Green leaf volatiles: hydroperoxide lyase pathway of
oxylipin metabolism
Kenji Matsui
Green leaf volatiles (GLVs) are C6 aldehydes, alcohols, and their
esters formed through the hydroperoxide lyase pathway of
oxylipin metabolism. Plants start to form GLVs after disruption
of their tissues and after suffering biotic or abiotic stresses. GLV
formation is thought to be regulated at the step of lipid-
hydrolysis, which provides free fatty acids to the pathway.
Recently, studies dissecting the physiological significance of
GLVs in plants have emerged, and it has been postulated that
GLVs are important molecules both for signaling within and
between plants and for allowing plants and other organisms
surrounding them to recognize or compete with each other.
Addresses
Department of Biological Chemistry, Faculty of Agriculture,
Yamaguchi University, Yamaguchi 753-8515, Japan
Corresponding author: Matsui, Kenji (matsui@yamaguchi-u.ac.jp)
Current Opinion in Plant Biology 2006, 9:274–280
This review comes from a themed issue on
Physiology and metabolism
Edited by Eran Pichersky and Krishna Niyogi
Available online 3rd April 2006
1369-5266/$ – see front matter
# 2005 Elsevier Ltd. All rights reserved.
DOI 10.1016/j.pbi.2006.03.002
Introduction
‘Green leaf volatiles’ (GLVs) are C6 aldehydes, alcohols,
and their esters (Figure 1). GLVs are named for the
distinctive scent that is produced when leaves are crushed
or otherwise injured [1]. Studies aimed at dissecting the
physiological significance of GLVs in plants are accumu-
lating. It has been postulated that GLVs are important
molecules for signaling within and between plants, and
are also important in allowing plants and other organisms
surrounding them to recognize or compete with each
other.
Pathway for GLV biosynthesis
GLVs are usually formed from linolenic and linoleic acids
(Figure 2). Lipoxygenase (LOX) catalyzes the stereospe-
cific oxygenation of the position 13 of linolenic acid to
form linolenic acid 13-hydroperoxide (13HPOT) (also
called 13(S)-hydroperoxy-(Z,E,Z)-9,11,15-octadecatrie-
noic acid). 13HPOT is further metabolized by fatty acid
13-hydroperoxide lyase (13HPL) to form (Z)-3-hexenal
and 12-oxo-(Z)-9-dodecenoic acid [2,3]. The b,g-
Current Opinion in Plant Biology 2006, 9:274–280
unsaturated carbonyl functionality is prone to isomeriza-
tion either enzymatically or non-enzymatically to form
(E)-2-hexenal and 12-oxo-(E)-10-dodecenoic acid. When
linoleic acid is the starting material, n-hexanal is formed.
C6-aldehydes formed thus can be further metabolized by
alcohol dehydrogenase to form the corresponding C6-
alcohol, for example, (Z)-3-hexen-1-ol. An acyltransfer-
ase catalyzes the formation of (Z)-3-hexen-1-yl acetate
from (Z)-3-hexen-1-ol and acetyl CoA [4]. 2-Alkenal
reductase, which was originally isolated as an Arabidopsis
gene that could enhance resistance against oxidative
stress in yeast, can reduce (E)-2-hexenal to n-hexanal
[5]. Another type of LOX can catalyze the formation
of fatty acid 9-hydroperoxides, which are cleaved by HPL
(9/13HPL). 9/13HPL can act on both 13- and 9-hydro-
peroxides at almost the same efficiency, resulting in the
formation of C9-aldehydes and C9-oxo acids. Previously,
9/13HPL was thought to be limited to a Cucurbitaceae
family but it has now been found in many species,
including alfalfa and rice [6,7]. A new type of HPL that
preferentially acts on 9-hydroperoxides (termed 9HPL)
has been identified in almond [8]. Interestingly, almond
9HPL associates with the surface of lipid bodies.
