Published in Analytical Chemistry Insights , the new analysis concluded: “DMAA, which is used in some nutritional supplements, has led some to question whether it is actually a constituent of the geranium plant and its oils.
“A validated method for quantification of DMAA in geranium plants has been established in the present investigation and has confirmed the presence of 1,3-DMAA and 1,4-DMAA in the plant tissue and essential oil.”
DMAA (1,3-Dimethylamylamine, also known as methyl hexaneamine (MHA), and several other names) has rarely been out of the headlines in recent months since FDA issued warning letters to 10 manufacturers and distributors of supplements containing DMAA.
There has been intense debate about whether DMAA, which was first manufactured synthetically by drug giant Eli Lily in the 1940s, is in fact a constituent of geranium.
According to a single analysis by Chinese researchers reportedly using gas chromatography-mass spectrometry (GC-MS) techniques and published in the Journal of Guizhou Institute of Technology (1996, Vol. 25, pp. 82-85) – ‘The Ping Paper’ – DMAA is a constituent of geranium oil, but no other published analysis has reported its presence… until now.
Putting the questions to rest?
Commenting on the new analysis, Kerri Toloczko, spokesperson for USPlabs – the company behind best-selling Jack3d supplement containing DMAA – said: “This study, confirming the presence of 1,3 dimethylamylamine and 1,4 dimethylamylamine in Chinese geranium, will put to rest any lingering questions about whether DMAA is a naturally occurring ingredient.
“It is essential to understand that because this study specifically tested fresh Chinese geranium and used a fully validated method, utilizing LC/MS/MS, designed specifically for identifying and quantitating DMAA in geranium plant and oil, that it was able to find these ingredients. Nevertheless, its presence in Chinese geranium should now be perceived as fact.”
USPlabs confirmed that additional analytical studies have been performed to “further corroborate these results including those performed at a major American university”, and these would be will be published in peer-reviewed journals in the near future.
Now you see it, now you don’t
In contrast to the Intertek analysis, there have been two other analyses published in recent months that showed that DMAA was not present in geranium. An analysis published in the Journal of Analytical Toxicology in June was described as ‘comprehensive’ and ‘robust’ by respected members of the industry.
Scientists from ElSohly Laboratories, Inc. (ELI), Phyto Chemical Services, Inc. (PSI), the National Center for Natural Products Research, The University of Mississippi, and the US Anti- Doping Agency (USADA) reported that gas chromatography–mass spectrometry (GC-MS) and liquid chromatography–tandem mass spectrometry (LC–MS-MS) analysis of geranium oils or young and mature, fresh and dried leaves and stems found no detectable levels of DMAA.
The scientists further confirmed the results using liquid chromatography–high-resolution mass spectrometry (high resolution LC–QTOF-MS).
This was followed by an analysis published in Drug Testing and Analysis by Dr Dan Armstrong et al at the University of Texas, Arlington which concluded that: “It appears unlikely that the DMAA in supplements originates from natural sources such as geranium oils for three reasons: The DMAA extracted from these supplement products had diastereomeric ratios that were indistinguishable from the synthetic DMAA standards; they are all racemic; and no DMAA was detected at a level of ≥10 ppb in any of the 8 geranium oil samples.”
For the new analysis, the Intertek scientists used a liquid chromatography–electrospray ionization/tandem mass spectrometry (LC-ESI/MS/MS) method to test for the presence of 1,3-dimethylamylamine (1,3-DMAA) and 1,4-dimethylamylamine (1,4-DMAA) in geranium plants (Pelargonium graveolens).
Stereochemistry has been a main part of the argument against the presence of DMAA in geranium, since the presence of stereoisomers at equal levels is indicative of synthetic production (known as a racemic mixture), while only one form tends to dominate in nature (because they are made via enzymatic processes and enzymes favor one form over another).
The Intertek analysis confirmed that the synthetic 1,3-DMAA reference material was racemic.
However, in an apparent challenge to nature, they also found that the DMAA in the geranium samples was racemic. “The results in the current study show that 1,3-DMAA in geranium plants and geranium oils appears to be an exception to this notion [that only one configuration would be present in plants]”, claimed the Intertek researchers.
They added that this is not the first report of a racemic mixture in plant tissue, and that racemic nerol oxide has previously “been demonstrated once before in the geranium plant as well”.
To conclude, the Intertek scientists wrote: “A simple and rapid procedure for sample extraction and purification has been developed.
“This LC/MS/MS method is sensitive and reliable and has been used successfully for the simple and rapid analysis of DMAA in the geranium plant and its oils.”
Several leading analytic experts have been contacted by NutraIngredients-USA for their reaction to the new paper. Because of the complex nature of such analyses, no comments were received prior to publication. NutraIngredients-USA will run this reaction next week.
Source: Analytical Chemistry Insights
Published online ahead of print, doi: 10.4137/ACI.S9969
“Identification and Quantification of Dimethylamylamine in Geranium by Liquid Chromatography Tandem Mass Spectrometry”
Authors: J.S. Li, M. Chen, Z.C. Li