1. Plant Derived Flavour and Fragrance Molecules Ray Marriott Biocomposites Centre, Bangor University

2. Contents Drivers for plant derived molecules Legislative framework Flavour and fragrance product overview Flavour and Fragrance molecules from plants Conclusions

3. Drivers for Plant Derived Molecules Flavour molecules Growth in “Natural” flavourings Consumer and retailer pressure Legislation – EC/1334/2008 (January 2011) Sustainability Fragrance molecules Less emphasis or need for “natural” Unique properties of plant derived molecules Cost effective ingredients

4. The worldwide flavours and fragrance ingredient market is worth approximately $7.8 billion (£4.9 billion) in 2011 with an average annual growth rate of 4.5% per year. “World demand for quality essential oils and their derivatives is likely to see increasing demand in the coming years, and natural products will continue to remain an important part of the flavours and fragrances industry” BCC Research: Report CHM034B Market for Plant Derived Molecules

5. Legislative Framework Flavouring molecules EC/1334/2008 – defines “Natural” substances and permitted methods of preparation 2009/32/EC and 2010/59/EC – defines permitted process solvents and MRLs 2232/96/EC and amendments – establishes a community list of flavouring substances Fragrance molecules Directive 93/35/EEC and amendments established a list of cosmetic ingredients (INCI list), section 2 lists perfume and aromatic raw materials 26 fragrance molecules are considered allergens and restricted under Cosmetics Directive 2003/15/EC - more may follow

6. Production of Natural Flavour Molecules Natural sources Extraction (Physical processes) Fractionation Renewable raw materials Fractionation Fermentation Extraction “White biotechnology” Fractionation Renewable raw materials Enzyme hydrolysis Extraction Renewable raw materials Microwave activation Extraction Clean synthesis Processes compliant with Annex II – EC/1334/2008 Natural flavour & fragrance molecules

7. Flavour and Fragrance Product Overview Extracted products Oleoresins – herbs and spices in particular Concretes Absolutes Enfluerage – aroma extracted into purified fats & oils Expressed products Mostly applied to citrus peel oils Essential oils Steam distilled from green or dried plant materials Often starting materials for aroma molecules mostly fragrance applications

8. Flavour and Fragrance molecules from plants F&F molecules are mostly secondary metabolites and plant chemotype specific Composition is also subject to climate, location, harvest date and post harvest processes Most plant derived molecules are: Terpenes Hydrocarbons, alcohols, aldehydes, esters Phenolics Alcohols, aldehydes, ethers, esters Aliphatic esters

9. Flavour and Fragrance molecules from plants Most aroma molecules are produced in specialised structures called trichomes Lavender trichomes Peppermint trichomes

10. Terpenes from plants Most terpenes used in flavour and fragrance formulations are mono (C=10) or sesquiterpenes (C=15) Monoterpenes and sesquiterpenes can be acyclic, mono, bi or very occasionally tricyclic myrcene  -terpinene camphene tricyclene  -farnesene  -bisabolene  -cadinene cyperene

11. Terpene hydrocarbons  -pinene sabinene  3 -carene  -pinene camphene limonene terpinen-4-ol myrcene caryophyllene humulene Picea abies Cupressocyparis leylandii Humulus lupulus = 60% = 60% + = 90% OH

12. Terpene alcohols, ketones and aldehydes L-menthol menthone L-carvone D-carvone Mentha piperita Mentha spicataCarum carvi 50-80% 50-65%

13. Welsh native Mentha species Mentha x villosa piperitone oxide menthofuran Mentha aquatica

14. Mentha gentilis oil First fractionResidue Middle fraction Linalool from Mentha sp.

15. Distribution of linalool isomers Enantiomeric distribution (%) (R) (S) Basil1000 Mentha sp.1000 Ho leaf1000 Lavender964 Hop928 Rose6040 Geranium5050 Grapefruit3763 Lemon3268 Rosemary2377 Lilac1189 Coriander1090 Jasmine496 Casabianca H, Graff JB, Faugier V, Fleig F, Grenier C (1997) Enantiomeric distribution studies of linalool and linalyl acetate. A powerful tool for authenticity control of essential oils. HRC J High Res Chrom 21:107-112 OT=0.7ppb OT=7.8ppb

16. Linalool from Coriandrum sativum Steam distillation Essential oil Fractional distillation CO 2 extraction Molecular distillation Triglycerides Petroselinic acid Lauric acidAdipic acid Nylon 66 (S)-(+)-linalool

17. Phenolics from plants O Thymol (35-55%) Carvacrol (>60%) Estragole (60-75%) Anethole (>75%) Vanillin (>95%*) Cinnamaldehyde (55-75%) Eugenol (75-90%) methyl salicylate (96-99%)

18. Plant derived aliphatic esters Aliphatic esters are much less common than terpenes or phenolic molecules Most “natural” esters are produced by enzymatic esterification of natural alcohols and fatty acids produced by fermentation (complies with EC/1334/2008) Aliphatic esters are found mostly in the families Asteraceae and Apiaceae

19. Esters from Chamaemelum nobile L. propyl tiglate Isobutyl angelate 2-methyl butyl angelate 60% of English chamomile oil comprises just three esters

20. Heracleum mantegazzianum Heracleum sphondylium Octyl esters – Heracleum species

21. 1. octan-1-ol 2. 3-octenyl acetate 3. octyl acetate 4. octyl 2-methyl propanoate 5. octyl butanoate 6. octyl 2-methyl butanoate 7. octyl hexanoate 8. octyl octanoate 1 3 2 4 5 67 8 4 3 6 5 2 9. hexyl 2-methyl propanoate 10. hexyl butanoate 11. hexyl 2-methyl butanoate 9 10 11 Composition of hydro-distilled oil Heracleum mantegazzianum Heracleum sphondylium

22. Multi product streams from Heracleum sp. Steam distillation Essential oil Fractional distillation CO 2 extraction Molecular distillation Triglycerides Petroselinic acid Psoralens Polymers Octyl and hexyl esters Pharmaceuticals and drug precursors

23. Conclusions Demand for plant derived F&F molecules is growing Plants are still an economic source of F&F molecules A wide range of terpenes, phenolics and aliphatic compounds can be obtained from UK plants But! Crops can often be grown and processed at lower cost in other parts of the world UK production needs to be highly efficient and where possible targeted at multi-product crops

24. Thank you for your attention! r.marriott@bangor.ac.uk

26. http://ec.europa.eu/food/food/chemicalsafety/flavouring/database/dsp_search.cfm Flavouring substances database

27. Composition of Heracleum sphondylium scCO 2 extract 1. octan-1-ol 2. 3-octenyl acetate 3. octyl acetate 4. octyl 2-methyl propanoate 5. octyl butanoate 6. octyl 2-methyl butanoate 7. octyl hexanoate 8. octyl octanoate 1 3 24 5 6 7 8

28. Psoralens from Heracleum sphondylium 5,8-Diethoxy-2,3-dimethylquinoxaline hentriacontane nonacosane  -sitosterol tetracosanol nonadecane hexadecanoic acid 5-methoxy psoralen 8-methoxy psoralen octadecanoic acid linoleic acid 5,8-dimethoxy psoralen 8-Isopentenoxy psoralen 9-[(3,3-Dimethyl-2-oxiranyl)methoxy]-7H-furo[3,2-g]chromen-7-one (R)-9-((3,3-Dimethyl-2-oxiranyl)methoxy)-4-methoxyfuro(3,2-g)chromen-7-one