Like other enzymes that are involved in oxylipin pathway
(i.e. allene oxide synthase [AOS, CYP74A] and divinyl
ether synthase [CYP74D]), HPL is a member of the
cytochrome P450 family (13HPL is CYP74B, 9/13HPL
is CYP74C). The CYP74 family specifically acts on a
hydroperoxy functionality in a lipid peroxide, completing
its catalysis without any cofactors [2]. Recently, it has
been shown that the primary product of HPL is a hemi-
acetal [9]. This information, together with knowledge of
lipid-peroxide-specific P450s in mammalian cells such as
prostacyclin synthase or thromboxane A2 synthase, sug-
gests that the homolytic cleavage of hydroperoxide and
the subsequent addition of the alkoxy radical to the
double bond (yielding an epoxy allyl radical) is the first
step in the reaction catalyzed by CYP74 enzymes [10].
Thereafter, each CYP74 enzyme must strictly direct the
fate of the highly epoxy allyl radical species to yield its
product(s). Rice 9/13HPL has been reported to form
small amounts of AOS products [7], which might be
the result of a ‘leak’ of the intermediate from the reaction
center.
Individual regulation of a branch of the
oxylipin pathway
Several isoforms of LOX exist in most plants, but only one
particular LOX isoform is essentially accountable for the
formation of GLV in soybean, potato, tobacco, and tomato
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Figure 1
Structures of GLVs commonly found in plants.
[11–13,14]. In Arabidopsis, the lipase enzyme DEFEC-
TIVE IN ANTHER DEHISCENCE1 (DAD1) is similar
to fungal lipase, and is involved in jasmonate (JA) synth-
esis in the anthers [15]. The ability of the dad1 mutant to
form GLV was, however, equivalent to that of wildtype
Arabidopsis (K Matsui et al., unpublished). Thus, it can be
assumed that there exist both a lipoxygenase and a lipase
that specifically serve substrates to different branches of
the pathway. Previously, it has been reported that AOS
and HPL appear to be routed to the inner and outer
membranes of the chloroplast envelope, respectively, by
different targeting pathways [16]. This has implications
for the independent operation of the two branches of
oxylipin metabolism. When cucumber 9HPL was over-
expressed in tomato fruits, hardly any C9-compounds
were formed even though the major LOX in tomato fruits
is 9LOX [17]. This was evident even when the transgenic
tomato fruits were extensively homogenized. This result
implies that there is an interaction among the enzymes
involved in GLV formation.
Regulation of GLV formation
In intact and healthy plant tissues, the amount of GLV is
low; however, GLV is formed rapidly when the tissues are
disrupted. Before homogenization, free linolenic acid and
13HPOT can hardly be detected, and the amounts of
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Green leaf volatiles Matsui 275
galactolipids decrease extensively after homogenization
[18]. Taken together, this evidence suggests that tissue
disruption triggers the hydrolysis of galactolipids to pro-
vide free fatty acids for GLV formation. The rapid degra-
dation of galactolipids could be explained by the mixing
of the substrate and enzyme after tissue disruption. The
details of this process have not been revealed, however,
essentially because the galactolipase that should be cru-
cial for the rapid formation of GLV has not been
identified.
GLVs are formed even in intact plant tissues. For exam-
ple, when the lower leaves of cotton were challenged by
herbivore attacks, GLV formation was increased in the
upper leaves [19]. This systemic release of GLVs was also
observed when lima bean leaf was wounded by
MecWorm, a mechanical caterpillar that simulates the
way a real caterpillar feeds [20]. Furthermore, the release
of GLVs from lima bean leaves during insect feeding
showed clear diurnal change [21]. This indicates that de-
compartmentalization caused by tissue disruption is not
the only way to induce GLV formation. Wounding, JA
treatment, or pathogen attack induces most of the LOXs
and HPLs investigated to date [3]. LOX and HPL
inductions must, however, accompany an increase in free
fatty acids to meet the demand of GLV formation. In fact,
when LOX or HPL was overexpressed in Arabidopsis,
there was little increase in the amounts of GLVs in intact
leaves (K Shiojiri et al., unpublished). Again, the lipid-
hydrolyzing step must be crucial in regulating the
amounts of GLVs formed in intact but stressed plants.
