The Quality Assessment of Commercial Lycium Berries Using LC-ESI-MS/MS and Chemometrics.

Lycium (also known as Goji berry) is used in traditional Chinese medicine (TCM) with claimed benefits, including eye and liver protection, immune system fortification and blood glucose control. The commercially available product comes from either the L. barbarum or L. chinense species, with the former dominating the marketplace due to its better taste profile. The main objective of this study was to develop a validated LC-ESI-MS/MS method to quantify multiple key bio-active analytes in commercially available Lycium berries and to qualitatively assess these samples using a principal component analysis (PCA). A LC-ESI-MS/MS method for the quantitation of seven analytes selected using the Herbal Chemical Marker Ranking System (Herb MaRS) was developed. The Herb MaRS ranking system considered bioavailability, bioactivity and physiological action of each target analyte, its intended use and the commercial availability of an analytical standard. After method optimization combining high resolving power with selective detection, seven analytes were quantified and the Lycium samples were quantitatively profiled. Chromatographic spectra were also obtained using longer run-time LC-UV and GC-MS methods in order to qualitatively assess the samples using a principal component analysis (PCA). The result of the method validation procedure was a 15.5 min LC-ESI-MS/MS method developed for the quantification of seven analytes in commercial Lycium samples. Wide variation in analyte concentration was observed with the following results (analyte range in mg/g): rutin, 16.1-49.2; narcissin, 0.37-1.65; nictoflorin, 0.26-0.78; coumaric acid, 6.84-12.2; scopoletin, 0.33-2.61; caffeic acid, 0.08-0.32; chlorogenic acid, 1.1-9.12. The quantitative results for the L. barbarum and L. chinense species samples indicate that they cannot be differentiated based on the bio-actives tested. A qualitative assessment using PCA generated from un-targeted LC-UV and GC-MS phytochemical spectra led to the same conclusion. The un-targeted quantitative and qualitative phytochemical profiling indicates that commercial L. barbarum and L. chinense cannot be distinguished using chemical analytical methods. Genetic fingerprinting and pharmacological testing may be needed to ensure the efficacy of commercial Lycium in order to validate label claims.

Quality Control and Variability Assessment of an Eight-Herb Formulation for Hypertension Using Method Validation and Statistical Analysis.

Background-The quality control (QC) for commercial herbal formulations is sparse due to a lack of well-developed HPLC-ESI-MS/MS methods. Objective-This study reports the quantification of nine selected analytes for a commercial eight-herb formulation known as Qi Ju Di Huang Wan (QJDHW) used to relieve hypertension. Methods-An HPLC-ESI/MS method for the quantitation of analytes selected using the Herbal Chemical Marker Ranking System (Herb MaRS) was developed. The Herb MaRS ranking system which takes into account bioavailability, bioactivity, and physiological action related to its intended use and the commercial availability of the standard. After a method optimization, seven analytes were found to be ideal for quantitation. Results-The target analytes were identified using an electrospray ionization-tandem MS molecular breakdown comparison between the herbal peak and the commercial standard. The quantitative aspect of analyte variability of eleven samples was studied using fold variation. The fold variation of selected analytes among eleven samples ranged from 1.5 to 28.9. The qualitative aspect of variability was studied using principal component analysis (PCA) and hierarchical cluster analysis (HCA). Conclusions-There is a great degree of chemical variability in herbal formulations which are due to raw material harvesting times, storage techniques, and plant subspecies variability. Highlights-Commercial QJDHW formulations need to be standardised using HPLC-ESI-MS/MS to ensure better product quality control (QC) and product efficacy for the consumer.

High-performance liquid chromatography coupled with tandem mass spectrometry technology in the analysis of Chinese Medicine Formulas: A bibliometric analysis (1997-2015).

