secondary metabolites and plant defence

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Metadata of the chapter that will be visualized online Series Title Progress in Biological Control Chapter Title Secondary Metabolites and Plant Defence Chapter SubTitle Copyright Year 2012 Copyright Holder Springer Science+Business Media B.V. Family Name Goyal Particle Given Name Shaily Corresponding Author Suffix Division Laboratory of Bio-Molecular Technology, Department of Botany Organization M.L. Sukhadia University Address 313001, Udaipur, India Email Family Name Lambert Particle Given Name C. Author Suffix Division GESVAB – EA 3675, Institut des Sciences de la Vigne et du Vin Organization University of Bordeaux Address CS50008, 210, Chemin de Leysotte, F-33882, Villenave d’Ornon, France Email Family Name Cluzet Particle Given Name S. Author Suffix Division GESVAB – EA 3675, Institut des Sciences de la Vigne et du Vin Organization University of Bordeaux Address CS50008, 210, Chemin de Leysotte, F-33882, Villenave d’Ornon, France Email Family Name Merillon Particle Given Name J. M. Author Suffix Division GESVAB – EA 3675, Institut des Sciences de la Vigne et du Vin Organization University of Bordeaux Address CS50008, 210, Chemin de Leysotte, F-33882, Villenave d’Ornon, France Email [email protected] Family Name Ramawat Particle Author Given Name Kishan G.

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Metadata of the chapter thatwill be visualized online

Series Title Progress in Biological Control

Chapter Title Secondary Metabolites and Plant Defence

Chapter SubTitle

Copyright Year 2012

Copyright Holder Springer Science+Business Media B.V.

Family Name GoyalParticleGiven Name Shaily

Corresponding Author

SuffixDivision Laboratory of Bio-Molecular Technology, Department of BotanyOrganization M.L. Sukhadia UniversityAddress 313001, Udaipur, IndiaEmail

Family Name LambertParticleGiven Name C.

Author

SuffixDivision GESVAB – EA 3675, Institut des Sciences de la Vigne et du VinOrganization University of BordeauxAddress CS50008, 210, Chemin de Leysotte, F-33882, Villenave d’Ornon, FranceEmailFamily Name CluzetParticleGiven Name S.

Author

SuffixDivision GESVAB – EA 3675, Institut des Sciences de la Vigne et du VinOrganization University of BordeauxAddress CS50008, 210, Chemin de Leysotte, F-33882, Villenave d’Ornon, FranceEmailFamily Name MerillonParticleGiven Name J. M.

Author

SuffixDivision GESVAB – EA 3675, Institut des Sciences de la Vigne et du VinOrganization University of BordeauxAddress CS50008, 210, Chemin de Leysotte, F-33882, Villenave d’Ornon, FranceEmail [email protected]

Family Name RamawatParticle

Author

Given Name Kishan G.

SuffixDivision Laboratory of Bio-Molecular Technology, Department of BotanyOrganization M.L. Sukhadia UniversityAddress 313001, Udaipur, IndiaEmail [email protected]

Abstract Infected or elicited plants accumulate an array of plant defensive compounds. Now-a-days, it is wellaccepted that plant SECONDARY METABOLITES are involved in this plant defence system. The processof inducing resistance using elicitors is environmental friendly and is advantageous over the chemicalbased pesticides. It is like stimulation of the plant’s own “immune” potential rather than on suppression ofpathogens. The resistance developed in this way has prolonged effect. This strategy could be an alternativesolution to reduce the use of pesticides.

Keywords (separated by'-')

Plant defence - Elicitors - Isoflavones - Stilbenes

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J.M. Merillon and K.G. Ramawat (eds.), Plant Defence: Biological Control, Progress in Biological Control 12, DOI 10.1007/978-94-007-1933-0_5, © Springer Science+Business Media B.V. 2011

Abstract Infected or elicited plants accumulate an array of plant defensive compounds. Now-a-days, it is well accepted that plant SECONDARY METABOLITES are involved in this plant defence system. The process of inducing resistance using elicitors is environmental friendly and is advantageous over the chemical based pes-ticides. It is like stimulation of the plant’s own “immune” potential rather than on suppression of pathogens. The resistance developed in this way has prolonged effect. This strategy could be an alternative solution to reduce the use of pesticides.

Keywords  Plant defence • Elicitors • Isoflavones • Stilbenes

5.1 Introduction

In nature, plants protect themselves against pathogen attack mainly by mechanical and chemical defences. Mechanical defences include structures such as spines, trichomes, thick cuticle, and hard, sticky, or smooth surfaces which prevent pathogens from picking for food or laying eggs. Chemical defences include a variety of substances that are toxic, repellent, or that render plant tissues indigestible to

S. Goyal (*) • K.G. RamawatLaboratory of Bio-Molecular Technology, Department of Botany, M.L. Sukhadia University, Udaipur 313001, Indiae-mail: [email protected]

C. Lambert • S. Cluzet • J.M. MerillonGESVAB – EA 3675, Institut des Sciences de la Vigne et du Vin, University of Bordeaux, CS50008, 210, Chemin de Leysotte, Villenave d’Ornon, F-33882, Francee-mail: [email protected]

[AU1]

Chapter 5Secondary Metabolites and Plant Defence

Shaily Goyal, C. Lambert, S. Cluzet, J.M. Merillon, and Kishan G. Ramawat

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animals [1]. Chemical defence due to secondary metabolites is prominently developed in plants, providing protection to the plant [2]. Mechanical and chemical defence can be either independent of each other [3] or they can work in combination such as glandular trichomes and secretory canals. They interact to entrap pathogen in sticky and toxic secretions [4]. Many plants produce resins, gum, lattices and mucilage, which are stored under pressure in networks of canals throughout the cortex of the stems and in the leaves, where they follow the vascular bundles. These secretions are rich in several secondary metabolites: for example, oleoresin present in Abies grandis is a complex mixture of monoterpenes, sesquiterpenes and diterpe-noid acids, used to deter insect pests and their symbiotic fungal pathogens [5]. Some Bursera species resins, rich in mostly monoterpenes and sesquiterpenes [6] are under considerable pressure, and so when a leaf is damaged, resin may be released in a spectacular syringe- like squirt. This squirt may travel up to 2 m and lasts a few seconds, so it represents a good example of mechanical and chemical defence inter-action [7]. Some species of Asclepias (milkweeds) latex contains cardenolides and cardiac glucosides which help the plant in defence response [8]. These toxic ste-roids have an interesting use in monarch butterflies. Adult monarch butterflies store the cardenolides they have built-up during their larval stage, feeding mostly on Asclepias.  This  stored  cardenolide  content  in  butterflies  deters  them  from  their vertebrate predators.

The chemical defence can be further classified as constitutive and inducible chemical defences. The term constitutive means that the defence is present in the plant whether the predator attacks or not. Many constitutive defence chemicals are produced by epidermal hairs that can trap and kill insect larvae. Inducible systems are those that are absent before a pathogen or predator attack, but are induced when the attack occurs. Defence related responses can occur in the plant organ originally attacked (local response) or in distant unaffected parts (systemic response). Examples of chemical defences can be found in article by Field and co-workers [9].

Plants can have a compatible response towards its pathogen, where their contact lead to a successful infection, or they can have a non-compatible response where a plant and pathogen contact lead to a non-successful infection. In incompatible inter-actions, infection by pathogens inducts a set of local responses in and around the infected host cell which can lead to cell death [10]. Thus, the pathogen may be “trapped” in dead cells and this prevents the infection from being spread. Local responses in the cells include oxidative burst, changes in cell wall composition that can inhibit penetration by the pathogen, and de novo synthesis of antimicrobial com-pounds such as phytoalexins and pathogenesis related (PR) proteins. Phytoalexins are mainly characteristics of the local response, PR proteins occur both locally and systemically [11].