The molecular identity of the lipid-hydrolyzing enzyme
must be determined to reveal the system that regulates
GLV formation.
Physiological significance of GLVs
Effects on microorganisms
GLVs show antibacterial activities against both gram-
negative and gram-positive bacteria [22], thus, their use
to improve the shelf-life and safety of processed fruits has
been considered [23]. Among GLVs, (E)-2-hexenal is
highly bactericidal, essentially because of its a,b-
unsaturated carbonyl moiety that has high reactivity in
forming adducts with nucleophiles such as sulfhydryl or
amino groups through Michael-type addition reactions
[24]. However, comprehensive survey of the antibacterial
activities of a variety of GLVs showed that (Z)-3-hexenal
and (E)-3-hexenal were most active [22]. It is also remark-
able that C6-alcohols are also potent antibacterial com-
pounds. Taken together, the antibacterial activities of
GLV might be partly explained by their chemical
reactivities but other mechanism to inhibit the growth
of bacteria must exist. GLVs also have fungicidal activity,
and it has been suggested that the hydrophobic properties
of GLVs were important for this activity [25]. GLVs are
also toxic to several phytopathogenic bacteria and fungi
[3], which suggests that one physiological significance of
Current Opinion in Plant Biology 2006, 9:274–280
276 Physiology and metabolism
Figure 2
Biosynthetic pathway for oxylipins in plants. Only a portion of the pathway is shown. Each metabolite stems out from linolenic acid
hydroperoxide; however, recent studies indicate that specific lipases and lipoxygenases exist to form the hydroperoxides in each branch.
GLVs is to protect plants from infection. GLVs were
formed during the hypersensitive resistance response of
beans against Pseudomonas, and the amounts formed were
sufficient to be toxic to the pathogenic bacteria [26].
Interestingly, low concentrations of GLVs were able to
enhance the germination of some pathogenic fungi [27].
These fungi might have acquired a system to recognize
injured plants during co-evolution with plants. In certain
plant–pathogen systems, infection by a nonpathogenic
bacterium sometimes enhances the resistance of plants to
a pathogen, a process known as ‘priming’. Priming of bean
plants by nonpathogenic Pseudomonas putida reduced
disease symptoms caused by pathogenic Botrytis cinerea
by stimulating the LOX pathway and providing greater
potential to form GLVs [28]. This evidence also suggests
that GLVs are involved in defense against pathogens.
Effects on insects
Insects have very sensitive chemical sensors. Recently,
one pheromone receptor was revealed to be a G-protein-
coupled receptor [29], and it is believed that its homologs
Current Opinion in Plant Biology 2006, 9:274–280
are used as olfactory receptors in animals. There is no
doubt that insects can ‘smell’ GLVs, but their responses
to GLVs differ from species to species [30]. Observing the
performance of Manduca sexta larvae on HPL-suppressed
tobacco revealed that GLVs stimulate the feeding of
these insects [31] but, by contrast, suppression of
HPL in potato resulted in increased aphid performance
[32]. In some insects, GLVs have a synergistic effect on
the aggregation and on the action of sex pheromones [33].
Such a wide variety of effects of GLVs on insects might be
the result of co-evolution within a specific plant–insect
interaction.
GLVs can also be involved in ‘indirect defense’. A good
example of indirect defense can be found in a tritrophic
system. Attack by herbivores induces plants to emit sets
of volatile compounds that differ depending on the
herbivore species [34,35]. These volatile compounds
attract natural enemies of the herbivore, such as carni-
vorous insects or parasitic wasps [21]. Recently, Shiojiri
et al. evaluated the significance of GLVs by using an
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Arabidopsis mutant (all84) that was deficient in GLV
formation (unpublished). The mutant and wildtype Ara-
bidopsis plants were equally infested with larvae of cab-
bage white butterfly (Pieris rapae) and presented to its
specialist parasitic wasps (Cotesia glomerata) in a choice
test. The wasps preferred to fly to the wildtype leaves.
