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metabolic pathways of_diseased_potato

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Halliwell-Asada enzyme pathway O H CH3 CH3 CH3 CH3 gal gamma-solanine Shikimate pathway Phenylpropanoid biosynthesis Polyamine biosysnthesis Glycoalkaloids Ethylene biosynthesis SAM cycle Sesquiterpene phytoalexin biosynthesis Fatty acid degradation Phosphoinositide cascade COOH COO-gluc COSCoA COSCoA HO COSCoA O SCoA O COOH HO H O COOH COOH COOH COOH COS-CoA OH OH OH OH OH OH OCH3 OCH3 OCH3 HO H3CO COMT C4H phenylalanine hydroxylase F5H COMT 4CL 4CL 4CL 4CL 4CL putrescine hydroxycinnamoyl transferase UDP-glucose: sinapic acid glucosyltransferase (SGT) C3H hydroxylase trans-cinnamic acid cinnamoyl- glucose cinnamoyl-CoA 3-hydroxy-3- phenylpropionyl-CoA 3-oxo-3- phenylpropionyl-CoA 3-hydroxy-3- phenylpropanoic acid p-coumaric acid caffeic acid ferulic acid 5-hydroxyferulic acid sinapic acid OH COS-CoA OCH3 COS-CoA OH OH OH COS-CoA OCH3 HO COS-CoA OCH3 H3CO CCoA3H CCoAOMT COMT F5H? F5H F5H CCoAOMT COMT COMT p-coumaryl-CoA caffeoyl-CoA caffeoyl aldehyde feruloyl-CoA 5-hydroxyferuloyl-CoA sinapoyl-CoA sinapoyl glucose COOH OH CH2OH OH CH2OH OCH3 CH2OH OCH3 HO OH coniferyl alcohol OH CH2OH OCH3 H3CO OH 5-hydroxyferulyl alcohol (5-hydroxyconiferyl alcohol) sinapyl alcohol CCR CCR CCR CCR CAD CAD CAD CAD p-coumaryl alcohol o-hydroxycinnamic acid (o-coumaric acid) OH COOH COOH NH2 PAL (multiple isozymes) CoA ligase coumarin ? guaiacyl lignin syringyl lignin p-hydroxyphenyl lignin COOH OH SCoA O OH salicylic acid 4-hydroxy- benzoic acid benzoic acid 2-hydroxylase COO-conjugate COOH O-gluc benzoic acid conjugate hydroxyl radical salicyloyl-CoA salicylic acid glucoside In Arabidopsis AtPBS3 gene is transcriptionally regulated by AtWRKY46 affecting levels of SA-glucoside ? ? salicylic acid 2-O-glucosyl -transferase HOOC OH CH2 CH COOH NH2 arogenic acid arogenate dehydratase phenylalanine COOH NH2 OH tyrosine tyramine COOH OH O p-hydroxy- phenylpyruvic acid isodityrosine intramolecular cross-link between HRGPs peroxidase tyrosine aminotransferase tyrosine decarboxylase glutamine synthetase phenol oxidase COOH NH2 O O Dopaquinone tyrosine 3-monooxygenase (phenol oxidase) OH HOOC CH2 C COOH O prephenic acid chorismic acid chorismate mutase 2-3 isozymes in potato prephenate aminotransferase anthranilate indole-3-glycerol phosphate 1-(o-carboxyphenylamino)- 1-deoxyribulose 5-phosphate 5-phosphoribosyl- anthranilate tryptophan indole-3-pyruvic acid indole 5-enolpyruvylshikimate 3-phosphate (EPSP) 3-phosphoshikimic acid (shikimate 3-phosphate) shikimic acid shikimate kinase OH O protein protein ATP ADP NADPH NADP+ shikimate dehydrogenase 3-dehydroshikimic acid COOH NH2 OH OH NH2 OH OH Dopa dopamine norepinephrine normetanephrine OH COOH OH O HO 3-dehydroquinic acid 3-phosphoquinic acid OH COOH OH HO HO quinic acid hemiterpenes OH COOH OH CH2 HO 3-deoxy-D-arabino-heptulosonate 7-phosphate (DAHP) (Inhibited by phenylalanine. Located in chloroplasts. May be redox regulated) PO3H2O phosphoenolpyruvic acid D-erythrose 4-phosphate DAHP synthase 1-deoxyxylulose 5-phosphate synthase Mn2+ CH3COCOOH pyruvic acid acetyl-CoA HO-(CH2)15-COOH w-hydroxypalmitic acid HS-CoA HHT OH OCH3 O NH(CH2)4NH2 NH2(CH2)4NH2 NH2(CH2)4NHCH3 OH OH O NH(CH2)4NH2 feruloylputrescine putrescine putrescine-N- methyltransferase pyrroline dehydrogenase N-methylputrescine oxidase (MPO) polyamine oxidase diamine oxidase polyamine oxidase N-caffeoylputrescine OH OH COO-gluc OH O-gluc COOH 1-caffeoyl-B-D-glucoside caffeic acid 3-glucoside 4-coumaroyltyramine p-coumaroyl shikimic acid p-coumaroyl quinic acid caffeoyl shikimic acid caffeoyl CoA chlorogenic acid OH OH OH COOH HO HO O O OH OH COOH HO HO OH O O OH OH O O 'normal' chlorogenic acid (5 caffeoylquinic acid) chlorogenic acid (4 caffeoylquinic acid) chlorogenic acid (3 caffeoylquinic acid) OH OH COOH HO O OH O O O isochlorogenic acid (4,5 caffeoylquinic acid) OH OH COOH HO OH O O OH OH O O isochlorogenic acid (3,5 caffeoylquinic acid) quinic acid melanin Gary D. Lyon O O NH NH CH2CH(NH2)COOH NH skatole CH3 NH NH pyruvate + L-glutamate L-glutamine OH COO-Glu OCH3 H3CO OH CHO OCH3 OH coniferyl aldehyde (coniferaldehyde) CHO OCH3 HO OH 5-hydroxyferuloyl aldehyde (5-hydroxyconiferaldehyde) CHO OCH3 H3CO OH sinapyl aldehyde (sinapaldehyde) CHO OH p-coumaryl aldehyde protocatechualdehyde a-hydroxyacetosyringone syringic acid OH CHO OCH3 vanillin OH COOH OCH3 vanillic acid catechin catechin has been detected in potato OH COOH OH O2 + NADPH2 HCHO + NADP CHOHCH2NH2 OH octopamine feruloyl-CoA CH2CH2NH2 OH feruloyloctopamine (both N-transand N-cisdetected) feruloyltyramine (both N-transand N-cisdetected) feruloyltyramine-feruloyltyramine dimer (grossamide) and feruloyltyramine-feruloyloctopamine dimers have been isolated. THT THT THT C3' hydroxylase CYP98A3 CST brassinosteroid-6- oxidase 2 (P450) hydroxycinnamoyl-CoA:shikimate hydroxycinnamoyltransferase (CST) or hydroxycinnamoyl-CoA:quinate hydroxycinnamoyltransferase (CQT) vanilloside (glucovanillin) O O S-CoA O S-CoA OH HOOC OH OH HOOC OP OH HOOC acetoacetyl-CoA acetyl-CoA acetyl-CoA HMG-CoA HMG-CoA reductase regulated by SnRK1 in Arabidopsis mevalonic acid mevalonic acid 5-phosphate (5-phosphomevalonate) HMGR (multiple isozymes) inactive HMGR inactive ACC acetyl-CoA carboxylase acetyl-Co-A malonyl-CoA fatty acid fatty acyl-CoA triglycerides HMGR kinase kinase kinase PP2A PP2C OPP OH HOOC mevalonic acid 5-pyrophosphate (5-pyrophosphomevalonate) OPP OPP dimethylallyl pyrophosphate (DMAPP) isopentenyl pyrophosphate (IPP) isopentenyl pyrophosphate (IPP) farnesyl diphosphate (farnesyl pyrophosphate, FPP) nerolidyl pyrophosphate (NPP) geranyl pyrophosphate (GPP) isomerase an aldehyde + NAD(+) + H2O an acid + NADH aldehyde dehydrogenase sedoheptulose 7-phosphate + D-glyceraldehyde 3-phosphate D-erythrose 4-phosphate + fructose 6-phosphate transaldolase (gene upregulated in incompatible P. infestans/potato interaction) OPP neryl pyrophosphate monoterpenes OPP geranylgeranyl pyrophosphate (GGPP) squalene squalene 2,3-epoxide secologanin synthase (a P450) 7-deoxyloganin 7-hydroxylase (a P450) squalene 2,3-epoxidase cycloartenol cyclase cycloartenol chlorophylls diterpenes carotenoids ABA geranylgeranyl pyrophosphate synthetase isopentyl pyrophosphate + NADPH O H CH3 CH3 CH3 CH3 gluc gamma-chaconine H CH3 CH3 CH3 CH3 N N solanthrene HO H CH3 CH3 CH3 CH3 N N demissidine O H CH3 CH3 CH3 N O gluc rham rham O H CH3 CH3 CH3 N O gluc rham rham solamargine NH CH3 H CH3 CH3 CH3 solasodiene NH CH3 O vetispiradiene vetispiradiene synthase HO OH HO OH OH OCOCH3 OH OCOCH3 O OH OCOCH3 HO OCOCH3 HO O phytuberin OCOCH3 O O OH O O phytuberol colnelenic acid 9-[1'(E),3'(Z),6'(Z)-nonatrienyloxy]-8(E)-nonenoic acid colneleic acid 9-[1'(E),3'(Z)-nonadienyloxy]-8(E)-nonenoic acid Potato tuber phospholipids contain colneleic acid in the 2-position O solavetivone O CH2OH oxysolavetivone O CH2OH isolubimin fungal degradation HO CH2OH 15-dihydrolubimin HO CHO lubimin HO CHO HO 3-hydroxylubimin HO HO rishitin HO HO OH 13-hydroxyrishitin (rishitin-M-1) HO HO O 11,12-epoxyrishitin HO O rishitinone O HO hydroxyglutinosone OH mono- oxygenase O2 tyramine NH4+ COOH OH OH CHO OH COOH OH p-hydroxybenzoic acid NADH NAD+ p-hydroxybenzaldehyde dehydrogenase O CHO 2-dehydrolubimin O O O 11,12-epoxycyclodehydro- isolubimin O HO O O HO 2-dihydrocyclodehydro- isolubimin (cyclolubimin) O O cyclodehydroisolubimin O CH2OH HO CH2OH HO CHO 3,4-dehydroisolubimin 15-dihydro-10-epilubimin 10-epilubimin O O OH OH O OH O-gluc anhydro-beta-rotunol ((+)-spirovetiva-1(10),3, 11-trien-2-one) O solanoscone linolenic acid (C18:3) 13-lipoxygenase linolenic 13-hydroperoxide (13(S)-hydroperoxy-9(Z),11(E),15(Z)- octadecatrienoic acid) (13(S)-HPOT or 13(S)-HPOTE) COOH 12-oxo-9(Z)-dodecenoic acid COOH O COOH O 12-oxo-phytodienoic acid reductase COOH O COOH O COOH O epi-jasmonic acid ((+)-7-epi-jasmonic acid) COOCH3 O methyl (-)-jasmonate tuberonic acid 12-hydroxy-jasmonate sulphate COOH O OH COOH O OSO3H CH2OH O O IF IF IF alcohol dehydrogenase 3Z-hexen-1-ol 2E-hexenal 3(E)-hexenal CH2OH CH2OH 2E-hexenol 10-oxo-11,15(Z)-phytodienoic acid (2-oxo-5-[2'(Z)-pentenyl]-3-cyclopentene-1-octanoic acid) ( a cyclopentenone regioisomer of 12-oxo-10,15(Z)-phytodienoic acid) 3(E)-hexenol OH CHO OH CH3-S-CH2-CH2-CO-COOH 2-keto-4-methylthiobutyric acid (KMB) CH3-S-CH2-CH2-CH-COOH NH2 methionine CH3-S-CH2-CH2-CH-COOH CH2 OH OH Ade O NH2 CH3-S CH2 OH OH Adenine O CH3-S CH2 OH OH OPO3H O C H2C H2C COOH NH2 ACC synthase nicotianamine synthase 5'-methylthioadenosine nucleosidase MTR kinase ACC CH2 CH2 ethylene ETR1 ETR2 ERS1 ERS2 EIN4 CTR1 (a MAPKKK) EIN2 P5C reductase ornithine-alpha- aminotransferase ornithine- delta- aminotransferase proline dehydrogenase MAPKK (eg SIMKK) MAPK (eg SIMK, MMK3 MPK6 (MPK13)) Responses (eg induction of stress response genes including Eca response gene-1) ETR1 (= EIN1) is an ethylene receptor (a histidine kinase) CTR1 is a putative serine/threonine protein kinase (Raf-like) and negatively regulates ethylene responses EIL1-3 (EIN3-like protein) PK12 is a protein kinase (possibly located in the nucleus) (the signaling sequence is being studied in Arabidopsis and is still only 'postulated' for potato) ERN is an ethylene-regulated nuclear-localised protein. ACC: 1-aminocyclopropane-1-carboxylic acid SAM: S-adenosylmethionine R-CO-COOH R-CH-COOH NH2 ATP PPi + Pi ADP ATP HPO4 + HCOOH O2 ACC oxidase (cofactors iron and ascorbate Gene up-regulated by salicylic acid or IAA application) SAM nicotianamine 5'-methylthioadenosine (MTA) 5-methylthioribose 1-phosphate (MTR-1-P) CH3-S CH2 OH OH OH O 5-methylthioribose (MTR) p-hydroxybenzaldehyde IF= isomerization factor 9(S)-hydroperoxy-10(E),12(Z)-octadecadienoic acid (9(S)-HPOD or 9(S)-HPODE) 10(S),11(S)-epoxy-9(S)-hydroxy -12(Z)-octadecenoic acid 9(S),10-epoxy-10,12(Z)-octadecadienoic acid (an allene oxide) 9(S),10(S),11(R)-trihydroxy -12(Z)-octadecenoic acid 12(R),13(S)-epoxy-9(S)-hydroxy -10(E)-octadecenoic acid 9(S),12(S),13(S)-trihydroxy -10(E)-octadecenoic acid epoxy alcohol synthase allene oxide synthase epoxy alcohol synthase epoxide hydrolase epoxide hydrolase divinyl ether synthase (P450, CYP74D) O2 NADPH + H+ NADP+ beta-oxidation alpha-dioxygenase (a pathogen inducible oxygenase (PIOX) beta-oxidation beta-oxidation hydroxy-jasmonate