Advertisement

Evaluation of the Presence of 1,3-Dimethylamylamine in Pelargonium Leaves and Essential Oils by Mass Spectrometric and Chromatographic Methods

  • Maíra Kerpel dos SantosEmail author
  • Gabriela Blauth Walber
  • Tainá Kreutz
  • Krissie Soares
  • Leticia Jacobi Danielli
  • Kristiane de Cassia Mariotti
  • Mara Ritter
  • Glen P. Jackson
  • Luis E. Arroyo
  • Renata Pereira Limberger
Short Communication
  • 26 Downloads

Abstract

1,3-Dimethylamylamine (DMAA) is known to be added to dietary supplements from synthetic sources and, presumably, from natural geranium oil. However, the natural occurrence of DMAA in geranium oil (Pelargonium graveolens) has been controversial as published studies report contradicting findings. It is unclear if the difference in detection of DMMA in Pelargonium species is a result of the loss during extraction methods, different detection capabilities of analytical methods or if the content of DMAA is dependent of the species and geographical origins. Consequently, the purpose of this study is threefold: (1) to compare the analytical performance of mass spectrometry methods for the detection of DMMA, including GC/MS, DART–MS/MS and LC–MS/MS; (2) to evaluate if DMMA is lost during the extraction of essential oils from Pelargonium leaves of species from Brazil testing headspace extraction, and (3) to evaluate if DMMA is naturally present in a variety of essential oils originating from six countries. This study shows that for detection of more volatile compounds, headspace GC–MS proved to be more favorable than hydrodistilled essential oil analyzed by direct injection in GC–MS. DART–MS/MS showed to be a good alternative for identification of essential oils compounds and DMAA without sample preparation; LC–MS/MS proved to be sensitive for DMMA identification. Nevertheless, even after the analysis using mentioned methods, all essential oils and for the first time, the volatile components extracted from leaves, showed to be absent of DMAA, proving that its presence is not natural in these species.

Graphical Abstract

Keywords

1,3-Dimethylamylamine DMAA Pelargonium Headspace Essential oil 

Notes

Acknowledgements

The authors are thankful to CAPES-scholarship (Coordenação de Aperfeiçoamento de Pessoal de Nível Superior), CNPq (Conselho Nacional de Desenvolvimento Científico e Tecnológico) and FAPERGS (Fundação de Amparo à pesquisa do Estado do RS) (PqG 02/2014) by financial support; and to Laszlo Aromaterapia- Ltda, Brazil, Ferquima Ltda and Verbena Ltda for donation of essential oils.

Compliance with Ethical Standards

Conflict of interest

The authors declare that they have no competing interests.

Supplementary material

10337_2019_3715_MOESM1_ESM.pdf (365 kb)
Supplementary material 1 (PDF 365 kb)