Thus, we can conclude that GLVs are important cues for
natural enemies to find their hosts in some plant–herbi-
vore–carnivore/parasitoid interactions. However, this
conclusion cannot be applied to every interaction
because HPL-suppressed tobacco plants and wildtype
tobacco plants grown in native habitats were equally
damaged by herbivores, whereas the herbivore damage
to LOX-suppressed tobacco was greater [36]. The sig-
nificance of GLV might differ depending on the
interaction.
Effects on plants
The exposure of plants to GLVs results in various plant
defense responses. Treating cotton boll with GLVs
resulted in the accumulation of phytoalexins [37]. (E)-
2-Hexenal also triggered local and systemic emissions of
volatile compounds from tomato [38]. A subset of defense
genes were also induced by exposing intact plant tissues
to GLVs [39–42]. GLV treatment enhanced the resis-
tance of Arabidopsis and Citrus against fungal pathogens,
such as Botrytis cinerea and Alternaria alternata (Figure 3:
[40,42]). Greater resistance to B. cinerea could be ascribed
to the lignification and accumulation of various antifungal
substances that are caused by GLV treatment; thus, we
can assume that the treatment could induce a wide range
of defense reactions. The response of Arabidopsis to (E)-2-
hexenal or (Z)-3-hexenal were partly dependent on both
JA-dependent and ethylene-dependent signals (K Kishi-
moto, unpublished).
Plant-talk, or eavesdropping, has long been hypothesized
(Figure 4: [43,44]). GLVs are formed rapidly after stress
Figure 3
Effect of treatment with vaporized (E)-2-hexenal on the susceptibility of Arabidopsis seedlings to a necrotrophic fungal pathogen, Botrytis
cinerea. Three-week old Arabidopsis seedlings were treated with 1 mmol/L (E)-2-hexenal for 24 h then sprayed with conidia of B. cinerea.
Photographs were taken 48 h later.
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Green leaf volatiles Matsui 277
and are highly volatile, and so they are expected to
function as plant-to-plant signals. However, recent
experiments to assess such interactions have generally
used plants that are enclosed in glass vessels, and the
unrealistically high concentrations of volatiles obtained in
these experiments has raised doubts about the in vivo
validity of the results thus obtained. For example, treat-
ment of plants with as much as 1 mmol/L (equivalent to
about 100 mg/L) of GLV was needed to cause a clear
induction of defense responses, and one-tenth of this
concentration failed to induce such responses [40]. This
high concentration of GLV could not be found in nature.
However, GLVs are heavier than air, and do not usually
diffuse in every direction but stay low to the ground.
Furthermore, when plants were exposed to volatile com-
pounds, their adsorption is probably facilitated by hydro-
phobic interactions with plant parts, such as cuticular wax
or cell membrane. According to Choh et al. [45], more than
50% of (E)-b-ocimene and dimethylnanotriene were
adsorbed by lima bean leaves and re-emitted. It is also
known that the leaf boundary layer, which is about 5 mm
deep, provides a microenvironment that is different from
the surrounding area [46]. These factors imply that GLVs
that flow over plant tissues can be trapped and concen-
trated on the tissues. If this is the case, even low con-
centrations of GLVs could exert their action on plants, as
has been found for maize plants [47]. Furthermore,
treatment with a low concentration of GLV ‘primed’ corn
plants against herbivore attacks [48]. This type of invi-
sible priming effect must also be taken into account.
Regardless of the likelihood of the involvement of GLVs
in plant-talk, the cumulative evidence indicates that
plants can perceive GLVs and evoke defense systems
in response. Plants have candidate genes that have simi-
larities with genes that encode olfactory receptors found
in animals, but their functions in plants have not yet been
revealed.
