alkaloids in Fritillaria species using liquid chromatography coupled with electrospray ionization quadrupole time-of-flight tandem mass spectrometry.

Liquid chromatography coupled with electrospray ionization quadrupole time-of-flight tandem mass spectrometry (LC/ESI-QTOF-MS/MS) was performed to study the fragmentation behaviors of steroidal alkaloids from Fritillaria species, the antitussive and expectorant herbs widely used in traditional Chinese medicine. We propose, herein, a strategy that combining key diagnostic fragment ions and the relative abundances and amounts of major fragment ions (the ions exceeding 10% in abundance) to distinguish different sub-classes of Fritillaria alkaloids (FAs). It was found that hydrogen rearrangement and induction effects result in ring cleavage of the basic skeletons occurred in the MS/MS process and produced characteristic fragment ions, which are useful for structural elucidation.

Characterization and identification of saponins in Achyranthes bidentata by rapid-resolution liquid chromatography with electrospray ionization quadrupole time-of-flight tandem mass spectrometry.

A rapid-resolution liquid chromatography (RRLC) method coupled with electrospray ionization quadrupole time-of-flight tandem mass spectrometry (Q-TOF MS/MS) has been developed for analysis of oleanane-type triterpenoid saponins in Achyranthes bidentata. Collision-induced dissociation techniques were used to fragment the precursor molecular ions and the resulting product ions. A retro-Diels-Alder rearrangement from the oleanane aglycone skeleton in the MS/MS process yielded characteristic fragment ions in positive ion mode.

Oleanane-type triterpene glucuronides from the roots of Glycyrrhiza uralensis Fischer.

Investigation of characteristic constituents of the roots of Glycyrrhiza uralensis Fischer led to isolation of four new triterpene glucuronides, namely uralsaponins C-F (1-4), an artificial product, namely the methyl ester of glycyrrhizin (5), as well as six known triterpene glucuronides (6-11). These new compounds were identified by 1D and 2D NMR spectroscopic analysis. The cytotoxicity of the selected compounds and their aglycones were evaluated against HeLa and MCF-7 cancer cell lines, and the preliminary structure-activity relationship was also elucidated.

Characterization of novel astragaloside malonates from Radix Astragali by HPLC with ESI quadrupole TOF MS.

A structurally identified new compound named malonylastragaloside I was isolated and obtained from Radix Astragali. This novel compound was found to be unstable especially under high temperature and pH value. Using sonication extraction, addition of formic acid, and an efficient medium pressure ODS C(18) column chromatography method, a high yield of 40 mg of this compound was obtained from 150 g of powdered crude herbal medicine.

Rapid analysis of constituents of Radix Cyathulae using hydrophilic interaction-reverse phase LC-MS.

A hydrophilic interaction chromatography (HILIC) and reverse-phase liquid chromatography (RPLC) coupled with electrospray TOF MS method was developed for the analysis and characterization of constituents in the radix of Cyathula officinalis Kuan. Separation parameters of HILIC such as buffer pH, mobile phase strength, and organic modifier were evaluated. Fructose, glucose, and sucrose were identified by HILIC-ESI/TOF MS.

Identification of metabolites of Danggui Buxue Tang in rat urine by liquid chromatography coupled with electrospray ionization time-of-flight mass spectrometry.

A method coupling liquid chromatography with electrospray ionization time-of-flight mass spectrometry (LC/ESI-TOF/MS) has been developed for rapid and sensitive analysis of rat urinary metabolite profile of Danggui Buxue Tang (DBT), a well-known Chinese herbal formula. After oral administration of DBT, urine samples were collected during 0-24 h, and then pretreated by solid-phase extraction. A total of 68 compounds including 13 parent compounds and 55 metabolites were detected in the drug-containing urines compared with blank urines.

Organic solvent extraction and metabonomic profiling of the metabolites in erythrocytes.

