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Application of Solid Phase-Microextraction

(SPME) and Electronic Nose Techniques to


Differentiate Volatiles of Sesame Oils Prepared
with Diverse Roasting Conditions
C: Food Chemistry

Min Hee Park, Min Kyu Jeong, JuDong Yeo, Hee-Jin Son, Chae-Lan Lim, Eun Jeung Hong, Bong-Soo Noh, and JaeHwan Lee

Abstract: Headspace volatiles of sesame oil (SO) from sesame seeds roasted at 9 different conditions were analyzed
by a combination of solid phase microextraction (SPME)-gas chromatography/mass spectrometry (GC/MS), electronic
nose/metal oxide sensors (MOS), and electronic nose/MS. As roasting temperature increased from 213 to 247 ◦ C, total
headspace volatiles and pyrazines increased significantly (P < 0.05). Pyrazines were major volatiles in SO and furans,
thiazoles, aldehydes, and alcohols were also detected. Roasting temperature was more discrimination factor than roasting
time for the volatiles in SO through the principal component analysis (PCA) of SPME-GC/MS, electronic nose/MOS,
and electronic nose/MS. Electronic nose/MS showed that ion fragment 52, 76, 53, and 51 amu played important roles
in discriminating volatiles in SO from roasted sesame seeds, which are the major ion fragments from pyrazines, furans,
and furfurals. SO roasted at 213, 230, and 247 ◦ C were clearly differentiated from each other on the base of volatile
distribution by SPME-GC/MS, electronic nose/MOS, and electronic nose/MS analyses.
Keywords: electronic nose analyses, headspace volatiles, roasting condition, sesame oil, SPME

Practical Application: The results of this study are ready to apply for the discriminating samples using a combinational
analysis of volatiles. Not only vegetable oils prepared from roasting process but also any food sample possessing volatiles
could be targets for the SPME-GC/MS and electronic nose assays. Contents and types of pyrazines in sesame seed oil
could be used as markers to track down the degree of roasting and oxidation during oil preparation.

Introduction (2000) analyzed volatiles in SO prepared from 110 to 230 ◦ C


Sesame (Sesamum indicum L.) seeds have been cultivated in Asia roasted sesame seeds using simultaneous distillation and extraction
and Africa as an important oilseed crop. Sesame oil (SO) can be method and reported 26 pyrazines, 11 pyridines, 9 thiazoles, 6
produced through roasting sesame seeds and pressing the roasted furans, 8 pyrroles, 5 phenols, 8 aldehydes, 8 hydrocarbons, 7 al-
seeds with or without further refining (Namiki 1995; Lee and cohols, 2 indoles, 3 ketones, 10 acids, 4 nitriles, 7 esters, and 5
others 2010b). SO has been used as seasoning ingredient or nat- other compounds. Schieberle (1996) used aroma extract dilution
ural salad oil due to its characteristic odor and taste, and even analysis and stable isotope dilution assays to analyze an extract
cooking oil (Abou-Gharbia and others 2000). Phytochemicals in from moderately roasted SO and found 41 odor-active volatiles
SO including tocopherols, phytosterols, resveratrol, lignans, and including 2-acetyl-1-pyrroline (roasty), 2-furfurylthiol (coffee-
sesamol have been reported to possess physiological functions such like), 2-phenylethylthiol (rubbery), and 4-hydroxy-2,5-dimethyl-
as antioxidant activity (Shahidi and Naczk 2004; Lee and others 3(2H)-furanone (caramel-like) as important odor contributors for
2010b). SO. Shimoda and others (1996) analyzed steam distillated SO
Flavor characteristics of SO has been studied by many re- and identified 134 individual peaks. Among them, sulfur- and
searchers with diverse volatile analyzing methods. Nakamura and nitrogen-containing compounds such as 1-(5-methyl-2-furanyl)-
others (1989) reported 221 compounds including pyrazines, fu- 1-propanone, 2-propyl-4-methylthiazole, 2-ethyl-4-methyl-1H-
rans, pyrroles, pyridines, and sulfur-containing compounds from pyrrole, 2-ethyl-5-methylpyrazine, and 1-(1-methyl-1H-pyrrol-
the neutral fractions of steam distillated SO. Kim and others 2-yl)ethanone were reported as principal odor contributors for SO.
Generally, sulfur-containing compounds, pyrroles, and pyrazines
seem to play important roles in the characteristic odor for SO.
Solid phase microextraction (SPME) is a volatile extracting and
MS 20100719 Submitted 6/26/2010, Accepted 9/12/2010. Authors Park, Jeong, concentration method without using organic solvent. SPME has
Yeo, and Lee are with Dept. of Food Science and Technology, Seoul Natl. Univ. of been successfully adapted to analyze volatiles from fats and oils
Science and Technology, Seoul 139-743, Korea. Authors Son, Lim, Hong, and Noh
are with Dept. of Food Science and Technology, Seoul Women’s Univ., Seoul, Korea. including thermally oxidized free fatty acids (Lee and others 2007),
Direct inquiries to author Lee (E-mail: jhlee@snut.ac.kr). photosensitized lards (Lee and Min 2009), or vegetable oils such as
corn, soybean, olive, sunflower, and rapeseed oils (Jelen and others


R

C 2010 Institute of Food Technologists
C80 Journal of Food Science r Vol. 76, Nr. 1, 2011 doi: 10.1111/j.1750-3841.2010.01954.x
Further reproduction without permission is prohibited
Volatile analysis in roasted sesame oil . . .