Current Opinion in Plant Biology 2006, 9:274–280
278 Physiology and metabolism
Figure 4
GLVs might function as intra- and interplant volatile signals. When leaves are damaged by herbivores, they begin to form GLVs. A portion of
these GLVs diffuse into the leaves and induce defense responses (indicated in red). The others are vaporized and reach other leaves of the
same or neighboring plants, where they might induce a defense response.
Conclusions
GLVs were identified more than 50 years ago that have
been studied extensively. In an ecosystem in which
plants are surrounded by herbivores, carnivores, patho-
gens, non-pathogenic microorganisms and/or other plants,
GLVs are used as cues to allow organisms to recognize or
compete with each other. Recent advances in studies on
GLVs have yielded many challenges. Even though the
biosynthetic pathway to form GLVs has been mostly
clarified, the enzyme responsible for its first commitment
step, namely the lipid-hydrolyzing step, has not yet been
revealed. Furthermore, identifying the plant system for
the perception of GLVs is an important task that has just
begun, and so work on these classic compounds is enter-
ing a new era.
Acknowledgements
I am grateful to Kyutaro Kishimoto for providing information on the
fungicidal activity of GLVs and Ca2+ monitoring. Most of the work carried
out in my laboratory was financially supported by the Core Research for
Evolutional Science and Technology (CREST) program, the Japan Science
and Technology Corporation (JST) and The Novartis Foundation (Japan)
for the Promotion of Science.
References and recommended reading
Papers of particular interest, published within the annual period of
review, have been highlighted as:
 of special interest
 of outstanding interest
1. Hatanaka A: The biogeneration of green odour by green leaves.
Phytochemistry 1993, 34:1201-1218.
2. Howe GA, Schilmiller AL: Oxylipin metabolism in response to
stress. Curr Opin Plant Biol 2002, 5:230-236.
3. Blée E: Impact of phyto-oxylipins in plant defense. Trends Plant
Sci 2002, 7:315-321.
4. D’Auria JC, Chen F, Pichersky E: Characterization of an
acyltransferase capable of synthesizing benzylbenzoate and
other volatile esters in flowers and damaged leaves of Clarkia
breweri. Plant Physiol 2002, 130:466-476.
Current Opinion in Plant Biology 2006, 9:274–280
5. Mano J, Torii Y, Hayashi S, Takimoto K, Matsui K, Nakamura K,
Inzé D, Babiychuk E, Kushinir S, Asada K: The NADPH:quinone
oxidoreductase P1-z-crystallin in Arabidopsis catalyzes the
a,b-hydrogenation of 2-alkenals: detoxication of the lipid
peroxide-derived reactive aldehydes. Plant Cell Physiol 2002,
43:1445-1455.
6. Noordermeer MA, Veldink GA, Vliegenthart JFG: Alfalfa contains
substantial 9-hydroperoxide lyase activity and a 3Z:2E-enal
isomerase. FEBS Lett 1999, 443:201-204.
7. Kuroda H, Oshima T, Kaneda H, Takashio M: Identification and
functional analyses of two cDNAs that encode fatty acid 9-/13-
hydroperoxide lyase (CYP74C) in rice. Biosci Biotechnol
Biochem 2005, 69:1545-1554.
8. Mita G, Quarta A, Fasano P, De Paolis A, Di Sansebastiano GP,
 Perrotta C, Iannacone R, Belfield E, Hughes R, Tsesmetzis N et al.:
Molecular cloning and characterization of an almond 9-
hydroperoxide lyase, a new CYP74 targeted to lipid bodies. J
Exp Bot 2005, 56:2321-2333.
This is the first report of an HPL that specifically acts on 9-hydroper-
oxides. Interestingly, this HPL localized on lipid bodies. We do not know
whether GLV is formed on lipid bodies or why the HPL localizes on lipid
bodies.