sulphotransferase anthranilate synthase phosphoribosyl- anthranilate transferase phosphoribosyl- anthranilate isomerase tryptamine tryptophan decarboxylase tryptophan aminotransferase CH2CH2NH2 NH salicylate hydroxylase catechol NADPH + H+ NADP+ oxidised glutathione (GSSG) reduced glutathione (GSH) glutathione reductase glucose-6-phosphate dehydrogenase 6-phosphogluconate dehydrogenase isocitrate dehydrogenase dehydroascorbate reductase NAD(P)+ NAD(P)H glycine ubiquinone + NAD glutamate + cysteine ubiquinol + NAD(+) ubiquinol plays a role in antioxidant defense of cells and may prevent lipid peroxidation monodehydro- ascorbate reductase ascorbate non-enzymatic (by reduced ferredoxin) monodehydro- ascorbate ascorbate peroxidase ascorbate oxidase amine oxidase NADH ubiquinone reductase H2O2 2H2O O2 dehydroascorbate Dehydroascorbate has been shown to inhibit some kinases in HeLa cells and may therefore do the same in plants. photosynthesis O2- O2- HO2. superoxide Most superoxide is probably produced by photosystem I via the reduction of oxygen through the ferredoxin/ferredoxin NADP+ oxidoreductase system. superoxide dismutase H+ photorespiration fatty acid oxidation photosynthesis oxidative phosphorylation catalase H2O + O2 O2 peroxidase (includes E.C. 1.11.1.12) RH + H2O RH2 Fe+++ (Cu++) Fe++ (Cu+) Fenton reaction (non-enzymic) superoxide superoxide Vitamin B6 (pyridoxine) and its derivatives are efficient singlet oxygen quenchers. hydroperoxyl radical HO- + HO. + H+ H2O2 NADPH + O2 O2. CH3 OH CH3 geosmin FPP synthase FPP synthase OPP geranylgeranylated proteins gibberellins inactive HMGR kinase PP1 PP2A exogenous fatty acid OH COOH OH PO OH COOH OH HO OH COOH OH O OH COOH OH PO HO OH COOH O C COOH CH2 PO OH COOH O C COOH CH2 Last modified 24 December 2012 squalene synthase O2 O2 monooxygenase HMGR kinase is not AMP-activated in potato O-gluc CHO OCH3 phosphatidylinositol 4,5-bisphosphate (PtdIns(4,5)P2) phospholipase C (receptor-triggered activation) inositol-1,4,5- trisphosphate (IP3) diacylglycerol (DAG) diacylglycerol kinase phosphatidate cytidyltransferase (cdp.dg synthase) PI synthase CH2CHO NH indole-3-acetaldehyde 1-O-(indole-3-acetyl)-b-glucose CH2COOH NH indole-3-acetic acid (IAA/auxin) IAA-aspartic acid conjugate in Arabidopsis (affects disease development) tyrosine aminotransferase prephenate dehydratase phenylpyruvate COOH O CHO benzaldehyde benzaldehyde benzaldehyde dehydrogenase 2,5-dihydroxybenzoic acid (gentisic acid) COOH OH HO 2,3-dihydroxybenzoic acid COOH OH OH phosphatidylinositol (PtdIns) 1,3,4,5-IP4 Ins(1,4,5,6)-P4 Ins(1,2,3,4,5)P5 Ins(1,2,4,5,6)P5 1,3,4-IP3 3,4-IP2 3,6-IP2 1,2-IP2 2-IP 1-IP 3,4,6-IP3 1,2,6-IP3 1,2,3-IP3 inositol 3-phosphate inositol degradation by phytases inositol may exist in different isomers (myo-inositol, chiro-, scyllo-, neo-). GPI = glycosylphosphatidylinositol inositol 4-phosphate 1,4-IP2 OH HO O O esculetin O-gluc HO O O esculin H3CO HO O O scopoletin H3CO gluc-O O O scopolin gluc-O O O CH3O CH3O isofraxidin-7-glucoside peroxidase BAHD acyltransferases are involved with incorporation of ferulate into suberin suberization-asociated anionic peroxidase enhances deposition of lignin and suberin in cell walls peroxidase peroxidase CH2CHO OH CH3 phenylacetaldehyde p-cresol (phosphatidic acid) lysophosphatidic acid bisphosphatidic acid phosphatidic acid has been reported to bind to a number of proteins eg PEPC, HSP90, tubulin, PP2A regulatory subunit, GTP-binding like, SNF1-related kinase, and 14-3-3, in Arabidopsis diacylglycerol pyrophosphate (DGPP) cytidine diphosphate 1,2-diacylglycerol (opens Ca2+channels) adenine Pathogenesis-related proteins B-1,3-glucanases (PR-2) There are acidic (gluA) and basic (gluB) gene families Basic glucanases: 36 and 36.2 kDa chitinases (PR-3, -4, -8, -11) acidic (ChtA) and basic (ChtB) chitinases are induced in leaves by infection and elicitor treatment whereas a glycosylated chitinase (ChtC) is constitutively expressed in leaves. Basic endochitinases: 32.2, 32.6, 33.2, 34.3, 38 and 38.7 KDa ATP ADP ADP ATP ATP 1-deoxyxylulose-5-P (DOXP) pyruvate + glyceraldehyde-3-phosphate ADP + Pi + CO2 OPP Comments and additional information should be sent to: [email protected] Chart can be viewed on the internet at www.potatometabolicpathways.webs.com Metabolic pathways of the diseased potato PPi NADP + PPi Phosphoinositide cascade (poorly described in plants; though some information from Arabidopsis. Some of the detail shown here is from animal and yeast systems. The potato scheme may therefore differ slightly and some biosynthetic routes will be more strongly favoured than others). protein farnesylation protein farnesyltransferase (FTase) Isoprenylation is a post-translational modification of proteins involving covalent attachment of an isoprenyl moiety (either farnesyl or geranylgeranyl) to the cysteine residue at the C-terminus of proteins. Prenylated proteins can be further modified by palmitoylation, COOH-terminal proteolysis and methylation. Most prenylated proteins are associated with signal transduction cascades. GGTase ent-kaurene synthase ent-kaurene oxidase ent-kaurenoic acid oxidase copalyl diphosphate synthase phytoene synthase O2 Transcription of protein-coding genes in eukaryotes occurs through a co-ordinated group of general transcription factors (eg TFIIA, TFIIB, TFIID, etc). For example, TFIID is composed of TATA box-binding protein (TBP) and TBP-associated factors (TAFs). TFIID may have histone acetyltransferase activity. Cellular localization of histone deacetylases may be regulated by 14-3-3 proteins. NADH tyrosine ammonia -lyase (only occurs in monocots ?) O2 NADP+ NADPH mevalonic acid kinase mevalonic acid 5-phosphate kinase mevalonate 5-pyrophosphate decarboxylase isopentenyl pyrophosphate isomerase geranylgeranyl pyrophosphate synthase geranylgeranyl pyrophosphate synthase COOH OH OH HO O O umbelliferone Linolenic and linoleic acids are the two main substrates for lipoxygenase in plants. Potato has 9-LOX activity with linoleic acid but 5-LOX activity with arachidonic acid. Arachidonic acid is present in Phytophthora infestansbut is reported to be absent in higher plants. 3-kinase tyrosine laminarin, a B-1,3-glucooligosaccharide, induces the accumulation of N-p-coumaroyloctopamine and increases THT, PAL, 4CL and tyrosine decarboxylase activity (presumably through up-regulation of the genes) ? cycloartenol methyltransferase (sterol methyltransferase; SMT1) sterol methyltransferase; SMT2 24-methylene cycloartenol 24-methylene lophenol 24-ethylidene lophenol isofucosterol sitosterol OCH3 CH3 OH O O2 + NADPH NADP OCH3 CH2OH OH O acetovanillone a-hydroxyacetovanillone acetovanillone a-hydroxylase: a P450-dependent monooxygenase present in Solanum khasianum EIN3 EIL1-3 (nuclear) ADP-ribosylation factors (ARFs) are small GTP-binding proteins that function in the assembly of coated vesicles that transport proteins between intracellular organelles. Some lipid peroxidation products: 4-hydroxy-2-nonenal (HNE) 4-hydroxy-2-hexenal malondialdehyde (MDA) HNE originates from peroxidation of arachidonic acid and linoleic acids in eukaryotes. HNE reacts with thiols eg GSH, cysteine, and proteins containing thiol groups to form thioether adducts which undergo cyclization to form hemiacetals. HNE also reacts with other amino acids in proteins to form stable adducts. HNE can inhibit alternative oxidase. UDP-glucose UDP-glucose: solanidine glucosyltransferase (SGT2) p-coumaryl-CoA p-coumaryl-CoA decarboxylated S-adenosylmethionine S-adenosylmethionine decarboxylase (SAMDC) spermidine spermine Spermine and spermidine have been reported to activate nonspecific acid phosphatase (EC 3.1.3.2) by lowering the K(m) value. Binding of polyamines to 14-3-3 proteins may be involved in regulation of growth and devlopment. putrescine N-methylputrescine N-methylpyrrolinium N-methylaminobutanal delta1-pyrroline 1,3-diaminopropane 1-(3-aminopropyl)-pyrroline agmatine N-carbamoylputrescine arginine ornithine ornithine pyrroline-2- carboxylate proline spontaneous hydroxyproline alpha-keto-delta- aminovalerate arginine decarboxylase agmatine iminohydrolase (agmatine deiminase) N-carbamoylputrescine amidohydrolase ornithine decarboxylase arginase spermidine synthase spermine synthase w-feruloyloxypalmitic acid C OH OCH3 O O (CH2)15 COOH suberin involved in wound healing OH COOH O C COOH CH2 isochorismic acid OH Mg2+ anthraquinones phylloquinones isochorismate synthase Mg2+ In Arabidopsis isochorismate synthase gene ACS1 is transcriptionally regulated by AtWRKY28. ACC synthase and ACC oxidase activity may be controlled by kinases and phosphatases in mung bean (no experimental evidence yet for potato) C OH OCH3 O O (CH2)n CH3 CH2 n=14 : hexadecyl ferulate n=16 : octadecyl ferulate n=18 : eicosyl ferulate n=20 : docosyl ferulate n=22 : tetracosyl ferulate n=24 : hexacosyl ferulate n=26 : octacosyl ferulate Mevalonate pathway Enzyme activity and subcellular localization is often controlled through post-translational modification involving proteolysis, phosphorylation, prenylation, glycosylation, acylation, methylation, sulphation, hydroxylation and carboxylation. Some Eukaryotic cellular proteins have a covalently attached myristoyl group at the amino terminus - such proteins may be involved in controlling calcium- sensitive processes: (calcium-myristoyl switches). Myristoyl CoA:protein N-myristyltransferase is the enzyme involved in protein myristoylation. HMG-CoA synthase thiolase (acetyl-CoA acetyltransferase) pyruvate decarboxylase phosphoenolpyruvate carboxykinase rhamnogalacturonan O-acetyl-transferase NADPH NADP+ HMGR encoded by three genes. Hmg1is strongly induced by wounding leading to accumulation of glycoalkaloids, whereas hmg2and hmg3are enhanced by arachidonic acid and P. infestans. There is evidence that PAL can be phosphorylated and hence activity may be controlled, in part, by phosphorylation. In tobacco, basic PR proteins accumulate in the vacuole whilst acidic PR proteins accumulate extracellularly. P. infestansinduces accumulation of osmotin-like proteins in potato. These proteins may have a dual function in osmotic stress and disease resistance. A silencing element binding factor (SEBF) has been shown to bind to the promoter sequence of a number of PR proteins - this may be involved in down regulation of genes. Phosphorylated enzymes may, in specific cases, be more active or less active than the unphosphorylated enzyme. A variation on this theme is where an enzyme may be controlled by an inhibitor protein whose activity is controlled by phosphorylation. 