References

  1. 1.
    da Justa Neves DB, Caldas ED (2015) Dietary supplements: international legal framework and adulteration profiles, and characteristics of products on the Brazilian clandestine market. Regul Toxicol Pharmacol 73:93–104.  https://doi.org/10.1016/j.yrtph.2015.06.013 CrossRefGoogle Scholar
  2. 2.
    Ping ZJQ (1996) A study on the chemical constituents of geranium oil. J Guizhou Inst Technol 25:82–85Google Scholar
  3. 3.
    Lisi A, Hasick N, Kazlauskas R, Goebel C (2011) Studies of methylhexaneamine in supplements and geranium oil. Drug Test Anal 3:873–876.  https://doi.org/10.1002/dta.392 CrossRefGoogle Scholar
  4. 4.
    Zhang Y, Woods RM, Breitbach ZS, Armstrong DW (2012) 1,3-Dimethylamylamine (DMAA) in supplements and geranium products: natural or synthetic? Drug Test Anal 4:986–990.  https://doi.org/10.1002/dta.1368 CrossRefGoogle Scholar
  5. 5.
    El AsbahaniA, Miladi K, Badri W et al (2015) Essential oils: from extraction to encapsulation. Int J Pharm 483:220–243.  https://doi.org/10.1016/j.ijpharm.2014.12.069 CrossRefGoogle Scholar
  6. 6.
    das Brasil M, de San VS (2010) Farmacopéia Brasileira. Diário Of da União 1:546.  https://doi.org/10.1590/S0102-33062006000100002 Google Scholar
  7. 7.
    Ferreira SLC, Bruns RE, Ferreira HS et al (2007) Box–Behnken design: an alternative for the optimization of analytical methods. Anal Chim Acta 597:179–186.  https://doi.org/10.1016/j.aca.2007.07.011 CrossRefGoogle Scholar
  8. 8.
    Adams R (2007) Identification of essential oil components by gas chromatography/mass spectroscopy, 4th edn. Allured Publishing Corporation, Carol StreamGoogle Scholar
  9. 9.
    Kerpel dos Santos M, Gleco E, Davidson JT et al (2018) DART–MS/MS screening for the determination of 1,3-dimethylamylamine and undeclared stimulants in seized dietary supplements from Brazil. Forensic Chem 8:134–145.  https://doi.org/10.1016/j.forc.2018.03.005 CrossRefGoogle Scholar
  10. 10.
    Elsohly MA, Gul W, Elsohly KM et al (2012) Pelargonium oil and methyl hexaneamine (MHA): analytical approaches supporting the absence of MHA in authenticated pelargonium graveolens plant material and oil. J Anal Toxicol 36:457–471CrossRefGoogle Scholar
  11. 11.
    Sgorbini B, Bicchi C, Cagliero C et al (2015) Herbs and spices: characterization and quantitation of biologically-active markers for routine quality control by multiple headspace solid-phase microextraction combined with separative or non-separative analysis. J Chromatogr A 1376:9–17.  https://doi.org/10.1016/j.chroma.2014.12.007 CrossRefGoogle Scholar
  12. 12.
    Li JS, Chen M, Li ZC (2012) Identification and quantification of dimethylamylamine in geranium by liquid chromatography tandem mass spectrometry. Anal Chem Insights 7:47–58.  https://doi.org/10.4137/ACI.S9969 CrossRefGoogle Scholar
  13. 13.
    Avula B, Smillie TJ, Wang Y-H et al (2015) Fast identification of 1,3-dimethylamylamine using direct analysis in real time-QToF-MS. J AOAC Int 98:757–759.  https://doi.org/10.5740/jaoacint.14-223 CrossRefGoogle Scholar
  14. 14.
    Sisco E, Verkouteren J, Staymates J, Lawrence J (2017) Rapid detection of fentanyl, fentanyl analogues, and opioids for on-site or laboratory based drug seizure screening using thermal desorption DART–MS and ion mobility spectrometry. Forensic Chem 4:108–115.  https://doi.org/10.1016/j.forc.2017.04.001 CrossRefGoogle Scholar
  15. 15.
    Austin KG, Travis J, Pace G, Lieberman HR (2014) Analysis of 1,3 dimethylamylamine concentrations in Geraniaceae, geranium oil and dietary supplements. Drug Test Anal 6:797–804.  https://doi.org/10.1002/dta.1491 CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2019

Authors and Affiliations

  • Maíra Kerpel dos Santos
    • 1
    Email author
  • Gabriela Blauth Walber
    • 1
  • Tainá Kreutz
    • 1
  • Krissie Soares
    • 1
  • Leticia Jacobi Danielli
    • 1
  • Kristiane de Cassia Mariotti
    • 2
  • Mara Ritter
    • 3
  • Glen P. Jackson
    • 4
  • Luis E. Arroyo
    • 4
  • Renata Pereira Limberger
    • 1
  1. 1.Graduate Program of Pharmaceutical Sciences, Toxicology Laboratory, Faculty of PharmacyFederal University of Rio Grande do SulPorto AlegreBrazil
  2. 2.Federal Police, Superintendence of the Federal Police of Rio Grande do SulPorto AlegreBrazil
  3. 3.Graduate Program of Botanic, Bioscience InstituteFederal University of Rio Grande do SulPorto AlegreBrazil
  4. 4.Department of Forensic and Investigative ScienceWest Virginia UniversityMorgantownUSA

Personalised recommendations