plant derived flavour and fragrance molecules ray marriott biocomposites centre, bangor university
TRANSCRIPT
Contents
Drivers for plant derived molecules
Legislative framework
Flavour and fragrance product overview
Flavour and Fragrance molecules from plants
Conclusions
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
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
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
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
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
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
Flavour and Fragrance molecules from plants
Most aroma molecules are produced in specialised structures called trichomes
Lavender trichomes
Peppermint trichomes
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 b-terpinene camphene tricyclene
a-farnesene a-bisabolene g-cadinene cyperene
Terpene hydrocarbons
a-pinene sabinene D3-carene
a-pinene camphene limonene terpinen-4-ol
myrcene caryophyllene humulene
Picea abies
Cupressocyparis leylandii
Humulus lupulus
= 60%
= 60% +
= 90%
OH
Terpene alcohols, ketones and aldehydes
L-menthol menthone
L-carvone D-carvone
Mentha piperita
Mentha spicata Carum carvi
14-Jun
05-Jul
29-Jul
15-Aug
15-Sep
30-Sep
30-Oct
0
10
20
30
40
50
60
menthone
menthol
menthyl acetate
menthofuran
50-80% 50-65%
Distribution of linalool isomers
Enantiomeric distribution (%)
(R) (S)
Basil 100 0
Mentha sp. 100 0
Ho leaf 100 0
Lavender 96 4
Hop 92 8
Rose 60 40
Geranium 50 50
Grapefruit 37 63
Lemon 32 68
Rosemary 23 77
Lilac 11 89
Coriander 10 90
Jasmine 4 96
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
Linalool from Coriandrum sativum
Steam distillation Essential oil
Fractionaldistillation
CO2 extraction
Molecular distillation
Triglycerides
Petroselinic acid
Lauric acid Adipic acid
Nylon 66
(S)-(+)-linalool
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%)
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
Esters from Chamaemelum nobile L.
propyl tiglate
Isobutyl angelate
2-methyl butyl angelate
60% of English chamomile oil comprises just three esters
1. octan-1-ol2. 3-octenyl acetate3. octyl acetate4. octyl 2-methyl propanoate5. octyl butanoate6. octyl 2-methyl butanoate7. octyl hexanoate8. octyl octanoate
1
3
24
5
6 7
8
4
3
652
9. hexyl 2-methyl propanoate10. hexyl butanoate11. hexyl 2-methyl butanoate
9
10
11
Composition of hydro-distilled oil
Heracleum mantegazzianum
Heracleum sphondylium
Multi product streams from Heracleum sp.
Steam distillation Essential oil
Fractionaldistillation
CO2 extraction
Molecular distillation
Triglycerides
Petroselinic acid
Psoralens
Polymers
Octyl and hexyl esters
Pharmaceuticals and drug
precursors
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
http://ec.europa.eu/food/food/chemicalsafety/flavouring/database/dsp_search.cfm
Flavouring substances database
Composition of Heracleum sphondylium scCO2 extract
1. octan-1-ol2. 3-octenyl acetate3. octyl acetate4. octyl 2-methyl propanoate5. octyl butanoate6. octyl 2-methyl butanoate7. octyl hexanoate8. octyl octanoate
1
3
2 4
5
6
7
8
Psoralens from Heracleum sphondylium
5,8-Diethoxy-2,3-dimethylquinoxaline
hentriacontane
nonacosane
b-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