Use of diffusion-ordered NMR spectroscopy and HPLC-UV-SPE-NMR to identify undeclared synthetic drugs in medicines illegally sold as phytotherapies

• Published in: Magnetic resonance in chemistry Vol. 51; no. 9; pp. 541 - 548
• Main Authors: Silva, Lorena M. A., Filho, Elenilson G. A., Thomasi, Sérgio S., Silva, Bianca F., Ferreira, Antonio G., Venâncio, Tiago
• Format: Journal Article
• Language: English
• Published: England Blackwell Publishing Ltd 01.09.2013; Wiley Subscription Services, Inc
• Subjects: Analgesics - analysis; Analgesics - chemical synthesis; Anti-Inflammatory Agents, Non-Steroidal - analysis; Anti-Inflammatory Agents, Non-Steroidal - chemical synthesis; Biological Products - analysis; Brazil; Chromatography, High Pressure Liquid - instrumentation; Diffusion; DOSY; drug adulteration; Drug Labeling; Drugs; Herbal medicine; HPLC-UV-SPE-NMR; illegal e-commerce; Internet; Magnetic Resonance Spectroscopy - instrumentation; Medical; Molecular Structure; Plant Preparations - analysis; Ranitidine; Remedies; Reproduction; Solid Phase Extraction - instrumentation; Spectrophotometry, Ultraviolet - instrumentation; unknown formulas; DOSY; illegal e-commerce; drug adulteration; HPLC-UV-SPE-NMR; unknown formulas
• ISSN: 0749-1581; 1097-458X
• DOI: 10.1002/mrc.3984

The informal (and/or illegal) e‐commerce of pharmaceutical formulations causes problems that governmental health agencies find hard to control, one of which concerns formulas sold as natural products. The purpose of this work was to explore the advantages and limitations of DOSY and HPLC–UV–SPE–NMR. These techniques were used to identify the components of a formula illegally marketed in Brazil as an herbal medicine possessing anti‐inflammatory and analgesic properties. DOSY was able to detect the major components present at higher concentrations. Complete characterization was achieved using HPLC–UV–SPE–NMR, and 1D and 2D NMR analyses enabled the identification of known synthetic drugs. These were ranitidine and a mixture of orphenadrine citrate, piroxicam, and dexamethasone, which are co‐formulated in a remedy called Rheumazim that is used to relieve severe pain, but it is prohibited in Brazil because of a lack of sufficient pharmacokinetic and pharmacodynamic information. Copyright © 2013 John Wiley & Sons, Ltd. Phytotherapies are wrongly considered as healthy treatment, and many profiteers have been using the Internet for selling dangerous allopathic formulas as phytotherapies. The cheap and easy acquisition of these formulas, provided without any medical recommendation, is a serious problem that affects mainly the poor countries. Regarding their advantages and limitations, the combined use of DOSY–NMR and LC–UV–SPE–NMR can fully resolve the mixture, detecting undeclared compounds without use of additional analyses.