Flavor and Fragrance

Materials of Natural Origin

Expression
Enfleurage
Jasmine
Jasmine
Distillation
Steam Distillation
$30 – $300/kg
250 – 300 tonnes/yr

Steam/Oil vapor mixture

Plant
material
H2O out

Condensor

Still H2O in

Steam

Water of
Essential oil Cohobation
Lavendar
Sandalwood
Fractional Distillation

Water condensor

Water condensor

Condensor/
Fractionating column
Extraction/Isolation

ethanol Natural Material

extraction

enfleurage
Tincture solvent
extraction
distillation

Concrete Pomade
distillation
(Resinoid)
ethanol
Essential Oil ethanol extraction
extraction

Absolute
Gas Chromatography / Mass Spectrometry (GCMS)
Headspace analysis
GC-MS of Soft Soap
GC-MS of Multipurpose
cleaner
GC-MS of Dishwashing
detergent
 VOLATILE COMPONENTS IN ROAST BEEF

_
160
I-/
I40 I20 100 00 GO
TIME, PAINUTES
Figure 1. Gas chromatogram of a concentrate of volatile constituents from roast beef drippings. Attenuation 256, sample size 0.3 p1,
Column A
May 1, 2002 on http://pubs.acs.org | doi: 10.1021/jf60179a009
ownloaded by ALMA COLLEGE on July 1, 2009

I60 I40 120 100 80 60 50 20

-
TIME, MINUTES

Figure 2. Gas chromatogram of a concentrate of volatile constituents from roast beef. Attenuation 256, sample size 1.8 ~ 1 Column
, A

RESULTS AND DISCUSSION
The concentrated samples exhibited pleasant meaty odors
with a somewhat fatty nuance fot roast beef concentrates and
slightly burned fcr the drippings. The odors of the drippings
samples were considerably stronger than the meat odors and
were distinctive of drippings.
Figures 1 and 2 show chromatograms of concentrates from
figures. Identified compounds which are not labeled appear
in the chromatograms between two labeled peaks in the order
given in the table. No numbers were assigned t o these
constituents because the experimental conditions for the glc-
ms analyses were different from the conditions for glc analyses,
resulting in slight changes in peak sizes and retention times.
The chromatograms shown in the figures were recorded on the
 Table I. Volatile Constituents of Roast Beef and Roast Beef Drippings
Peak no. Compd Sample Peak no. Compd
1 Diethyl ether (solvent) M, D 23 It-Nonanal
Ethyl acetate (solvent M, D 24 2-Octenal
impurity) 25 1-Heptanol
Ethanol (solvent impurity) M, D Benzaldehyde
2-Methylbutanal M, D 26 2-n-Heptylfuran
3-Methylbutanal M, D Ca-benzene
2,3-Butanedione M 2,4-Octadienal (tent,)
5 n-Pentanal M, D 2,3-Butanediol
n-Nonane M, D 2-Decanone
1-Propanol D rz-Tetradecane
2,3-Pentanedione M rz-Decanal
7 Toluene M, D 28 y-Butyrolactone
Dimethyl disulfide M 29 2-Nonenal
8 n-Hexanal M, D 30 1-Octanol
n-Decane M, D 31 2-n-Octylfuran
n-Butanol M, D Butyric acid
1,4-DimethyIbenzene M, D 6( ?)-Methyltetradecane
1,ZDimethylbenzene M Phenylacetaldehyde
9 3-Heptanone D 32 2-Octen-1-01
n-Undecane M, D n-Pentadecane
2-Heptanone M, D 34 2-Undecanone
10 n-Heptanal M, D y-Hexalactone
2-Hexenal D n-Undecanal
12 3-Hydroxy-2-butanone M, D 35 2-Decenal
Published on May 1, 2002 on http://pubs.acs.org | doi: 10.1021/jf60179a009

