Timothy P. Murphy

Pelargonium Oil and Methyl Hexaneamine (MHA): Analytical Approaches Supporting the Absence of MHA in Authenticated Pelargonium graveolens Plant Material and Oil

Methylhexaneamine (MHA) has been marketed in dietary supplements based on arguments that it is a constituent of geranium (Pelargonium graveolens) leaves, stems, roots or oil, and therefore qualifies as a dietary ingredient. The purpose of this study is to determine whether P. graveolens plant material (authenticated) or its oil contains detectable quantities of MHA. Two analytical methods were developed for the analysis of MHA in P. graveolens using gas chromatography-mass spectrometry and liquid chromatography-tandem mass spectrometry. The results were further confirmed using liquid chromatography-high-resolution mass spectrometry. Twenty commercial volatile oils, three authenticated volatile oils and authenticated P. graveolens leaves and stems (young and mature, and fresh and dried) were analyzed for MHA content. In addition, three dietary supplements containing MHA that alleged P. graveolens as the source are analyzed for their MHA content. The data show that none of the authenticated P. graveolens essential oils or plant material, nor any commercial volatile oil of Pelargonium (geranium oil) contain MHA at detectable levels (limit of detection: 10 ppb). The dietary supplements that contained MHA as one of their ingredients (allegedly from geranium or geranium stems) contained large amounts of MHA. The amounts of MHA measured are incompatible with the use of reasonable amounts of P. graveolens extract or concentrate, suggesting that MHA was of synthetic origin.

Chemical Fingerprinting of Cannabis as a Means of Source Identification

Marijuana is the most widely abused and readily available illicit drug in the United States, with an estimated 11.5 million current users annually purchasing more than

Methylhexanamine is not detectable in Pelargonium or Geranium species and their essential oils: A multi‐centre investigation

10 billion of the drug (1). Drug enforcement agencies are therefore keenly interested in trafficking routes of both foreign and domestically grown supplies of marijuana. From confidential sources to satellites, these agencies employ a multitude of methods to gather intelligence to direct resources, plan control operations, and develop policies. A practical means to recognize the source of seized marijuana would be a valuable tool for those purposes. Based on findings from 1990 to 1992 and described here, one way to determine origin is by using a chemical fingerprint system, a method that has shown promise as an effective intelligence tool to ascertain the geographic origin of confiscated marijuana samples. Of the many factors that affect the chemical constituents of marijuana, it is apparent that environmental factors consistently induce profiles unique to each environ. An “environ of origin” as broad as a continent or as small as an indoor garden may be differentiated based on the chemical fingerprint, or “signature,” of marijuana cultivated there—if a statistically significant number of samples grown in that environ are available for comparison. However, because all environs are not unique, the chemical fingerprint of cannabis is not considered to be an ultimate tool for forensic applications, although the technique may effectively support other types of evidence and is certainly of particular value in intelligence operations.

LC–MS-MS Analysis of N,α-Diethylphenethylamine (N,α-ETH) and Its Positional Isomer N,β-Diethylphenethylamine (N,β-ETH) in Dietary Supplements

In an earlier study, we developed two sensitive and reliable procedures for gas chromatography-mass spectrometry (GC-MS) and liquid chromatography-tandem mass spectrometry (LC-MS/MS) analysis of methylhexaneamine (MHA) in P. graveolens plant materials and volatile oils. None of the analyzed plant materials or oils showed any detectable levels of MHA which was further substantiated by high resolution liquid chromatography-quantum time of flight-mass spectrometry (LC-QTOF-MS) analysis with a limit of detection of 10 ppb. However, other laboratories (two studies) reported the presence of MHA in some samples of P. graveolens and pelargonium oil acquired by the investigators from China. Because of the controversy of whether Pelargonium species or pelargonium oil contains MHA, it was recommended that splits of multiple samples be analyzed by different laboratories. In this investigation, multiple plant materials and oil samples were collected from around the world. These samples were submitted to four different sites for analysis. All sites adopted a similar extraction method. All the analysis sites used LC-MS/MS or LC-QTOF-MS and detection limit was set close to the 10 ng/mL as previously reported. A total of 18 plant samples belonging to 6 different Pelargonium species and 9 oils from different locations around the world were split among 4 different analytical laboratories for analysis (each lab received the same samples). None of the laboratories detected MHA in any of the samples at or around the 10 ppb detection level of the procedure used.

Pharmacokinetics and excretion of gamma-hydroxybutyrate (GHB) in healthy subjects.

In a previous publication, we reported on the analysis of several dietary supplement/exercise formulas and the quantitation of N,α-diethylphenethylamine (N,α-ETH, 3: ). In this article we report on the reanalysis of these products using LC-MS-MS and GC-MS methods capable of clearly separating the N,α-isomer ( 3: ) from its N,β-isomer (N,β-ETH, 4: ). The reanalysis, by both methods, showed that all samples previously reported as containing N,α-ETH ( 3: ) do contain only that isomer with no detectable concentrations of the N,β-ETH ( 4: ).