title: Detection, identification and quantification by 1H NMR of adulterants in 150 herbal dietary supplements marketed for improving sexual performance.
abstract: One hundred and fifty dietary supplements (DS) marketed to increase sexual performance were analyzed. All these formulations were claimed to contain only natural compounds, plant extracts and/or vitamins. (1)H NMR spectroscopy was used for detecting the presence of adulterants and for their identification and quantification. Mass spectrometry was used as a complementary method for confirming the chemical structures. 61% of DS were adulterated with phosphodiesterase-5 inhibitors (PDE-5i) (27% with the PDE-5i medicines sildenafil, tadalafil and vardenafil, and 34% with their structurally modified analogues). Among them, 64% contained only one PDE-5i and 36% mixtures of two, three and even four. The amounts of PDE-5i medicines were higher than the maximum recommended dose in 25% of DS tainted with these drugs. Additional 5.5% DS included other drugs for the treatment of sexual dysfunction (yohimbine, flibanserin, phentolamine, dehydroepiandrosterone or testosterone). Some DS (2.5%) contained products (osthole, icariin) extracted from plants known to improve sexual performance. Only 31% of the samples could be considered as true herbal/natural products. A follow-up over time of several DS revealed that manufacturers make changes in the chemical composition of the formulations. Lack of quality or consistent manufacture (contamination possibly due to inadequate cleaning of the manufacturing chain, presence of impurities or degradation products, various compositions of a given DS with the same batch number, inadequate labelling) indicated poor manufacturing practices. In conclusion, this paper demonstrates the power of (1)H NMR spectroscopy as a first-line method for the detection of adulterated herbal/natural DS and the need for more effective quality control of purported herbal DS.
authors.affiliation: Groupe de RMN Biomédicale, Laboratoire SPCMIB (UMR CNRS 5068), Université Paul Sabatier, 118 route de Narbonne, 31062 Toulouse cedex 9, France.
authors.forename: Véronique
authors.initials: V
authors.lastname: Gilard
authors.affiliation: Groupe de RMN Biomédicale, Laboratoire SPCMIB (UMR CNRS 5068), Université Paul Sabatier, 118 route de Narbonne, 31062 Toulouse cedex 9, France.
authors.forename: Stéphane
authors.initials: S
authors.lastname: Balayssac
authors.affiliation: Groupe de RMN Biomédicale, Laboratoire SPCMIB (UMR CNRS 5068), Université Paul Sabatier, 118 route de Narbonne, 31062 Toulouse cedex 9, France.
authors.forename: Aurélie
authors.initials: A
authors.lastname: Tinaugus
authors.affiliation: Service commun de spectrométrie de masse, Université Paul Sabatier, 118 route de Narbonne, 31062 Toulouse cedex 9, France.
authors.forename: Nathalie
authors.initials: N
authors.lastname: Martins
authors.affiliation: Groupe de RMN Biomédicale, Laboratoire SPCMIB (UMR CNRS 5068), Université Paul Sabatier, 118 route de Narbonne, 31062 Toulouse cedex 9, France.
authors.forename: Robert
authors.initials: R
authors.lastname: Martino
authors.affiliation: Groupe de RMN Biomédicale, Laboratoire SPCMIB (UMR CNRS 5068), Université Paul Sabatier, 118 route de Narbonne, 31062 Toulouse cedex 9, France. Electronic address: martino@chimie.ups-tlse.fr.
authors.forename: Myriam
authors.initials: M
authors.lastname: Malet-Martino
mesh_terms: D001046:Aphrodisiacs / Q000032:analysis* / Q000191:economics; D019587:Dietary Supplements / Q000032:analysis* / Q000191:economics; D004340:Drug Contamination; D006859:Hydrogen; D009682:Magnetic Resonance Spectroscopy / Q000379:methods*; D040541:Marketing / Q000191:economics; D058986:Phosphodiesterase 5 Inhibitors / Q000032:analysis / Q000191:economics; D028321:Plant Preparations / Q000032:analysis* / Q000191:economics; D012725:Sexual Behavior / Q000187:drug effects
chemical_list: D001046:Aphrodisiacs; D058986:Phosphodiesterase 5 Inhibitors; D028321:Plant Preparations; D006859:Hydrogen
keywords: Adulteration; Dietary supplements; Mass spectrometry; NMR; PDE-5 inhibitors