12 1-Pentanol M, D 36 2,4-Nonadienal
13 2-n-Pentylfuran M, D 6-Valerolactone (tent.) D
Trimethylbenzene M y-Heptalactone D
Methylethylbenzene M Dimethyl sulfone
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14 3-Octanone M, D 2-Dodecanone
Trimethylbenzene M, D n-Hexadecane
4-Heptanol (tent.) D 39 2,4-Decadienal
3-Heptanol D n-Dodecanal
15 2-Octanone M,D 40 2-Undecenal
n-Dodecane M, D 41 2,4-Decadienal
16 6-Heptalactone
n-Octanal M, D n-Heptadecane
17 2-Heptenal M, D Heptadecene
2,3-Octanedione M Acetylpyrrole
Dieth ylbenzene M y-Octalactone
18 1-Hexanol M, D 43 2-Tridecanone
Acetic acid D 12-Tridecanal
19 C8-benzene M 44 2-Dodecenal
20 2-n-Hexylfuran D 6-Octalactone
n-Butylbenzene M 45 2,4-Undecadienal
Ca-benzene M n-Octadecane
Dimethylpyrazine (tent.) D 47 y-Nonalactone M, D
4-Octanol (tent.) D 2-Tridecenal D
3-Octanol D 2,4-Dodecadienal D
2-n-butox yet hano M 6-Nonalactone D
22 2-Nonanone M, D y-Decalactone D
n-Tridecane M, D 2-Pentadecanone D
a M : Compolund was found in roast beef meat; D : Compound was found in roast beef drippings.
 Volatile Composition of Some Brazilian Fruits: Umbu-caja
(Spondias citherea), Camu-camu (Myrciaria dubia), Araça-boi
(Eugenia stipitata), and Cupuaçu (Theobroma grandiflorum)
Maria Regina B. Franco*,† and Takayushi Shibamoto‡
Faculdade de Engenharia de Alimentos, UNICAMP, Campinas-SP, CP 6121, CEP 13081-970, Brazil, and
Department of Environmental Toxicology, University of California, Davis, California 95616-8588

1264 J. Agric. Food Chem., Vol. 48, No. 4, 2000 Franco and Shibamoto
Twenty-one volatile compounds were identified for the first time by GC-MS in umbu-caja and in
camu-camu,
Table 1. Volatile plusof
Composition 30the
volatile compounds
Umbu-caja Samplewere identified
Table 2. in araça-boi
Volatile samples.of
Composition Terpenic compounds
the Camu-camu Sample
predominated
compound among the volatile
Kovats index compounds
% area in these fruit samples, with
compound the index
Kovats major compounds
% area
being identified as cis-β-ocimene and caryophyllene in the northeastern fruit; R-pinene and
NIa 725 0.42 ethyl acetate 820 0.17
ethyl acetate
d -limonene were the most abundant
824
volatile
1.71
compounds in the headspace of1009
R-pinene
the Amazonian 66.2
fruit
NI camu-camu. Sesquiterpenes were
900 the most
0.21 abundant compounds
R-fenchene in the araça-boi
1029 sample, with
0.09
NI germacrene D presenting a 925higher relative
0.20 percentage.
ethylThe chemical class of1048
butyrate esters predominated
0.16
NI in the cupuaçu sample. Ethyl butyrate0.23
932 and hexanoate were the major compounds
camphene 1052 in the headspace
0.20
R-pinene of this Amazonian fruit. 1010 1.48 NIa 1065 trb
Published on March 10, 2000 on http://pubs.acs.org | doi: 10.1021/jf9900074

NI 1038 0.29 β-pinene 1102 0.48

ethyl butyrate 1043 1.90 car-3-ene 1142 tr
toluene 1055 3.60 β-myrcene 1155 1.11
butyl acetate Keywords: Volatile comp1100 ounds; hea0.72
dspace; identR-phellandrene
ification; chromatography1160 -mass spectrome0.27 try;
β-pinene tropical fruits 1100 0.43 NI 1162 0.33
Downloaded by ALMA COLLEGE on July 1, 2009

