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Plant-derived flavor

compounds

Flavor compounds
Flavor molecules constitute a heterogeneous
group of compounds, with straight-chain,
branched-chain, aromatic and heteroaromatic
backbones
bearing diverse chemical groups such as
hydroxyl, carbonyl, carboxyl, ester, lactone,
amine, and thiol functions. More than 700 flavor
chemicals have been identified and catalogued
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Natural Aroma Chemicals

large variety of acids,


alcohols,
ketones,
aldehydes,
other organic compounds

Cinnamaldehyde
http://www.hellochem.com/xz/img/img0/986.gif

Ethyl vanillin
http://www.bmrb.wisc.edu/metabolomi
cs/standards/Ethyl_vanillin/lit/jr_167.p
ng

Chemical synthesis VS Biosynthesis


Most commercial flavorants are nature identical, which
means that they are the chemical equivalent of natural
flavors but are chemically synthesized, mostly from
petroleum-derived precursors

Bioproduction, including the extraction from natural sources,


de novo microbial processes (fermentation), and bioconversion
of natural precursors using micro-organisms or isolated
enzymes

Examples of Natural Aroma Chemicals

Chemical

Odor

Diacetyl

Buttery

Isoamyl acetate

Banana

Benzaldehyde
Cinnamic aldehyde

Bitter almond and


cherry
Cinnamon

Ethyl propionate

Fruity

Methyl anthranilate

Grape
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Examples of Natural Aroma Chemicals


Chemical

Odor

Ethyl-(E,Z)-2,4decadienoate
Allyl hexanoate

Pear
Pineapple

Ethyl maltol

Sugar, cotton candy

Ethyl vanillin

Vanilla

Methyl salyicyllate

Wintergreen

Limonene

Orange
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Biological functions of plant volatiles


associated with defensive and attractive roles
Compounds emitted by flowers most probably serve to attract and
guide pollinators
volatiles might also protect the carbohydrate-rich nectar by inhibiting
microbial growth.
vegetative plant tissue release volatiles following herbivore damage.
Some of these substances attract arthropods that prey upon or
parasitize the herbivores.
Volatiles also act as direct repellents or toxicants for herbivores and
pathogens.
In fruits, volatile emission and accumulation facilitate seed dispersal by
animals and insects.

vegetative tissues often produce and release many of the


volatiles after their cells are disrupted. These volatile flavor
compounds may exhibit anti-microbial activity.
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Aromatic compounds responsible for odor


and flavor of fruits comprise;

Alcohols R-OH
Carbonyls RR-CO-R

Acids

CHO

R-COO-R

Esters

Lactones
O

R
CO

R-COOH Phenols
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Estimated world
consumption of
selected aroma
chemicals in flavor
and fragrance
compositions

CHO

OCH3
OH

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CO2 + H2O
hn

PRIMARY METABOLISM
Photosynthesis

Glucose

SECONDARY
METABOLISM

Building Blocks
Phenylpropanoids
Flavonoids
Alkaloids

Amino Acids
Proteins
synthesis
enzymes
regulation
Nucleic
Acids
reproduction
RNA DNA

G
L
Y
C
O
L
Y
S
I
S

Carbohydrates
SECONDARY
METABOLISM

Fatty Acids
Lipids
Acetyl CoA
Citric Acid
Cycle

CO2 + H2O + ATP

Acetogenins
Terpenes
Steroids
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Glucose

hn

CH2OH (6 carbons)
O

CH2OH
O

OH
HO

CO2

OH

OH
OH

HO

photosynthesis

CH2OH
O

CH2OH
O

OH

OH
O
OH

O
OH

O
OH

starch

glycolysis
CHO
CH OH

CHO

CH OH

HC OH

CH2OP

CH2OP

erythrose4-phosphate

CH2OH
C O

CH2
C OP

COOH

HO

COOH

shikimic
acid

anthanilic
acid

OH
OH

NH2

phenylpropanes

lysine
ornithine

phenylalanine
tyrosine
tryptophan

alkaloids

phosphoenol
pyruvate (PEP)

H3C C SCoA

oxaloacetate

nicotinic
acid

lipids
fatty acids

H3C C CH2 C CH2

(3 carbons)

COOH

polyketides
acetogenins

CH2OP

aspartic
acid

acetylcoenzymeA
(2 carbons)

HO

CH3

mevalonic
acid
citric
acid
cycle

energy (ATP)
+ CO2 + H2O
NH3
glutamic acid

terpenes
steroids
carotenoids
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Amino acid synthesis


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isoprenoid biosynthesis proceeds either via the


"classical" or most well studied, mevalonate pathway
(cytosolic) (for the synthesis of sterols, sesquiterpenes,
triterpenoids)
or via the non-mevalonate (1-deoxy-D-xylulose-5phosphate, DXP) pathway for plastidic isoprenoids
(carotenoids, phytol [side-chain of chlorophylls], plastoquinone,
isoprene, monoterpenes and diterpenes).
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Biosynthesis of flavors in vegetables and fruits

Fruit flavors
are formed during brief ripening period

Vegetable flavors
develop when tissue damage occurs
(Intact vegetable generally contains few
volatiles)
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BIOGENESIS OF FRUIT AROMA

develops entirely during ripening period of plant

Minute quantities of lipids, CHO, protein (amino


acids) are enzymatically converted to volatile
flavors.