2000). Limited numbers of studies have reported on the volatile SO from sesame seed roasted at 247 ◦ C for 28 min was designated
changes of SO using SPME method. Chen and others (2007) used as 247/28 and control sample from unroasted sesame seeds was
SPME-GC/MS to analyze capsule formulation containing sesame abbreviated as 0/0. All samples were prepared triplicates.
oil and reported the presence of 2,4,-decadienal from thermal
degradation of linoleic acid. Analysis of volatiles by SPME
Electronic nose, one of the analytical instrumentations for Analysis conditions of SPME for volatile compounds were
volatile analysis, can provide volatile information rapidly for the adapted from the methods of Lee and others (2007). Total of

C: Food Chemistry
monitoring of food quality. In the literature, several examples 400 mg of SO was put in a 10-mL bottle and sealed air-tightly
demonstrate the possibility of using electronic nose with metal with a Teflon-coated rubber septum and an aluminum cap. Sam-
oxide sensors or surface acoustic wave sensors for the charac- ple bottles were placed in the dark for 1 h at room temperature
terization of olive oil (Gan and others 2005; Cosio and others to equilibrate the volatile compounds in the headspace of bot-
2007), vegetable oils (Shen and others 2001), and coconut oil tles. Headspace volatiles of each SO were isolated using a 65-μm
(Han and others 2006). However, lack of information on eluci- PDMS/DVB solid phase at 30 ◦ C for 30 min in a circulating water
dating major contributing volatiles has limited the extensive appli- bath (RW-0525G, Lab Camp, Gyeonggi-do, Korea) (Lee and Min
cation of electronic nose. To overcome the limitation, electronic 2010). The isolated volatile compounds were determined using
nose coupled with mass spectrometry (MS), which can provide GC/MS. Solid phase of SPME was exposed in an injector for
information on the ion fragments contributing volatile discrim- 3 min.
ination among tested samples, has been developed (Fenaille and
others 2003; Vinaixa and others 2005). Mass spectrometry-based Gas chromatography condition
electronic nose can be an alternative device to metal oxide sensor- Volatiles attached in the solid phase of SPME were separated
based electronic nose in food quality applications (Noh and others and identified using a Hewlett-Packard 6890 GC equipped with
2005). Vinaixa and others (2005) used electronic nose with mass a 5971A mass selective detector (MS) (Agilent Technology, Palo
spectrometry to detect rancidity in potato crisps and discriminate Alto, Calif., U.S.A.) and a HP-5ms column (30 m × 0.25 mm
infant formula oxidation using electronic nose/MS. i.d., 0.25 μm film thickness, Agilent Technology). All mass spectra
Although many studies have conducted to analyze the volatile were obtained at 70eV and 220 ◦ C ion source temperature (Lee
profiles among SO, combination studies using SPME-GC/MS, and Min 2009). The peaks were compared and identified using a
electronic nose/MOS, and electronic nose/MS on the distribution combination of NIST Mass Spectra, linear retention indices (RI)
of headspace volatiles in SO have not been reported in the litera- using n-paraffins as external references, and gas chromatographic
ture. Correlation studies in the results of headspace volatiles from retention times of standard compounds. Helium was carrier gas at
SPME and ion fragments from electronic nose analyses may pro- 1 mL/min and the oven temperature was held at 40 ◦ C for 2 min
vide better information on the characteristics of headspace volatiles and increased from 40 to 160 ◦ C at 6 ◦ C/min and from 160 to
in SO. Also, it would be necessary to select proper and representa- 220 ◦ C at a rate of 10 ◦ C/min.
tive volatiles, which can be used as markers to discriminate volatile
profiles among SO with different roasting conditions. Electronic nose/MOS analysis
The objective of this study was to evaluate the usefulness of com- For the electronic nose/MOS analysis, 6 metal oxide sensors
binational approaches of SPME-GC/MS, electronic nose/MOS, (TGS 800, 825, 826, 842, 2610, and 2620; Figaro, Tokyo, Japan)
and electronic nose/MS on determining major volatiles in SO were used as detectors for the electronic nose. Total of 1 g of sesame
prepared from sesame seeds with different roasting condition. oil was placed in a 40-mL bottle with 4 min equilibrium time.
Purified air at 10 mL/min flow was used to purge the headspace
Materials and Methods from a sample bottle and introduced to the injector of electronic
nose/MOS. The resistance of the metal oxide sensors for the
Materials injected gas was determined and used for the statistical analysis.
Packaged white sesame seeds were purchased from a local gro- The electronic nose analysis was triplicate for each treatment. All
cery market (Seoul, Korea). Teflon-coated rubber septa, 65 μm measurements were conducted at 35 ◦ C
polydimethylsiloxane/divinylbenzene (PDMS/DVB), aluminum
caps, serum bottles, glass liners, and a fiber assembly holder were Electronic nose/MS analysis
R
purchased from Supelco Inc. (Bellefonte, Pa., U.S.A.). Standard Electronic nose system (SMart Nose 300, SMart Nose, Marin-
volatile compounds and n-paraffin were purchased from Sigma- Epagnier, Switzerland) was equipped with an automatic headspace
Aldrich (St. Louis, Mo., U.S.A.). sampler (SMart Nose Autosampler) and with a mass spectrometer
detector (Quadrupole Mass Spectrometer, Balzers Instruments,
Sample preparation Marin-Epagnier, Switzerland). Total of 1 g of SO was put in a 10-
Preparation condition for the production of SO was adapted mL vial with an adequate septum closure (Pharma Fix. Chemmea,
from the method of Lee and others (2010b). Briefly, using a drum Slovakia). The syringe and the injector were purged and cleaned
of a coffee roaster (Model CBR-101, Genesis Co. Ltd., Gyeonggi- with a dry nitrogen flow after each sampling. The analysis was
do, Korea), raw sesame seeds were roasted at the temperature of performed in bargraph mode, to have a fingerprint of the sample
217, 230, and 247 ◦ C with 7, 14, and 21 min for each roasting as complete as possible.
temperature. Roasted sesame seeds were pressed for SO produc-
tion using an oil maker with a pressing unit (Model DO-9990, Statistical analysis
Dong-A Oscar Co. Ltd., Seoul, Korea). Controls were SO from Results of total peak areas and some selected volatiles were sta-
unroasted sesames seeds. Crude SO from the oil maker was cen- tistically analyzed by analysis of variance (ANOVA) and Duncan’s
trifuged (Model Mega 17R, Hanil Science Ltd. Gyeonggi-do, multiple range test using commercially available software pack-
Korea) at 2208 × g for 20 min and supernatant was recovered. age SPSS software program (SPSS Inc., Chicago, Ill., U.S.A.). A