9. Grechkin AN, Hamberg M: The ‘heterolytic hydroperoxide lyase’
 is an isomerase producing a short-lived fatty acid hemiacetal.
Biochim Biophys Acta 2004, 1636:47-58.
The authors identified the unstable primary product of HPL as a hemi-
acetal. From this finding, the reaction mechanism of the lyase can be
deduced.
10. Ullrich V: Thoughts on thiolate tethering. Tribute and thanks to
a teacher. Arch Biochem Biophys 2003, 409:45-51.
11. Matoba T, Hidaka H, Kitamura K, Kainuma N, Kito M:
Lipoxygenase-2 isozyme is responsible for generation of n-
hexanal in soybean homogenate. J Agric Food Chem 1985,
33:852-855.
12. Leon J, Royo J, Vancanneyt G, Sanz C, Silkowski H, Griffiths G,
Sanchez-Serrano JJ: Lipoxygenase H1 gene silencing reveals a
specific role in supplying fatty acid hydroperoxides for
aliphatic aldehyde production. J Biol Chem 2001, 277:416-423.
13. Halitschke R, Baldwin IT: Antisense LOX expression increases
herbivore performance by decreasing defense responses and
inhibiting growth-related transcriptional reorganization in
Nicotiana attenuata. Plant J 2003, 36:794-807.
14. Chen G, Hackett R, Walker D, Taylor A, Lin Z, Grierson D:
 Identification of a specific isoform of tomato lipoxygenase
(TomloxC) involved in the generation of fatty acid-derived
flavor compounds. Plant Physiol 2004, 136:2641-2651.
www.sciencedirect.com

Tomato fruits have at least five LOXs. Antisense-suppression of one of
them (TomloxC) resulted in a marked decrease in the amount of GLVs.
TomloxC is localized in chloroplasts, indicating that these subcellular
organelles are the sites of GLV formation.
15. Ishiguro S, Kawai-Oda A, Ueda J, Nishida I, Okada K: The
DEFECTIVE IN ANTHER DEHISCENCE1 gene encodes a novel
phospholipase A1 catalyzing the initial step of jasmonic acid
biosynthesis, which synchronizes pollen maturation, anther
dehiscence, and flower opening in Arabidopsis. Plant Cell 2001,
13:2191-2209.
16. Froehlich JE, Itoh A, Howe GA: Tomato allene oxide synthase
and fatty acid hydroperoxide lyase, two cytochrome P450s
involved in oxylipin metabolism, are targeted to different
membranes of chloroplast envelope. Plant Physiol 2001,
125:306-317.
17. Matsui K, Fukutomi S, Wilkinson J, Hiatt B, Knauf V, Kajwara T:
Effect of overexpression of fatty acid 9-hydroperoxide lyase in
tomatoes (Lycopersicon esculentum Mill.). J Agric Food Chem
2001, 49:5418-5424.
18. Matsui K, Kurishita S, Hisamitsu A, Kajiwara T: A lipid-hydrolysing
activity involved in hexenal formation. Biochem Soc Trans 2000,
28:857-860.
19. Rose U, Manukian A, Heath RR, Tumlinson JH: Volatile
semiochemicals released from undamaged cotton leaves (a
systemic response of living plants to caterpillar damage). Plant
Physiol 1996, 111:487-495.
20. Mithofer A, Wanner G, Boland W: Effects of feeding Spodoptera
littoralis on lima bean leaves. II. Continuous mechanical
wounding resembling insect feeding is sufficient to elicit
herbivory-related volatile emission. Plant Physiol 2005,
137:1160-1168.
21. Arimura G, Kost C, Boland W: Herbivore-induced,
indirect plant defences. Biochim Biophys Acta 2005,
1734:91-111.
22. Nakamura S, Hatanaka A: Green-leaf-derived C6-aroma
compounds with potent antibacterial action that act on both
Gram-negative and Gram-positive bacteria. J Agric Food Chem
2002, 50:7639-7644.