The aim of this review is to reveal new avenues of research in the area of elicitor imparted secondary metabolites production in plants which provide them resistance against diseases.

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5.2 Secondary Metabolites and Defence

Plants (>300,000 species) and insects (likely >1,000,000 species) have co-evolved, still plants dominate the landscape [12]. This is due to the presence of secondary metabolites that make the plants both repellent and toxic to most pathogens, insects and other grazing animals. Secondary metabolites are the molecules that appear to be dispensable for normal growth, or are required only under particular conditions, whereas primary metabolites are involved in the physiological functions. These secondary products are the key components of active and potent defence mecha-nisms in plants [13, 14]. They are the active part of the chemical war between plants and their pathogens.

About 1–10% of the dry mass of some plants is made up of chemicals designed for defence against predators. Plants synthesize a huge array (around several tens of thousands) of different secondary metabolites [14]. Synthesizing a particular chem-ical so that it accumulates in the plant to a significant level has an associated cost. Various biosynthetic pathways are involved in secondary metabolites production and there is requirement of substantial amount of ATP. Besides their synthesis dur-ing the time of attack by pathogen, their storage in the vacuole requires energy as well. The energy for uphill transport and often for trapping the metabolite in the vacuole is provided by H+ – ATPase. In addition, some metabolites are transported into the vacuole with the help of ATP-binding cassette transporters (ABC-transporter) which depend on ATP [15]. It can be seen that if the cost of producing a defence compound is minimal and allows the plant that produces it to leave more offspring, then that plant has a greater evolutionary fitness than its non-defended colleagues. This can readily be demonstrated by partially defoliating plants or giving them a mild bacterial, fungal, or viral infection. Such plants grow much less vigorously and produce fewer seeds. However, if secondary metabolisms have not been very impor-tant in the biology of different organisms, evolution would not have selected and maintained the complex pathways leading to secondary metabolism [14].

Most of the secondary metabolites are derived from the isoprenoid, phenylpro-panoid, alkaloid or fatty acid/polyketide pathways [14, 16]. It is observed that related plant families generally make use of related chemical structures for defence, e.g. sesquiterpenes in the Solanaceae, stilbenes in the Vitaceae, isoflavones in the Leguminosae, sulfur-based glucosinolate–myrosinase in the Brassicaceae and limonoids among members of the families Meliaceae and Rutaceae. In plants, the best understood secondary metabolites are implicated in pathogen defence, sensing and signaling. This list is continuously growing by the extensive use of biochemical and genetic approaches to reveal the undiscovered metabolites and their complex signaling pathways that mediate plant disease resistance.

Pathogens, insects, and other parasites initially establish physical interactions with hosts via surface contact, and the plant surface initiate chemical signaling in response to it. The secondary metabolites content of the surface exempt of disease is also an important aspect to be studied in order to discover new defence molecules.

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For that, accurate methods of detection and quantification are required. Now-a days desorption  electrospray  ionization  mass  spectrometry  (DESI-MS)  have  made possible fine scale evaluation of compounds on native surfaces of the plants. Lane and co-workers [17] reported presence of bromophycolides, antimicrobial compounds, on the surface of macroalga Callophycus serratus in sufficient quantity for inhibition of Lindra thalassiae, a marine fungal pathogen. Hamm and co-workers [18] have used laser desorption/ionisation time-of-flight mass spectrometry (LDI-ToFMS) to analyze phytoalexins at the surface of Vitis vinifera leaves. They have found that the amounts of resveratrol and pterostilbene are directly related to the degree of Plasmopara viticola contamination.

Several large groups, such as phenolics, alkaloids, terpenoids, iridoid glycosides, cardenolides, and cyanogenic glycosides have been implicated in plant defence systems. The literature on secondary metabolites is extensive. Here we summarized phenolics related to plant defence system.

5.3 Phenolics and Disease Resistance

Phenolics are represented by having at least one aromatic ring with one or more hydroxyl groups attached, and are widely present throughout the plant kingdom [19]. They are known to contribute to pigmentation of different organs along with their role against different biotic and abiotic stresses [20]. Phenolics occurring naturally  in plant  tissue can be classified into two groups,  the flavonoids and the non-flavonoids.

Depending on the structural complexity of flavonoids (with an estimated 10,000 structurally different members), particularly on the oxidation state of the central ring C, flavonoids are themselves subclassified as flavonols, flavones, flavan-3-ols (catechins and their oligomers: proanthocyanidins), anthocyanidins, flavanones and isoflavones and  those  that  are present  in  less  quantity  in diet  are dihydroflavonols, flavan-3, 4-diols, chalcones, dihydrochalcones, and aurones [21] (Fig. 5.1). Majority of  flavonoids  exist  naturally  as  glycosides.  Both,  the  hydroxyl  groups  and  sugars, increase water solubility of flavonoids [22]. Flavonoids in general are polyphenolic compounds comprising of 15 carbons, with 2 aromatic rings connected by a 3-carbon bridge (C

6–C

3–C

6). They consist mainly of 2-phenylchromans and also 3-phenyl-

chromans  for  isoflavonoids.  The  key  enzyme  for  the  formation  of  the  flavonoid skeleton is chalcone synthase, which catalyses the stepwise condensation of three acetate units from malonyl-CoA with 4-coumaryl-CoA to the intermediate chalcone. Flavonoids play important role in defence against microorganisms and pests.

There are many instances which describe their potent role in disease resistant. A recent investigation by Koskimäki and co-workers [23] observed that accumulation of individual phenolic compounds could be specific for a particular infection. They demonstrated biosynthesis of different phenolic compounds in bilberry (Vaccinium myrtillus) after infection by a fungal endophyte (Paraphaeosphaeria sp.) and a pathogen (Botrytis cinerea). A study of barley mutants showed that proanthocyanidins

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O

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O

Isoflavone

O

O

Flavone

OH

O

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O

O Flavanones

OH

O+

Anthocyanidins

OH

O

Flavan-3-ol

Fig. 5.1  Basic flavonoid structure and its derivatives

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and even small amounts of dihydroquercetin are involved in the defence against Fusarium species [24]. The wild species of groundnut, Arachis kempff-mercadoi is resistant to tobacco armyworm Spodoptera liture due to its flavonols quercetin and its glycoside rutin [25]. Similarly, nematode resistance in banana is due to flavan-3,4-diols and condensed tannins [26]. Flavonoids also play a major role in postharvest resistance of fruits and vegetables [27]. High concentrations of flavonoids mainly in unripe fruits prevent them from pathogens; thus, ripe fruits are usually more sensible to fungal decay.

There are also several classes of non-flavonoids, dominated by phenylpropanoids containing only the C

6−C

3 phenylpropane skeleton and these compounds are directly

linked to lignin (polymer phenyl propanoid) biosynthesis in vascular plants. The most important examples are cinnamic acids and their derivatives such as chlorogenic acid, p-coumaric, ferulic and sinapic acids. Another class of non-flavonoid polyphenols which are less frequently found in diets (except for the grapes and peanuts) is the stilbenes with C6–C2–C6 skeletons [28, 29]. Hydroxycinnamic acids and flavonoid classes are widely present in higher plants whereas classes like isoflavones (e.g., Fabaceae) and stilbenes (e.g., 23 families only: Vitaceae, Cyperaceae, Dipterocarpaceae, Iridaceae, Fabaceae, Moraceae, Orchidaceae and Polygonaceae) are limited to particular families.