Vol. 76, Nr. 1, 2011 r Journal of Food Science C81


Volatile analysis in roasted sesame oil . . .

P-value < 0.05 was considered significant. Principal component SO. However, previous studies used a steam distillation or a si-
analysis (PCA) for volatiles in SO by SPME-GC/MS was con- multaneous distillation and extraction method as volatile isolation
ducted using Microsoft Excel software program. and concentration procedure. SPME just isolates and concentrates
For the data from electronic nose, intensities of the different the headspace volatiles only rather than trapped in the matrix.
channels were recorded in a matrix. The software reduced the Haiyan and others (2007) analyzed volatiles in SO with SPME-GC
raw data and the comparison of the sets of values lead to the method using a polydimethylsiloxane/Carbowax/divinylbenzene
desired plot of the discriminated samples. The variables used in solid phase and reported 10 peaks of volatiles.
C: Food Chemistry

each case for the PCA calculation were selected by comparing In unroasted control samples, major volatiles were aldehydes in-
their variance among the groups. The SMart NoseTR software in cluding hexanal, 2-heptenal, and nonanal consisting of 72.16%,
electronic nose/MS selected 20 most discriminant ions out of 100 4.96%, and 3.24% to the peak areas of total volatiles, respectively
to 150 of the ion intensities generated from the different samples (Table 1). Hexanal, 2-heptenal, and nonanal are typical oxidized
by the “discriminant power” function. The processed data lead volatiles from fatty acids including linoleic and oleic acids (Frankel
to PCA analyses and only the most discriminating variables have 1985; Lee and others 2007; Lee and Min 2009). Preliminary study
been used for the calculation. on the fatty acid analysis in control SO showed that the rela-
tive contents of palmitic (16 : 0), stearic (18 : 0), oleic (18 : 1),
Results and Discussion linoleic (18 : 2), and linolenic acid (18 : 3) were 8.57%, 5.18%,
40.48%, 44.87%, and 0.33%, respectively, and it is reasonable that
Volatiles in sesame oil from different roasting conditions hexanal or 2-heptenal were detected in control SO due to the
by SPME-GC/MS oxidation of linoleic acids and nonanal from oxidation of oleic
Changes of total volatiles, pyrazines, furans and furfurals, and acid.
thiazole and thiazolines in SO from sesame seeds with different As the roasting time and temperature increased, amount of
roasting conditions are shown in Figure 1. As sesame seeds were pyrazines, furans and furfurals, and thiazole and thiazolines in-
roasted at longer time and higher temperature, total volatiles in creased significantly (P < 0.05) (Figure 1). Pyrazines, which were
SO increased significantly (P < 0.05). Total volatiles in 247/28 not detected in control SO, are predominant volatiles comprising
were higher than those in control SO (0/0), 213/28, and 230/28, up to 64.26% of total volatiles in 247/28. Total of 12 pyrazines
by 23.89, 3.85, and 1.65 times, respectively. It is clearly observed including pyrazine, 2-methylpyrazine, 2,5-dimethylpyrazine,
that SO from sesame seeds roasted at higher thermal energy can ethylpyrazine, 2,3-dimethylpyrazine, vinylpyrazine, 2-ethyl-
generate more volatiles (Figure 1). 6-methylpyrazine, trimethylpyrazine, 2-ethyl-6-methylpyrazine,
Major volatiles in SO from different roasting conditions by acetylpyrazine, 2-ethyl-3,6-dimethylpyrazine, and 1-(6-methyl-2-
SPME-GC/MS are shown in Table 1. Total of 44 volatiles includ- pyrazinyl)-ehtanone were detected in SO. Peak areas of 2-methyl
ing 12 pyrazines, 10 furan and furfurals, 7 thiazole and thiazolines, pyrazine and 2,5-dimethylpyrazine were abundant compared to
6 aldehydes, and 9 other miscellaneous compounds were detected other pyrazines in SO. Pyrazines are typical volatiles detected in
in SO by SPME. Compared to previous reports, the number of roasted seeds including coffees and soybeans (Jung and others 1997;
identified volatiles in this study was not high. Nakamura and others Franca and others 2009). Jung and others (1997) roasted soybeans
(1989) reported 221 compounds, Kim and others (2000) separated at 130, 150, and 170 ◦ C and extracted 3.07, 9.46, and 19.7 mg
119 volatiles, Schieberle (1996) reported 41 odor-active volatiles, total pyrazines per 100 g recovered oils from roasted soybeans,
and Shimoda and others (1996) isolated 134 individual peaks from respectively.