3-dehydroquinate dehydratase NADPH oxidase glycosyltransferase catechin oxidase (from fungi and bacteria) glycosyltransferase 5-enolpyruvylshikimate 3-phosphate (EPSP) synthase Pectin methyltransferases are the main enzymes involved in the control of methylesterification of pectin. SAM synthetase After ATP, SAM is the major high energy intermediate in the cell and is the major methyl donor of a wide range of compounds including proteins, nucleic acids, sugars, pectin and chlorophyll. (in nahG transformed plants) hydroperoxide lyase (a cytochrome P450; CYP74B) IF arogenate dehydrogenase glutamine 2-oxoglutaric acid glutamic acid reduced ferredoxin oxidised ferredoxin glutamine NH4+ from PAL GOGAT = glutamine: 2-oxo-glutarate amidotransferase) homocysteine + adenosine homocysteine homocysteine cystathione threonine isoleucine cysteine cysteine plays an important role in the immune response of Arabidopsis O-acetylserine serine homoserine aspartate O-phosphohomoserine S-adenosyl-L homocysteine (SAHc) CH3 activated CH3 Methylation reactions eg for pectin methylation, norepinephrine to normetanephrine, and to COOH-terminal S-farnesylated cysteine of prenylated proteins (prenyl protein-specific methyltransferase; PPSEP) adenine inosine adenosine nucleosidase adenine phosphoribosyl- transferase methionine synthase adenosine deaminase adenosine kinase cystathione gamma-synthase O-acetylserine (thiol) lyase (OASTL) cystathione beta-lyase threonine synthase SAH hydrolase COOH O hydroperoxide cyclase hydroperoxide dehydratase allene oxide COOH O HO COOH O HO alpha-ketol gamma-ketol COOH COOH OOH cholesterol HO H CH3 CH3 CH3 CH3 CH3 HO H CH3 CH3 CH3 CH3 CH3 cholesteranol HO H CH3 CH3 CH3 HO CH3 HO H CH3 CH3 CH3 H2N CH3 HO H CH3 CH3 CH3 H2N CH3 HO HO H CH3 CH3 CH3 CH3 N CH3 NH H CH3 CH3 solasodine HO CH3 HO H CH3 CH3 CH3 CH3 HO HO H CH3 CH3 CH3 CH3 H2N O H CH3 CH3 CH3 N O NH CH3 HO soladulcidine H CH3 CH3 CH3 CH3 HO NH tomatidenol NH4+ HO H CH3 CH3 CH3 CH3 HO HO dormantinol HO H CH3 CH3 CH3 CH3 HO O dormantinone HO H CH3 CH3 CH3 CH3 solanidine HO H CH3 CH3 CH3 CH3 N verazine HO H CH3 CH3 CH3 CH3 N OH etioline Possible biosynthetic pathways from cholesterol and cholesteranol to aglycones. L-arginine has been reported to be the most likely N source in glycoalkaloid biosynthesis OCCH3 acetyldehydrorishitinol O OH OH rishitinol polyphenol oxidase (tyrosinase) dopa decarboxylase OH OH RO O chlorogenic acid O O RO O chlorogenic acid quinone O O RO O H H H P-X OH O RO O H P-X OH O RO O H X-P R = quinic acid P-X = protein X = NH2, OH, SH polyphenol oxidase H+ OH O-gluc arbutin vanillic acid glucoside (vanillate glucoside) COOH O-gluc p-hydroxybenzoic acid glucoside OH OCH3 O NH-CH-CH2-COOH feruloylaspartate COOH C N H O OH HO C N H O OH HO OCHCOO-gluc OH p-coumaroyl- D-glucose COO-gluc OH OH caffeoyl- D-glucose COO-gluc t-cinnamoyl- D-glucose UDPG:cinnamate glucosyl transferase O-gluc COOH OCH3 COOCH3 O methyl (+)-jasmonate COR O amino acid conjugates of (-)-jasmonic acid (R=leucine, isoleucine, valine) 11,12-epoxycyclolubimin Potato lectin is a hydroxyproline-rich glycoprotein (HRGP) which can bind oligomers of N-acetylglucosamine. Extensin and PAL mRNA levels as well as cell wall hydroxyproline increase in response to wounding and subsequent aerobic incubation but not under anaerobic conditions. NH2(CH2)4NH(CH2)3NH2 CH3-S-CH2-CH2-CH2-NH2 CH2 OH OH Ade O NH2(CH2)3NH(CH2)4NH(CH2)3NH2 H-γ-Glu-Cys-Gly-OH (g-Glu-Cys-Gly)2 H C N O OH HO OCHOH protein adducts (allene oxide synthase: A cytochrome P450 ; CYP74A) (allene oxide cyclase) 3-dehydroquinate synthase ornithine delta-pyrroline -5-carboxylate malonyl-ACC jasmonic acid-ACC malonyl transferase quinate dehydrogenase R OH OH OH R O O R cresolase catecholase complex brown polymers Reaction scheme of tyrosinase Sulfhydryl (SH or thiol) compounds such as cysteine, N-acetyl-L-cysteine, and reduced glutathione, as well as ascorbic and citric acids, are good inhibitors of PPO which catalyzes enzymic browning. ERFs PK12 ? ERN ERFs are a family of ethylene-responsive transcription factors. (Previously called ethylene-responsive element-binding proteins or ERBPs). In Arabidopsis, F box proteins EBF1 and EBF2 interact with EIN3/EIL transcription factors. EIN3 is degraded through a ubiquitin/proteasome pathway mediated by EBF1 and EBF2. L-tyrosine tyrosine decarboxylase chorismate synthase pyruvate lyase? indole-3-glycerol- phosphate synthase tryptophan synthase a tryptophan synthase b inositol-1,4,5- trisphosphate 5-phosphatase Ins PolyP 2-kinase phosphatidylinositol -3-phosphatase inositol-3,4-bisphosphate 4-phosphatase inositol-1,4-bisphosphate 1-phosphatase InsP6kinase InsP7kinase A number of derivatives of jasmonic acid have been detected in other plants including amino acid conjugates (JA-Ile, JA-Val, JA-Leu JA-Phe; possibly synthesised via a JA-amino synthetase), JA conjugated to the ethylene precursor ACC, and hydroxylated forms. F box proteins are involved in JA-Ile perception in Arabidopsis. In Arabidopsis JA-Ile signals through the COI1-JAZ coreceptor complex and AtCYP94B3 is involved in JA-Ile turnover providing negative feedback of JA-Ile levels. 12-hydroxy-JA-Ile has been identified in Arabidopsis. H CH3 CH3 CH3 CH3 N N gluc gluc xyl dehydrodemissine gal H CH3 CH3 CH3 CH3 N N gluc gluc gluc dehydrocommersonine gal The relative amounts of glycoalkaloids and their aglycones vary between different Solanumspecies. O O OH COOH HO HO COOH HOOC traumatic acid (implicated in wound signalling) H CH3 CH3 CH3 N O tomatidine HO CH3 NH H CH3 CH3 CH3 CH3 N N gal gluc gluc xyl demissine O H CH3 CH3 CH3 CH3 N N gal gluc gluc gluc commersonine A feruloytyramine trimer has been isolated from scab lesions. O H CH3 CH3 CH3 N O gal gluc gluc tomatine NH CH3 xyl O H CH3 CH3 CH3 N O gal rham gluc solasonine NH CH3 O OH elicitor-active oligogalacturonides plant pectin AtSNI1 is a negative regulator of SAR and HR in Arabidopsis. AtBRCA2 is downstream of AtNPR1 and is a major regulator of defense-related gene transcription. The BRCA2-RAD51 complex is involved with HR and in plant immune responses. WRKY transcription factor pectic enzymes from plant pathogens phosphorylation of an approx 34 kDa protein (pp34) resistance responses (includes basic chitinase, phytoalexin and protease inhibitor accumulation) Why1 Pti4 SEBF PR10a COOH COOH NH2 NH2 OH O COOH COOH HOOC COOH NH2 H2N NH2 H2N OH O O OH isodityrosine di-isodityrosine protein kinase C triacylglycerol (triglyceride) Ca2+ mobilisation C N H O OH HO OH 4-coumaroyloctopamine C N H O OH OH HO OH 4-coumaroylnoradrenaline C N H O OH OH cinnamomyloctopamine + cinnamic acid C N H O OH + cinnamic acid cinnamomyltyramine receptor receptor resistance responses including StLTPa7, PR proteins, erg-1, and StrbohB (an NADPH oxidase) resistance responses including PR proteins (reported to be different from those induced by salicylic acid) receptor Many induced responses including induction of aspartic proteinase inhibitor epoxide hydrolase, threonine deaminase, leucine aminopeptidase, and StLTPa7 Increases lipoxygenase activity. Does not induce sesquiterpene phytoalexin accumulation nor PR protein P4. Induces putrescine N-methyltransferase in tobacco, Acetyl-CoA carboxylase in bean, and multicystatin in tomato. Suppresses StCPK2 gene transcription. OH HO H CH3 CH3 CH3 CH3 hydroxy-solanidine OOCH3 HO H CH3 CH3 CH3 CH3 acetyl-solanidine (in S. chacoense) acetylase hydroxylase leptinine I leptinine II leptine I leptine II UDP-galactose: solanidine galactosyltransferase (SGT1) UDP-galactose Extracellular signal receptor MAP kinase kinase kinase (MAPKKK) MAP kinase kinase (MAPKK or MEK) MAP kinase (MAPK or ERK - extracellular signal-regulated kinase) MAP kinase phosphatases involved in dephosphorylation of MAPKs. Act by negative feedback regulation of MAPK activity. Responses NADPH oxidase gene S-nitrosylation of NADPH oxidase associated with cell death in plant immunity in Arabidopsis ROS production Programmed cell death also involves reorganisation of the plant cytoskeleton involving microtubules and microfilaments. StCDPK5 directly involved with regulating the oxidative burst via phosphorylation of the NADPH oxidase StRBOHB NO Alternaric acid (from Alternaria solani) stimulates in vitro phosphorylation of His-tagged RiCDPK1 from potato cv Rishiri) NO associated (NOA gene) HR ? P. infestanshyphal wall components, salicylic acid, arachidonic acid. activation of protein kinase p51-PK phosphorylation and activation of nuclear and cytoplasmic elements stigmasterol 6-deoxoteasterone 6-deoxotyphasterol 6-deoxocastasterone castasterone brassinolide campesterol H CH3 CH3 CH3 N O gal rham gluc alpha-solamarine NH CH3 O H CH3 CH3 CH3 N O gluc rham rham beta-solamarine NH CH3 O pulcherosine (in tomato) PtdIns(3,4,5)P3 PI3K 3-phosphatase 4-phosphatase phosphatidylinositol 4-phosphate (PtdIns(4)P) PIP5K (PtdIns-4-phosphate 5-kinase) (inositol 1,4- bisphosphate) IP35- phosphatase Ca2+regulation HQT glutathione S-transferase COOH O dinor-oxo-phytodienoic acid (dnOPDA) (increases in wounded tissues) 7,10,13-hexadecatrienoic acid (16:3) wound signalling ? Ubiquitin may serve as a marker for targeting proteins for their subsequent degradation. Ubiquitin may also attach to stable proteins, eg some cell surface receptors, where ubiquitination in response to ligand binding acts as an internalisation signal. Genes for ubiquitin carrier protein and ubiquitin-ribosomal fusion protein have been reported to be up-regulated in response to infection. arginine citrulline sesquiterpene phytoalexin induction eg rishitin lipid peroxidation, DNA damage NADPH NADP+ NO. NO2- NO+ nitrosated proteins (nitrosylation) R-NO NO- ONOO- RCH2NH2 + O2+ H20 RCHO + NH3+ H2O2 ONOOH H+ NO synthase ? nitrate reductase? NAD(P)H-dependent nitrate reductase or nitrite reductase peroxynitrite anion peroxynitrous acid 1,3,-IP2 1-IP phytate 1,3,4,6-IP4 1,2,5,6-IP4 diphosphoinositol tetrakisphosphate (5-PP-Ins(1,3,4,6)P4) 5,6-bis-PP -Ins(1,2,3,4)P4 1,2,3,6-IP4 1,3,4,5,6-IP5 1,2,3,5,6-IP5 diphosphoinositol pentakisphosphate (5-PP-Ins(1,2,3,4,6)P5) IP6 3,4,5,6-IP4 IP3receptor IP21-phosphatase