**1. Introduction**

The oxidation products of unsaturated fatty acids are collectively known as oxylipins. These compounds represent a highly diverse group of substances that are involved in a number of developmental processes and various stress responses in plants (Andersson et al., 2006). Plant oxylipins can be formed enzymatically, by initial oxidation by lipoxygenases (LOXs) or α-dioxygenases (α-DOXs); however, non-enzymatic autoxidation of polyunsaturated fatty acids (PUFA) also contribute to oxylipin formation in plant (Göbel and Feussner, 2009). An array of these substances are known to exert protective activities either as signaling molecules in plants during development, wounding, and insect and pathogen attack, or direct anti-microbial substance that are toxic to the invader. Despite the recent progress in deciphering the function of some oxylipins, the role of the vast majority of plant oxylipins remains unclear. Particularly well studied examples of the plant oxylipins are jasmonates (JAs) including jasmonic acid (JA) and its derivatives such as methyl jasmonate (MeJA), *cis*jasmone, jasmonoyl isoleucine (JA-Ile), jasmonoyl ACC (JA-ACC) and several other metabolites. Another important group of plant oxylipins is green leaf volatiles (GLV). Increasing evidence supports GLVs function in defense responses against herbivore. GLVs are C6 aldehydes, alcohols, and their esters formed through the hydroperoxide lyase (HPL) pathway downstream of LOXs. GLV can further trigger local and systemic volatile organic compounds (VOC) emissions upon insect feeding (Farag and Paré, 2002). A large number of VOC including monoterpenes, sesquiterpenes and carotenoid-type compounds can be biosynthesized in plants from the shikimic, lipidic and terpenic pathways (Fons et al., 2010). Most VOCs are not products of the LOX pathway but similar to LOX derivatives serve as signals for insects to choose a suitable host or to lay eggs (Müller and Hilker, 2001). The third better studied group of plant oxylipins is phytoprostanes, a category of non-

© 2013 Kolomiets et al., licensee InTech. This is an open access chapter distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. © 2013 The Author(s). Licensee InTech. This chapter is distributed under the terms of the Creative Commons Attribution License http://creativecommons.org/licenses/by/3.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

enzymatically formed oxylipins, which play overlapped roles with OPDA in plant stress responses (Eckardt, 2008).

Jasmonate Biosynthesis, Perception and Function in Plant Development and Stress Responses 395

plant-pathogen or -insect interactions. Gibberellins (GA) interact with JA to control flower fertility in *Arabidopsis*. In maize, JA positively regulates ABA and ET biosynthesis in senescing leaves (Yan et al., 2012). In summary, it is clear that JA signaling exert its functions via interaction with multiple plant hormones; however the crossroads of these

In 1962, a floral scent compound, the methyl ester of jasmonic acid (MeJA) was isolated for the first time from the aromatic oil of *Jasminum grandiflorum* (Demole et al., 1962). However, the physiological effects of MeJA or its free acid (JA) were unknown until the 1980's when a senescence-promoting effect of JA (Ueda and Kato, 1980) and growth inhibition activity of MeJA to *Vicia faba* (Dathe, 1981) were observed. Now JA and derivatives (JAs) are the best characterized group of oxylipins in plants and are regarded as one of the the major

Biosynthesis of JAs originates from polyunsaturated fatty acids (PUFA) and is synthesized by one of the seven distinct branches of the lipoxygenase (LOX) pathway, the allene oxide synthase (AOS) branch (Feussner and Wasternack, 2002). The remaing six branches form other oxylipins including GLVs as well as epoxy-, hydroxy-, keto- or ether PUFA and epoxyhydroxy-PUFA (Feussner and Wasternack, 2002) (Figure 1). In the oxylipin biosynthesis (Figure 1), only 13-hydroperoxide from α-linolenic acid (18:3, α-LeA) can be utilized by the AOS branch for JA production. Other fatty acid hydroperoxides such as 9- 13- and 2-hydroperoxide, oxygenated by 9-LOX, 13-LOX and α-dioxygenase (α-DOX), respectively, or those whose substrates originate from α-LeA, hexadecatrienoic acid (16:3, HTA) or linoleic acid (18:2, LA) may be channeled to form other oxylipin subgroups. Biological functions of the majority of estimated 400-500 oxylipins is mostly unknown.