3.0 Figure 1–Changes of total volatiles


f and major volatiles in SO from sesame
seeds with different roasting
conditions. Different letters on the
Peak areas in ion counts (× 109)

2.5 Total peak areas bars are significant at 0.05 among the
same volatile. “ND” indicates
Pyrazines volatiles were not detected.

2.0 Furans and furfurals


e
de g

Thiazoles and thiazolines de

1.5 d

f f

1.0 c e
de
bc
abc cd
0.5 bc
bc de e cde cde
bc c
ab bcd c c
bc b
a ab ab b
a a a a
ND ND ND a
0.0
0/0 213/14 213/21 213/28 230/14 230/21 230/28 247/14 247/21 247/28

Sesame oil

C82 Journal of Food Science r Vol. 76, Nr. 1, 2011


Volatile analysis in roasted sesame oil . . .

Table 1–Distribution of major volatiles in sesame oils prepared from different roasting conditions by SPME-GC/MS (×108 ion
counts).
Peak areas
RIA Volatile compound 0/0B 213/14 213/21 213/28 230/14 230/21 230/28 247/14 247/21 247/28 IDC
Pyrazines
717 Pyrazine NDD ND 0.10abE 0.18b 0.12ab 0.34c 0.42cd 0.55d 0.49cd 0.42cd MS, RS
(2.30)F (3.25) (1.57) (2.79) (3.19) (3.70) (2.86) (1.94)

C: Food Chemistry
801 2-Methylpyrazine ND 0.26ab 1.06bc 1.51c 2.05c 3.27d 3.79de 4.52ef 5.05f 5.19f MS, RI
(14.28) (24.58) (26.81) (27.31) (27.27) (28.79) (30.19) (29.80) (23.94)
886 2,5-Dimethylpyrazine ND 0.31ab 0.46abc 0.52abc 0.73abc 0.95bc 1.15c 1.98d 2.48d 5.05e MS, RI, RS
(16.65) (10.75) (9.24) (9.71) (7.91) (8.76) (13.24) (14.63) (23.30)
891 Ethylpyrazine ND ND 0.17a 0.22a 0.28ab 0.39bc 0.46cd 0.58de 0.63e 0.90f MS, RI, RS
(4.05) (3.84) (3.68) (3.27) (3.48) (3.84) (3.71) (4.14)
894 2,3-Dimethylpyrazine ND 0.04a 0.18b 0.21b 0.31c 0.42d 0.48d 0.64e 0.62e 0.59e MS, RI, RS
(2.18) (4.20) (3.68) (4.10) (3.50) (3.63) (4.28) (3.68) (2.70)
906 Vinylpyrazine ND ND ND ND ND ND 0.05ab 0.06b 0.06b 0.13c MS, RS
(0.37) (0.38) (0.38) (0.60)
974 2-Ethyl-6-methylpyrazine ND 0.03ab 0.07bc 0.09cd 0.11cde 0.14de 0.16e 0.27f 0.24f 0.34g MS
(1.87) (1.65) (1.56) (1.49) (1.14) (1.18) (1.80) (1.80) (1.55)
978 Trimethylpyrazine ND 0.15a 0.26ab 0.27bc 0.36bcd 0.43cde 0.39cde 0.44de 0.52e 0.91f MS, RI, RS
(8.17) (6.15) (4.86) (4.79) (3.56) (2.93) (2.94) (2.94) (4.18)
980 2-Ethyl-3-methylpyrazine ND ND ND ND ND ND ND 0.18b 0.10ab 0.02a MS, RS
(1.20) (1.20) (0.07)
999 Acetylpyrazine ND ND ND 0.02a 0.04ab 0.09c 0.08c 0.16d 0.10c 0.07bc MS, RI
(0.35) (0.51) (0.72) (0.63) (1.08) (1.08) (0.31)
1057 2-Ethyl-3,6-dimethylpyrazine ND 0.04ab 0.07abc 0.07abc 0.10bcd 0.11bcd 0.13cd 0.22e 0.17de 0.23e MS
(2.15) (1.70) (1.26) (1.36) (0.89) (0.98) (1.47) (1.47) (1.08)
1100 1-(6-Methyl-2-pyrazinyl)-1 ND ND ND ND 0.01ab 0.05c 0.07cd 0.10d 0.04bc 0.06cd MS
-ethanone (0.11) (0.44) (0.54) (0.64) (0.64) (0.29)
Furans and furfurals
599 2-Methylfuran ND ND 0.01a 0.04ab 0.06b 0.11c 0.15cd 0.13c 0.18de 0.19e MS, RI, RS
(0.23) (0.63) (0.81) (0.92) (1.11) (0.86) (1.04) (0.88)
693 2,5-Dimethylfuran ND ND ND 0.04a 0.03a 0.03a 0.07ab 0.06ab 0.13bc 0.17c MS, RS
(0.67) (0.46) (0.24) (0.53) (0.40) (0.78) (0.77)
709 2-Vinylfuran ND ND ND ND ND 0.04a 0.10b ND 0.11b 0.12b MS
(0.37) (0.74) (0.65) (0.54)
812 2-Furancarboxaldehyde ND 0.09a 0.47bc 0.79d 0.55c 0.50bc 0.42b ND ND ND MS, RS
(4.76) (11.01) (14.00) (7.30) (4.19) (3.21)
832 2-Allylfuran ND ND ND ND ND 0.07bc 0.08c 0.03ab 0.04abc ND MS
(0.58) (0.60) (0.18) (0.22)
836 2-Furanmethanol ND ND 0.16a 0.38ab 0.47ab 1.06c 1.28c 0.85bc 1.07b 1.01b MS, RI
(3.72) (6.75) (6.30) (8.85) (9.70) (5.66) (6.33) (4.66)
941 5-Methylfurfural ND ND 0.08a 0.17b 0.06a 0.18b 0.20b 0.11a 0.06a ND MS
(1.75) (3.00) (0.86) (1.52) (1.53) (0.70) (0.37)
967 2-Pentylfuran 0.08a 0.08a 0.11abc 0.08a 0.11abc 0.13bc 0.09a 0.09ab 0.14c 0.28d MS, RI, RS
(8.92) (4.59) (2.54) (1.46) (1.40) (1.12) (0.67) (0.63) (0.84) (1.27)
971 Furfurylacetate ND ND ND ND ND 0.02ab 0.03ab 0.03b 0.06c 0.14d MS, RI
(0.17) (0.22) (0.23) (0.38) (0.65)
1192 Furfurylmethylsulfide ND ND ND ND ND ND 0.01ab 0.02b ND 0.02b MS, RI
(0.07) (0.14) (0.11)
Thiazoles and thiazolines
785 2-Methylthiazole ND ND 0.02a 0.04ab 0.08bc 0.13cde 0.16de 0.12cd 0.18de 0.19e MS
(0.51) (0.77) (1.12) (1.11) (1.22) (0.81) (1.08) (0.88)
795 4-Methylthiazole ND ND ND ND 0.06a 0.22b 0.29bc 0.35c 0.49d 0.55d MS, RS
(0.86) (1.80) (2.17) (2.35) (2.91) (2.54)
827 5-Methylthiazole ND ND ND ND 0.05a 0.12a 0.16a 0.47b 0.23ab 0.24ab MS
(0.63) (1.00) (1.25) (3.16) (1.38) (1.13)
861 2,4-Dimethylthiazole ND ND ND ND 0.03a 0.17b 0.22bc 0.31d 0.28cd 0.30d MS, RI, RS
(0.36) (1.38) (1.67) (2.07) (1.64) (1.38)
913 2-Methylthiazoline ND ND ND ND ND 0.02a 0.03ab 0.05bc 0.08c 0.08c MS, RI, RS
(0.13) (0.25) (0.33) (0.48) (0.36)
921 2,5-Dimethylthiazole ND ND ND ND ND 0.01a ND 0.01a 0.02a 0.04b MS
(0.09) (0.05) (0.10) (0.19)
931 2,4-Dimethyl-delta-2-thiazoline ND ND ND ND 0.07a 0.14a 0.18a 0.43b 0.50b 0.47b MS
(0.87) (1.15) (1.36) (2.87) (2.98) (2.16)
(Continued)