5.3.1 Isoflavones

Isoflavones are characterized by having the B-ring attached at C3 rather than the C

2

position [30] (Fig. 5.1). Till now about 1,600 isoflavones have been identified and the list is continuously growing [31]. The isoflavones like daidzein, genistein, and glycitein are synthesized via the phenylpropanoid pathway and stored in the vacuole as glucosyl-  and malonyl glucose conjugates. The pathway  to daidzein branches from the phenylpropanoid pathway, that is common to most plants, following the chalcone synthase reaction (Fig. 5.2) through a legume specific enzyme, chalcone reductase. Glycitein synthesis is likely to be derived from isoliquiritigenin. Genistein synthesis shares the naringenin intermediate with the flavonoid/anthocyanin branch of the phenylpropanoid pathway. In all cases, the unique aryl migration reaction to create the isoflavones is mediated by isoflavone synthase [32]. Oxidative rearrange-ment of naringenin (flavanone) with a 2.3-aryl shift yields the isoflavone. The initiating step  in  isoflavone  formation  may  be  an  epoxidation  catalysed  by  a  cytochrome p-450-dependent mono-oxygenase. After structural rearrangement, aryl shift and addition of a hydroxyl ion to C-2, elimination of water by a dehydratase gives the isoflavone structure. Details of isoflavones structure can be found in the article of Veitch, 2007 [31].

These  compounds  were  initially  recognized  for  their  roles  in  plant  disease resistance and as signal molecules to promote Rhizobium nodulation [16]. They also serve as precursors for the production of major phytoalexins during plant –microbe interactions [33] and inhibit pathogen attack [34–37]. Isoflavones have demonstrated 

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efficient antimicrobial and antifungal activities. The isoflavones like daidzein inhibits the growth of Fusarium culmorum, while glycitein and formononetin can reduce mycelial development in Aspergillus ochraceus [38]. Biochanin A and genistein exhibit antifungal activity against Rhizoctonia solani and Sclerotium rolfsii [39]. Antimicrobial  and  antifunagl  properties  of  various  isoflavones  have  been  well demonstrated. Isoflavones from stem bark of Flemingia paniculata [40] and from F. stropbilifera [41] showed significant antibacterial activity. Extract of Tamarix gallica containing quercetin [42],  Prunus  Americana  containing  isoflavones  [43] and  Glycirrhiza  glabra  containing  glabridin  [44] showed promising antimicrobial activity. On elicitation by Aspergillus sojae, Soybean produced antifungal glyceol-lins [45] effective against Fusarium oxysporum, Phytophthora capsici, Sclerotina sclerotiorum and Botrytis cinerea, while lactofen induced isoflavones were  correlated with defence responses [46].

Phenylalanine

Cinnamate

p - Coumarate

p - Coumarate CoA

Liquiritigenin

Naringenin

Dihydroflavonol

AnthocyaninsCondensed tannins

Genistein

Glyceollins

Glycitein

Daidzein

Cinnamic acid 4 - hydroxylase

Chalcone isomerase

Isoflavone hydroxylaseIsoflavone reductase

Isoflavone synthase

Anthocyaninsynthase

4 reductase

-

IsoliquiritigeninFlavone

Flavonol

Phenylalanineammonia lyase

-

4-Coumarate:CoA ligase

Chalcone synthase

Chalcone reductase

Flavone synthase

Flavan - 3,4 - diol

Flavan-3,4 - diol

+ 3 malonylCoAChalcone isomerase

Isoflavone synthase

Fig. 5.2  Biosynthetic route of isoflavones production

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5.3.2 Stilbenes

Stilbenes are a group of phenylpropanoid-derived compounds characterized by a 1,2-diphenylethylene backbone (C

6–C

2–C

6). Stilbenes exist in the stereo isomeric

forms (E and Z forms) depending on the position of where the functional groups are attached in relation to one another on either side of the double bond. Stilbenes constitute an important group of natural products that are of particular interest owing to their wide range of biological activities [47]. Combretastatins, piceatannol, pinosylvin, rhapontigenin, pterostilbene and resveratrol are some of the naturally occurring stilbenes. Of these, combretastatins and resveratrol have been extensively studied. Most plant stilbenes are derivatives of the basic unit trans-resveratrol (3,5,4-0-trihydroxy-stilbene). From this relatively simple structure, over a thousand stilbenoid compounds have been characterized,  resulting from different chemical substitutions patterns like methylation, glycosylation or isoprenylation, in addition to oxidative condensations of monomers into dimers (for example viniferins) and subsequent condensations of these [48]. All higher plants seem to be able to synthe-size malonyl-CoA and CoA-esters of cinnammic acid derivatives, but only few plant species are able to produce stilbenes, as the stilbene synthase (STS), the fundamen-tal enzyme of stilbene synthesis, is present in a limited number of plant species, for example Vitis spp., Arachis hypogea, Pinus spp., Rheum spp. and Fallopia spp. STS genes exist as a family of related genes in these plants [49]. Stilbene synthase cata-lyzes,  in  a  single  reaction,  the  biosynthesis  of  the  stilbene  backbone  from  three malonyl-CoA and one CoA-ester of a cinnamic acid derivative (Fig. 5.3). Grapevine genome contains more than 20 STS genes [50] and nearly all of them are expressed in grape following infection with Plasmopara viticola [51].

Some plant species, such as Fallopia japonica (formely Polygonum cuspidatum), pine (Pinus spp.) and grapevine (Vitis spp.) constitutively accumulate large amounts of stilbenes [49]. However, most studies concerning stilbene biosynthesis have been conducted on peanut, grapevine and pine. Induction of stilbenes synthesis is well known in response to a wide range of abiotic and biotic stresses. As example in grapevine, upon infection with different fungal pathogens, including powdery mildew (Erysiphe necator) [52], downy mildew (P. viticola) [53, 54], or gray mold (B. cinerea) [55, 56], coordinated activation of STS and upstream enzymes in this pathway occurred.

Stilbenes can accumulate in plant tissues to concentrations necessary to inhibit fungal growth [57, 58]. Stilbenes like pinosylvin and pinosylvin 3-O-methyl ether, which occur naturally in conifers, have strong antifungal activity in in vitro assays. These compounds are active in vitro against Coriolus versicolor and Gloeophyllum trabeum, two wood-destroying fungi [59]. Other stilbene like resveratrol inhibits conidial germination of Botrytis cinerea (the gray mold agent on grapes) [53] and also reduces the germination of sporangia of Plasmopara viticola (the downy mil-dew agent) whereas its glucoside piceid reduces fungal spore germination [60] at concentrations compatible with the activity range of other phytoalexins. It is inter-esting to note that trans-resveratrol, piceids, viniferins and pterostilbene concentrations

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reach up to 50–400 mg/g DW in infected grapevine leaves [49, 61]. Pterostilbene, the dimethylated form of resveratrol, had a five-fold higher activity than resveratrol in inhibiting fungal growth in vitro, indicating that methylation of hydroxyphenyl groups could lead to increased biocidal activity of phenolics [62].

