Essential Oil Drugs – Terpene Composition of Aromatic Herbs

Essential oils (EO) are plant secondary metabolites that are known for their fragrance and food flavour properties. They consist of a complex mixture of mono- and sesquiterpenes, phenyl propanoids and oxygenated compounds. EOs can be present in different plant organs and materials, and their storage is related to specialised secretory structures. The yield of EOs from plant raw materials by distillation or pressing may on average vary from 0.1 – 1%, thus restricting the major EO production to the plant group of aromatic plants. Due to their function as signalling compounds between different types of organisms and diverse biological systems, their general antimicrobial and antioxidative effects and medicinal activity, EOs offer a promising potential for future applications within the fields of agriculture, medicine, pharmaceutical industry and biotechnology.Changed consumer demands and raised interest in natural product compounds, especially essential oils, have formed the basis for initiating the research project “Norwegian Herb Production (Norsk Urteproduksjon NUP)” to encourage the cultivation, processing, marketing and distribution of aromatic and medicinal plants. The production, composition and quality characteristics of EOs (yield and terpene composition) from chamomile, lemon balm, oregano, peppermint, sachalinmint, thyme and yarrow have been investigated in the project period between 1994-1998.Much focus has been put on the application of solid-phase microextraction (SPME) coupled with gas chromatography-mass spectrometry (GC-MS) for the analysis of EO volatiles from various aromatic and medicinal plants. SPME is a fast, solvent-free and non- destructive sample preparation technique where the analytes are extracted from fluid or solid matrices by headspace (HS) or direct immersion sampling (DI). Apart from EO isolation by common distillation, the applicability and sensitivity of the SPME fibre has made it feasible to carry out qualitative and semi-quantitative HS analyses of aromatic plants with regard to changes of EO metabolism during ontogenesis and plant development.Based on NUP-results from field trials in the period between 1995-1996, the mint species peppermint (Mentha × piperita L.) and sachalinmint (Mentha sachalinensis (Briq.) Kudo) have been studied in detail (Papers B, D and E). Comparative analyses by applying distillation sampling and SPME have been carried out in order to study the advantages and disadvantages of both techniques (Papers B and E). It could be shown, that SPME offers a fast and reliable method for detecting quality-impact compounds from the p-menthane group (menthol, menthone, neomenthol, isomenthone and menthyl acetate). A distinct increase in the menthol/menthone ratio in the basipetal direction could be detected for peppermint and sachalinmint by applying SPME, thus revealing within-plant quality differences according to pharmacopeial requirements. Taking the increase of EO production from the vegetative to the generative growth stage into account, the harvest of mint plants in bloom will result in better EO yield and quality with regard to higher amounts of menthol.When applying HS-SPME on complex EO volatile matrices such as known for yarrow (Achillea millefolium L.; Paper C), one might deal with fibre-partitioning effects of the different mono- and sesquiterpenes due to their physical and chemical properties. Despite these disadvantages, HS-SPME appears to be a sensitive extraction method for the screening of EO volatiles from complex sample matrices. Comparative analyses of volatiles from rose root rhizomes (Rhodiola rosea L.) have been carried out in order to characterize the rose-like odour compounds (Paper F). A total of 75 and 59 compounds have been identified by distillation sampling and HS-SPME, respectively, thus underscoring the excellent extraction properties and applicability of the SPME fibre.Paper A gives a brief overview of EO biosynthesis and chemical structures, plant sources and methods of EO production. Before leading over to the main topic of HS-SPME applications by referring to numerous examples from the research work at The Plant Biocenter in the past 5 years, an introduction of solid-phase microextraction with regard to devices, procedures and extraction parameters is given.The advantages and disadvantages of distillation vs. SPME are outlined on the background of comparative analyses of peppermint, chamomile, basil and dill. Furthermore, the utilization of HS-SPME for quantitative studies with regard to extraction time and analyte concentration is being highlighted. Examples for the screening of chemotypes (hops −Humulus lupulus L.) and cultivars (dill – Anethum graveolens L.) and ontogenetic studies are given (Mentha species; arnica −Arnica montana L.). Finally, the applicability of HS-SPME for the quality assessment of processed herbs (sweet basil −Ocimum basilicum L.) and phytomedicinal preparations (red coneflower – Echinacea purpurea L.) is being discussed.The advantages of HS-SPME over classical distillation and headspace applications are impressive due to drastically reduced analysis time and will introduce new frontiers in plant volatile research with regard to secondary metabolism, plant-insect interactions and in vivo studies. The user-friendliness of operating SPME will initiate the development of future applications and equipment for the monitoring of volatiles for plant biological and environmental studies, extraction automation, on-site sampling and on-fibre storage of analytes.