HPLC-DAD–MS, HPLC–MSn and NMR Spectroscopy Analyzes the Herbal dietary supplement, Olivis

Although dietary supplements are not considered food, occasionally we will present blog posts about them since supplements often present analytical challenges that are similar to those encountered in food analysis. In this case, analysis was undertaken to determine labeling accuracy as well as to detect adulteration – both of which are common goals for various types of food testing. Olivis is a European dietary supplement taken as a remedy for hypertension. The herbal supplement is advertised to contain a blend of four plants, including Crataegus oxyacantha L., Olea europea L., Capsella bursa-pastoris L. and Fumaria officinalis L. Following reported cases of patients experiencing hypotensive events which caused them to collapse after taking Olivis, researchers were interested in analyzing the supplement to determine if the contents of the supplement could be linked to the adverse health effects. Using a combined analytical approach, researchers from the University of Florence analyzed two samples of Olivis purchased from a local herbalist.¹ Olivis samples were analyzed using high-performance liquid chromatography with a diode array detector a followed by mass spectrometry (HPLC-DAD–MS). NMR spectrometry was also performed to identify the constituents present in the Olivis samples. Ultimately, the researchers concluded that the four declared herbal ingredients were not present in high enough concentrations to cause the adverse side effects reported by those using Olivis. One ingredient, O. europea, was the most likely candidate to cause the reported side effects because of its known hypotensive effects; however, the researchers failed to find markers of O. europea present in the Olivis samples, indicating that it was either not present at all, or present at levels undetectable by this analysis. Surprisingly, there also some unexpected ingredients which required a more direct analysis employing high-performance liquid chromatography and tandem mass spectrometry HPLC Surveyor coupled to a LTQ equipped with an ESI interface (Thermo Scientific). The researchers identified the undeclared ingredients as indole alkaloids originating from plants of the Rauwolfia sp. In particular, the alkaloids ajmaline and reserpine were present. Ajmaline is used as an anti-arrythmic drug, but was not high enough in concentration to be to blame for the adverse side effects. Reserpine, on the other hand, was present in Olivis at high enough levels to affect blood pressure, and depending on the dosages of Olivis that were taken, could have been to blame for the reported side effects. The authors of this study suggest that more strict regulations need to be put in place for herbal supplements to ensure that declared ingredients are present and undeclared ingredients—especially those with the potential to be harmful, are not present. Reference