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FRUIT FLAVOR COMPOUNDS


Apple

n-hexanal, ethyl butyrate, 1-propyl propionate, 1butyl acetate, trans-2-hexenal, ethyl 2methylbutyrate, 2-methylbutyl acetate, 1-hexanol,
hexen-1-ol, trans-2-hexen-1-ol, hexyl acetate,
Esters; alcohols; aldehydes; ketone; acids; including
hexanal; ethyl 2-methyl butyrate

Banana

alcohols; esters, including amyl acetate, isoamyl


acetate, butyl butyrate, amyl butyrate

Peach

Ethyl acetate, dimethyl disulfide, cis-3-hexenyl


acetate, methyl octanoate, ethyl octanoate, 6-pentyl
alpha pyrone, gamma decalactone
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Lipids Polysaccharide Proteins/Enzymes


Malonyl CoA
Fatty acid
Acetyl-CoA

Aliphatic
Acids
Alcohols
Esters
Carbonyls
lactones

Carbohydrate
Pyruvate
Acetyl CoA

Lignins

Amino acid
Shikimic acid

Terpene
Mevalonyl CoA

Terpenes
Sesquiterpenes
Hydrocarbons
Alcohols
Carbonyls
monoterpenes

Cinnamic acid

Methyl-Branched
Alcohols
Acids
Esters
carbonyls

Biosynthesis of fruit volatiles

Aromatic
Alcohols
Acids
Esters
carbonyls

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Flavorants from carbohydrate metabolism

Only a limited number of natural volatiles


originate directly from carbohydrates without
prior degradation of the carbon skeleton.

Furanones and pyrones


fruit constituents
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Furanones and pyrones

Carbohydrate-derived flavor molecules, including 4-hydroxy-2,5-dimethyl-3(2H)furanone (furaneol), 2,5-dimethyl-4-methoxy-3(2H)-furanone (methoxyfuraneol), 4hydroxy-5-methyl-3(2H)-furanone (norfuraneol), 2-ethyl-4-hydroxy-5-methyl-3(2H)furanone (homofuraneol), 4-hydroxy-2-methylene-5-methyl-3(2H)- furanone (HMMF)
and 3-hydroxy-2-methyl-4H-pyran-4-on (maltol).

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Flavorants from carbohydrate metabolism


Glucose (6C)

2 Pyruvate (3C)
CO2

-O2

-O2
+O2

Ethanol

Lactate
TCA Cycle/
Citric Cycle

Glycolysis

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Pyruvic acid

CH3COCOOH

Acetic acid

CH3COOH

Acetyl CoA

CH3COSCoA

+ CO2
Malonyl CoA

HOOCCH2COSCoA

Malonic Acid

HOOCCH2COOH
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Flavorants from carbohydrate metabolism


the most interesting is terpene biosynthesis
Terpenoids are enzymatically synthesized from acetyl CoA and
pyruvate provided by the carbohydrate pools in plastids and the
cytoplasm.
Terpenoids constitute one of the most diverse families of
natural products, with over 40 000 different structures of
terpenoids
Many of the terpenoids produced are non-volatile and are
involved in important plant processes such as membrane
structure (sterols), photosynthesis (chlorophyll side chains,
carotenoids), redox chemistry (quinones) and growth regulation
(gibberellins, abscisic acid, brassinosteroids)
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Important plant-derived volatile terpenoids.

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Biosynthesis of Terpenes
isoprene is derived from acetyl-CoA

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MEVALONIC ACID PATHWAY


FORMATION OF MEVALONIC ACID FROM ACETYL UNITS
O

O
HO

CH2 C SCoA

3 acetylCoA
H3C

HO
C

NADPH
H3C

CH2 C SCoA
O

O
HO
C
H3C

HO
C

CH2 CH2 OH

H2O

H3C

H
CH2 C
O:
: ..

HO

CH2 C SCoA
CH2 CH2 OH

SCoA

CH2 C OH

CH2 C SCoA

NADPH

H3C

CH2 C SCoA
CH2 C H
O

mevalonic acid

(continued next slide)

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THERE ARE TWO CARBONYL GROUPS IN THE 2-UNIT POLYKETIDE CHAIN


EITHER ONE CAN REACT
O

O
H

..

CH2

CoA
CH3

- CO2

CH3 C

S CoA

CH2

LINEAR

BRANCHED

mevalonic acid

CH3
CH2
HO

CH2

OH
C

CH2
CH2 COOH

TERPENES

C
CH3

CH2

H3C

S CoA

CH2

O
CH2

SCoA

S CoA

CH2
O C

POLYKETIDE CHAINS
SCoA

STEROIDS

ACETOGENINS
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MEVALONIC ACID PATHWAY


The isopentenyl and 3,3-dimethylallyl pyrophosphate intermediates
O
HO
C
H3C

ADP
AMP

2 ATP

CH2 C OH

O
C
H3C

CH2 CH2 OH

:B-Enz

O
CH2 C

CH2 CH2 O

H
P

mevalonic acid
These five-carbon
intermediates are
responsible for the
formation of all the
terpenes.