IP36-kinase IP4 5-kinase 4-phosphatase PtdIns- 4 kinase CDP-diacylglycerol- inositol 3-phosphatidyltransferase (phosphatidylinositol synthase) diacylglycerol-3-P OH OH catechol asparagine synthetase glutamine + aspartate asparagine + glutamate anthranilate 1,2 dioxygenase dehydroshikimic acid dehydratase ? protocatechuic acid amine oxidase indole-3-pyruvic acid decarboxylase indole-3-acetaldehyde oxidase COO-gluc OH glucosyl salicylate (salicyloyl-glucose ester) salicylic acid carboxyl glucosyltransferase ? ? OH methyl salicylate methyl salicylate is an SAR signal in potato. salicylic acid methyl- transferase COOCH3 SAM-dependent methylase PI3K PtdIns(3,4)P2 PtdIns(3,4)P2 regulation of specific protein kinases ? THT stimulated by Mg2+ or Ca2+ 4,5-PIP2 also regulates actin regulatory proteins, activation of phospholipase D, an ADP-ribosylation factor, and proteins containing the pleckstrin homology domain (involved in signal transduction) in animals. regulation of specific protein kinases ? rearrangement of actin cytoskeleton (in animal cells) PtdIns(3)P PIP4K PtdIns(3,5)P2 PIP5K PIP5K inositol (poly)phosphate 5-phosphatase (SHIP) oxidised glutathione (GSSG) phospholipid hydroperoxide glutathione peroxidase (PHGPX; E.C. 1.11.1.9) L-OOH L-OH may conjugate with HNE Glutathione is said to be a scavenger of active oxygen species. Glutathione can conjugate with electrophiles such as Dopaquinone. oxidative phosphorylation inactivation of protein phosphatase palmitoyl-CoA + serine 3-ketosphinganine sphinganine 1-phosphate serine palmitoytransferase hexadecanal 3-ketosphinganine reductase (sphingosine is a potent inhibitor of protein kinase C in animals) sphinganine 1-phosphate lyase sphinganine 1-phosphate phosphatase glycerolipids COOH COOH OOH COOH O 13-lipoxygenase O2 hydroperoxide dehydratase (allene oxide synthase) 13(S)-hydroperoxy-9(Z),11(E)- octadecadienoic acid (13(S)-HPOD or 13(S)-HPODE) COOH O 12-oxo-phytodienoic acid COOH O 12-oxo-phytodienoic acid reductase COOH O 3-oxo-2-(2'-pentenyl)cyclopentaneoctanoic acid (OPC-8:0) NADPH + H+ NADP+ beta-oxidation 3-oxo-2-(2'-pentenyl)cyclopentanehexanoic acid (OPC-6:0) COOH O COOH O 3-oxo-2-(2'-pentenyl)-cyclopentanebutanoic acid (OPC-4:0) epi-jasmonic acid ((-)-7-epi-jasmonic acid) beta-oxidation beta-oxidation jasmonic acid carboxyl methyltransferase hydroperoxide cyclase (allene oxide cyclase) COOH O COOH O 12-oxo-phytodienoic acid reductase NADPH + H+ NADP+ 12-oxo-phytodienoic acid reductase NADPH + H+ NADP+ COOH O COOH O 3-oxo-2-(2'-pentyl)cyclopentaneoctanoic acid (DH-OPC-8:0) b-oxidation beta-oxidation COOH O COOH O b-oxidation beta-oxidation COOH O COOH O b-oxidation beta-oxidation COOH O COOH O (+)-7-epi-dihydrojasmonic acid (-)-7-epi-dihydrojasmonic acid COOH O (-)-9,10-dihydrojasmonic acid 15,16-dihydro-12-oxo-phytoenoic acid (DH-12-oxo-PDA) 3-oxo-2-(2'-pentyl)cyclopentanehexanoic acid (DH-OPC-6:0) 3-oxo-2-(2'-pentyl)cyclopentanebutanoic acid (DH-OPC-4:0) 3-oxo-2-(2'-pentenyl)cyclopentaneoctanoic acid (OPC-8:0) 3-oxo-2-(2'-pentenyl)cyclopentanehexanoic acid (OPC-6:0) 3-oxo-2-(2'-pentenyl)-cyclopentanebutanoic acid (OPC-4:0) 3-oxo-2-(2'-pentyl)cyclopentanehexanoic acid (DH-OPC-6:0) 3-oxo-2-(2'-pentyl)cyclopentanebutanoic acid (DH-OPC-4:0) Oxylipin pathway 3-oxo-2-(2'-pentyl)cyclopentaneoctanoic acid (DH-OPC-8:0) linoleic acid (C18:2) Ceramide signalling 13-KOD 12,13(S)-epoxy-9(Z),11-octadecadienoic acid (13(S)EOD) 12,13(S)-epoxy-9(Z),11,15(Z)-octadecatrienoic acid (13(S)EOT) (12-oxo-10,15(Z)-phytodienoic acid) 12-oxo-phytodienoic acid (12-oxo-10,15(Z)-phytodienoic acid) ceramide kinase (acylsphingosine kinase) ceramidase In plants PtdIns(4)P is 10-20 fold higher than PtdIns(4,5)P2 (in animals the ratio is 1:1). COOH O O OOH lipoxygenase O2 O OH 9-hydroxy-traumatin (4-hydroxy-2(Z)-dodecenal) 12-oxo-9(Z)-dodecenoic acid (9(Z)-traumatin) peroxygenase hydroperoxide lyase hydroperoxide lyase hexanal 3(Z)-hexenal 3(E)-hexenal O O O2 4-hydroxy-2(E)-hexenal lipoxygenase peroxygenase peroxygenase O OOH O OH (steps for traumatin shown in soybean and alfalfa) COOH O (13-keto-9(Z),11(E)-octadecadienoic acid) COOH O HO g -ketol O COOH HO a -ketol OH OH NH2 sphinganine (dihydrosphingosine) OH OH NH2 OH phytosphingosine sphingosine O OH NH2 cerebroside is the most abundant class of sphingolipid in plants, consisting of 8-unsaturated sphingoid bases, 2-hydroxyfatty acids (potato= 16:0, 20:0, 22:0, 23:0, 24:0, 25:0, and 26:0) and glucose. dihydroceramide In Arabidopsis several WRKY proteins are SUMO1 targets, and each of them can be phosphorylated by MAPK kinases. ceramide glucosylceramide ceramide can stimulate PP2A and MAP kinase ceramide 1-phosphate sphingosineacetyl transferase phytoceramide acylsphingosine deacylase inositol-phosphorylceramide(IPC) mannose-inositol-P-ceramide (MIPC) mannose-(inositol-P)2-ceramide (M(IP)2C) M(IP)2C synthase phosphatidylinositol phosphatidylinositol IPC synthase OH OH NH2 OH OH O COOH HO OH NH COOH NH2 HO OH COOH NH2 S cysteinyldopa leucodopachrome + cysteine (COOH) HO OH NH eumelanin polymerization (COOH) COOH NH2 HO N S benzothiazine derivative COOH NH2 HO (COOH) N S phaeomelanin polymerization O2 NADPH + H+ NADP+ ceramide synthase (sphinganine acyltransferase) N-acyl sphinganine dehydrogenase sphingosine kinase sphingosine- 1-phosphate phosphatase (SPPase) glutathione synthetase γ-glutamylcysteine synthetase γ-glutamylcysteine sphingolipids unsaturated analogues unsaturated analogues The unsaturated analogues 4E and 8E of sphinganine are the most abundant cerebroside base. Ceramides are thought to be involved in apoptosis (programmed cell death) MAP kinases are downstream of these long chain bases in PCD. Different LOX isoforms are encoded in complex multigene families. Three LOX gene families occur in potato:- 9-LOX expressed mainly in tubers and roots 13-LOX (2 families) expressed in leaves in response to wounding. COOH O COOH O 9-lipoxygenase 9-lipoxygenase possible modulation of DAG kinase by arachidonic acid in mammals annexin (from pepper) inhibits phospholipase A2 phosphatidylcholine thaumatin-like (PR-5) proteinase inhibitors (PR-6) proteinase (PR-7) peroxidases (PR-9) ribonuclease-like (PR-10) plant defensins (PR-12) thionins (PR-13) lipid transfer proteins (PR-14) phospholipase A2 phospholipase D phosphatidate kinase DGPP phosphatase phosphatidic acid phosphatase copalyl pyrophosphate ent-kaurene AMP OOH COOH OH O COOH OH O COOH OH OH OH COOH OH OH OH COOH 9(S)-hydroperoxy-10(E),12(Z),15(Z)-octadecatrienoic acid (9(S)-HPOT or 9(S)-HPOTE) 10(S),11(S)-epoxy-9(S)-hydroxy -12(Z),15(Z)-octadecadienoic acid 9(S),10(S),11(R)-trihydroxy -12(Z),15(Z)-octadecadienoic acid 12(R),13(S)-epoxy-9(S)-hydroxy -10(E),15(Z)-octadecadienoic acid 9(S),12(S),13(S)-trihydroxy -10(E),15(Z)-octadecadienoic acid epoxy alcohol synthase epoxy alcohol synthase epoxide hydrolase epoxide hydrolase spontaneous hydrolysis Sesquiterpenes H H H O sesquisabinene alpha-cadinol alpha-zingiberene alpha-humulene beta-sesquiphellandrene (+)-germacrene germacrenes 2-(1',2'-dihydroxy-1'- methylethyl)-6,10-dimethylspiro [4,5]dec-6,9-dien-8-one bicyclogermacrene (-)-germacrene (germacrene D) HO ledol caryophyllene oxide cedrol H H beta-caryophyllene trans-beta-bergamotene trans-apha-bergamotene H H germacrene D-4-ol OH A transcriptional coadaptor or coactivator, the multiprotein bridging factor 1 (MBF1), is up-regulated by fungal infection and wounding. Some pathogen response genes are regulated by WRKY transcription factors. inositol-1 (or 4) -phosphatase methyl jasmonate induction gene up-regulated by MeJ in bean COOH arachidonic acid (20:4) COOH eicosapentaenoic acid from P. infestans 5-lipoxygenase (inhibited by alpha-tocopherol in vitro) peroxygenase protein kinase C homolog 5(S)-hydroperoxy-6E,8Z,11Z,14Z-eicosatetraen-1-oic acid (5-S-HPETE) 5(S)-hydroxy-6E,8Z,11Z,14Z-eicosatetraen-1-oic acid (5-S-HETE) from P. infestans Induced responses including necrosis, LOX, sesquiterpene phytoalexin induction, peroxidase, NADPH oxidase, and increased PAL activity. Also induces systemic resistance. SAR not induced against P. infestansin nahG plants. Induces local but not systemic induction of a PR1-like protein. Increases GAPDH (glyceraldehyde-3-phosphate dehydrogenase), alcohol dehydrogenase (ADH) and ferritin gene transcripts. [GAPDH is involved in glycolysis]. Induces PR proteins P4 and PR-10a but not wound-inducible proteinase inhibitor PINII. Induces cystatin in tomato. 5,6-leukotriene A4 ? cyclooxygenase (detected in tobacco but not yet in potato. There is now some doubt as to whether this is a true cyclooxygenase or is an alpha-dioxygenase) thromboxanes prostaglandins Products of cyclooxygenase have not yet been isolated from potato. diHETE products ? StPRp27 reported to contribute to race-nonspecific resistance to P. infestans. Cu co-factor Post-translational covalent linkage of polyamines to proteins is catalysed by transglutaminases. ERF1 interacts with the GCC box of ethylene response genes OH CH2OH OH O CH3O OH OH O CH3O OCH3 'high energy' diphosphorylated inositol polyphosphates ? COOH OH Phosphatidylinositol transfer protein (PI-TP) and the non-specific transfer protein (nsL-TP) belong to a large and diverse family of lipid-binding proteins. 135 nsLtps (non-specific lipid transfer proteins) have been identified in the Solanaceae. The reduced form of ubiquinone, ubiquinol, functions as an antioxidant, protecting membrane phospholipids from peroxidation, and mitochondrial DNA and membrane proteins from free-radical-induced oxidative damage. Abbreviations C3H: coumarate-3-hydroxylase C4H: cinnamate-4-hydroxylase 4CL: hydroxycinnamate:CoA ligase (4-coumaroyl:CoA ligase) CAD: cinnamyl alcohol reductase CCoA3H: coumaroyl-CoA-3-hydroxylase CCoAOMT: caffeoyl-CoA 3-O-methyltransferase CCR: cinnamyl:CoA reductase COMT: caffeic acid 3-O-methyltransferase DAHP: 3-deoxy-D-arabino-heptulosonate-7-phosphate DMAPP: dimethylallyl pyrophosphate F5H: ferululate-5-hydroxylase FHT: fatty w-hydroxy acid /fatty alcohol hydroxycinnamoyl transferase FPP: farnesyl pyrophosphate GGTase: protein geranylgeranyltransferase GTase: UDP-glucose:salicylic acid 3-O-glucosyltransferase HHT: hydroxycinnamomyl-CoA:w-hydroxypalmitic acid- -O-hydroxycinnamomyltransferase HMGR: 3-hydroxy-3-methylglutaryl-CoA reductase HQT: hydroxycinnamoyl-CoA quinate transferase PAL: phenylalanine ammonia-lyase PEP: phosphoenolpyruvate THT: tyraminehydroxycinnamomyl transferase PPO malondialdehyde O O PLASTID CYTOSOL Elicitor-induced activation of the potato pathogenesis-related gene PR-10a requires a 30-bp promoter sequence termed the ERE (elicitor response element) that is bound by the nuclear factor PBF-2 (PR-10a binding factor 2) DOXP pathway (in plants in general) pseudotropine forming tropinone reductase tropine forming tropinone reductase tropinone tropine phenyl- lactic acid (S)-hyoscyamine (S)-scopolamine pseudotropine N OH OH OH calystegine A3 N OH HO OH OH calystegine B1 N OH OH OH OH calystegine B2 N OH OH OH OH calystegine B3 N OH OH OH OH calystegine B4 Polyhydroxylated tropane alkaloids (calystegines) are potent inhibitors of glycosidases and found in potato but no direct evidence that they are associated with resistance. gamma-aminobutyric acid (GABA) beta-alanine Some oxidised polyamines have been reported to possess antimicrobial activity - but not yet proven in potatoes. 