We used erythrocytes as the model tissue to evaluate an optimal solution for the extraction of intracellular metabolites and time-dependent variation of the metabolome in living cells. Projection to latent structure (PLS) of the GC/MS and LC/MS data suggested that the most efficient solution for the extraction of metabolites from wet erythrocytes (50 mg) could be a methanol-chloroform-water mixture (950 microL, 700:200:50, v/v/v). PLS-discriminant analysis (DA) clearly profiled a time-dependent alternation of metabolic phenotype of erythrocytes.

Identification and quantification of 32 bioactive compounds in Lonicera species by high performance liquid chromatography coupled with time-of-flight mass spectrometry.

Flos Lonicerae, referred to the flower buds of several medicinal Lonicera species, is a commonly used traditional Chinese herbal medicine. A multi-component-assay quality control method, using high performance liquid chromatography coupled with electrospray ionization time-of-flight mass spectrometry (HPLC-ESI/TOF MS), has been developed for the simultaneous identification and quantification of 32 bioactive compounds in Flos Lonicerae. The limits of detection (LOD) and quantification (LOQ) were in the range of 0.

Application of liquid chromatography-electrospray ionization time-of-flight mass spectrometry for analysis and quality control of compound Danshen preparations.

A liquid chromatography coupled with electrospray ionization time-of-flight mass spectrometry (LC-ESI-TOF-MS) method has been developed to evaluate the quality of three formulas of compound Danshen preparations (CDPs), through a simultaneous determination of 22 marker constituents (nine major phenolic acids, eight major saponins and five major diterpenoids). Optimum separations were obtained with a Zorbax C(18) column, using a gradient elution with 0.1% aqueous formic acid and acetonitrile.

Application of high-performance liquid chromatography-electrospray ionization time-of-flight mass spectrometry for analysis and quality control of Radix Astragali and its preparations.

A high-performance liquid chromatography coupled with electrospray ionization time-of-flight mass spectrometry (HPLC-ESI-TOF-MS) method has been developed for qualitative and quantitative analysis of isoflavonoids and saponins, as well as for the quality control of Radix Astragali and its preparations. The selectivity, reproducibility and sensitivity are compared with HPLC with diode array detection (DAD) and evaporative light scattering detection (ELSD). Limits of detection and quantification fell in ranges of 9-40 and 23-103 ng/mL for 13 analytes with a injection of 10 microL samples, and all calibration curves showed good linear regression (r(2)>0.

Simultaneous determination of 15 marker constituents in various radix Astragali preparations by solid-phase extraction and high-performance liquid chromatography.

An improved quality control method was developed to simultaneously determine 15 major constituents (eight flavonoids and seven saponins) in various radix Astragali preparations, using SPE for pretreatment of samples, HPLC with diode-array and evaporative light scattering detectors (DAD-ELSD) for quantification in one run, and HPLC-ESI-TOF/MS for definite identification of compounds in preparations. Optimum separations were obtained with a ZORBAX C(18) column, using a gradient elution with 0.3% aqueous formic acid and ACN.

Development and validation of a liquid chromatography/electrospray ionization time-of-flight mass spectrometry method for relative and absolute quantification of steroidal alkaloids in Fritillaria species.

Steroidal alkaloids are naturally occurring nitrogen-containing compounds in many edible or medicinal plants, such as potato, tomato, Fritillaria and American hellebore, which possess a variety of toxicological and pharmacological effects on humans. The aim of this study is to explore the potential of liquid chromatography/electrospray ionization time-of-flight mass spectrometry (LC/ESI-TOF-MS) method in the determination of these important alkaloids in plant matrices. The application of this method has been proven through 26 naturally occurring steroidal alkaloids in Fritillaria species.

Simultaneous qualitation and quantification of thirteen bioactive compounds in Flos lonicerae by high-performance liquid chromatography with diode array detector and mass spectrometry.

A high-performance liquid chromatography (HPLC) with diode array detector (DAD) and electrospray ionization mass spectrometry (ESI-MS) was established for the simultaneous determination of thirteen bioactive compounds in Flos Lonicerae. The optimal chromatographic conditions were obtained on a C(18) column (250x4.6 mm, 5.