β-myrcene 1154 1.29 R-terpinene 1169 0.11

d-limonene 1184 7.09 d-limonene 1195 23.72
INTRODUCTION
β-phellandrene 1192 trc flavor, is native to the northeastern
β-phellandrene 1200 region 0.29
of Brazil. It
cis-β-ocimene 1236 36.30 is also mainly consumed 1208
eucalyptol as juice. tr
Brazil has a natural abundance of1250
tropical fruits with
trans-β-ocimene 7.45 To date, there is no published
γ-terpinene 1238 scientific information
0.58
ethyldistinctive
hexanoate exotic flavors appealing1252
to the foreign
0.77 con- pin
-cimene 1267
the literature on the volatile compositions 0.31 of these
hexylsumer.
acetate However, the flavors of the majority 0.20
1289 of these terpinolene
fruits, except for cupuaçu. 1271 0.40
fruits have not yet been characterized.
1,5,5,6-tetramethyl-1,3-cyclohexadiene b 1365 Characterization
0.62 fenchol 1554 tr
ethylofoctanoate 1442 for thetrdelinea-
the volatile compounds would allow Alves and Jennings studied
β-caryophyllene 1563 canned cupuaçu
4.61 pulp
R-copaene 1450 0.59
tion of a processing procedure that would retain a high (1979) using
4-terpineol a Nickerson-Lickens
1574 simultaneous
tr distil-
β-caryophyllene 1556
quality of aroma and flavor in the 1606
26.8
finished product. lation-extraction apparatus
humulene 1606and found thattresters were
R-caryophyllene 4.49 NI
important contributors to 1636
the cupuaçu aroma.0.20 Ethyl
0 on http://pubs.acs.org | doi: 10.1021/jf9900074

Umbu-caja, camu-camu, araça-boi,

β-selinene and cupuaçu
1679 1.22 were NI
butanoate and hexanoate1744 0.16
were the major volatile com-
the fruits selected for this study1685
1,2,3,4,4a,5,6,8a-octahydro-4a,8- because 1.65
of their
dimethylnaphthalene b pounds.
a NI, not Methyl
identified. tr an s
b Traces. -2-hexenoate, methyl crotonate,
economic potential.
δ-cadinene 0.32 and hexanoic acid were the major compounds when
Araça-boi is a round fruit, about 12 cm in diameter,
ALMA COLLEGE on July 1, 2009

cupuaçu
There was anpulp was studied
inversion by a solid-phase
in the order of elution ofextraction
ethyl
a
with
NI, notaidentified.
yellow skin. The edible part, a creamy-white
b Tentative identification: based on only
technique
hexanoate and(Fischer et al., 1995).
trans-β-ocimene when performed by gas
masspulp,
spectra anc acid
data.
has Traces.
flavor. This Amazonian fruit has an
chromatography. However, the sequence of elution of
excellent economic potential because the tree grows
in aeasily
small and
insulated these compoundsAND
MATERIALS in the total ion current chromatogram
METHODS
beginsbox. (U.S. federal
to produce within laws prohibit
two years. Thethefruits
entrance (obtained by mass detection) was the same as indicated
haveofa raw
highmaterial into of
percentage thepulp,
country.)
presenting an attractive Selection of Raw Material. Ripe umbu-caja fruits were
Gas Chromatographic Analysis. The by their theoretical Kovats indices.
aroma and flavor, adequate for mixture of volatile of
the manufacture bought in January 1997 from a market inwere
Recife,predomi-
Pernambuco.
compounds
juices, was separatedand
ice creams, on adesserts.
DB-Wax bonded phase, fused The volatile compounds of umbu-caja
They were immediately frozen in a 500 g polyethylene bag and
silica capillary column (30 m in length and 0.2 mm i.d.) in an nantly terpenic compounds (87.5%), followed by esters.
sent by airplane to Campinas, São Paulo. Fresh ripe camu-
HP gasCamu-camu
chromatograph, is model
also a5890,
round fruit with
equipped (2-2.5 cm in
an FID Nevertheless, this class of compounds accounted for only in
diameter), with a red skin and pink pulp. Because camu and araça-boi fruits were acquired at a market
detector and a Spectra-Physics integrator, model 4290. The of 5.3%Manaus,
of the Amazonas,
total relative percentage. cis-β-Ocimene
its acid flavor it is consumed mainly as juice.type
It isofalso in January 1997 and transported by
chromatographic parameters used were as follows: (36%), a monoterpene hydrocarbon, and β-caryophyllene
GC-Olfactory (GC-O)
Infrared Spectroscopy
Limonene
 OH