To demonstrate the role of these phytoalexins in plant disease resistance, the stilbene synthase VST1 gene fused to an alfalfa pathogen-inducible promoter was introduced in 41B grapevine rootstock. Resulting transgenic plants produced more resveratrol under biotic and abiotic stress conditions and showed reduced symptoms after infection with B. cinerea [63]. Two stilbene synthase genes VST1 and VST2 from grapevine (Vitis vinifera L.) and the pinosylvin synthase gene PSS from pine (Pinus sylvestris L.) were stably transferred into bread wheat. Upon inoculation with the biotrophic pathogen Puccinia recondita f.sp. tritici several VST transgenic wheat lines showed a significant reduction of disease symptoms compared to wild-type

Phenylalanine

Phenylalanine ammonia lyase(PAL)

Cinnamic acid

Cinnamate 4-hydroxylase(C4H)

p-coumaric acid

4-coumarate CoA ligase(4CL)

p-coumaroyl-CoA+ 3 malonyl-CoA

Chalcone synthaseStilbene synthase

Tetraketide intermediate

Stilbene synthaseChalcone synthase

Chalcone Resveratrol

Fig. 5.3 Steps of stilbene biosynthesis

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plants. The reduction of disease symptoms was even more obvious after inoculation with the facultative biotrophic pathogen Septoria nodorum Berk [64]. Similarly, the transfer of stilbene synthase genes to tobacco, tomato, barley and rice leads to the accumulation of resveratrol and the resistance of the resulting transgenic plants to fungal pathogens [65–67]. In some cases, such as in kiwifruits and poplars , the heterologous expression of stilbene synthase did not result in an improved pathogen resistance, but resveratrol glucosides (less active on fungi than the aglycon form) were accumulated [68, 69].

Resveratrol is one of the most extensively studied natural products. Plethora of studies have demonstrated that resveratrol has preventive effect against a wide variety of diseases including cancer, cardiovascular diseases, as well as AIDS [70, 71].

5.3.3 Mechanism of Secondary Metabolites Action

Flavonoids and phenylpropanoids are widely distributed in plants and exhibit different mode of action against the pathogens. It is interesting to know that hundreds of clinical antifungal drugs in use, target only 6 different processes. Mostly they act as analogues of cellular signal compounds or substrates. They affect various physio-logical process and the parts of the pathogens like biomembranes, enzyme inhibi-tion, estrogenic properties and DNA alkylation [72]. These molecules usually have several phenolic hydroxyl groups in common, which can dissociate in negatively charged phenolate ions. Phenolic hydroxyl groups form hydrogen and ionic bonds with proteins and peptides. The higher the number of hydroxyl groups, the stronger the astringent and denaturing effect [73].

Proteins can only work properly if they have the correct three-dimensional structure, called conformation. Conformational changes alter their properties and can prevent effective crosstalk between proteins, and between proteins and DNA or RNA. Most secondary metabolites interact with proteins in one or another way by binding, complexing, denaturing, thereby changing protein conformations. Most secondary metabolites form covalent bond with protein, often by binding to free amino-, SH- or OH- groups, e.g., phenylpropanoids binds to amino groups, SH reagents and epoxides couple to free SH groups. The covalent modification can lead to a conformational change and thus loss of activity; or protein turnover is altered because proteases can no longer break down the alkylated protein. Polyphenols (phenylpropanoids, flavonoids, catechins, tannins, lignans, quinines, anthraquinones) interact with proteins by forming hydrogen bonds and the much stronger ionic bonds with electronegative atoms of the peptide bonds and or the positively charged side chains of basic amino acids (lysine, histidine, arginine). A single of these non-covalent bonds is quite weak. But because several of them are formed concomi-tantly when a polyphenols encounters a protein, a change in protein conformation or a loss in protein flexibility is likely to occur that commonly leads to protein inac-tivation. Since most polyphenols are quite polar and therefore, hardly absorbed after oral intake, they are usually not regarded as serious toxins [74].

255

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The effect of two stilbene compounds, pinosylvin and resveratrol, on the growth of several fungi was evaluated in plate tests. Wood decay tests were carried out with birch and aspen samples impregnated with the two stilbenes. In plate experiments, resveratrol had an enhancing effect on growth at concentrations where pinosylvin was already enough to prevent the growth of most fungi studied [75]. Looking at the efficient mode of action of plant SECONDARY METABOLITES against insects and pathogens pesticides, they are gaining increased attention and interest among those concerned with environment friendly, safe, and integrated crop management approaches [76].

5.4 Elicitation

Infected or elicited plants accumulate an array of plant defencive compounds. Now-a-days, it is well accepted that plant SECONDARY METABOLITES are involved in this plant defence system [77]. In 1982, Wolters and Eilert [78] reported for the first time that in rue callus cultures the acridone alkaloid content increased when it was co-cultivated with fungi. Through the years, fungal cell wall components, microbial preparations, various heavy metals, UV irradiation or ultrasound treatment are able to enhance SECONDARY METABOLITES accumulation in plants. Plants treated with non-specific elicitors develop a general defence mechanism. This induced defence is a phenotypic trait. The process of inducing resistance using elicitors is environmental friendly and is advantageous over the chemical based pesticides. It is based on induction of the native “immune” potential of the host plant rather than on suppression of phytopathogens. The resistance developed in this way has prolonged effect. This strategy could be an alternative solution to reduce the use of pesticides.

Elicitors are physical or chemical factors which when comes in contact in small concentrations to a living plant cell system triggers morphological and physiological responses such as phytoalexins accumulation. Elicitation is the process in which elicitor induct a sequence of reaction in the living cell, particularly related to biosynthesis of metabolites such as phytoalexins.

On the basis of their nature, elicitors can be divided into two types namely biotic and abiotic. Abiotic elicitors are the substances of non –biological origin, like organic salts and physical factors acting as elicitors (Table 5.1). Biotic elicitors are substances with biological origin, like polysaccharides, derived from plant cell walls (pectin or cellulose), plant gums and microorganisms (chitins or glucans) and glycoproteins or intracellular proteins whose functions are coupled to receptors and act by activating or inactivating a number of enzymes or ion channels [79]. Biotic elicitors can be further divided on the basis of their source into exogenous and endogenous groups. Exogenous elicitors are considered as the primary signals in plant pathogen interactions. They originate in the pathogen itself, mostly have a limited mobility within plant tissues, and evoke a response in cells in the immediate vicinity to the pathogen. Endogenous elicitors are of plant origin and arise as a

296

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result of the interaction with the pathogen. Most appear to be apoplastic and their function may be to modulate the extent of the response in the surrounding tissue. This modulation can be exerted independently of the presence of exogenous elici-tors or in a synergistic manner [80].

Table 5.1 List of commonly used biotic and abiotic elicitors

Abiotic elicitors2-amino-2-deoxy-d-galactopyranose

(galactosamine)Freezing and thawing cycles

2-amino-2-deoxy-d-glucose (glucosamine) Fungicides (Maneb, Butylamine, Benomyl)6,1¢,6¢-triamino-6,1¢,6¢-trideoxysucrose

(saccharosamine)Gentamycin

b-cyclodextrin Herbicides (Acifluorofen)Activated carbon Methyl jasmonateArachidonic acid Nitric oxideColchicine Oxidative stress, amino acid starvationCopper Sulphate Salicylic acidCopper/Cadmium/Aluminium Chloride Sodium ferric ethylenediamine di-(o-hydroxyphe-

nylacetate) FeEDDHACu+2, Cd+2, Ag+ Trifluoroethyl salicylate (TFESA)Curdlan UV lightDenatured proteins (RNase) Vanadium/Vanadyl sulphateDiethyl amino ethyl dichlorophenyl ether XAD-4Electromagnetic treatment Xanthan

