Analysis and Confirmation of 1,3-DMAA and 1,4-DMAA in Geranium Plants Using High Performance Liquid Chromatography with Tandem Mass Spectrometry at ng/g Concentrations

Department of Chemistry, The University of Memphis, Memphis, TN, USA.
Analytical Chemistry Insights 11/2012; 7(1):59-78. DOI: 10.4137/ACI.S10445
Source: PubMed


1,3-Dimethylamylamine (1,3-DMAA) is a stimulant commercially sold in a variety of dietary supplements as a chemical species derived from geranium plants (Pelargonium graveolens). Whether 1,3-DMAA naturally occurs in geranium plants or other dietary ingredients, it has important regulatory and commercial ramifications. However, the analysis of 1,3-DMAA in geranium plants is not trivial due to low concentrations and a complex environmental matrix, requiring high selectivity and sensitivity. An extraction method combined with high performance liquid chromatography and tandem mass spectrometry is used to determine 1,3-DMAA and 1,4-dimethylamylamine (1,4-DMAA) concentrations in geranium plants with both external calibration and standard addition method. Samples from the Changzhou, Kunming, and Guiyang regions of China during both winter and summer were analyzed for 1,3-DMAA and 1,4-DMAA. The diastereomer ratios of the 1,3-DMAA stereoisomers of a racemic standard and the extracted plant were also quantified.

Download full-text


Available from: Heather L Fleming
  • Source
    • "[13] For LC-MS, extraction as an additional sample preparation step was necessary to overcome the matrix effect. [12] [15] The developed methodology was used for analysis of 16 products (Table 1). It should be mentioned that J-resolved experiments are required for confirmation, when matrix effect was present (samples S7 and S8). "
    [Show abstract] [Hide abstract]
    ABSTRACT: 1,3-Dimethylamylamine (DMAA) is a stimulant that can be found in pre-workout sports nutrition and dietary supplements. This practice is illegal because DMAA is not a safe food ingredient but rather an unapproved medicinal compound due to its pharmacological action. In order to determine the DMAA content in such products, a nuclear magnetic resonance (NMR) spectroscopic method was developed and validated (DMAA was quantified as DMAA-HCl). For quantification, the collective integral from two of the methyl groups of the molecule in the range δ 0.92-0.84 ppm was used. The method was linear over the examined range of 1-21 g/kg (R(2) = 0.9937). The recoveries from spiked concentrations (0.1-6 g/kg) ranged between 85% and 105% (96% on average), with a relative standard deviation (RSD) of 1% for an authentic sample. The detection limit was 0.03 g/kg and the quantification limit was 0.08 g/kg (calculated for 75 mg sample weight). The actual DMAA-HCl content in the sample was quantified using calibration curves (external standardization) or 3,5-dinitrobenzoic acid as single-point internal standard. The developed NMR methodology was applied for the analysis of 16 products, from which 9 samples were found positive (the DMAA-HCl concentration varied between 3.1 g/kg and 415 g/kg). The method can be recommended for routine use in food testing, customs or doping control laboratories. Copyright © 2014 John Wiley & Sons, Ltd.
    Full-text · Article · Sep 2014 · Drug Testing and Analysis
  • Source
    • "In a similar study, Fleming et al6 analyzed geranium plants harvested during three different seasons and from three different areas of China (Changzhou, Guiyang and Kunming) for the presence of 1,3- and 1,4-DMAA using an HPLC-ESI-QQQ method. The extraction procedure was adapted from the procedure reported by Li et al.5 Geranium plant materials are first extracted with 0.5 N HCl by sonication.6 After centrifugation, the aqueous layer was extracted once with hexane, then separated, further diluted with HCl as necessary, and filtered with a 0.45 μm nylon filter prior to injection in the HPLC. "
    [Show abstract] [Hide abstract]
    ABSTRACT: 1,3-Dimethylamylamine (1,3-DMAA) is an aliphatic amine with stimulant properties that are reportedly found naturally only in geranium plants (Pelargonium graveolens). The presence of 1,3-DMAA in geranium plants was first reported in a paper published in 1996, but some have questioned the identification of 1,3-DMAA in that study. Since then, a number of additional studies have been published, largely reporting the absence of 1,3-DMAA in geranium plants and commercial geranium oils. However, in two recent studies, 1,3-DMAA was detected in geranium plant tissues and a geranium oil sample using a simplified extraction approach on tissues and oil sourced from China. Whether or not 1,3-DMAA is found naturally in plants has significant implications as to how commercial products containing 1,3-DMAA are regulated by the US Food and Drug Administration. In this paper, differences in source materials, extraction procedures, and analytical approaches are reviewed in an attempt to rationalize the apparently conflicting evidence for the presence of 1,3-DMAA in geranium plant materials.
    Preview · Article · Jun 2013 · Analytical Chemistry Insights
  • [Show abstract] [Hide abstract]
    ABSTRACT: The timely update of the list of prohibited substances and methods of doping (as issued by the World Anti-Doping Agency) is an essential aspect of international anti-doping efforts and represents consensual agreement by expert panels regarding substances and the methods of performance manipulation in sports. The annual banned-substance review for human doping controls critically summarizes recent innovations in analytical approaches; its purpose is to improve the quality of doping controls by reporting emerging and advancing methods that focus on detecting known and recently outlawed substances. This review surveys new and/or enhanced procedures and techniques of doping analysis together with information relevant to doping control that has been published in the literature between October 2009 and September 2010.
    No preview · Article · Jan 2011 · Drug Testing and Analysis
Show more