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 di_erentiated 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

The chemical and pharmacological variability of key bio-actives present in commercially available Angelica sinensis, Glycyrrhiza uralensis and Rhodiola rosea samples

There is global demand for better quality control (QC) of medicinal herbs including standardisation of bio-active chemical components and pharmacological testing. The quantitative variability of key chemical markers in A. sinensis, G. uralensis and R. rosea from several sources and the pharmacological activity was determined to confirm that the chemical markers’ variability is linked to the biological activity. To quantify the chemical variation, three novel, simple and rapid UPLC-PDA-ESI-MS/MS methods were developed and validated. The qualitative chemical variability of the bio-actives was further studied using 1H NMR metabolomics and principal component analysis (PCA). The pharmacological anti-inflammatory activity of the commercials extracts and marker compounds was assessed using the Griess reagent NO scavenging assay. The A. sinensis samples exhibited the greatest chemical fold-variation while G. uralensis showed the least chemical variability. R. rosea samples indicate the presence of other Rhodiola sub-species. The PCA clustering was consistent with observed trends and identified adulteration. The bioactivity of the selected marker compounds was linked to the extracts activity. The use of PCA analysis and in vitro anti-inflammatory testing improve and provide rationale for better QC of herbal extracts