Vol. 76, Nr. 1, 2011 r Journal of Food Science C83


Volatile analysis in roasted sesame oil . . .

2-Furanmethanol, one of the most abundant furan com- this compound can be detected easily in thermally oxidized oils
pounds, was detected in all SO from roasted sesame seeds except too. Lee and others (2007) identified substantial amount of 2-
213/14. Thiazoles and thiazolines, including 2-methylthiazole, pentylfuran from thermally oxidized mixtures of free fatty acids at
4-methylthiazole, 5-methylthiazole, 2,4-dimethylthiazole, 2- 93 ◦ C.
methylthiazoline, 2,5-dimethylthiazole, and 2,4-dimethyl--2- Aldehydes such as acetaldehyde, butanal, hexanal, 2-heptenal,
thiazoline were detected in some samples of SO roasted at 213, benzaldehyde, and nonanal were detected in some of SO. Ben-
230, and 247 ◦ C. 4-Methylthiazole was one of abundant thia- zaldehyde was detected in SO from 247 ◦ C roasted sesame seeds
C: Food Chemistry

zoles in SO. Pyridine and 1H-pyrrole, which were not detected while acetaldehyde was found in 230/21, 230/28, and SO from
in control, were formed and increased significantly in SO pre- 247 ◦ C roasted sesame seeds. Butanal, which can be formed from
pared from 213, 230 and 247 ◦ C roasted sesame seeds (P < 0.05) degradation of linolenic acid (Frankel 1985), was detected in SO
(Table 1). from roasted sesame seeds but not in control samples. Other ox-
Maillard reaction has been regarded as major mechanisms for the idized volatiles from fatty acids including hexanal and nonanal
formation of pyrazines and pyridine in potato chips (Lojzova and (Frankel 1985) were detected in all SO samples. 2-Heptenal was
others 2009) and of 2-furanmethanol in model systems containing not detected in 230/28 and SO from 247 ◦ C roasted sesame seeds
amino acids and sugars or in red ginseng with explosive puffing implying that the thermal stability of 2-heptenal was not high
process roasted coffee (Franca and others 2009; Lee and others enough compared to those of hexanal and nonanal.
2010a). Maillard reaction is one of the major chemical reactions Many volatiles identified in this study were already reported in
during roasting process in sesame seeds, which might be confirmed the previous studies on SO (Nakamura and others 1989; Schieberle
by the formation and increase of pyrazines, furans, pyridine, and 1996; Shimoda and others 1996; Kim and others 2000). Difference
2-furanmethanol. of the number and profiles of detected volatiles among current
Some volatiles including 2-pentylfuran, butanal, hexanal, and study and the previous reports may be due to the difference of
nonanal in SO are oxidized products of lipids rather than Maillard volatile analysis methods and of sample preparation. SPME isolates
reaction products. 2-Pentylfuran is one of undesirable reversion and concentrates volatiles based on the affinity between solid phase
flavor in soybean oil and it can be formed from oxidation of linoleic of coating materials and volatiles, and relatively limited types of
acid. Min and others (2003) identified 2-pentylfuran in soybean oil volatiles are separated from headspace of SO depending on the
containing 5 ppm chlorophyll stored under light only. However, characteristics of solid phase.