The biosynthesis of JA and MeJA was elucidated by Vick and Zimmerman (1983), and Hamberg and Hughes (1988). The original precursors PUFA are released from chloroplast membranes by the action of lipid hydrolyzing enzymes. Upon α-LeA liberation, a molecular oxygen is incorporated by a 13-LOX at carbon atom 13 of the substrate leading to the formation of a fatty acid hydroperoxide, 13-HPOT (13*S*-hydroperoxy-(*9Z*,11*E*,15) octadecatrienoic acid) (Figure 2). This intermediate compound can proceede to seven distinct enzymatic branches (Figure 1), one of which is dehydration by the allene oxide synthase (AOS) to an unstable allene oxide, 12,13-EOT ((9*Z*,13*S*,15*Z*)-12,13-oxido-9,11,15 octadecatrienoic acid) which can be cyclized to racemic 12-oxo-phytodienoic acid (OPDA). In the presence of an allene oxide cyclase (AOC), preferential product is the enantiomer, 9*S*,13*S/cis* (+)-OPDA (Figure 2). All the reactions from α-LeA to OPDA take place within a plastid. *cis* (+)-OPDA is subsequently transported into the peroxisome, where it is further converted into (+)-7-*iso*-JA by 12-oxo-phytodienoic acid reductase (OPR) and three beta oxidation steps involving three peroxisomal enzymatic functions (acyl-CoA oxidase, multifunctional protein, and l-3-ketoacyl-CoA thiolase) (Figure 2). (+)-7-*iso*-JA often epimerizes

interactions still remain to be explored.

**2. JA biosynthesis pathway and regulation** 

hormones regulating both defense and development.

**2.1. The scheme of JA biosynthesis pathway** 

JA biosynthesis and signaling pathways have been extensively investigated in dicotyledonous plants such as *Arabidopsis*, tobacco and tomato. In monocotyledonous species, only a scant number of JA biosynthetic enzymes have been described (Tani et al., 2008; Yan et al., 2012). Jasmonates are formed from the LOX-catalyzed peroxidation of trienoic fatty acids at carbon atom 13 to form 13-hydroperoxide, which is modified to an allene oxide fatty acid and subsequently cyclized to the compound 12-oxo-phytodienoic acid (OPDA). Jasmonic acid (JA) is synthesized from OPDA by the reduction of a double bond and three consecutive rounds of β-oxidation. The pathway can accept C18-PUFA (linolenic acid) as well as C16-PUFA (hexadecatrienoic acid), in the latter case the intermediate is the so-called dinor-OPDA that may also be metabolized to JA. JA can be further enzymatically converted into numerous derivatives or conjugates, some of which have well-described biological activity such as free JA, MeJA, *cis*-jasmone and JA–Ile.

JA signaling pathway, the transition process of JA-Ile as a chemical signal to biological signal, was elucidated in recent years. JA initiates signaling process upon formation of a SCFCOI1-JA-Ile-JAZ ternary complex (JAZ: jasmonate ZIM-domain protein; Sheard et al., 2010), in which the JAZ repressors are ubiquitinated and subsequently degraded to release transcription factors, e.g., MYC2, causing downstream transcription activation of defense responses or developmental regulation (Chini et al., 2007; Thines et al., 2007). The only jasmonate receptor identified to date has been the COI1 protein (Katsir et al., 2008; Yan et al., 2009), but interestingly, only JA-Ile was found as a ligand of the SCFCOI1 E3 ubiquitin ligase complex (Thines et al., 2007).

Since discovered in the 1960s as secondary metabolites from the oils of jasmine flowers (Demole *et al.*, 1962), the biological roles of JA have received increased attention of researchers in the past decades. Jasmonates have gradually become realized as a defense and fertility hormone, and as such modulate numerable processes relating to development and stress responses. In *Arabidopsis* and tomato, JAs are directly involved in stamen and trichome development, vegetative growth, cell cycle regulation, senescence, anthocyanin biosynthesis regulation, and responses to various biotic and abiotic stresses (Creelman and Mullet, 1997; Wasternack, 2007; Howe and Jander, 2008; Browse, 2009; Avanci et al., 2010; Pauwels and Goossens, 2011). In monocots, much less is known about the role of JAs, however, it has been shown they are required for sex determination, reproductive bud initiation and elongation, leaf senescence, pigmentation of tissues and responses to the attack by pathogens and insects (Engelberth et al., 2004; Tani et al., 2008; Acosta et al., 2009; Yan et al, 2012).

In plants, the JA signal acts co-operatively with other plant hormones. A number of studies have already attracted attention to plant hormone cross-talk as it relates to defense responses. In *Arabidopsis,* JA was shown to interact synergistically with ethylene (Xu et al 1994), and, depending on particular stress, both synergistically and antagonistically with salicylic acid (Beckers and Spoel, 2006) and abscisic acid (ABA) (Anderson et al 2004) in plant-pathogen or -insect interactions. Gibberellins (GA) interact with JA to control flower fertility in *Arabidopsis*. In maize, JA positively regulates ABA and ET biosynthesis in senescing leaves (Yan et al., 2012). In summary, it is clear that JA signaling exert its functions via interaction with multiple plant hormones; however the crossroads of these interactions still remain to be explored.
