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

Plant Derived Flavour and

Fragrance Molecules

Ray Marriott

Biocomposites Centre, Bangor University

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%

Welsh native Mentha species

Mentha x villosa

piperitone oxide

menthofuran

Mentha aquatica

Mentha gentilis oil

First fraction ResidueMiddle fraction

Linalool from Mentha sp.

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

Heracleum mantegazzianum

Heracleum sphondylium

Octyl esters – Heracleum species

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

Thank you for your attention!

[email protected]

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