Table 1–(Continued)
Peak areas
RIA Volatile compound 0/0B 213/14 213/21 213/28 230/14 230/21 230/28 247/14 247/21 247/28 IDC
Aldehydes
643 Acetaldehyde ND ND ND ND ND 0.05a 0.09b 0.08ab 0.12c 0.11c MS, RI
(0.46) (0.67) (0.51) (0.73) (0.52)
646 Butanal ND 0.27d 0.20c 0.16bc 0.21c 0.13b 0.11b 0.05a 0.04a ND MS, RI, RS
(14.60) (4.74) (2.82) (2.74) (1.05) (0.83) (0.32) (0.23)
777 Hexanal 0.65d 0.29ab 0.31ab 0.29ab 0.30ab 0.50c 0.33ab 0.18a 0.35b 0.44bc MS, RI
(72.16) (15.98) (7.25) (5.24) (4.06) (4.18) (2.52) (1.23) (2.05) (2.01)
933 2-Heptenal 0.05a 0.05a 0.09b 0.08b 0.08b 0.15c ND ND ND ND MS, RI, RS
(4.96) (2.66) (2.19) (1.51) (1.06) (1.23)
938 Benzaldehyde ND ND ND ND ND ND ND 0.03a 0.06b 0.10c MS, RI, RS
(0.19) (0.37) (0.44)
1082 Nonanal 0.03a 0.02a 0.04a 0.03a 0.06a 0.06a 0.05a 0.02a 0.11b 0.16c MS, RI, RS
(3.24) (1.29) (0.89) (0.49) (0.58) (0.51) (0.39) (0.16) (0.63) (0.72)
Other miscellaneous compounds
- Methanethiol ND 0.01a ND ND 0.07b 0.16d 0.11c ND ND ND MS
(0.32) (0.88) (1.35) (0.83)
533 Carbon disulfide ND ND ND ND 0.71b 1.05c 0.91c 0.60b 0.13a 0.09a MS, RI
(9.46) (8.74) (6.93) (3.98) (0.78) (0.42)
600 Hexane 0.04ab 0.09b 0.17c 0.05ab 0.08ab 0.06ab 0.08b 0.07ab 0.06ab 0.02a MS, RI
(4.57) (4.91) (4.00) (0.88) (1.04) (0.47) (0.64) (0.44) (0.32) (0.10)
728 Pyridine ND 0.01a 0.06ab 0.11abc 0.10ab 0.22bcd 0.31cd 0.41d 1.05e 1.45f MS, RS
(0.64) (1.46) (2.03) (1.32) (1.86) (2.33) (2.71) (6.21) (6.70)
738 1H-Pyrrole ND 0.00a 0.05ab 0.14bc 0.10abc 0.18bc 0.25de 0.30ef 0.36fg 0.40g MS
(0.23) (1.16) (2.53) (1.29) (1.49) (1.89) (1.99) (2.13) (1.86)
748 1-Pentanol 0.06ab 0.09ab 0.14bc 0.13bc 0.13bc 0.19c 0.02ab 0.09a 0.09ab 0.30d MS, RI
(6.15) (4.74) (3.18) (2.37) (1.76) (1.60) (0.61) (0.15) (0.54) (1.36)
947 Dimethyltrisulfide ND ND ND ND ND ND ND 0.08a 0.10a 0.15b MS, RI
(0.56) (0.59) (0.70)
1073 Phenol ND ND ND ND 0.02a 0.11ab 0.37b 0.36c 0.36c 0.68d MS, RI
(0.24) (0.94) (1.49) (2.48) (2.15) (3.15)
1175 2-Pentylpyridine ND ND ND ND ND 0.01ab 0.01ab 0.01ab 0.02b 0.08c MS, RI, RS
(0.06) (0.07) (0.07) (0.14) (0.38)
A
Linear retention indices (RI) were determined using n-paraffin as external references and compared with those in flavornet (http://flavornet.org; Accessed on Apr. 30, 2010).
B
Sesame oil from sesame seeds roasted at 213 ◦ C for 14 min was designated as 213/14. “0/0” represents oil from unroasted sesame seeds.
C
Volatile identification was performed through a combination of NIST Mass spectra library (MS), linear retention index (RI), and retention times of standard compounds (RS).
D
Not detected.
E
Different letters are significant at 0.05 among the same row.
F
Relative percentage (%).

C84 Journal of Food Science r Vol. 76, Nr. 1, 2011


Volatile analysis in roasted sesame oil . . .