Biotic elicitorsArachidonic acid LaminarinAlginate oligomers MonilicolinAlginate oligomers Pectic acidAlteromonas macleodii PectinAspergillus niger/sojae Phytopthora megasperma/cryptogea/sojaeBlue green algae crude Plants gumsBotrytis cinerea PolyaminesCellulase Poly-L-lysineChitosan Pythium aphanidermatumColletotrichum trifolii Rhizoctonia bataticolaCuscuta extract Rhizoctonia solaniDiaporthe phaseolorum Rhizopus arrhizusEicosapentanoic acid Sacharomyces cerevisiaeEnterobacter sakazaki Spodoptera frugiperdaExogenous cork pieces Streptomyces melanosporofaciensFlagellin SyringolideFusarium conglutanis SysteminGlucans Trichoderma virideGlucomannose ulvaGlycoproteins Verticillum dahliaeHarpins Volicitin (N-linolenoyl –L-glutamine)Hemicellulase Yeast elicitorHepta-b –glucosides

337

338

339

340

t1.1

t1.2

t1.3

t1.4

t1.5

t1.6

t1.7

t1.8

t1.9

t1.10

t1.11

t1.12

t1.13

t1.14

t1.15

t1.16

t1.17

t1.18

t1.19

t1.20

t1.21

t1.22

t1.23

t1.24

t1.25

t1.26

t1.27

t1.28

t1.29

t1.30

t1.31

t1.32

t1.33

t1.34

t1.35

t1.36

t1.37

t1.38

t1.39

t1.40

t1.41

t1.42

t1.43

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5 Secondary Metabolites and Plant Defence

In  order  to  initiate  defence,  elicitors  must  be  recognized  by  plant  receptors localized to the plasma membrane or the cytoplasm. Elicitors subsequently or indi-rectly activate the corresponding effectors such as G-proteins, lipases and kinases, which then transduce the elicitor signal to downstream defence responses. The defence reaction involves synthesis of pathogenesis related proteins or defence secondary metabolites [81].

The influx of Ca2+ is a critica1 event in elicitor induced signal transduction that leads to accumulation of plant secondary metabolites. For example, treatment of grapevine cells with various elicitors rapidly triggers Ca2+ influx, alkalinization of extracellular medium, oxidative burst, activation of MAP kinases and protein phosphorylation/dephosphorylation events. These early events are followed by the induction of defence gene expression (including PAL and STS), resulting in the production of resveratrol, piceid and є-viniferins [15, 82, 83].

5.5 In Vitro and In Vivo Studies

5.5.1 Abiotic Elicitors

5.5.1.1 Jasmonic Acid

Jasmonic acid (JA), an oxylipin-like hormone with its more active derivative methyljasmonate (MeJA) is derived from oxidized linolenic acid. Intensive investi-gations by many laboratories about the signal cascade of elicitation process resulted in the identification of JA and its derivatives as important elicitors [84]. It plays a key role in the elicitation of defence signaling pathways involved in resistance to pathogens, especially necrotrophs. JA is also used in a large number of cell and organ culture systems to increase the secondary metabolite yields [85].

Fungal diseases are a major problem in grapevine cultivation around the world. In order to limit these infections some alternative eco-friendly strategies like elicita-tion of plants with elicitors has been adapted. Several studies report the stimulation of stilbene production by exogenous application of MeJA in grapevine cell cultures (Table 5.2). Some in vivo studies demonstrated that MeJA-treated leaves showed increased transcript levels, coding pathogenesis related proteins and coding enzymes involved in phytoalexin biosynthesis (phenylalanine ammonia lyase and stilbene synthase) (Table 5.3). This was correlated with the accumulation of stilbenes (antimicrobial compounds). The eliciting activity of MeJA was confirmed by enhanced tolerance of grapevine foliar cuttings and vineyard against powdery mildew (75% and 73%, respectively) [109]. On the basis of these original results, MeJA could therefore, act as an efficient elicitor in an alternative strategy of grapevine protection.

Similarily, MeJA treated in vitro cultures of plants like Pueraria montana, P. candollei, P. tuberosa, Medicago truncatula accumulated significantly increased

341

342

343

344

345

346

347

348

349

350

351

352

353

354

355

356

357

358

359

360

361

362

363

364

365

366

367

368

369

370

371

372

373

374

375

376

377

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Tabl

e 5.

2 E

ffec

t of

elic

itors

on

the

stilb

enes

con

tent

of

in-v

itro

gro

wn

plan

ts

S. N

o.Pl

ant s

peci

esC

ultu

re ty

pes

Elic

itors

use

dPr

oduc

tsR

efer

ence

s

1C

ayra

tia

trif

olia

Roo

t cul

ture

sY

east

ext

ract

, sal

icyl

ic a

cid,

met

hyl j

asm

onat

e,

ethr

elPi

ceid

, res

vera

trol

, vi

nife

rin,

am

pelo

psin

[86]

2C

ayra

tia

trif

olia

Cel

l cul

ture

Salic

ylic

aci

d, m

ethy

l jas

mon

ate,

eth

rel a

nd y

east

ex

trac

t, sa

licyl

ic a

cid

and

angi

ospe

rm p

aras

ite

Cus

cuta

Pice

id, r

esve

ratr

ol,

vini

feri

n, a

mpe

lops

in[8

7, 8

8]

3Vi

tis

rupe

stri

s an

d Vi

tis

vini

fera

cvs

In v

itro

pla

nts

UV

irra

diat

ion,

alu

min

um c

hlor

ide,

and

Bot

ryti

s ci

nere

aR

esve

ratr

ol[8

9]

4Vi

tis

spp

Non

-em

bryo

geni

c ca

llus

UV

-C ir

radi

atio

nR

esve

ratr

ols

and

pice

ids

[90]

5Vi

tis

vini

fera

Cel

l cul

ture

sM

ethy

l jas

mon

ate

tran

s-R

esve

ratr

ol a

nd

pice

ids

[85,

91]

6Vi

tis

vini

fera

Cel

l cul

ture

Cyc

lode

xtri

nsR

esve

ratr

ol[9

2] 7

Viti

s vi

nife

raC

ell c

ultu

reC

hito

san

Res

vera

trol

[93,

94]

8Vi

tis

vini

fera

Cel

l cul

ture

Met

hylja

smon

ate,

cyc

lode

xtri

nsR

esve

ratr

ol[8

3, 9

5] 9

Viti

s vi

nife

raC

ell c

ultu

reD

imet

hyl b

-cyc

lode

xtri

nR

esve

ratr

ol[9

6, 9

7]10

Viti

s vi

nife

raC

ell c

ultu

reSa

licyl

ic a

cid,

Na-

orth

ovan

adat

e, ja

smon

ates

, ch

itosa

n an

d th

e m

onom

ers

d-gl

ucos

amin

e

and

N-a

cety

l-d-

gluc

osam

ine,

am

pici

llin

and

rifa

mpi

cin

Res

vera

trol

[98]

11Vi

tis

vini

fera

Cal

lus

cultu

res

UV

irra

diat

ion

tran

s-R

esve

ratr

ol[9

9]12

Vitis

vin

ifera

cv.