23. Lanciotti R, Gianotti A, Patrignani F, Belletti N, Guerzoni ME,
Gardini F: Use of natural aroma compounds to improve shelf-
life and safety of minimally processed fruits. Trends Food Sci
Technol 2004, 15:201-208.
24. Almeras E, Stolz S, Vollenweider S, Reymond P, Mene-Saffrane L,
Farmer EE: Reactive electrophile species activate
defense gene expression in Arabidopsis. Plant J 2003,
34:205-216.
25. Kubo I, Fujita K, Kubo A, Nihei K, Lunde CS: Modes of antifungal
action of (2E)-alkenals against Saccharomyces cerevisiae.
J Agric Food Chem 2003, 51:3951-3957.
26. Croft K, Juttner F, Slusarenko AJ: Volatile products of the
lipoxygenase pathway evolved from Phaseolus vulgaris (L.)
leaves inoculated with Pseudomonas syringae pv.
phaseolicola. Plant Physiol 1993, 101:13-24.
27. Fallik E, Archbold DD, Hamilton-Kemp TR, Clements AM,
Collins RW, Barth MM: (E)-2-Hexenal can stimulate Botrytis
cinerea growth in vitro and on strawberries in vivo during
storage. J Am Soc Hortic Sci 1998, 123:875-881.
28. Ongena M, Duby F, Rossignol F, Fauconnier M-L, Dommes J,
 Thonart P: Stimulation of the lipoxygenase pathway is
associated with systemic resistance induced in bean by a
nonpathogenic Pseudomonas strain. Mol Plant Microbe Interact
2004, 17:1009-1018.
Priming is a well-known phenomena within many patho-systems. In this
instance, the LOX pathway is a key component of priming for infection by
pathogens. GLV formation was also potentiated although its significance
has not been addressed.
29. Sakurai T, Nakagawa T, Mitsuno H, Mori H, Endo Y, Tanoue S,
Yasukochi Y, Touhara K, Nishioka T: Identification and
functional characterization of a sex pheromone receptor in the
silkmoth Bombyx mori. Proc Natl Acad Sci USA 2004,
101:16653-16658.
www.sciencedirect.com
Green leaf volatiles Matsui 279
30. Bruce TJA, Wadhams LJ, Woodcock CM: Insect host location: a
volatile situation. Trends Plant Sci 2005, 10:269-274.
31. Halitschke R, Ziegler J, Keinanen M, Baldwin IT: Silencing of
 hydroperoxide lyase and allene oxide synthase reveals
substrate and defense signaling crosstalk in Nicotiana
attenuata. Plant J 2004, 40:35-46.
The authors suppressed HPL and AOS in tobacco and analyzed the
responses of the transgenic plants to herbivores. They found that GLVs
are feeding stimulants for Manduca sexta larvae. At the same time, they
also found that substrate flux, but not the transcriptional regulation, of
HPL controls GLV formation.
32. Vancanneyt G, Sanz C, Farmaki T, Paneque M, Ortego F,
Castanera P, Sanchez-Serrano JJ: Hydroperoxide lyase
depletion in transgenic potato plants leads to an increase in
aphid performance. Proc Natl Acad Sci USA 2001, 98:8139-8144.
33. Reddy GVP, Guerrero A: Interactions of insect pheromones and
plant semiochemicals. Trends Plant Sci 2004, 9:253-261.
34. Ozawa R, Arimura G, Takabayashi J, Shimoda T, Nishioka T:
Involvement of jasmonate- and salicylate-related signaling
pathways for the production of specific herbivore-induced
volatiles in plants. Plant Cell Physiol 2000, 41:391-398.
35. Leitner M, Boland W, Mithofer A: Direct and indirect defences
 induced by piercing-sucking and chewing herbivores in
Medicago truncatula. New Phytol 2005, 167:597-606.
The authors clearly showed that the compositions of volatiles emitted
from Medicago truncatula plants that were infected by different herbi-
vores were qualitatively and quantitatively different.