1,5-diazabicylononane H2O2 H2O2 +NH3 H2O2 O2 + H2O O2 + H2O O2 + H2O chorismate mutase is activated by tryptophan high levels of phenylalanine and tyrosine inhibit chorismate mutase (feedback mechanism) OH OH NH C R O OH OH NH2 4,8-sphingadienine OH OH OH NH2 4-hydroxy-8-sphingenine CH2CHCOOH O NH Cu2+ Cu2+ p-coumaroyl tyramine feruloyl tyramine COOH COO-gluc benzoic acid benzoyl-glucose benzoyl-CoA Two pathways leading to benzoic acid have been proposed in plants though the "non-oxidative" route via benzaldehyde now seems to be unlikely or of minor importance. B-oxidation route "non-oxidative" route O 3(Z)-hexenal O COOH 12-oxo-10(E)-dodecenoic acid O divinyl ether synthase O COOH alpha-ketol) (a cyclopentenone) Both 9(R),13(R) and 9(S),13(S) enantiomers are produced. OH O COOH Acetyl-CoA COOH OH COOH OH O 13-OH-9(Z),11(E),15(Z)-octadecatrienoic acid (13-HOT) 15,16-epoxy-13-OH-9(Z),11(E)-octadecadienoic acid peroxygenase hydroperoxide reductase COOH O 13-keto-9(Z),11(E),15(Z)-octadecatrienoic acid lipoxygenase b-oxidation O COOH allene oxide synthase glutathione peroxidase (from P. infestans) COOH O ? non-enzymic cyclization non-enzymic cyclization 9-hydroxy-10-oxo-12(Z)-octadecenoic acid a macrolactone a macrolactone ? ? O C5H11 O O O C5H11 O O (an 10-oxo-11-phytoenoic acid (2-oxo-5-pentyl-3-cyclopentene-1-octanoic acid) OOH COOH O 3(E)-hexen-1-ol O 3(Z)-nonenal COOH O 9-oxononanoic acid O 3(Z),6(Z)-nonadienal 3(Z)-nonen-1-ol 4-hydroxy-2(E)-nonenal (HNE) 2(E)-nonenal 2(E)-nonen-1-ol 2(E),6(Z)-nonadienal 2(E),6(Z)-nonadien-1-ol 3(Z),6(Z)-nonadien-1-ol OH O COOH OH O COOH OH OH OH COOH OH OH OH COOH In plants, calcium-dependent protein kinases (CDPK's), are modulated by changes in Ca2+ concentration. Protein phosphorylation ADP Dephosphorylated enzyme Phosphorylated enzyme ATP Pi H2O protein kinase phosphatase Enzyme control by phosphorylation and/or 14-3-3 proteins 14-3-3 protein may bind to phosphorylated enzyme 14-3-3 Calmodulin-binding protein binds to calmodulin which is involved in calcium regulation. Bakker et al. (2011) identified 280 TIR-NB-LRR and 448 CC-NB-LRR sequences in S. tuberosum ssp. tuberosum. O-linked N-acetylglucosamine (O-GlcNac) is present in all eukaryotes and may be involved in posttranslational modification of some proteins protein protein protein protein O-GlcNac PO4 O-GlcNAcase serine/threonine kinase serine/threonine phosphatase O-GlcNac transferase possible regulatory mechanism 4-hydroperoxy-2(Z)-dodecenal 9-hydroxy-13-oxo-10(E)-octadecenoic acid 12-oxo,13-hydroxy-9(Z)-octadecenoic acid autoxidation HO COOH epoxide hydrolase epoxide hydrolase non-specific lipid transfer protein (PR-14) may be involved in biosynthesis of epicuticular wax or cutin. 9,10-epoxystearic acid (9R,10S ; 9S,10R) 18-hydroxy-9,10-epoxystearic acid 9,10-dihydroxystearic acid 9,10,18-trihydroxystearic acid monomers of cutin oleic acid (C18:1) azelaic acid (reported to increase salicylic acid in Arabidopsis) stearic acid (C18:0) Cyt.-P450 Cyt.-P450 epoxygenase -desaturase COOH O COOH OH O COOH HO HO COOH HO HO OH 10-hydroxy-hexadecan-1,16-dioic acid 9-hydroxy-hexadecan-1,16-dioic acid OH COOH HOOC OH COOH HOOC 10-hydroxy-16-oxo-hexadecanoic acid 9-hydroxy-16-oxo-hexadecanoic acid OH CHO HOOC OH CHO HOOC 9,16-dihydroxypalmitic acid 10,16-dihydroxypalmitic acid OH OH HOOC OH OH HOOC protein methionine S-oxide + reduced thioredoxin protein methionine + oxidized thioredoxin peptide methionine sulfoxide reductase = chacotriose = solatriose gluc rham rham gal rham Type-2 nuclear histone deacetylases (HDACs) act as negative regulators of elicitor-induced cell death in tobacco suggesting that HR is controlled by post-translational modifications including (de)acetylation of nuclear proteins (Bourque et al., 2011). gluc R . = non oxygen free radical RO . = alcoxyl radical ROO . = peroxyl radical OH . = hydroxyl radical ONOO- = peroxynitrite GS-NO = nitrosoglutathione O-acetylation of plant cell wall polysaccharides (e.g. pectin) OH HO OH COOH OH HO OH COOH HO HO OH COOH Lipid peroxidation Lipoxygenase e- Lipoxygenase - Fe+++ Lipoxygenase - Fe++ - L. Lipoxygenase - Fe++ - LOO. O2 LOOH H+ LH H+ LH = fatty acids LOOH = hydroperoxy fatty acids (active enzyme) Lipoxygenase (LOX) catalyses the hydroperoxidation of unsaturated fatty acids which have a cis-1,4- pentadiene moiety within their structure. R R OOH H H R R H H O. R R H H O R R H H OH R R H OH . R R OH . R R OH OO. hydroxyalkenals O2 LH L. peroxide radical cutin H O OH N PROTEIN lysyl residue NH3 PROTEIN lysyl residue + HNE N OH O PROTEIN Michael adducts OH O linolenic acid (C18:3) 2(R)-hydroperoxy-9(Z),12(Z),15(Z)- octadecatrienoic acid 2(R)-hydroxy-9(Z),12(Z),15(Z)- octadecatrienoic acid 8(Z),11(Z),14(Z)- heptadecatrienal 8(Z),11(Z),14(Z)- heptadecatrienoic acid COOH linolenic acid (C18:3) dinor isoprostane E1 type II PPD1 type II dinor isoprostane E1 type I PPD1 type I F1-phytoprostanes COOH OOH O O COOH OOH O O COOH OH O HO COOH OH O HO COOH OH O HO COOH OH HO O COOH OH HO HO COOH OH HO HO free radical catalysed autoxidation to form phytoprostanes OH HO HO COOH OH OH HO COOH Fe(II) Fe(II) Fe(III) Fe(III) sphingosine sphingosine transfer protein accelerates the transfer of sphingosine between membranes. OH OH NH2 COOH OH linoleyl alcohol 9- and 13-hydroperoxyoctadecadien-1-ols In the presence of a free radical scavenger the following are the major products formed:- 9(S)-hydroperoxy-10E,12Z-octadecadien-1-ol 13(S)-hydroxy-9Z,11E-octadecadien-1-ol lipoxygenase 1-monolinoleoyl-rac-glycerol 1-[9-hydroxy-10E,12Z-octadecadienoyl]-rac-glycerol (9-(E,Z)HODE-GE) O O OH OH O O OH OH OH other products of lipoxygenase degradation of 1-monolinoleoyl-rac-glycerol include :- 1-[13-hydroxy-9Z,11E-octadecadienoyl]-rac-glycerol (13-(Z,E)-HODE-GE) 1-[13-hydroxy-9E,11E-octadecadienoyl]-rac-glycerol (13-(E,E)HODE-GE) 1-[9-hydroxy-10E,12E-octadecadienoyl]-rac-glycerol (9-(E,E)HODE-GE) lipoxygenase COOH O O-beta-gluc tuberonic acid-12-O-beta-D-glucoside (TAG) (O- -D-glucopyranosyltuberonic acid) β COOCH3 O O-beta-gluc methyl tuberonate glucoside (MeTAG) O-beta-gluc COOH O 11-hydroxyjasmonic acid glucoside OH COOH O epi-4'-hydroxyjasmonic acid (epi-4'-OHJA) threonine dehydratase (threonine deaminase) L-threonine 2-oxobutanoate gene up-regulated by MeJA NH3 H2O NH2 OH Snakin-1 is an antimicrobial peptide. Cystatin (a cysteine protease inhibitor) is induced in tomato by arachidonic acid and gamma linolenic acid. A harpin binding protein (HrBP1) has been identified in potato A number of authors have shown 2-oxoglutarate-dependent dioxygenase (2-ODD) genes to be up-regulated in response to infection. But, as 2-ODD exists as a family of genes it is not clear which enzyme activity these proteins possess. isopropylmalate dehydrogenase 3-methyl- 2-oxobutanoate dehydrogenase isovaleryl-CoA dehydrogenase 3-methyl- glutaconyl-CoA hydratase branched chain amino acid transaminase 2-oxo-isocaproate leucine isovalery-CoA methyl crotonyl-CoA methyl-crotonyl-CoA carboxylase gene up- regulated in Arabidopsis by MeJ 3-methyl- glutaconyl-CoA 3-isopropylmalate H2C HC H2C O O R1 R2 O X O C C P O O- phospholipase D phospholipase C phospholipase A1 phospholipase A2 O O NH2 OH OH HO NH2 OH HO OCH3 ascorbate dehydroascorbate SAM-dependent methylase O OH OH O OH HO OH salicylic acid pyruvate WRKY? pathway proposed in Arabidopsis but not yet proven in potato COOH OH SO4 2- SO4 2- S2- CHLOROPLAST CYTOSOL COOH COOH OOH COOH OH CHO COOH 9 -desaturase 12 -desaturase 15 Membrane lipids acyl hydrolase lipase O N O H CH3 CH3 CH3 CH3 gal rham gluc alpha-solanine N beta-chaconine beta-solanine O H CH3 CH3 CH3 CH3 gluc rham rham alpha-chaconine N N N O N N CHO OH OH C3' hydroxylase CYP98A3 feruloyl-3'-methoxyoctopamine H C N O OH HO OCHOCHOH NADH NAD Hsp70-like chaperone dehydratase glucose-6-phosphate isomerase phosphomannose isomerase glucosamine-6- phosphate synthase phosphomannomutase GDP-mannose pyrophosphorylase galactose dehydrogenase oxidase/ dehydrogenase galactono-1,4 lactone dehydrogenase GDP-mannose 3",5"-epimerase epimerase/ reductase GDP-fucose NADPH GDP-gulose gulose stress gulono- 1,4-lactone GDP-galactose phosphate GMP GDP-4-keto,6-deoxy-mannose GDP-mannose mannose-1-phosphate mannose-6-phosphate ascorbic acid fructose-6-phosphate glucosamine-6-phosphate fructose-1,6-bisphosphate NADP NADPH NADPH NADP(+) ATP chloroplast G6PDH is subject to phosphorylation differential transcription of G6PDH genes in parsley by fungal elicitors Pi T6P is considered as a key regulatory molecule glucose-6-phosphate trehalose-6-phosphate (T6P) trehalose In Arabidopsis bZIP11 is involved with carbohydrate metabolism including T6P and SnRK1 UDP-glucose trehalose-6-phosphate synthase gene upregulated by P. infestans glucono-1,5-lactone 6-phosphate (6-phosphogluconolactone) 6-phosphogluconate ribulose-5-phosphate glyceraldehyde- 3-phosphate dihydroxyacetone phosphate glycerol-3- phosphate (G3P) glycerol-3-phosphate interacts with the lipid transfer protein DIR1 to induce SAR in plants. phosphatidic acid diacylglycerol acyl-G3P (lyso-phosphatidic acid) glyceraldehyde- 3-phosphate 1,3-bisphosphoglycerate 3-phosphoglycerate 2-phosphoglycerate phosphoenolpyruvate oxaloacetate Glyoxylate cycle erythrose-4-phosphate plastid enzymes of G6PDH are redox regulated phosphoglucomutase trehalose-6- phosphate synthase trehalose-6- phosphate