There is a recognized challenge in analyzing traditional Chinese medicine formulas because of their complex chemical compositions. The application of modern analytical techniques such as high-performance liquid chromatography coupled with a tandem mass spectrometry has improved the characterization of various compounds from traditional Chinese medicine formulas significantly. This study aims to conduct a bibliometric analysis to recognize the overall trend of high-performance liquid chromatography coupled with tandem mass spectrometry approaches in the analysis of traditional Chinese medicine formulas, its significance and possible underlying interactions between individual herbs in these formulas. Electronic databases were searched systematically, and the identified studies were collected and analyzed using Microsoft Access 2010, Graph Pad 5.0 software and Ucinet software package. 338 publications between 1997 and 2015 were identified, and analyzed in terms of annual growth and accumulated publications, top journals, forms of traditional Chinese medicine preparations and highly studied formulas and single herbs, as well as social network analysis of single herbs. There is a significant increase trend in using high-performance liquid chromatography coupled with tandem mass spectrometry related techniques in analysis of commonly used forms of traditional Chinese medicine formulas in the last 3 years. Stringent quality control is of great significance for the modernization and globalization of traditional Chinese medicine, and this bibliometric analysis provided the first and comprehensive summary within this field.

Effects of a novel herbal formulation JSK on acute spinal cord injury in rats.

PURPOSE: Acute spinal cord injury (SCI) triggers multiple cellular and molecular pathways; therapy aimed at only one pathway is unlikely to succeed. Anecdotal reports indicate that a novel herbal formulation (JSK-Ji-Sui-Kang) may enhance recovery in humans with SCI. We investigated whether JSK's therapeutic effects could be verified in a well-established SCI model in rats. METHODS: Therapeutic effects of JSK were tested using a standard behavioral assessment, histological, immunochemical and microarray analysis. Phytochemical fingerprinting of JSK was performed using high performance liquid chromatography coupled with photodiode array detection and electrospray ionization-mass spectrometry. JSK or vehicle was gavaged to rats 24 hours after SCI and daily thereafter for 3 weeks. RESULTS: Locomotor function significantly improved (n = 12; p < 0.05), tissue damage was reduced (p < 0.01; n = 6) and more axons and myelin were observed in JSK-treated compared with vehicle control animals. JSK significantly enhanced expression of neuroglobin, vascular endothelial growth factor and growth-associated protein 43, and reduced the expression of caspase 3, cyclooxygenase-2, RhoA (p < 0.05; n = 6) and fibrinogen (p < 0.01; n = 6). RNA microarray indicated that JSK altered transcription of genes involved in ischemic and inflammatory/immune responses and apoptosis (p < 0.05; n = 3). CONCLUSIONS: JSK appears to target multiple biochemical and cellular pathways to enhance functional recovery and improve outcomes of SCI. The results provide a basis for further investigation of JSK's effects following SCI.

LC determination of albiflorin and paeoniflorin in Bai Shao (Paeonia lactiflora) as a raw herb and dried aqueous extract.

A validated analytical method is reported for the analysis of paeoniflorin and albiflorin in Bai Shao (Paeonia lactiflora) as a dried raw herb and commercially prepared dried aqueous extract. The samples were extracted by sonication in methanol and the extract analyzed by LC-photodiode array with identity confirmation by electrospray ionization-tandem MS. A C18 column was used with an acetonitrile-water gradient mobile phase. Paeoniflorin and albiflorin were quantified at 230 nm. Ions with m/z 121 and 327 were produced with the MS detector, using the paeoniflorin precursor ion with m/z 479. For albiflorin, the precursor ion with m/z 479 produced the m/z 121 and 77 ions. The amounts of paeoniflorin and albiflorin found in the raw herb were 33.2 and 1.8 mg/g, respectively; and in the dried aqueous extract, the amounts were 34.8 and 15.7 mg/g, respectively. The LODs for paeoniflorin and albiflorin were 0.37 and 1.39 mg/g, respectively, for the raw herb and 0.25 and 0.06 mg/g, respectively, for the dried aqueous extract.