E. T. Contis et al.

(Editors)
Food Flavors: Formation, Analysis and Packaging Influences
© 1998 Elsevier Science B.V. All rights reserved 345

GC-MS analysis of volatile compounds in durian (Durio zibethinus Murr.)

J. Jiang^ S.Y. Choo\ N. Omar^ and N. Ahamad^

^ Singapore Productivity and Standards Board, Food Biotechnology Centre, 1 Science Park
Drive, Singapore 118221.

^ Malaysian Agricultural Research and Development Institute, Peti Surat 12301, Pejabat Besar
Pos, 50774, Kuala Lumpur, Malaysia.

Abstract

Volatile compounds were extracted from durian by vacuum distillation followed by

dichloromethane extraction and GC-MS analysis. A total of 108 compounds were identified,
including 49 esters, 18 sulfur compounds, 16 carbonyl compounds, 11 alcohols, 7
hydrocarbons, and 7 miscellaneous components. Of the identified compounds, 52 have not
been previously reported as durian flavor components. Esters, ketones and sulfur compounds
were the major compounds. Acetoin, ethyl 2-methylbutanoate and diethyl disulfide were
predominant, accounting for 34.1-37.5%, 20.7-21.9% and 5.6-6.1% of the total volatiles,
respectively. The esters and sulfur compounds are obviously responsible for durian's strong
fruity and sulfury odors while ketones, especially acetoin, most likely contribute to its creamy
flavor.

1. EVTRODUCTION

Durian {Durio zibethinus Murr.) is one of many tropical fruits native to South East Asia.
The capsule fruit is usually large (up to 4 kg) and is characterized by a green to brownish skin
fully covered by numerous thick spikes. Its edible aril is soft and creamy with white or
yellowish color. The aril has a sweet taste and strong odor dominated by fruity (estery) and
unique sulfury notes. Due to its unique and highly characteristic flavor, durian is deemed as a
delicacy and even regarded as the King of Fruits by local people.
Volatile composition of durian fruit had been studied by a number of researchers. Baldry
et al.^ identified 26 volatile compounds in durian fruits from Malaysia and Singapore,
including 12 esters, 7 sulfur-containing compounds, 4 alcohols, 2 aldehydes, and 1 aromatic
hydrocarbon. The predominant flavor compounds of Thai durian were identified by Moser et
al^ as 1,1-diethoxyethane, ethyl 2-methylbutanoate, ethyl acetate, hydrogen sulfide, ethyl
hydrodisulfide and several dialkyl polysulfides. Fischer et al^ investigated Malaysian durian
and reported that 17 sulfur-containing compounds and 33 non-sulfury components which were
thought to contribute to the sulfury and fruity notes, respectively. Apriyantono and Septina'*
346

reported that of the 10 positively identified flavor compounds, 1,1-diethoxyethane, ethyl 2-

methylbutanoate, ethyl (Z)-4-decenoate and acetoin were the major volatile components of
Indonesian durian. A total of 63 volatile components, mostly esters, sulfur compounds,
alcohols and ketones, were identified in 3 clones of Malaysian durian by Wong and Tie.^
Ethyl 2-methylbutanoate, ethyl propanoate and acetoin were the predominant components.
Weenen et al^ identified 18 sulfur-containing compounds and 18 non-sulfur components in
three varieties of Indonesian durian. Acetoin, ethyl 2-methylbutanonate and hexadecanol were
the most prominent components. All the published papers reported generally similar results,
but significant differences did exist among different reports with regard to both qualitative and
quantitative data on the major flavor components of durian fruits.