Citronellol
 O

Carvone
Nuclear Magnetic Resonance (NMR)
2-D NMR
Biosynthesis
 Cellulose Glucose Acetyl Coenzyme A

Biosynthesis
Terpene Biosynthesis
O Claisen O
+ condensation
CoAS CoAS O CoAS O
(substitution)
Acetoacetyl-CoA
Terpene Biosynthesis
O Claisen O
+ condensation
CoAS CoAS O CoAS O
(substitution)
Acetoacetyl-CoA

O O O HO O O HO O
Aldol reaction H2O
+
CoAS O SCoA CoAS SCoA HO SCoA
(addition) (hydrolysis)
Acetyl-CoA b-hydroxy-b-methyl-glutaryl-CoA
Acetoacetyl-CoA
Terpene Biosynthesis
O Claisen O
+ condensation
CoAS CoAS O CoAS O
(substitution)
Acetoacetyl-CoA

O O O HO O O HO O
Aldol reaction H2O
+
CoAS O SCoA CoAS SCoA HO SCoA
(addition) (hydrolysis)
Acetyl-CoA b-hydroxy-b-methyl-glutaryl-CoA
Acetoacetyl-CoA

O HO O NADPH + H+ O HO ATP O HO O O
PP = P O P OH
HO SCoA (reduction) HO OH (convert to good HO OPP
leaving group) OH OH
mevalonic acid mevalonic acid diphosphate
Terpene Biosynthesis
O Claisen O
+ condensation
CoAS CoAS O CoAS O
(substitution)
Acetoacetyl-CoA

O O O HO O O HO O
Aldol reaction H2O
+
CoAS O SCoA CoAS SCoA HO SCoA
(addition) (hydrolysis)
Acetyl-CoA b-hydroxy-b-methyl-glutaryl-CoA
Acetoacetyl-CoA

O HO O NADPH + H+ O HO ATP O HO O O
PP = P O P OH
HO SCoA (reduction) HO OH (convert to good HO OPP
leaving group) OH OH
mevalonic acid mevalonic acid diphosphate

O HO

HO OPP OPP OPP

(decarboxylation)

mevalonic acid diphosphate isopentyl-pyrophosphate dimethylallyl-pyrophosphate

 Isoprene Units

+
OPP OPP OPP OPP
prenyl pyrophosphate isopentyl pyrophosphate geranyl pyrophosphate farnesyl pyrophosphate

O
OPP OH H

geranyl pyrophosphate geraniol citral

Acyclic (rose) (lemon)

Monoterpenoids O OH O
OH H O

citronellol citronellal linalool geranyl acetate

(rose) (lemon/citrus) (floral) (floral)
 OH
Cyclic limonene
(citrus)
α-terpineol
(lilac)
α-pinene
(pine)
β-pinene

Monoterpenoids O O O

OH
camphor

l-(-) menthol (S)-carvone (R)-carvone

(mint) d-(+) l-(-)
 OH
Sesquiterpenoids
OH

α-bisabolol cedrol

chamomile oil Virginian and Chinese

HO
(anti-inflammatory) cedarwood oil

OPP
O patchouli alcohol
farnesyl pyrophosphate OH
H patchouli oil

α-santalol
zizinal
East Indian
vetiver oil
sandalwood oil
 OH

ambreine

Ambergris
O H H

O
OH
dihydro-γ-ionone ambrinol ambrox

Moist, soft, creamy, persistent, warm,

animalic, woody, amber
 32 lb Ambergris = $750,000

Australian beach, 2006

 Polyketide, Terpenoide or Shikimate?
O OH

O O O O
OPP OPP
CoA CoA
prenyl pyrophosphate isopentyl pyrophosphate HO OH
acetylcoenzyme A (polyketide) (terpenoid) OH
shikimic acid (shikimate)

OCH3 OMe
H3CO
OMe
O
O

O O
OMe
ethyl everninate methyl jasmonate β-asarone

O O OH
O
OH
OH
OH

O O
OH
polyketide
polyketide
OH
OH

HO
OH
O

shikimate
 O

O O

O
deodarone dehydrocostus lactone