Bar

bera

Cel

l cul

ture

Jasm

onic

aci

d, m

ethy

ljasm

onat

e an

d N

a-or

thov

anad

ate

tran

s- a

nd c

is-r

esve

ratr

ol;

tran

s-re

sver

atro

l and

pi

ceid

s

[100

, 101

]

13Vi

tis v

inife

ra c

vs M

iche

le

Palie

ri a

nd R

ed G

lobe

Cel

l cul

ture

sM

ethy

l jas

mon

ate

tran

s-Pi

ceid

and

e-v

inif

erin

[102

]

t2.1

t2.2

t2.3

t2.4

t2.5

t2.6

t2.7

t2.8

t2.9

t2.1

0

t2.1

1

t2.1

2

t2.1

3

t2.1

4

t2.1

5

t2.1

6

t2.1

7

t2.1

8

t2.1

9

t2.2

0

t2.2

1

t2.2

2

t2.2

3

t2.2

4

t2.2

5

t2.2

6

Uncor

recte

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5 Secondary Metabolites and Plant Defence

amount of isoflavones in comparison to control cultures. The isoflavone like daidzein is the precursor to the major phytoalexins including medicarpin which are produced in Medicago and Glycine, respectively [32]. There are reports for the increased production of these metabolites by using MeJa and other biotic elicitors (Table 5.4). There are studies on Medicago truncatula which demonstrated that on infection with fungal pathogen Macrophomina phaseolina, genes involved in flavonoid and isoflavonoid biosynthesis were strongly up-regulated in the shoot. In addition, some genes in jasmonates (JAs) or ethylene (ET) pathways were not strongly induced in infected root tissue. Treating plants with methyl jasmonate (MJ) induced partial resistance in M. truncatula plants [130].

5.5.1.2 Ethephon

Ethephon is an ethylene-releasing compound. It has been known for a long time as an inducer of phenylpropanoid biosynthesis which may be related to a general wound and/or stress response. An ethephon related increase of PAL activity had

Table 5.3 Effect of elicitors on the stilbenes content of in-vivo grown plants

S. No. Plant speciesPlant parts elicited Elicitors used Products References

1 Vitis vinifera Whole plants Laminarin Resveratrol and e-viniferin

[103]

2 Vitis vinifera sylvestris, Vitis vinifera sativa

Postharvest grapes

Ultraviolet C Total stilbenes [104]

3 Vitis vinifera Plants Plasmopara viticola infection, ultraviolet light, and AlCl

3

Pterostilbene [105, 106]

4 Vitis vinifera L. cv. Barbera

Berries Aspergilli japonicus, A. ochraceus, A. fumigatus and isolates of A. carbonarius

trans-Resveratrol [107, 108]

5 Vitis vinifera Plants; berries Methyl jasmonate Stilbenes [109, 110]6 Vitis vinifera Grapevine

detached leaves and grapevine foliar cuttings

Ethephon Resveratrol, piceid, viniferins pterostilbene

[111]

7 Vitis vinifera cv. Barbera

Berries Aspergillus carbonarius

trans-Resveratrol and piceatannol

[112]

8 Vitis vinifera Flowers, berries UV radiation Resveratrol [113]

379

380

381

382

383

384

385

386

387

388

389

390

391

392

t3.1

t3.2

t3.3

t3.4

t3.5

t3.6

t3.7

t3.8

t3.9

t3.10

t3.11

t3.12

t3.13

t3.14

t3.15

t3.16

t3.17

t3.18

t3.19

t3.20

t3.21

t3.22

t3.23

t3.24

t3.25

t3.26

t3.27

t3.28

t3.29

t3.30

Uncor

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Tabl

e 5.

4 E

ffec

t of 

elic

itors

 on 

the 

isofl

avon

es c

onte

nt o

f in

-vit

ro g

row

n pl

ants

S. N

o.Pl

ant s

peci

esC

ultu

re ty

pes

Elic

itors

Prod

ucts

Ref

eren

ces

1A

lbiz

zia

kalk

ora

Roo

t cul

ture

sSt

rain

s of

Rhi

zobi

um s

pD

aidz

ein 

and 

geni

stei

n[1

14]

2C

icer

ari

etin

umC

allu

s/tis

sues

Hyp

nea

mus

cifo

rmis

(re

d al

gae)

Form

onon

etin

, maa

ckia

in, n

arin

gin

and

nari

ngin

mel

onat

e[1

15]

3G

lyci

ne m

axH

airy

roo

tsF

usar

ium

sol

ani

Gen

istin

, dai

dzin

, gly

citin

 and

 thei

r m

alon

yl c

onju

gate

s an

d ag

lyco

nes,

cou

mes

trol

and

gl

yceo

llin

[116

]

4G

lycy

rrhi

za e

chin

ata

Cel

l cul

ture

sY

east

ext

ract

Form

onon

etin

 and

 dai

dzei

n[1

17]

5L

upin

us a

lbus

Seed

lings

Puri

fied

yeas

t cel

l wal

lPr

enyl

ated

 isofl

avon

e ag

lyco

nes

[118

] 6

Man

ihot

esc

ulen

taC

ell c

ultu

res

Yea

st e

xtra

ctPh

enyl

prop

anoi

ds a

nd s

copo

letin

[119

] 7

Med

icag

o tr

unca

tula

Cel

l cul

ture

sY

east

ext

ract

and

met

hyl j

asm

onat

eFo

rmon

onet

in a

nd b

ioch

anin

-A

med

icar

pin 

and 

daid

zin

[120

]

8P

hase

olus

vul

gari

sSe

edlin

gsC

uCl 2,

chito

san,

gen

tam

ycin

, sac

char

o-sa

min

e, g

alac

tosa

min

e an

d gl

ucos

amin

ePh

aseo

llin,

cou

mes

trol

, gen

iste

in

and 

daid

zein

[121

]

9P

sora

lea

cory

lifo

lia

Hai

ry r

oots

Yea

st e

xtra

ct, c

hito

san,

sal

icyl

ic a

cid

Dai

dzei

n an

d ge

nist

ein

[122

]10

Pso

rale

a co

ryli

foli

aC

ell c

ultu

res

Yea

st e

xtra

ct, c

hito

san,

sal

icyl

ic a

cid

Dai

dzei

n an

d ge

nist

ein

[123

]11

Pue

rari

a ca

ndol

lei v

ar.

cand

olle

i and

P. c

ando

llei

va

r. m

irifi

ca

Cel

l cul

ture

Cop

per

sulf

ate,

met

hyl j

asm

onat

e (M

eJA

),

and

yeas

t ext

ract

, chi

tosa

n, la

min

arin

Isofl

avon

es[1

24]

12P

uera

ria

cand

olle

iH

airy

roo

tsM

ethy

l jas

mon

ate,

chi

tosa

n, s

alic

ylic

aci

d,

Agr

obac

teri

um, a

nd y

east

ext

ract

Isofl

avon

es[1

25]

13P

uera

ria

mon

tana

Hyd

ropo

nica

lly

grow

n se

edlin

gsC

ork

piec

es, X

AD

-4, a

nd m

ethy

l jas

mon

ate

Dai

dzei

n, g

enis

tein

, dai

dzin

, ge

nist

in, a

nd p

uera

rin

[126

]

14P

uera

ria

tube

rosa

Cel

l cul

ture

sY

east

ext

ract

, sal

icyl

ic a

cid,

met

hyl

jasm

onat

e, e

thre

lPu

erai

n, g

enis

tin, d

aidz

ein 

and 

geni

stin

[127

, 128

]

15Tr

ifol

ium

pra

tens

eSe

edlin

gsC

hito

hexo

se C

oppe

r C

hlor

ide

Form

onon

etin

e-7-

O-g

luco

syl-

6″-

mal

onat

e an

d M

aack

iain

-3-

O-g

luco

syl-

6″-m

alon

ate.