2. MATERIALS AND METHODS

Ripe fruits of Malaysia durian were purchased from a local market in Singapore. The
fruits showed no signs of over ripeness, such as splitting of the capsule and wateriness of the
aril. Extraction of volatile components was performed immediately after the fruits were
brought back to the laboratory.
A blended mixture of durian aril (60 g) and deionized water (lOOmL) was distilled under
vacuum (20 mBar, 40°C) until the mixture was almost dry. The vapor was condensed in a
cooling coil (-3°C) and a liquid nitrogen trap and collected in a 200mL flask. The distillate
(127mL) collected in the flask was transferred to a 250mL separating funnel. Residue in the
cooling coil and trap was rinsed with 50mL of dichloromethane (DCM) into the separating
funnel. A magnetic bar was carefully put into the separating funnel. After the funnel was
firmly capped, the content in the funnel was stirred on a magnetic stirrer for 15 minutes at a
speed that enabled the distillate and DCM layers to be constantly mixed. After the aqueous
and DCM layers were fially separated, DCM layer was collected in a 200mL conical flask.
The extraction was repeated twice following the same procedure. The combined DCM
extracts were concentrated to 0. ImL under a flow of pure nitrogen.
The concentrated extract was analyzed using a Unicam Automass 150 GC-MS system
(Unicam Automass, Argenteuil, France). The components of the extract were separated using
a 40m X 0.25mm x 0.3 |im DB-Wax column (J&W Scientific, Folsom, CA, USA). Column
temperature was increased from 40 to 250°C at a rate of 3°C/min and maintained for 15 min.
Injector temperature was set at 250°C. MS parameters were as follow: EI mode with an
ionization voltage 70 eV, ion source temperature 150°C and scan range from 20 to 350 amu.
Analysis of the extract was also performed using a 40m x 0.18mm x 0.4 jim DB-1 column
(J&W Scientific, Folsom, CA, USA) and identical GC and MS conditions.
Unknown compounds were identified either by comparison of their spectra with those in
an NIST Mass Spectra Library or by comparison of both spectral and retention data obtained
from the durian sample and authentic chemical standards.

3. RESULTS AND DISCUSSION

A total of 108 compounds were identified from the durian extract, including 49 esters, 18
sulfur compounds, 16 carbonyls (aldehydes/ketones), 11 alcohols, 7 hydrocarbons, and 7
 347

miscellaneous components. Of the 108 identified compounds in this study, 52 had not been
previously reported as durian volatile components and most of them were detected in
extremely low concentrations (Table 1). Esters and ketones each accounted for approximately
40% of the total volatiles while sulfur-containing compounds accounted for nearly 8%.
Presence of these volatile flavor compounds in relatively large quantities explained the
characteristic durian odor with strong fruity (ester-like), creamy and unique sulfiiry notes.

3.1 Ester Compounds

Esters were found to contribute significantly to durian volatile composition both in terms
of quantity and the total number of detected components. These compounds are responsible
for the strong fruity and estery notes of durian fruits. In this study, a total of 49 esters were
identified, covering a wide range of ester molecules, mainly ethyl, methyl and propyl esters of
C2-10 carboxylic acids. Of the 49 identified esters, 19 have not been previously reported as
durian volatile components. Of the five esters of unsaturated carboxylic acids, propyl (E)-!-
methyl-2-butenoate and ethyl (Z)-4-octenoate were for the first time identified in durian. All
the five unsaturated esters were previously reported in various fruits except propyl (E)-2-
methyl-2-butenoate which had only been detected in camomile oil.^ Esters accounted for
about 40% of the total volatiles in the durian variety studied in our laboratory. In a previous
study, esters were found in a much higher proportion (49.25-57.88%) in 3 Malaysian durian
varieties.^ In our study, majority of the identified esters were detected in very small quantities
except seven of them with a percentage above 1%. Ethyl 2-methylbutanoate was the
predominant ester, accounting for 20.73-21.87% of the total volatiles. Its predominance has
been reported in Malaysian durian by Baldry et al.^ and Wong and Tie^, in Thai durian by
Moser et al.^ and in Indonesian durian by Weenen et al^ and Apriyantono and Septiana'*. In
some previous studies, other esters were also found as the major components in Malaysian
durian, such as ethyl acetate with a concentration over 10%^ and ethyl propanoate with a
concentration around 20%^ Both ethyl acetate and ethyl propanoate were detected in our
study, but in much lower concentrations, 0.36-0.97% and 2.14-3.11% respectively. In a
recent study, Weenen et al^ could not detect ethyl propanoate in the three Indonesian durian
varieties studied.

