2
282
K. MATSUI et al.
Table 3. EŠect of Glutathione Peroxidase on the Amounts of
Volatiles and Linoleic Acid Hydroxides
could be detected, although its amount showed no
change (data not shown). Neither 9- nor 12-H(P)OD
could be detected. As we have shown, 13-H(P)OD
cannot be converted into 1-octen-3-ol; thus, of the
HPODs detected here, only 10-HPOD could have
been the intermediate for the formation of 1-octen-
Content (nmol
Wg fresh weight)
Linoleic acid
+
Control Linoleic acid
glutathione
peroxidase
3
-ol.
1
n
1
1
-octen-3-ol
-hexanal
0-HOD
3-HOD
27.7
350
87.2
90.2
±
±
±
±
3.9
147
1641
61.6
226
±
±
±
±
11.0
79.2
16.6
21.2
76.3
±
6.8
188
29.7
14.7
1007
±
62.1
38.9
328
250
1987
±
References
±
1
2
)
Rapior, S., Gavalie
á
, S., Andary, C., Pe
á lissier, Y.,
Marion, C., and Bessie
á
re, J.-M., Investigation of
some volatile components of seven fresh wild
mushrooms (Basidiomycetes). J. Essent. Oil Res., 8,
hydroperoxide lyases involved in the formation of
the two volatile compounds can be discriminative.
It has been postulated that 10-HPOD is the inter-
1
99–201 (1996).
)
Lizårraga-Guerra, R., Guth, H., and Lopez, M. G.,
Identiˆcation of the most potent odorants in huit-
lacoche (Ustilago maydis) and austern pilzen (Pleuro-
tus sp.) by aroma extract dilution analysis and static
head-space samples. J. Agric. Food Chem., 45,
1329–1331 (1997).
4
,9)
mediate for 1-octen-3-ol formation;
however,
there is no direct evidence for the formation of 10-
HPOD as the intermediate to form the C8 compound
from linoleic acid. Glutathione peroxidase is an
enzyme that reduces organic hydroperoxides to
the corresponding hydroxides in the presence of
glutathione and it has been widely used to trap an
3) Wurzenberger, M., and Grosch, W., Origin of the
oxygen in the products of the enzymatic cleavage
reaction of linoleic acid to 1-octen-3-ol and 10-
oxo-trans-8-decenoic acid in mushrooms (Psalliota
bispora). Biochim. Biophys. Acta, 794, 18–24 (1984).
1
0)
intermediate having a hydroperoxy group.
As
shown in Table 3, the addition of linoleic acid
enhanced the formation of 1-octen-3-ol, but when
the reaction was performed in the presence of
glutathione peroxidase and glutathione, this forma-
tion was eŠectively inhibited. This suggests that a
fatty acid hydroperoxide(s) was the intermediate for
the formation of 1-octen-3-ol. When the crude
enzyme solution was incubated without any additive,
4
)
Wurzenberger, M., and Grosch, W., The formation
of 1-octen-3-ol from the 10-hydroperoxide isomer of
linoleic acid by a hydroperoxide lyase in mushrooms
(Psalliota bispora). Biochim. Biophys. Acta, 794,
25–30 (1984).
5) Matsui, K., Properties and structures of fatty acid
hydroperoxide lyase. Belg. J. Bot., 131, 50–62 (1998).
6) Matsui, K., Miyahara, C., Wilkinson, J., Hiatt,
B., Knauf, V., and Kajiwara, T., Fatty acid
hydroperoxide lyase in tomato fruits: Cloning and
properties of a recombinant enzyme expressed in
1
0- and 13-H(P)OD could be detected. In the
presence of linoleic acid, no increase in the amount
of 10-H(P)OD was apparent; however, a four-fold
greater amount of it could be detected after the
further addition of glutathione peroxidase, con-
comitant with a decrease of the amount of 1-octen-3-
ol. The decrease in the amount of 1-octen-3-ol in the
Escherichia coli
189–1196 (2000).
Labeque, R., and Marnett, L. J., 10-Hydroperoxy-
. Biosci. Biotechnol. Biochem., 64,
1
7
)
8
,12-octadecadienoic acid: A diagnostic probe of
presence of the peroxidase (ca. 70 nmol
weight) was smaller than that of 10-HOD trapped
ca. 190 nmol g fresh weight). Although the diŠer-
W
g fresh
alkoxyl radical generation in metal-hydroperoxide
reaction. J. Am. Chem. Soc., 109, 2828–2829 (1987).
(
W
8) Wu, C. M., and Wang, Z., Volatile compounds in
fresh and processed shiitake mushrooms (Lentinus
edodes Sing.). Food Sci. Technol. Res., 6, 166–170
ence between these two values cannot be fully ex-
plained, it can be assumed that some of 10-HPOD
formed might have been converted to compounds
other than 1-octen-3-ol such as the 10-oxo form of
linoleic acid. The amount of 13-H(P)OD increased
more than two fold after additing linoleic acid, and
further addition of glutathione peroxidase resulted in
an almost 20-fold higher amount of 13-H(P)OD.
(
2000).
Asaaf, S., Hadar, Y., and Dosoretz, C. G., 1-Octen-
-ol and 13-hydroperoxylinoleate are products of dis-
tinct pathways in the oxidative breakdown of linoleic
9
)
3
acid by Pleurotus pulmonarius
Technol., 21, 484–490 (1997).
. Enzyme Microb.
1
0) Kangsadan, B., Matsui, K., Akakabe, Y., Yotukura,
N., and Kajiwara, T., Hydroperoxy-arachidonic acid
Again, the amount of
n-hexanal inhibited was
smaller than that of 13-HPOD trapped. Other than
these two oxygenated fatty acids, a compound that
was thought to be 11-HOD from its MS spectrum
mediated
n
-hexanal and (
Z
)-3- and (
E
)-2-nonenal
formation in Laminaria angustata
63, 669–678 (2003).
.
Phytochemistry
,