[129

]

t4.1

t4.2

t4.3

t4.4

t4.5

t4.6

t4.7

t4.8

t4.9

t4.1

0

t4.1

1

t4.1

2

t4.1

3

t4.1

4

t4.1

5

t4.1

6

t4.1

7

t4.1

8

t4.1

9

t4.2

0

t4.2

1

t4.2

2

t4.2

3

t4.2

4

t4.2

5

t4.2

6

t4.2

7

t4.2

8

t4.2

9

t4.3

0

Uncor

recte

d Pro

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5 Secondary Metabolites and Plant Defence

been described long back [131–133]. There are some in vivo and in vitro studies which demonstrate increased stilbene and isoflavone accumulation in the plants by ethephon/ethrel treatment (Tables 5.2–5.4). In a study, Belhadj and co-workers [111] treated grapevine foliar cuttings (Cabernet Sauvignon) with ethylene- releasing ethephon. This resulted in an increase in the number of pathogenesis-related protein gene copies (CHIT4c, PIN, PGIP, and GLU) and in an enhancement of phytoalexin biosynthesis by inducing the PAL and STS genes that correlated with the accumula-tion of stilbenes (antimicrobial compounds). Moreover, ethephon treatment triggered the protection of grapevine detached leaves and grapevine foliar cuttings against Erysiphe necator, the causal agent of powdery mildew (64% and 70%, respectively). These studies emphasize the major role of ethylene in grapevine defence.

Production  of  isoflavones  like  puerarin,  daidzein,  genistin  and  genistein  were also increased in ethephon treated cell cultures of Pueraria tuberosa [128]. Effects of ethephon on isoflavones production in different plants still need attention.

5.5.1.3 UV Light

Resveratrol production and expression of the genes related to resveratrol biosynthesis were investigated in the skins of three Vitis vinifera cultivars. Resveratrol concentra-tion in the skins of all the grapes increased significantly when exposed to ultraviolet (UV-C, 254 nm) irradiation [134]. In another study, it was demonstrated that in V. rupestris UV irradiation induced a high, constant level of STS mRNA production which was correlated to resveratrol accumulation [89]. Another group of workers evaluated grape flowers and green berries of 72 grape genotypes for their ability to produce resveratrol in response to UV radiation. This was used to establish a selection criterion for screening genotypes for resistance to gray mold and powdery mildew. There was a strong negative correlation between UV-induced resveratrol production and susceptibility to Botrytis infection [135]. Callus culture of V. vinifera were exposed to 254 nm UV light. About 15 min of UV irradiation period was found to be effective for induction of (62 mg/g callus fresh weight) trans-resveratrol produc-tion [99]. Thus, UV light can be used as an efficient elicitation source for stilbene production (Tables 5.2 and 5.3).

5.5.1.4 Cyclodextrins

Cyclodextrins (CD) are cyclic oligosaccharides of 6,7 or 8 a –d- glucopyranoside residues linked by a 1→4 glucosidic bonds, which are called a-, b-, and g- CD. They have an hydrophilic external surface and hydrophobic central cavity that can trap a polar compounds [136]. The production of cyclodextrins is relatively simple and  involves  treatment of  ordinary  starch with  a  set  of  easily  available  enzymes [137]. Dimethyl -b-cyclodextrin (DIMEB), an oligosaccharide consisting of 2,6-methylated cyclic a (1→4)- linked glucopyranose moieties, has shown to be capable of inducing stilbene biosynthesis in liquid Vitis vinifera cell cultures, also

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in the absence of pathogenic organisms [96] (Table 5.2). This molecule seems to mimic a defence elicitor which enhances the physical barriers of the cell, stops cell division and induces phytoalexin synthesis [97].

A grapevine liquid cell culture system was used to examine the properties of CDs as inducers of defence responses. This work shows that the chemically pure heptakis (2,6-di-O-methyl)-b CD caused a dramatic extracellular accumulation of the phytoalexin resveratrol and changes in peroxidase activity and isoenzymatic pattern. Other modified CDs tested on several grapevine cell lines resulted in different eliciting capacities of CDs and different sensibilities of the cell lines. The spent medium of elicited cultures containing polyphenolic compounds released by plant cells was shown to disturb Botrytis cinerea growth in a plate assay [92].

5.5.1.5 Phosphites

Phosphite  is  a  neutralized  solution  of  the  phosphonate  anion  [138]. Phosphite contains one less oxygen (O) than phosphate, making its chemistry and behavior quite different. Phosphite is less chemically stable and more soluble than phosphate, when applied to plants, it is quickly absorbed by leaves, roots and branches, thus high concentrations can be toxic for plants. It is able to move in both, xylem and phloem. Unlike phosphates, phosphites stimulate the pathogen defence mechanisms in plants and have antifungal activity by inducing production of phytoalexins. It is effective against fungi like Plasmopara viticola, Pythium sp. and Phytophthora nicotianae. The relatively limited fungicidal effect – combined with its ability to stimulate plants to make a broad spectrum of biologically active metabolites – makes phosphite relatively benign to the environment and safe to use [139]. Now-a- days there are many reports on phosphite induced cellular responses to pathogen challenge and suppressed pathogen ingress in both in vitro and in vivo cultures [140, 141]. Different mechanism of phosphite actions were postulated by Grant and co-workers [142]. With the indirect actions, phosphite is hypothesized to cause the pathogen to produce elicitors or inhibit its production of suppressors, allowing plant defence responses to halt invasion by the pathogen [143].

5.5.1.6 Pulsed Electric Field

Pulsed electric field (PEF) an external stimulus or stress, is proposed as a promising new abiotic elicitor for stimulating secondary metabolite biosynthesis in plant cell cultures. The effects of PEF on growth and secondary metabolite production by plant cell culture were investigated by using suspension cultures of Taxus chinensis as a model system. A significant increase in intracellular accumulation of taxuyun-nanine C (Tc), a bioactive secondary metabolite, was observed by exposing the cells in the early exponential growth phase to a 30-min PEF [144]. The effects of PEF and ethephon on growth and secondary metabolites accumulation were also investi-gated in suspension culture of Vitis vinifera L. cv. Gamay Fréaux as a model system.

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After the treatments production levels of extracellular phenolic acids, 3-O-glucosyl-resveratrol was increased in the cultures [145]. In another recent study, isoflavones production in the Glycine cell culture increased with pulsed electric field (PEF) application at 1.6 kV, and aglycone forms were influenced to a greater extent [146]. These results show that PEF induced a defence response of plant cells and may have altered the cell/membrane’s dielectric properties.

5.5.2 Biotic Elicitors

5.5.2.1 Chitosan

Chitosan is a polysaccharide called poly [b-(1→ 4)-2-amino-2-deoxy -d-glucopyranose]. It is a plant defence booster derived from deactylation of chitin which is extracted from the exoskeleton of crustaceans such as shrimps and crabs, as well as from the cell walls of some fungi [147, 148]. The primary unit in the chitin polymer is poly [b-(1→4)-2-acetamido-2-deoxy -d-glucopyranose]. The units are combined by 1,4 glycosidic linkages, forming a long chain linear polymer. Removal of most of the acetyl groups of chitin by treatment with strong alkalis yields chitosan [149]. Agricultural applications of chitosan are for stimulation of plant defence. The chitosan molecule triggers a defence response within the plant, leading to the formation of physical and chemical barriers against invading pathogens [150].

Chitosan conferred a high protection of grapevine leaves against grey mould caused by Botrytis cinerea. Treatment of grapevine leaves by chitosan led to marked induction of lipoxygenase (LOX), phenylalanine ammonia-lyase (PAL) and chitinase activities, three markers of plant defence responses. Strong reduction of B. cinerea infection were achieved with 75–150 mg/l chitosan [151]. In some studies it was observed that grapevines with higher assays of chitinase or ß-1,3-glucanase had greater resistance to powdery mildew, and when combined had even greater field resistance against powdery mildew (Uncinula necator) [152].