3.2 Sulfur Compounds

In this current study, 18 sulfur-containing compounds were identified, constituting the

second largest group of durian volatile components in terms of the number of components.
Mass spectra of at least 10 other unidentified peaks showed typical characteristics of sulftir
compounds, and therefore the total number of sulfur-containing compounds should be more
than 18. These sulfiir compounds are obviously responsible for the unique sulfiiry and onion-
like odor notes typical to durian fruits. The sulfiir-containing compounds not reported
previously in durian included ethylene sulfide, sulfur dioxide, butanethiol, carbon disulfide,
butyl ethyl disulfide and dipropyl trisulfide. The majority of the sulfur compounds have been
reported in Allium species, various meats and dairy products, but rarely found in fruits and
alcoholic beverages. Butyl ethyl disulfide, the newly identified sulfur component in durian, has
not been reported in any food material. The identified sulfiar compound in this study account
for about 8% of the total volatiles. Diethyl disulfide (5.60-6.13%) and ethyl propyl disulfide
348

Table 1
Durian volatile compounds extracted by vacuum distillation followed
by dichloromethane extraction and separated on 2 different columns.
% of Total^
Compounds ID^ DB-Wax DB-1 Reference'^
Hydrocarbons
pentadecane MS+R 0.05
methylbenzene MS+R 0.08 0.11
ethylbenzene MS+R 0.36 0.06 1
1,2-dimethylbenzene MS 0.17 0.21
1,4-dimethylbenzene MS 0.04 0.03
P-caryophyllene MS+R 0.19 0.22
a-caryophyllene MS+R 0.03
Alcohols
ethanol MS+R 0.12 0.11 1
l-propanol MS+R 2.42 0.98 1,3,5
2-methyl-1 -propanol MS+R 0.02 3,5,6
1 -methoxy-2-propanol 0.07
1-butanol MS+R 1.68 1.40 5
2-methyl-1 -butanol MS+R 0.91 0.50 5
3 -methyl-1 -butanol MS 0.11 1,3,5
2,3-butanediol MS+R 0.44 0.14 3,5
2,4-dimethyl-3-pentanol MS 0.45
1,2-pentanediol MS 0.01
3-hexanol MS+R 0.04
Aldehydes
propanal MS+R 0.09 1
butanal MS 0.01
2-butenal MS 0.02
2-methyl-2-butenal MS 0.01 5
Ketones
acetone MS+R 0.13
2-butanone MS+R 0.04
1 -hydroxy-2-butanone MS+R 0.06 0.02
3 -hydroxy-2-butanone MS+R 34.09 37.49 3, 4, 5, 6
3 -methyl-2-butanone MS+R 0.03
2,3-butanedione MS+R 0.19 0.11 3,5
2-hydroxy-3 -pentanone MS 1.75 5,6
3 -hydroxy-2-pentanone MS 1.69 1.29 5
1 -ethoxy-4-methyl-2-pentanone MS t
4-hydroxy-3 -hexanone MS 0.04 0.04 5
2,6-dimethyl-3-heptanone MS 0.08
l,2-dioxolan-2-one MS 0.01 0.01
 349