phosphatase triosephosphate isomerase phosphofructokinase fructose 1,6- bisphosphate aldolase glycerol-3- phosphate dehydrogenase glyceraldehyde-3-phosphate dehydrogenase phosphoglycerate kinase phosphoglycerate mutase pyruvate kinase enolase glucose-6-phosphate dehydrogenase (G6PDH) 6-phosphogluconolactonase 6-phosphogluconate dehydrogenase glucose-1-phosphate glucose-1-phosphate + ATP diphosphate + ADP-glucose galactono- 1,4-lactone galactose Pathway suggested from work on Arabidopsis. No confirmation yet that this pathway is correct for potato ferricytochrome c ferrocytochrome c p-hydroxyphenyl pyruvate dioxygenase homogentisate phytyltransferase p-hydroxy- phenylpyruvic acid homogentisate tocopherol 2-methyl-6-phytyl- benzoquinol glucose-6-phosphate myo-inositol-1-phosphate synthase (MIPS) (pathway from tobacco) ABC transporter acid phosphatase like actin depolymerizing factor 6 alcohol:NADP+ oxidoreductase allantoinase ankyrin-like allene oxide synthase (AOS3) like amino acid transporter aspartic proteinase 2 ATP/ADP transporter auxin induced (e.g. GH3) biotic cell death associated bromo-adjacent homology (BAH) domain CAAX prenyl protease calcineurin calcium binding protein calmodulin calnexin catechol oxidase Cf-like chalcone reductase citrate binding protein copper amine oxidase cyclophilin cysteine protease (cathepsin B like) cysteine protease inhibitor cytochrome f cytokinin oxidase decarboxylate carrier protein dehydration responsive element-binding protein DnaJ like DND1 like DOF transcription factor enhanced disease susceptibility (EDS1) like enhanced disease susceptibility (EDS5) like elongation factor 1-alpha Erwinia-induced protein (ei1) Erwinia-induced protein (ei2) esterase exocyst subunit exostosin like extensin F box family ferredoxin ferritin fibrillin/CDSP34 protein (plastid lipid-associated) formin homology 2 domain-containing protein glycogenin glucosyltrasferase like Hcr-like heat shock protein hexose transporter HIN1 like jasmonic acid 2 lipase lipid transfer protein lipid desaturase luminal binding protein metal transporter metalothionein metallocarboxypeptidase inhibitor MRP-like MYB transcription factor Na/K proton exchanger NAC (N-acetylcysteine) domain protein NADP-dependent malic enzyme NADP(H) oxidoreductase Nam-like NDR1 like nectarin 5 like NPR1 like NtPRp27-like 2-oxoglutarate dehydrogenase oxysterol-binding protein PAD4 PEN1 PEN2 like PEP carboxylase kinase peroxyredoxin phosphate transporter (StPT3) pleiotropic drug resistant (PDR1, PDR2, PDR3, PDR4) poly(A) binding protein porin (mitochondrial) 26S proteasome AAA-ATPase prp1 protein kinase (shaggy-like) proteinase inhibitor (pinII) protein synthesis initiation factor 4G pSTH-2 pSTH-21 PUB17 R1 gene RAR1 like respiratory burst oxidase RING box like ripening regulated protein senescence-associated protein 5 sesquiterpene synthase SGT1 like SudD-like thaumatin like thaumatine like receptor kinase transducin family / WD40 repeat protein ubiquinol-cytochrome C reductase complex UPA16 (MTN3 like) vacuolar processing enzyme WD-40 repeat protein win1 win2 WIZZ (WRKY family) WRKY transcription factors wun1 wun2 xylosidase beta-1,4 yippee-like ZFP1 ZIK zinc finger proteins Other genes or proteins up-regulated by wounding or infection but not yet included in 'pathways' Dehydroascorbate has been shown to inhibit some kinases in HeLa cells and may therefore do the same in plants. HNE has been shown to activate some MAP kinases in animal cells. No evidence yet for plants. nicotinamide CONH2 N nicotinic acid SAM SAHc nicotinic acid betaine (trigonelline) COOH N COOH N CH3 nicotinic acid N-methyltransferase OH (E)-beta-farnesene (Z-beta-farnesene also detected) delta-cadinene germacrene A beta-elemene HO HO alpha-cadinol delta-cadinene beta-bisabolene beta-sesquiphellandrene alpha-cubebene beta-cubebene alpha-copaene alpha-gurjunene cross-linked N-trans-feruloyltyramine dimer and N-cis-feruloyltyramine dimer (down-regulated by compatible P. infestans infection) CO2+ H2O carbonic anhydrase H2CO3 GTP guanylyl cyclase cGMP ATP adenylate cyclase cAMP OH CHO 4-hydroxyhexenal OH CHO OH 4-hydroxynonenal (HNE) N1,N12-Bis(dihydrocaffeoyl)spermine (kukoamine A) and N1,N8-bis(dihydrocaffeoyl)spermidine have been isolated from potato. OH COOH 9(S)-HOT compounds which induce (some) resistance-related responses when applied exogenously to potato metabolic conversion signal transduction StMBF1 is up-regulated in response to oxidative stress and interacts with the TATA-box binding protein (Arce et al., 2006). nuclear factor PBF-2 (DNA binding protein p24) PR-10a CaPR10 interacts with CaLRR1 (in Capsicum annuum) The "Whirly" DNA binding protein StWhy1 protein is a transcriptional activator of genes containing the PBF2 binding PB promoter element. kunzeao OH SGT3 SGT3 Glutaminyl cyclase (an acyltransferase) catalyzes the conversion of N-terminal glutaminyl residues into pyroglutamic acid e.g. on pathogenesis-related proteins. The substrate for sesquiterpene synthase is farnesyl diphosphate. N-acylphosphatidylethanolamine (NAPE) phosphatidylethanolamine (PE) acylated sterolglycosides (ASG) increase in tobacco after elicitation N-acylethanolamine (NAE) elicitor stimulation in tobacco (e.g. N-lauroylethanolamine and N-myristoylethanolamine) phospholipase D NAPE synthase lipoxygenase ethanolamine kinase phosphoethanolamine N-methyltransferase phosphoethanolamine N-methyltransferase phosphoethanolamine N-methyltransferase cytidyltriphosphate -phosphocholine cytidyltansferase aminoalcohol -phosphotransferase choline kinase cytidyltriphosphate- phosphoethanolamine cytidyltransferase ethanolamine phosphoethanolamine phosphomonomethylethanolamine phosphodimethylethanolamine phosphatidyldimethylethanolamine phosphatidylmonomethylethanolamine phosphocholine cytidine 5'-diphosphate choline phosphatidylcholine Choline and phosphatidylcholine biosynthesis choline cytidyldiphosphate (CDP) ethanolamine (CH3)3N-CH2-CH2-OH (CH3)3N-CH2-CH2-O-P-OH O O free fatty acids NAPE synthase fatty acid amide hydrolase A leucine-rich repeat receptor-like protein kinase StLRPK1 is induced by P. infestans. A RING-H2 finger protein, StRFP1, is constitutivel expressed but is up-regulated by P. infestans A lectin receptor kinase has been shown to bind to the Phytophthora RXLR-dEER effector IPI-O in vitro. IPC synthase StMES1 hyoscyamine 6- hydroxylase (a 2- oxoglutarate-dependent dioxygenase) Thioredoxin catalyzes the SA-induced release of NPR1 monomers which translocate to the nucleus where they interact with TGA transcription factors. S-nitrosylation of NPR1 is mediated by S-nitrosoglutathione. strictosidine synthase (up-regulated by P. infestans) secologanin 3-alpha(S)-strictosidine 7-deoxyloganin loganin secologanin 4-coumaroyl-CoA malonyl-CoA tetrahydroxychalcone (naringenin chalcone) naringenin eriodictyol rutin (quercetin-3-rutinoside) nicotiflorin (kaempferol-3-O-rutinoside) ? chalcone synthase chalcone isomerase flavonoid 3’ hydroxylase dihydroquercetin quercetin conversion by V. dahliae 2-protocatechuoylphloroglucinolcarboxylic acid a flavanone and a flavonol-glucoside have been detected in potato in response to P. infestans. 4-methyl-umbelliferyl-β-glucoronide has been detected. flavonone 3 hydroxylase flavanol synthase quercetinase activation of phospholipase D phytosphingosine-1-phosphate mobilisation of Ca2+? programmed cell death sphinganine induces a calcium-dependent programmed cell death in tobacco BY-2 cells, and also triggers production of H2O2 via activation of NADPH oxidases, and induction of NO. OH O O OH OH P NH2 OH gallic acid OH OH O HO OH Mono-ubiquitination has different consequences to polyubiquitination. Further, depending on which amino acid is ubiquitinated may also affect the subsequent role of the protein. Some ubiquitinated proteins may therefore be involved in a proteasome- independent function such as signal transduction. The protein Star encodes a RING finger protein and is a putative E3 ubiquitin ligase. Sumoylation PROTEIN PROTEIN protease ligase SUMO SUMO precursor E1, E2, E3 AVR3a (from P. infestans) CMPG1 (an E3 ligase) R3a, R2,Rx PCD (independent of CMPG1) PCD E1 = ubiquitin activating enzyme E2 = ubiquitin conjugating enzyme E3 = ubiquitin ligase PROTEIN PROTEIN Ub Ub Ub Ub Ub Protein ubiquitination 26S proteasome (ATP dependent) peptides deubiquitinating enzymes may be involved in suppressing plant cell death, ie a negative regulator of HR. The COP9 signalosome (CSN) is a multi-protein complex that regulates the activities of cullin- RING E3 ubiquitin ligases (CRLs). CSN is involved with plant defense responses such as jasmonate- dependent responses. Ub Multiple isoforms of SUMO (small ubiquitin-related modifier) exists in plants. SUMO conjugation (sumoylation) of some proteins can regulate their activity and is associated with stress response. Enzymes include SUMO activating enzyme (SAE), SUMO-conjugating enzyme (SCE), SUMO ligase complex, and SUMO-specific proteases. SUMO conjugation plays a role in suppressing defence signalling in non-infected plants. NO3- nitrate reductase nitrotyrosine (peroxynitrite mediated nitration of protein tyrosine residues) cysteine S-nitrosylation GSH S-nitrosoglutathione (GSNO) PIP2 AVR3a from P. infestans interacts with and stabilizes potato E3 ubiquitin ligase CMPG1. P. infestans P. infestans Avr3a Avr3a inhibits cell death triggered by the INF1 elicitor from P. infestans R3a RanGAP2 interacts with R proteins Avr3b cystatin-like effector proteins (EPICs eg EPIC1, EPIC2B) (produced byP. infestans) inhibit potato proteases eg papain-like cysteine protease C14 R3b P. infestans PiAVR2 P. infestans SNE1 (suppressor of necrosis 1) is expressed during biotrophic growth stage and suppresses action of necrosis-inducing effectors (Nep1-like proteins) eg PiNPP1.1 R2 BSL1 (BSU-like protein1) C14 / EPIC complex R3b does not recognise Avr3a glucose-1-phosphate adenylyltransferase allyl alcohol acrolein (propenal or ethylene aldehyde) allyl-alcohol dehydrogenase + NADPH + H+ H H2C O OH+ NADP+ sucrose-phosphate synthase SPS regulated by SnRK1 in Arabidopsis SPS down-regulated in potato in response to P. infestans fructose 6-phosphate + UDP glucose UDP + sucrose 6-phosphate 2-keto acids (S)-2-hydroxy acids H2O2 O2 glycolate oxidase glutamic-gamma -semialdehyde OH O O HO R3a relocated to vesicles in endocytic pathway