Loading and score plots of PCA for the volatiles in SO The PCA technique has been adapted to evaluate the quality
by SPME-GC/MS are shown in Figure 2. PCA was con- of oil. Lee and others (1999) showed the characteristics of fatty
ducted to determine the relation between volatile distribution acids composition in vegetable oils through gas chromatography
and SO from different roasted sesame seeds. First principal com- and chemometrics. The researchers also suggested that PCA or
ponent (PC1) and second principal component (PC2) expressed discriminant analysis was a useful tool for many aspects including
65.28% and 13.88% of the volatile variability, respectively. Main pattern recognition and primary evaluation of category similarity,
volatiles positively correlated to PC1 are pyrazines, furans, fur- detection of adulterants, and quality control.

C: Food Chemistry
furals, thiazoles, and thiazolines and negatively correlated volatiles
to PC1 are aldehydes including 2-heptenal and butanal (Fig- Electronic nose/MOS and electronic nose/MS analysis
ure 2A). According to the scoring plot, PC1 and PC2 clearly Volatile profiles of SO with different roasting conditions de-
distinguished the SO with different roasting temperature (Fig- termined by electronic nose/MOS and electronic nose/MS are
ure 2-B). SO from the same roasting temperature were grouped shown in Figure 3. PC1 expressed 95.90% and 94.15% of the data
together. Roasting temperature gave more correlation to volatile variability of volatiles from electronic nose/MOS and electronic
distributions in SO than roasting time according to PCA results nose/MS, respectively, and PC2 explained 3.61% and 4.57%, re-
of SPME-GC/MS implying roasting temperature was more dis- spectively. Electronic nose/MOS analyses of SO volatiles showed
criminating factor than roasting time on the volatile distribution that samples roasted at 213 ◦ C were separated from those of the
in SO. samples roasted at 230 and 247 ◦ C (Figure 3-A). With increasing

1 Figure 2–Loading and score plots of PCA for


volatiles in SO by SPME-GC/MS. Volatiles were
A 941 expressed in linear retention indices (RI) instead
533
0.8 832 of chemical names to provide clear information.
- Chemical names of each RI are shown in Table 1.

0.6 999
PC2 (13.88%)

836
1100
717
812 0.4 894
827 785801
980 861
0.2 599
933 643
592 Pyrazines 1057 738
646 891
974 795
0 709 931
1192 913
-0.8 -0.6 -0.4 -0.2 0 0.2 0.4 Furans0.6 0.8 978 1 1.2
693 1073
-0.2 Furfurals
996 906
Thiazoles 886
777 Thiazolines 971 728
748 1082 921 947
-0.4
938
967 1175
-0.6

PC1 (65.28%)
2
B
1.5 230/28
230/21
1 247/14
230°C
PC2 (13.88%

0.5
247°C
230/14
213/28 0
247/21
-1.5 -1 -0.5 0 0.5 1 1.5 2 2.5
213/21
-0.5
213°C
213/14
0/0 -1

-1.5
247/28

-2

PC1 (65.28%)

Vol. 76, Nr. 1, 2011 r Journal of Food Science C85


Volatile analysis in roasted sesame oil . . .

roasting temperature, the PCA plot extended from the right side closely related with those by electronic nose/MS than by elec-
(positive value of PC1 score) through the middle to the left side tronic nose/MOS. This may come from the difference of data
(negative value of PC1 score) (Figure 3A). Electronic nose/MOS forms used for the PCA analysis. SPME-GC/MS and electronic
showed the clear difference of roasting temperature while not quite nose/MS produce ion fragments from headspace volatiles while
well separated among roasting times. electronic nose/MOS generates resistance values from the metal
For electronic nose/MS, as the roasting temperature increased, oxide sensors.
the PCA plot extended from the left side (negative value of PC1
C: Food Chemistry

score) to the right side (positive value of PC1 score) like results
of electronic nose/MOS (Figure 3-B). Compared to electronic Table 2–Ion fragments showing high discriminating power in SO
nose/MOS, samples with different roasting time at 230 and 247 ◦ C from electronic nose/MS.
were discriminated more clearly than those at 213 ◦ C by elec- Ion fragment R2 F
tronic nose/MS (Figure 3B). Results of PCA from SPME anal-
52 0.9987 1731
ysis (Figure 2B) showed similar discriminate pattern with those
76 0.9986 1609
from electronic nose/MS (Figure 3B) while those from electronic 53 0.9984 1387
nose/MOS did not share score plot patterns, which implies that 51 0.9980 1141
distributions of headspace volatiles by SPME analysis were more 65 0.9974 866

0.06 Figure 3–PCA for the volatile profiles of SO


from sesame seeds with different roasting
A conditions by electronic nose/MOS (A) and
213°C electronic nose/MS (B).
0.04

230°C
0.02
PC2(3.61%)

0.00
213/14
213/21
213/28
-0.02 230/14
230/21
247°C 230/28
-0.04 247/14
247/21
247/28
-0.06
-0.4 -0.2 0.0 0.2 0.4

PC1(95.90%)

2
B 213/14
213/21
213/28
230/14
1 230°C 230/21
230/28
247/14
PC2(4.57%)

247/21
247/28

0
247°C

213°C

-1

-8 -6 -4 -2 0 2 4 6 8 10

PC1 (94.15%)

C86 Journal of Food Science r Vol. 76, Nr. 1, 2011


Volatile analysis in roasted sesame oil . . .