Table 1: continued.
Esters
actetate, methyl 0.05 1
acetate, ethyl MS+R 0.36 0.97 1, 2, 3, 5, 6
acetate, butyl MS+R 0.02 0.01 5
propanoate, methyl MS+R 0.33 0.55 1,5,6
propanoate, ethyl MS+R 3.11 2.14 1,3,5,
propanoate, propyl MS+R 2.38 1.08 1,3,5
propanoate, butyl MS 0.02 5
propanoate, pentyl MS 0.05
2-methylpropanoate, methyl MS 0.09 3
2-methylpropanoate, ethyl MS 0.73 0.62 1,3,5
2-methylpropanoate, propyl MS 0.06 5
(iS')-2-hydroxypropanoate, ethyl MS t
2-methyl-2-propenoate, ethyl MS 0.02 1
butanoate, methyl MS 0.10 0.04 5
butanoate, ethyl MS+R 0.44 2.25 1,3,5
butanoate, propyl MS+R 0.12 0.23 3,5
2-butenoate, ethyl MS+R 0.04 5
DL-3-hydroxybutanoate, ethyl MS 0.37
2-methylbutanoate, methyl MS+R 2.25 2.01 1,5,6
2-methylbutanoate, ethyl MS+R 20.73 21.87 1,2,3,4,5, 6
3-methylbutanoate, ethyl MS+R 0.07 5
{E )-2-methyl-2-butenoate, ethyl MS 0.20 0.24 5
2-methylbutanoate, propyl MS+R 5.58 4.99 1,3,5
2-methylbutanoate, butyl MS 0.02
2-methylbutanoate, 2-methylpropyl MS t
2-ethyl acrylate, methyl MS 0.01 0.01
(£')-2-methyl-2-butenoate, propyl MS 0.07 0.09
butanedioate, diethyl MS t
pentanoate, ethyl MS 0.03 0.06 5
2-methylpentanoate, ethyl MS t
3 -methyl-2-oxo-pentanoate, methyl MS 0.08 0.08
4-methyl-2-oxo-pentanoate, methyl MS 0.01
hexanoate, methyl MS+R 0.08 5
hexanoate, ethyl MS+R 1.49 1.71 5,6
hexanoate, propyl MS 0.19
3-hydroxyhexanoate, ethyl MS 0.01
heptanoate, ethyl MS+R 0.12 0.16 5
heptanoate, propyl MS t
octanoate, methyl MS 0.05 5
octanoate, ethyl MS+R 0.50 0.56 5,6
octanoate, propyl MS 0.02
(Z)-4-octenoate, ethyl MS 0.02 0.03
350

Table 1: continued.
nonanoate, ethyl MS+R t 0.02
decanoate, ethyl MS+R 0.08 0.13 3,5
dodecanoate, ethyl MS+R 0.01 5
hexadecanoate, methyl MS+R 0.04
hexadecanoate, ethyl MS+R 0.09 6
carbonate, dimethyl MS t
carbonate, diethyl MS 0.02 5
Sulfur compounds
hydrogen sulfide MS 0.01 0.01 1,2
ethylene sulfide MS 0.01
sulfur dioxide MS 0.01 0.02
methanethiol MS t t 1
ethanethiol MS+R 0.07 1,5
propanethiol MS+R 0.21 1,5
butanethiol MS 0.01
ethanethioate,«?-ethyl MS 0.17 0.12 5,6
ethanethioate, tS'-(2-methylbutyl) MS 0.01
carbon disulfide MS t
disulfide, diethyl MS+R 5.60 6.13 1, 2, 3, 5, 6
disulfide, dipropyl MS+R 0.09 0.04 3
disulfide, methyl ethyl MS 0.19 0.17 3,5,6
disulfide, ethyl propyl MS 1.05 1.26 2, 3, 5,
disulfide, butyl ethyl MS 0.01
trisulfide, dipropyl MS+R 0.01 t
trans -3,5-dimethyl-1,2,4-trithiolane MS 0.09 0.06 3,5,6
cis -3,5 -dimethyl-1,2,4-trithiolane MS 0.24 0.14 3,5,6
Miscellaneous
5-ethyldihydro-2(3H)-fiiranone MS 0.04 0.01
ethylene oxide MS 0.08 0.06
trimethyloxirane MS 0.01
2-butyl-2-ethyl-1,3-dioxolane MS 0.01
hydroperoxide, 1-methylbutyl MS 0.04
hydroperoxide, 1-methylhexyl MS 0.12 0.19
peroxide, bis(l-methylethyl) MS 0.02
MS = based on mass spectral data; MS+R = based on mass spectral and retention data.
Percentage = 100(individual peak area/total peak area); t = trace (<0.01%).
Reference in which a component was reported; compounds without a refererence
number have not been previously reported.
 351

(1.05-1.26%) were the major sulfur compounds in this study while the remainder of sulfur-
containing compounds were detected only in extremely low levels. Diethyl disulfide has also
been found as a major sulfur compound in Malaysian durian by Baldry et al.^, Fisher et al^
and Wong and Tie^ as well as in Thai durian by Moser et al^ In another study, ^S-ethyl
thioacetate was found in 3 Indonesian durian varieties as the major sulfur compound with the
highest concentration among the 18 identified sulfiir compounds.^