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Page 1: Metabolic pathways of_diseased_potato

Halliwell-Asada enzyme pathway

O

H

CH3

CH3

CH3

CH3

gal

gamma-solanine

Shikimate pathwayPhenylpropanoidbiosynthesis

Polyaminebiosysnthesis

Glycoalkaloids

Ethylenebiosynthesis

SAM cycle

Sesquiterpenephytoalexinbiosynthesis

Fatty acid degradation

Phosphoinositide cascade

COOH

COO-gluc

COSCoA

COSCoA

HO

COSCoA

O

SCoAO

COOH

HO

HO

COOH COOH COOH COOH

COS-CoA

OH

OH OH OH OH

OH OCH3 OCH3 OCH3HO H3CO

COMT

C4Hphenylalaninehydroxylase

F5H COMT

4CL 4CL 4CL 4CL 4CL

putrescine hydroxycinnamoyl transferase

UDP-glucose: sinapic acidglucosyltransferase (SGT)

C3H

hydroxylase

trans-cinnamicacid

cinnamoyl-glucose

cinnamoyl-CoA

3-hydroxy-3-phenylpropionyl-CoA

3-oxo-3-phenylpropionyl-CoA

3-hydroxy-3-phenylpropanoic acid

p-coumaric acid ca�eic acid ferulic acid 5-hydroxyferulic acid sinapic acid

OH

COS-CoA

OCH3

COS-CoA

OH

OH

OH

COS-CoA

OCH3HO

COS-CoA

OCH3H3CO

CCoA3H CCoAOMT

COMT

F5H?

F5H

F5H

CCoAOMT

COMT

COMT

p-coumaryl-CoA ca�eoyl-CoA

ca�eoyl aldehyde

feruloyl-CoA 5-hydroxyferuloyl-CoA sinapoyl-CoA sinapoyl glucose

COOH

OH

CH2OH

OH

CH2OH

OCH3

CH2OH

OCH3HO

OHconiferyl alcohol

OH

CH2OH

OCH3H3CO

OH

5-hydroxyferulyl alcohol(5-hydroxyconiferylalcohol)

sinapyl alcohol

CCR CCR CCR CCR

CAD CAD CAD CAD

p-coumaryl alcohol

o-hydroxycinnamic acid(o-coumaric acid)

OH

COOH

COOH

NH2

PAL(multipleisozymes)

CoA ligase

coumarin

?

guaiacyl lignin syringyl ligninp-hydroxyphenyl lignin

COOH

OH

SCoAO

OH

salicylic acid

4-hydroxy-benzoic acid

benzoic acid2-hydroxylase

COO-conjugateCOOH

O-gluc

benzoic acidconjugate

hydroxyl radical

salicyloyl-CoAsalicylic acid glucoside

In Arabidopsis AtPBS3 gene is transcriptionallyregulated by AtWRKY46 a�ecting levels of SA-glucoside ?

?

salicylic acid2-O-glucosyl-transferase

HOOC

OH

CH2

CH

COOH

NH2

arogenic acid

arogenate dehydratase

phenylalanine

COOH

NH2

OHtyrosine

tyramine

COOH

OH

O

p-hydroxy-phenylpyruvicacid

isodityrosine intramolecularcross-link between HRGPs

peroxidase

tyrosineaminotransferase

tyrosinedecarboxylase

glutaminesynthetase

phenol oxidase

COOH

NH2

O

O

Dopaquinone

tyrosine3-monooxygenase(phenol oxidase)

OH

HOOC CH2

C

COOH

O

prephenic acid

chorismic acid

chorismatemutase2-3 isozymesin potato

prephenateaminotransferase

anthranilate

indole-3-glycerolphosphate

1-(o-carboxyphenylamino)-1-deoxyribulose 5-phosphate

5-phosphoribosyl-anthranilate

tryptophan

indole-3-pyruvic acid

indole

5-enolpyruvylshikimate3-phosphate (EPSP)

3-phosphoshikimic acid(shikimate 3-phosphate)

shikimic acid

shikimatekinase

OHO

protein

protein

ATP

ADP

NADPH NADP+

shikimatedehydrogenase

3-dehydroshikimic acid

COOH

NH2

OH

OHNH2

OH

OH

Dopa

dopaminenorepinephrine

normetanephrine

OH

COOH

OHO

HO

3-dehydroquinic acid

3-phosphoquinic acidOH

COOH

OHHO

HO

quinic acid

hemiterpenes

OH

COOH

OHCH2

HO

3-deoxy-D-arabino-heptulosonate7-phosphate (DAHP)

(Inhibited by phenylalanine.Located in chloroplasts.May be redox regulated)

PO3H2Ophosphoenolpyruvic acid

D-erythrose 4-phosphate

DAHPsynthase

1-deoxyxylulose 5-phosphate synthase

Mn2+CH3COCOOHpyruvic acid

acetyl-CoA

HO-(CH2)15-COOHw-hydroxypalmitic acid

HS-CoA

HHT

OH

OCH3

O NH(CH2)4NH2

NH2(CH2)4NH2

NH2(CH2)4NHCH3

OH

OH

O NH(CH2)4NH2

feruloylputrescine

putrescine

putrescine-N-methyltransferase

pyrrolinedehydrogenase

N-methylputrescine oxidase (MPO)

polyamine oxidase

diamine oxidase

polyamine oxidase

N-ca�eoylputrescineOH

OH

COO-gluc

OH

O-gluc

COOH

1-ca�eoyl-B-D-glucoside ca�eic acid 3-glucoside

4-coumaroyltyramine

p-coumaroyl shikimic acid

p-coumaroyl quinic acid

ca�eoyl shikimic acidca�eoyl CoA

chlorogenic acid

OH

OH

OH

COOH

HO

HO

O O

OH

OH

COOHHO

HO OH

O O

OH

OH

O O

'normal'chlorogenic acid(5 ca�eoylquinic acid)

chlorogenic acid(4 ca�eoylquinic acid)

chlorogenic acid(3 ca�eoylquinic acid)

OH

OH

COOHHO

O OH

O O

O

isochlorogenic acid(4,5 ca�eoylquinic acid)

OH

OH

COOH

HO

OH

O O

OH

OH

OO

isochlorogenic acid(3,5 ca�eoylquinic acid)

quinic acid

melanin

Gary D. Lyon

O

O

NH

NH

CH2CH(NH2)COOH

NH

skatole

CH3

NH

NH

pyruvate + L-glutamate

L-glutamine

OH

COO-Glu

OCH3H3CO

OH

CHO

OCH3

OH

coniferyl aldehyde(coniferaldehyde)

CHO

OCH3HO

OH

5-hydroxyferuloyl aldehyde(5-hydroxyconiferaldehyde)

CHO

OCH3H3CO

OHsinapyl aldehyde(sinapaldehyde)

CHO

OH

p-coumaryl aldehyde

protocatechualdehyde

a-hydroxyacetosyringonesyringic acid

OH

CHO

OCH3

vanillinOH

COOH

OCH3

vanillic acid

catechincatechin has beendetected in potato

OH

COOH

OH

O2 + NADPH2 HCHO + NADP

CHOHCH2NH2

OHoctopamine

feruloyl-CoA

CH2CH2NH2

OH

feruloyloctopamine(both N-trans and N-cis detected)

feruloyltyramine(both N-trans and N-cis detected)feruloyltyramine-feruloyltyramine

dimer (grossamide) andferuloyltyramine-feruloyloctopamine dimershave been isolated.

