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croatiandestructiveBiotechnology

Dec 9, 2012 (4 years and 8 months ago)

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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 s
tarting

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

D
3
-
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

0
10
20
30
40
50
60
14-Jun
05-Jul
29-Jul
15-Aug
15-Sep
30-Sep
30-Oct
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

Residue

Middle 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 acetat
e.
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

Fractional
distillation

CO
2

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
-
ol

2. 3
-
octenyl acetate

3.
octyl

acetate

4.
o
ctyl

2
-
methyl
propanoate

5.
o
ctyl

butanoate

6
.
o
ctyl

2
-
methyl
butanoate

7
.
o
ctyl

hexanoate

8.
o
ctyl

octanoate

1

3

2

4

5

6

7

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

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

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!

r.marriott@bangor.ac.uk

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

Flavouring substances database

Composition of
Heracleum

sphondylium

scCO
2

extract

1. octan
-
1
-
ol

2. 3
-
octenyl acetate

3.
octyl

acetate

4.
o
ctyl

2
-
methyl
propanoate

5.
o
ctyl

butanoate

6
.
o
ctyl

2
-
methyl
butanoate

7
.
o
ctyl

hexanoate

8.
o
ctyl

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

h
exadecanoic

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