36. Kessler A, Halitschke R, Baldwin IT: Silencing the jasmonate
 cascade: induced plant defenses and insect populations.
Science 2004, 305:665-668.
This is the first field study to reveal the significance of oxylipins in plant–
insect interactions. The results showed that LOX-dependent signaling
was important for ecological interactions and that the significance of HPL
was low. These results cannot rule out the possibility that HPL and GLV
function as components in establishing an ecosystem. Their significance
must also be evaluated with different plant species in a different eco-
system.
37. Zeringue HJ Jr: Effects of C6-C10 alkenals and alkanals on
eliciting a defence response in the developing cotton boll.
Phytochemistry 1992, 31:2305-2308.
38. Farag MA, Pare PW: C6-green leaf volatiles trigger local and
systemic VOC emissions in tomato. Phytochemistry 2002,
61:545-554.
39. Bate NJ, Rothstein SJ: C6-volatiles derived from the
lipoxygenase pathway induce a subset of defense-related
genes. Plant J 1998, 16:561-569.
40. Kishimoto K, Matsui K, Ozawa R, Takabayashi J: Volatile
C6-aldehydes and allo-ocimene activate defense genes and
induce resistance against Botrytis cinerea in Arabidopsis
thaliana. Plant Cell Physiol 2005, 46:1093-1102.
41. Arimura G, Ozawa R, Horiuchi J, Nishioka T, Takabayashi J:
Plant–plant interactions mediated by volatiles emitted from
plants infested by spider mites. Biochem Syst Ecol 2001,
29:1049-1061.
42. Gomi K, Yamasaki Y, Yamamoto H, Akimitsu K: Characterization
of a hydroperoxide lyase gene and effect of C6-volatiles on
expression of genes of the oxylipin metabolism in Citrus.
J Plant Physiol 2003, 160:1219-1231.
43. Baldwin IT, Kessler A, Halitschke R: Volatile signaling in plant–
plant–herbivore interactions: what is real? Curr Opin Plant Biol
2002, 5:351-354.
44. Dicke M, Agrawal AA, Bruin J: Plants talk, but are they deaf?
Trends Plant Sci 2003, 8:403-405.
45. Choh Y, Shimoda T, Ozawa R, Dicke M, Takabayashi J: Exposure
of lima bean leaves to volatiles from herbivore-induced
conspecific plants results in emission of carnivore
attractants: active or passive process? J Chem Ecol 2004,
30:1305-1317.
46. Holopainen JK: Multiple functions of inducible plant volatiles.
Trends Plant Sci 2004, 9:529-533.
Current Opinion in Plant Biology 2006, 9:274–280
280 Physiology and metabolism
47. Farag MA, Fokar M, Abd H, Zhang H, Allen RD, Pare PW: (Z)-3-
 Hexenol induces defense genes and downstream metabolites
in maize. Planta 2005, 220:900-909.
The authors treated intact maize plants with a continuous flow of low-
concentration (Z)-3-hexenol, which can be collected from the atmosphere
surrounding herbivore-infested plants. The treatment induced the expres-
sion of several defense genes. The experimental system reflected the
situation in nature, and so this result supports the hypothesis that GLV
is involved in plant-talk. Interestingly, (Z)-3-hexenol was taken up by the
plants and converted to the less-active molecule (Z)-3-hexenyl acetate.
Current Opinion in Plant Biology 2006, 9:274–280
48. Engelberth J, Alborn HT, Schmelz EA, Tumlinson JH: Airborne
 signals prime plants against insect herbivore attack. Proc Natl
Acad Sci USA 2004, 101:1781-1785.
The authors found that maize seedlings that had been exposed to GLV
from neighboring plants produced significantly more JA and volatile
sesquiterpenes when mechanically damaged and induced with cater-
pillar regurgitant than did seedlings that had not been exposed to
GLV. Concomitantly, GLV primed neighboring plants against herbivory
and might play a key role in plant–plant signaling and plant–insect
interactions.
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