In an investigation, chitosan increased the amounts of genistein and 2- hydroxygenistein monoprenyls in roots of white lupin and in the exudates [153]. Further studies indicated that chitosan triggers either the de-novo synthesis of phe-nolic compounds as the first defensive line designed to inhibit growth of the fungus and b-1,3-glucans act as a second mechanical barrier for blocking potential invasion by fungal cells and protecting the tissue against phytotoxic substances [154, 155]. Chitosan coating of litchi fruits increased their content of flavonoids and resistance to browning and postharvest decay [156]. Chitosan has also been used in cell cul-tures of Vitis vinifera and Psoralea corylifolia, Pueraria candollei to enhance the stilbene and isoflavone production, respectively (Tables 5.2 and 5.4). Besides its use in in vitro studies, chitosan is also used in in vivo studies to increase the isoflavones production (Table 5.5). Chitosan is a nontoxic biodegradable material, acting as an elicitor. Thus, has the potential to become a new class of plant protecting agent, assisting towards the goal of sustainable agriculture.

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Tabl

e 5.

5 E

ffec

t of 

elic

itors

 on 

the 

isofl

avon

es c

onte

nt o

f in

-viv

o gr

own

plan

ts

S. N

o.Pl

ant s

peci

esPl

ant p

art e

licite

dE

licito

rPr

oduc

tsR

efer

ence

s

1C

icer

ari

etin

umSe

edlin

gsR

educ

ed g

luta

thio

neB

ioch

anin

A, f

orm

onon

etin

and

m

edic

arpi

n an

d m

aack

iain

, ho

mof

erre

irin

and

cic

erin

Arm

ero

et a

l. [1

57].

2G

lyci

ne m

axSe

eds

Lip

o-ch

itool

igos

acch

arid

es,

chito

san,

Str

epto

myc

es

mel

anos

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in

EF-

76 a

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east

ext

ract

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dzei

n, g

enis

tein

, gly

cite

inA

l-Ta

wah

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al.

[158

].

3G

lyci

ne m

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and

seed

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ergi

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soja

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ll w

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59].

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lyci

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seol

orum

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 gen

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et a

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60].

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mes

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, gen

iste

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and

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geni

nK

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ar e

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[161

]

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titol

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63]

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tsC

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65]

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7-

O-g

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Jasi

ński

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l. [1

66]

11Tr

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ium

pra

tens

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ext

ract

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, dai

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 an

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67]

t5.1

t5.2

t5.3

t5.4

t5.5

t5.6

t5.7

t5.8

t5.9

t5.1

0

t5.1

1

t5.1

2

t5.1

3

t5.1

4

t5.1

5

t5.1

6

t5.1

7

t5.1

8

t5.1

9

t5.2

0

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1

t5.2

2

t5.2

3

t5.2

4

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recte

d Pro

of

5 Secondary Metabolites and Plant Defence

5.5.2.2 Laminarin

The molecule laminarin (also known as laminaran) is a linear glucan found in brown algae. Laminarin is clearly a high-energy carbohydrate. It is used as a food reserve in the same way that chrysolaminarin is used by phytoplankton. It is made up of b(1→3)-glucan with b(1→6)-linkages and a b(1→3):b(1→6) ratio of 3:1 [168]. In a study, b-1,3-glucan laminarin derived from the brown algae Laminaria digitata was shown to be an efficient elicitor of defence responses in grapevine cells and plants. It also effectively reduced B. cinerea and P. viticola development on infected grapevine plants. Defence reactions elicited by laminarin in grapevine cells include calcium influx, alkalinization of the extracellular medium, an oxidative burst, acti-vation of two mitogen-activated protein kinases, expression of 10 defence-related genes with different kinetics and intensities, increases in chitinase and b-1,3-gluca-nase activities, and the production of two phytoalexins (resveratrol and e-viniferin). When applied to grapevine plants, laminarin reduced infection of B. cinerea and P. viticola by approximately 55% and 75%, respectively [103]. In another study, laminarin  increased  the  isoflavones  accumulation  in  cell  cultures  of  Pueraria candollei (Table 5.4).

5.5.2.3 Yeast Extract

Yeast extract is the common name for various forms of processed yeast products made by extracting the yeast cell contents (removing the cell walls). Yeast has been proved to be an efficient elicitor for the increased accumulation of isoflavone and stilbene in different plants (Tables 5.2, 5.4, and 5.5). Yeast extract-treated suspension cultures of a new cell line, AK-1, of Glycyrrhiza echinata were induced to produce an  isoflavonoid  phytoalexin  (medicarpin).  From  these  cells,  putative  full-length cDNAs encoding cytochrome P450s, (2S)-flavanone 2-hydroxylase and isoflavone 2¢-hydroxylase, were cloned [169]. A cDNA encoding UDP-glucose: formononetin 7-O-glucosyltransferase, designated UGT73F1, was cloned from yeast extract-treated Glycyrrhiza echinata L. cell-suspension cultures. Recombinant UGT73F1 was expressed as a histidine-tag fusion protein in Escherichia coli. The purified recombinant  enzyme  was  selective  for  isoflavone,  formononetin  and  daidzein  as substrates [117]. Besides this, there are various reports where yeast extract was the most efficient elicitor in comparison to other elicitors [125].

5.6 Conclusions

The application of biotic and abiotic elicitors in developing plant resistance is still in the early stages of use. Currently, our knowledge is mainly based on the experi-mental trials. There are many reports which prove there efficacy as potent natural pesticides. It is well established that these elicitors impart disease resistance by

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elevating or developing some secondary metabolites in the plants. Effect of several elicitors on the production of stilbenes in different Vitis species and other stilbenes containing plants has been summarized in Tables 5.2 and 5.3. Similarly, the recent studies  on  the  effect  of  different  biotic  and  abiotic  elicitors  on  the  isoflavones production have been summarized in Tables 5.4 and 5.5.

Numbers of studies, especially concerning grapevine inoculated with various pathogens, have established a positive correlation between stilbene levels and pathogen resistance. More evidence supporting the role of stilbene (resveratrol) in resistance to pathogen infection was supplied by the transfer of stilbene synthase genes in plants that do not produce stilbenes, such as tobacco and alfalfa [65, 67].

Isoflavones function in both, the symbiotic relationship with rhizobial bacteria and  the plant defence  response. The  importance of  isoflavones can be  judged by different reports where in order to increase the disease resistance in plant, produc-tion of certain type of  isoflavones was enhanced by genetic manipulations [170]. The non-legume plants like Arabidopsis, Nicotiana tabacum and Zea mays (for human consumption) were metabolic engineered for isoflavones production. Due to complexities in regulation of inter-related biochemical pathways, metabolic engineering to affect the isoflavones biosynthetic capacity of a target plant tissue, presents a challenge [171]. However, by using elicitors this process can be simplified and can become more practically feasible in fields.

Use of elicitors has an added advantage over the chemicals used to prevent plants from diseases. There are increasing evidences, that elicitors could be used in the future as alternatives to traditional pesticides for managing pathogens and pests in agriculture and nursery production of forest trees. However, inappropriate use of elicitor treatments can change the chemical composition of the treated plant material. Therefore, with agricultural crops, suitable concentration of elicitors should be use which may not affect human health.

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Author QueriesChapter No.: 5 0001210227

Queries Details Required Author’s Response

AU1 Kindly confirm the corresponding author and provide e-mail id.

AU2 Kindly provide page numbers for the reference “Ramanujan (2008)”.

AU3 Please provide volume no. and page range for Cheng et al. (2011).

AU4 Please update the reference “Tamm et al. (2011)”.