3.3 Carbonyl Compounds

Carbonyl compounds, especially ketones, were also a prominent group of durian volatile
components, with a total percentage similar to that of esters (40%). However, the total
number of ketones/aldehydes identified in this study was much less than that of esters. The
most abundant individual component in this study was acetoin which accounted for 34.09-
37.49% of the total durian volatiles in this study. Two other hydroxyketones (2-hydroxy-3-
pentanone and 3-hydroxy-2-pentanone) were also found in relatively high concentrations,
compared to the rest carbonyl compounds. Acetoin had been previously reported as the
predominant component in the 3 Malaysian durian varieties studied by Wong and Tie^ and in
the 3 Indonesian varieties studied by Weenen et al^. This predominant component is most
likely responsible for durian's creamy note, as indicated in another study on Malaysian durian
by Fisher et al^

3.4 Miscellaneous Compounds

In addition to the three major groups of compounds, a number of alcohols, hydrocarbons

and miscellaneous compounds were also identified in this study. Most of theses components
were found in small or trace amounts except propanol and butanol which had relatively higher
concentrations. In some previous studies, ethanol^ and propanol^ were found as the major
durian volatiles. Two interesting hydrocarbons, a-caryophellene and p-caryophellene, were
for the first time identified as durian volatile components in this study. These two compounds
had been frequently found in many essential oils and some fruits.^ A common lactone, 4-
hydroxyhexanoic acid lactone or 5-ethyldihydro-2(3H)-furanone, was identified as a durian
component in this study. In a previous study, another lactone, y-butyrolactone, was also
detected in Malaysian durians.^
Careful examination of the results from this study and previous studies revealed some
generally agreeable information on the volatile flavor composition of durian fruits. Esters,
sulfur-containing compounds and carbonyls were the major groups of volatile constituents of
durian fruits. Other types of compounds were also reported as the major durian volatiles, such
as 1,1-diethoxyethane^''* and hexadecanol^, but these compounds were not detected by any
other researchers. It was also generally agreeable that ethyl 2-methylbutanoate, diethyl
disulfide and acetoin were the major individual components. Despite the similarities,
significant differences were obvious among the results obtained by different researchers,
especially on the qualitative and quantitative data of the major volatile flavor components.
Such differences could have been due to different varieties and maturities of durian fruits and
different techniques applied for the extraction and analysis of durian volatile compounds, as
discussed by Wong and Tie^ The results reported by Wong and Tie^ and Weenen et al.^
revealed obvious varietal differences in the volatile composition of durian fruits from the same
352

country. Durian lovers clearly know that durian fruits from different countries show
distinctive flavor characteristics. For example, Malaysian durians generally have a stronger
aroma than Thai durians. What makes such differences? Unfortunately, the answer is still not
known because there are no comparative data available on the qualitative and quantitative
differences in the volatile composition of durian fruits from different countries. It would be
very interesting and challenging to search for the answer.

4. REFERENCES
1 J. Baldry, J. Dougan, G.E. Howard. Phytochemistry, 11 (1972) 2081.
2 R. Moser, D. Duvel, R. Greve. Phytochemistry, 19 (1980) 79.
3 N. Fischer, F.J. Hammerschmidt, E.J. Brunke. Dragoco Rep. Flavor Inf Serv. (1994) 77.
4 A. Apriyantono and E.E. Septiana. Proceedings of EURO FOOD CHEM VIII, Vienna,
Austria September 18-20, 1995, Vol. 3, 745.
5 K.C. Wong and D.Y. Tie. Flavor and Fragrance J., 10 (1995) 79.
6 H. Weenen, W.E. Koolhaas and A. Apriyantono. J. Agric. Food Chem., 44 (1996) 3291.
7 H. Maarse, L.C. Willemsens and M.H. Boelens (eds.). Volatile Compounds in Food,
TNO-CIVO Food Analysis Institute, Zeist, The Netherlands, 1989.