Table 3–Major ion fragments of selected standard volatile compounds by SPME-GC/MS and electronic nose/MS.
Volatile Ion fragments from Ion fragments from Volatile Ion fragments from Ion fragments from
compound SPME-GC/MS electronic nose/MS compound SPME-GC/MS electronic nose/MS
Pyrazines Thiazoles and thiazolines
Pyrazine 80, 53, 68, 97a 80, 53, 54, 81 4-Methylthiazole 99, 71, 93, 78 99, 71, 72, 57
2-Methylpyrazine 94, 67, 53 94, 67, 53 2,4-Dimethylthiazole 113, 71, 59, 46 113, 71, 72, 59
2,5-Dimethylpyrazine 108, 58, 81, 52 108, 81, 80, 52 2-Methylthiazoline 60, 101, 55, 46, 71 101, 60, 59, 56

C: Food Chemistry
Ethylpyrazine 108, 80, 53 108, 107, 80, 53 Aldehydes
2,3-Dimethylpyrazine 67, 108, 58, 52 67, 108, 53, 60 Acetaldehyde 86, 71, 60, 55 89, 87, 60, 59
Vinylpyrazine 106, 79, 52, 95, 65 105, 106, 79, 52 Butanal 57, 86, 60, 71 72, 57, 60, 71
Trimethylpyrazine 122, 81, 53 122, 81, 53, 54 Hexanal 56, 85, 71, 45, 67 56, 57, 71, 72
2-Ethyl-3-methylpyrazine 122, 81, 67, 94 122, 81, 67, 94 2-Heptenal 55, 83, 68, 74, 100 83, 55, 68, 69
Acetylpyrazine 80, 52, 122, 94 80, 52, 94, 79 Nonanal 57, 114, 70, 85, 98 56, 57, 70, 71
Furans and furfurals Other miscellaneous compounds
2-Methylfuran 82, 53, 50, 57, 72 82, 83, 50, 53 Pyridine 79, 52, 46, 49, 61 79, 52, 51, 78
2,5-Dimethylfuran 96, 81, 53, 84, 50 96, 95, 81, 67 1-Pentanol 55, 70, 57 55, 70, 57
2-Furancarboxaldehyde 96, 67, 53, 82 95, 96, 80, 49 2-Pentylpyridine 93,106,120,65 93, 65, 78, 79
5-Methylfurfural 110, 53, 81 110, 109, 53, 67
2-Pentylfuran 81, 138, 53 81, 53, 83, 68
Furfurylacetate 81, 52, 98, 140 60, 81, 68, 98
a
Ion fragments are listed in the order of abundance.

Ion fragments results from electronic nose/MS can help to un- In this study, PCA analyses (Figure 2 and 3) and ion fragments
derstand which volatile components play important roles for the from SPME-GC/MS and electronic nose/MS (Table 3) can be
discriminating SO prepared from diverse roasted sesame seeds. Ion used to find out positively correlated major discriminating volatiles
fragments showing high discriminating power in SO from elec- among oils treated with different processing condition.
tronic nose/MS are shown in Table 2. Ion fragments of 52, 76, 53,
51, and 65 amu from volatiles were major discriminating factors Conclusions
in SO with high “F values” as 1731, 1609, 1387, 1141, and 866, Headspace volatile compounds in SO prepared from sesame
respectively (Table 2). seeds roasted with different roasting time and temperature
To determine the specific volatiles containing ion fragments were analyzed by a combination of SPME-GC/MS, electronic
of 52, 76, 53, 51, and 65 amu from electronic nose/MS, major nose/MOS, and electronic nose/MS. Roasting temperature was
ion fragments of identified volatiles from mass spectra of standard more important factor than roasting time on the formation of
volatile compounds by SPME-GC/MS are compared with those volatiles in SO determined by PCA of SPME and electronic nose
by electronic nose/MS (Table 3). Only some volatiles includ- analyses. Data from electronic nose/MS analyses provided ma-
ing 2-methylpyrazine, 2-ethyl-3-methylpyrazine, and 1-pentanol jor discriminating ion fragments, which may come from with
produced the same ion fragments by both SPME-GC/MS and pyrazines, furans, and furfurals in SO. A combination of SPME-
electronic nose/MS while other major volatiles generated slightly GC/MS, electronic nose/MOS, and electronic nose/MS anal-
different ion fragments from MS attached to SPME-GC and elec- yses for the profiles of volatiles could provide useful tools to
tronic nose. Major ion fragments of pyrazine by SPME-GC/MS discriminate samples each other and to track specific volatile com-
were 80, 53, 68, and 97 amu while those by electronic nose/MS pounds responsible for this discrimination. This combination for
were 80, 53, 54, and 81 amu in the order of abundance; in case the headspace analysis can be applied to discriminate food products
of acetylpyrazine, SPME-GC/MS produced 80, 52, 122, and 94 from different processing methods or storage conditions.
amu and electronic nose/MS generated 80, 52, 94, and 79 amu
(Table 3). Most of pyrazines, furans, and furfurals can generate Acknowledgment
either 53 or 52 amu ion fragments by both SPME-GC/MS and This study was supported by the financial fund provided by
electronic nose/MS while aldehydes did not produce these ion grant nr KRF-2008-313-F00108 from Basic Research Program
fragments (Table 3). Interestingly, 76 amu, which was calculated of the Korea Research Foundation.
as one of discriminating factor, was not found in tested volatiles
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