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1.
Introduction
Vegetable oils lose a signicant amount of their commercial value following air-oxidation and, moreover,
have been shown to have an adverse e#ect on the
living body when used to prepare food.1) It is well
known that hydroperoxides, which are formed by air
oxidation, play a role in these phenomena and that the
decomposition and formation are autocatalytically repeated.2) Therefore, it is important that a method be
developed to obtain the total trace amount of hydroperoxides (peroxide value, POV).3) The recognized
methods for determining the POV are basic indirect
chemical methods using iodine that were established
by the American Oil Chemists Society4) and Japanese
Oil Chemists Society.5) These methods are comparatively simple, considerably sensitive, highly reliable,
and excel in reproducibility. However, they are laborintensive and consume a considerably large quantity
of solvent, which raises environmental concerns.
Recently, various methods using di#erent equipment have been developed in place of the iodometric
method. Analysis of hydroperoxide can be achieved
using infrared spectroscopy6) and Fourier transform
infrared spectroscopy7) based on the OOH stretching
at 3400 cm1 and 3600 cm1. As for the method to
Correspondence to: Yoshiyuki MD8=>96, Department of
Material and Life Chemistry, Kanagawa University, 327
1 Rokkakubashi, Kanagawa-ku, Yokohama 2218686,
JAPAN, e-mail: mochiy01@kanagawa-u.ac.jp
obtain the oxidation-reduction potential of hydroperoxide, the use of the polarograph method8) and electrochemical method9) have been reported. Furthermore, a method using ultraviolet absorptiometry9) of
the conjugated double bond formed by the relocation
of hydroperoxide, was reported. An indirect method to
measure the amount of compound oxidized by hydroperoxides and the iodometric method were proposed.
Fourier transform infrared spectroscopy,10) ultraviolet
absorptiometry,11) and Fourier transform near-infrared
spectroscopy,12) in which the absorption band of the
triphenylphosphine oxide (TPPO) produced by the oxidation of triphenylphosphine (TPP) is measured, were
also reported. Other proposed methods include measuring the luminescence of luminol and the uorometry
of diphenyl-1-pyrenyl-phosphineoxide.13)
It is impossible to directly determine the POV of
hydroperoxides in oxidized vegetable oils using conventional spectrometry as many unspecied molecular
species exist. Moreover, it is very di$cult to ionize the
thermally hypersensitive hydroperoxide. Consequently, a method to obtain the total amount of hydroperoxides by mass spectrometry has not previously been
studied. As hydroperoxide reacts stoichiometrically
with TPP and produces TPPO,11)13) it can be considered
appropriate to adopt an indirect method in which the
amount of the related ions such as [TPPO], [TPPO
H], and base peak etc. of TPPO produced by the ionization of TPPO is used for measuring the POV by mass
spectrometry.
We have examined various problems which occurred
235
Experiments
Fig. 1.
EI mass spectra of triphenylphosphine (TPP) and triphenylphosphine oxide (TPPO). Electron energy: TPO was
carried out at 20 eV (spectrum A), and TPPO was carried out at 70 eV (spectrum B) and 20 eV (spectrum C).
236
Fig. 2.
Selected ion current chromatogram of the dehydride molecule of TPPO and mass spectrum of TPPO produced
from TPP with cumene hydroperoxide. Mass spectrum B) multiplied scan number 2737 of the selected ion
current chromatogram A). Next number of expresses magnication of ion strength. TPPO was obtained by
adding TPP (20 mg) and cumene hydroperoxide (40 mg) to the CM solvent (2 : 1 chloroform : methanol, 10 mL) and
keeping it in the dark at 60 for 60 min.
237
Fig. 3.
Selected ion current chromatogram of TPP a#ected during the preparation of ionization solution by dissolved air
in solution or by atmosphere. The nitrogen substitution was not carried out for the solutions and the experiment
parts. The preparation of the ionization solution is the same as in Fig. 2. The reactions were carried out at room
temperature A) and at 60 B) and C) for 60 min. Antioxidant, 3,5-di-t-butyl-4-hydroxy toluene, was added for C).
Next number of expresses magnication of ion strength.
Fig. 4.
238
Fig. 5.
Typical selected ion current chromatogram patterns of the dehydride molecule, [TPPOH], of desorbed TPPO
from asbestos for Gooch crucible and active carbon used as sample holder materials. The ionization solution was
TPPO (20 mg) added to CM solvent (5 mL).
Fig. 6.
The scattering microscope images of the quartz wool after repeated injection and ionization of the ionization
solution. Usual amount of the injection is 1 mL. The preparation of the ionization solution of A) and B) is by
adding TPPO (20 mg) to CM solvent (10 mL). See Fig. 2 for cumene hydroperoxide-TPP-CM solution for ionization
solution of C).
239
Fig. 7.
EI sample tubes used for EI method. A), B), D), E), and F) are handmade products and C) is a manufacturers
product.
Fig. 8.
Adaptation between the peroxide value (POV) by iodimetric method and TPPO concentration by a correction
curve. The [TPPOH] intensity of oxidized vegetable oil obtained by the EI-MS method was matched with the
[TPPOH] intensity obtained from the correction curve of TPPO, and a scale of the POV obtained with
iodimetric method was graduated to x axis in equal increments. The ionization of the TPPO-CM solution used 5
mL of the solution of CM solvent (10 mL) containing TPPO (6 mg) and antioxidant (200 mg). See Fig. 2 for the
preparation of the CM solvent. The ionization of oxidized vegetable oil used 5 mL of the solution of oxidized
vegetable oil (200 mg), antioxidant (200 mg), and CM solvent (10 mL), reacted in the test tube with screw stopping
(10 mm*50 mm) in the dark at 60 for 60 min. The preparation of the oxidized vegetable oil was carried out
by oxidizing the oil in an open plate and in outdoor sunlight.
3.4
ing (operated at the maximum dissipation of the equipment). The shape of the EI sample tube also signicantly inuenced desorption. Figure 7 shows examples of various types of handmade sample tubes. The
straight type (Fig. 7A) and the barrel type (Fig. 7B)
exhibited almost the same behavior as the
240
Table 1.
Value
[TPPOH] intensity/()
POVTPPO/(meq/kg)
POVIodine/(meq/kg)
Soybean oil
5
0.11
0.21 0.66 1.05 1.14
4.0
14
37
60
63
4.0
17
37
60
62
Sa%ower oil
4
0.06
0.33 0.69
2.15
2.0
18
40
122
1.5
20
40
120
0.06
0.65 1.54
2.0
36
87
2.0
30
87
Olive oil
1
0.21 0.73
12
42
12
38
See Fig. 8 for the preparation and ionization of the oxidized vegetable oil (analyte). [TPPOH] intensity: [TPPOH]
intensity is obtained from TPO in the sample by EI-MS method. POVTPPO : POV is determined from the correction curve of
TPPO concentration. POVIodine : POV is determined by iodometric method.
Conclusion
241
8)
References
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2)
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7)
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