CH3
H

CH3

P P O CH2

H+

CH2

P P O CH2

DMAPP
3,3-dimethylallyl
pyrophosphate

CH3

Enz-B:

IPP
isopentenyl
pyrophosphate
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Classification of Terpenes

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Apocarotenoid formation

Carotenoid substrates are oxidatively cleaved to yield the apocarotenoid derivatives


(right).
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Some of the volatile organic compounds in wine come from the grape's skin, or
exocarp, while others come from the grape's flesh, or mesocarp. Organic acids give
wine its tartness, and sugars give it sweetness. Terpenes provide floral or fruity
flavors. Norisoprenoids impart a honeylike character. Thiols are the sulfur-based
compounds behind complex wine aromas such as guava, passionfruit or grapefruit
but when thiols go wrong, they can make a wine taste "funky."
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Lipids
metabolic pathway for lipid biosynthesis plays
a significant role in flavor formation.

Oxidation via lipoxygenase


Alpha-, Beta-oxidation

products; acids, alcohols, diketones, ketones, esters of these compounds.


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Oxidation via Lipoxygenase


Lipoxygenase activity is believed to be the
major source of volatiles in plants.
Lipoxygenase enzymes (dioxygenase) catalyze reactions
between O2 and polyunsaturated fatty acids

Substrate: unsaturated fatty acid (linoleic and linolenic acids).


Major products: volatile C6 and C9 aldehydes and alcohols
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Linolenic acid-derived flavor molecules.

AAT, alcohol acyl CoA transferase; ADH, alcohol dehydrogenase; AER, alkenal
oxidoreductase; AOC, allene oxide cyclase; AOS, allene oxide synthase; HPL,
hydroperoxide lyase; JMT, jasmonate methyltransferase; LOX, lipoxygenase; OPR, 12oxo-phytodienoic acid reductase; 3Z,2E-EI, 3Z,2E-enal isomerase.
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Fatty acid precursors (Tomato)

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- and -oxidation of fatty acids


the specific pathways in plants are not well understood

Palmitoyl-CoA (16:0)

+ Acetyl-CoA

Myristoyl-CoA (14:0)

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Formation of pear flavors via beta-oxidation

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Lactones

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Amino Acid Metabolism

Amino acid metabolism yields short chain aliphatic and


aromatic alcohols, acids, carbonyls and esters

They are the primary source of branched chain


aliphatic flavor compounds

their pathways have been barely analyzed in plants.

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amino acid precursors


(Tomato)

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Biosynthesis of amino acid-derived


flavor compounds

(a) Catabolism of branched-chain amino acids leading to methyl branched flavor compounds, and
(b) postulated biosynthesis of sotolon. Formation of aldehyde (a) from amino acids requires the
removal of both carboxyl and amino groups. The sequence of these removals is not fully known
and could be the opposite to that shown or aldehyde could be formed in one step by aldehyde
synthase

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Starting amino acids: Tyrosine and phenylalanine products:


phenolic/spicy in character

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Shikimic acid formation

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Vegetable Flavors

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Vegetable flavors
flavor again arises from major metabolic processes e.g. Lipids, CHO & amino acids.

the precursors, enzymes and end flavors are quite


different from fruits.

The role or importance of S compounds to


vegetable flavor is quite significant.
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Carbohydrate
Fatty acid

Amino acid

Nonvolatile Precursors
Linoleic, Linolenic acid Thioglucosinolates

Cysteine-sulfoxides

Methyl-methionine

Precursor-splitting Enzymes
Lypoxygenase

Carbonyls
Alcohols
Oxo-acids

Thioglucosidases

Isothiocyanates
Nitriles
S C O
Thiocyanates

C-S-lyases

Polysulides
Alkylthosulfinates

Formation of flavor in vegetables

None (Heating)

CH3-S-CH3

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Vegetable Flavor Categories

Genus Allium
Enzymes produce volatiles from derivatives
of cysteine (sulfoxides)

Genus Brassica
Enzymes produce volatiles from glucosinolates
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Alliaceous vegetables
garlic (Allium sativum L.)
onion (Allium cepa L.)
chive (Allium schoenoprasum L.)
leek (Allium porrum L.)
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Characteristic flavors
not exist in the bulb before processing

are produced when the cellular tissues are


ruptured by cutting or chewing

flavor is produced very rapidly by the action


of an enzyme on the odorless precursors which
coexist in the cells
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Onion and Garlic Flavor


Enzymatic reaction of cysteine derivative

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GLUCOSINOLATES

Glucosinolate precursors are important to the


flavor of both the Brassica and Cruciferae family
Cruciferae family includes radish, horseradish,
mustard.

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Hydrolysis of the glucosinolate


glucosinolate

thioglucosidase

thiocyanate, nitrile, or isothiocyanate


& glucose

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Natural carbon pools for the production


of flavor compounds, and the pathways

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