THT

THT

THT

C3' hydroxylaseCYP98A3CST

brassinosteroid-6-oxidase 2 (P450)

hydroxycinnamoyl-CoA:shikimate hydroxycinnamoyltransferase (CST)or hydroxycinnamoyl-CoA:quinate hydroxycinnamoyltransferase (CQT)

vanilloside(glucovanillin)

OO

S-CoA

O

S-CoA

OHHOOC

OH

OHHOOC

OP

OHHOOC

acetoacetyl-CoA

acetyl-CoA

acetyl-CoA

HMG-CoA

HMG-CoA reductase regulatedby SnRK1 in Arabidopsis

mevalonic acid

mevalonic acid5-phosphate (5-phosphomevalonate)

HMGR(multipleisozymes)

inactive HMGR

inactive ACC

acetyl-CoAcarboxylase

acetyl-Co-A malonyl-CoA fatty acid fatty acyl-CoA triglycerides

HMGR kinase

kinase kinase

PP2APP2C

OPP

OHHOOC

mevalonic acid5-pyrophosphate(5-pyrophosphomevalonate)

OPP OPP

dimethylallyl pyrophosphate(DMAPP)

isopentenylpyrophosphate(IPP)

isopentenylpyrophosphate(IPP)

farnesyl diphosphate(farnesyl pyrophosphate, FPP)

nerolidyl pyrophosphate(NPP)

geranylpyrophosphate(GPP)

isomerase

an aldehyde + NAD(+) + H2O an acid + NADHaldehydedehydrogenase

sedoheptulose 7-phosphate + D-glyceraldehyde 3-phosphate

D-erythrose 4-phosphate + fructose 6-phosphate

transaldolase (gene upregulated in incompatible P. infestans/potato interaction)

OPP

neryl pyrophosphate

monoterpenes

OPP

geranylgeranylpyrophosphate(GGPP)

squalene

squalene 2,3-epoxide

secologanin synthase(a P450)

7-deoxyloganin7-hydroxylase(a P450)

squalene 2,3-epoxidase cycloartenol cyclasecycloartenol

chlorophylls

diterpenescarotenoids

ABA

geranylgeranylpyrophosphatesynthetase

isopentylpyrophosphate+ NADPH

O

H

CH3

CH3

CH3

CH3

glucgamma-chaconine H

CH3

CH3

CH3

CH3

NN

solanthrene

HO

H

CH3

CH3

CH3

CH3

NN

demissidine

O

H

CH3

CH3

CH3

NO

gluc

rhamrham

O

H

CH3

CH3

CH3

NO

gluc

rhamrham

solamargine

NHCH3

H

CH3

CH3

CH3

solasodiene

NHCH3

O

vetispiradiene

vetispiradiene synthaseHO

OH

HO

OH

OH OCOCH3OH OCOCH3

O

OH OCOCH3

HO

OCOCH3

HO

O

phytuberin

OCOCH3O

O

OHO

O

phytuberol

colnelenic acid9-[1'(E),3'(Z),6'(Z)-nonatrienyloxy]-8(E)-nonenoic acid

colneleic acid9-[1'(E),3'(Z)-nonadienyloxy]-8(E)-nonenoic acid

Potato tuber phospholipids containcolneleic acid in the 2-position

O

solavetivone

O CH2OH

oxysolavetivone

O CH2OH

isolubimin

fungal degradation

HO CH2OH

15-dihydrolubimin

HO CHO

lubimin

HO

CHOHO

3-hydroxylubimin

HO

HO

rishitin

HO

HO OH

13-hydroxyrishitin(rishitin-M-1)

HO

HO O

11,12-epoxyrishitin

HO

O

rishitinone

O

HO

hydroxyglutinosoneOH

mono-oxygenase

O2

tyramine

NH4+

COOH

OH

OH

CHO

OH

COOH

OHp-hydroxybenzoic acid

NADH

NAD+

p-hydroxybenzaldehydedehydrogenase

O CHO

2-dehydrolubimin

O

O

O11,12-epoxycyclodehydro-isolubimin

O

HO

O

O

HO

2-dihydrocyclodehydro-isolubimin (cyclolubimin)

O

O

cyclodehydroisolubimin

O CH2OH

HO CH2OH

HO CHO

3,4-dehydroisolubimin

15-dihydro-10-epilubimin

10-epilubimin

O

O

OHOH

O

OHO-gluc

anhydro-beta-rotunol((+)-spirovetiva-1(10),3,11-trien-2-one)

O

solanoscone

linolenic acid (C18:3)

13-lipoxygenase

linolenic 13-hydroperoxide(13(S)-hydroperoxy-9(Z),11(E),15(Z)-octadecatrienoic acid) (13(S)-HPOT or 13(S)-HPOTE)

COOH

12-oxo-9(Z)-dodecenoic acid

COOH

O

COOH

O

12-oxo-phytodienoic acidreductase

COOH

O

COOH

O

COOH

Oepi-jasmonic acid((+)-7-epi-jasmonic acid)

COOCH3

Omethyl (-)-jasmonate

tuberonic acid12-hydroxy-jasmonate sulphate

COOH

O OH

COOH

O OSO3H

CH2OH

O

O

IF

IF

IF

alcoholdehydrogenase

3Z-hexen-1-ol

2E-hexenal

3(E)-hexenal

CH2OH

CH2OH

2E-hexenol

10-oxo-11,15(Z)-phytodienoic acid(2-oxo-5-[2'(Z)-pentenyl]-3-cyclopentene-1-octanoic acid)( a cyclopentenone regioisomer of 12-oxo-10,15(Z)-phytodienoic acid)

3(E)-hexenol

OH

CHO

OH

CH3-S-CH2-CH2-CO-COOH2-keto-4-methylthiobutyric acid(KMB)

CH3-S-CH2-CH2-CH-COOH

NH2

methionine

CH3-S-CH2-CH2-CH-COOH

CH2

OHOH

AdeO

NH2

CH3-S

CH2

OHOH

AdenineO

CH3-S

CH2

OHOH

OPO3HO

CH2C

H2C COOH

NH2

ACC synthase

nicotianaminesynthase

5'-methylthioadenosinenucleosidase

MTR kinase

ACC

CH2 CH2

ethylene

ETR1ETR2ERS1ERS2EIN4

CTR1(a MAPKKK)

EIN2

P5Creductase

ornithine-alpha-aminotransferase

ornithine-delta-aminotransferase

prolinedehydrogenase

MAPKK(eg SIMKK)

MAPK(eg SIMK, MMK3MPK6 (MPK13))

Responses(eg inductionof stress responsegenes including Ecaresponse gene-1)

ETR1 (= EIN1) is an ethylene receptor (a histidine kinase)CTR1 is a putative serine/threonine protein kinase (Raf-like) and negatively regulates ethylene responsesEIL1-3 (EIN3-like protein)PK12 is a protein kinase (possibly located in the nucleus)(the signaling sequence is being studied in Arabidopsisand is still only 'postulated' for potato)ERN is an ethylene-regulated nuclear-localised protein.

ACC: 1-aminocyclopropane-1-carboxylic acidSAM: S-adenosylmethionine

R-CO-COOH

R-CH-COOH

NH2

ATP

PPi + Pi

ADP

ATP

HPO4 + HCOOHO2

ACC oxidase(cofactors iron and ascorbateGene up-regulated by salicylicacid or IAA application)

SAM

nicotianamine

5'-methylthioadenosine(MTA)

5-methylthioribose1-phosphate (MTR-1-P)

CH3-S

CH2

OHOH

OHO

5-methylthioribose (MTR)

p-hydroxybenzaldehyde

IF= isomerization factor

9(S)-hydroperoxy-10(E),12(Z)-octadecadienoic acid(9(S)-HPOD or 9(S)-HPODE)

10(S),11(S)-epoxy-9(S)-hydroxy-12(Z)-octadecenoic acid

9(S),10-epoxy-10,12(Z)-octadecadienoic acid(an allene oxide)

9(S),10(S),11(R)-trihydroxy-12(Z)-octadecenoic acid

12(R),13(S)-epoxy-9(S)-hydroxy-10(E)-octadecenoic acid

9(S),12(S),13(S)-trihydroxy-10(E)-octadecenoic acid

epoxy alcohol synthase

allene oxide synthase

epoxy alcohol synthase

epoxide hydrolaseepoxide hydrolase

divinyl ether synthase(P450, CYP74D)

O2

NADPH + H+

NADP+

beta-oxidation

alpha-dioxygenase(a pathogen inducibleoxygenase (PIOX)

beta-oxidation

beta-oxidation

hydroxy-jasmonatesulphotransferase

anthranilatesynthase

phosphoribosyl-anthranilatetransferase

phosphoribosyl-anthranilateisomerase

tryptamine

tryptophandecarboxylase

tryptophanaminotransferase

CH2CH2NH2

NH

salicylatehydroxylase

catechol

NADPH + H+

NADP+

oxidisedglutathione(GSSG)

reducedglutathione (GSH)

glutathionereductase

glucose-6-phosphate dehydrogenase6-phosphogluconate dehydrogenaseisocitrate dehydrogenasedehydroascorbate

reductase

NAD(P)+

NAD(P)H

glycine

ubiquinone + NADglutamate + cysteine

ubiquinol + NAD(+)

ubiquinol plays a role inantioxidant defense of cellsand may prevent lipid peroxidation

monodehydro-ascorbatereductase

ascorbate

non-enzymatic(by reduced ferredoxin)

monodehydro-ascorbate

ascorbateperoxidase

ascorbateoxidase

amineoxidase

NADH ubiquinonereductase

H2O2

2H2OO2

dehydroascorbate

Dehydroascorbate has been shown toinhibit some kinases in HeLa cells andmay therefore do the same in plants.

photosynthesis

O2-

O2- HO2.

superoxide

Most superoxide is probably produced by photosystem Ivia the reduction of oxygen through the ferredoxin/ferredoxinNADP+ oxidoreductase system.

superoxide dismutase

H+

photorespirationfatty acid oxidationphotosynthesisoxidative phosphorylation

catalase

H2O + O2

O2

peroxidase(includesE.C. 1.11.1.12)

RH + H2O

RH2

Fe+++(Cu++)

Fe++(Cu+)

Fenton reaction(non-enzymic)

superoxide

superoxide

Vitamin B6 (pyridoxine) and itsderivatives are e�cient singletoxygen quenchers.

hydroperoxylradical

HO- + HO.

+ H+

H2O2

NADPH + O2

O2.

CH3

OHCH3

geosmin

FPP synthase

FPP synthase

OPP

geranylgeranylated proteins

gibberellins

inactive HMGRkinase

PP1PP2A

exogenous fatty acid

OH

COOH

OHPO

OH

COOH

OHHO

OH

COOH

OHO

OH

COOH

OHPO

HO

OH

COOH

O C COOH

CH2

POOH

COOH

O C COOH

CH2

Last modi�ed 24 December 2012

squalenesynthase

O2

O2 monooxygenase

HMGR kinase is notAMP-activated in potato

O-gluc

CHO

OCH3

phosphatidylinositol4,5-bisphosphate (PtdIns(4,5)P2)

phospholipase C(receptor-triggeredactivation)

inositol-1,4,5-trisphosphate (IP3)

diacylglycerol (DAG)

diacylglycerol kinase

phosphatidatecytidyltransferase(cdp.dg synthase)

PI synthase

CH2CHO

NHindole-3-acetaldehyde

1-O-(indole-3-acetyl)-b-glucose

CH2COOH

NHindole-3-acetic acid(IAA/auxin)

IAA-aspartic acidconjugate in Arabidopsis(a�ects diseasedevelopment)

tyrosineaminotransferase

prephenatedehydratase

phenylpyruvate

COOH

O

CHO

benzaldehyde

benzaldehyde

benzaldehydedehydrogenase

2,5-dihydroxybenzoicacid (gentisic acid)

COOH

OH

HO

2,3-dihydroxybenzoicacidCOOH

OH

OH

phosphatidylinositol (PtdIns)

1,3,4,5-IP4

Ins(1,4,5,6)-P4

Ins(1,2,3,4,5)P5

Ins(1,2,4,5,6)P5

1,3,4-IP3

3,4-IP2

3,6-IP2

1,2-IP2

2-IP1-IP

3,4,6-IP3

1,2,6-IP3 1,2,3-IP3

inositol3-phosphate

inositol

degradation by phytases

inositol may exist in di�erent isomers(myo-inositol, chiro-, scyllo-, neo-).GPI = glycosylphosphatidylinositol

inositol4-phosphate

1,4-IP2

OH

HO

O

O

esculetinO-gluc

HO

O

O

esculin

H3CO

HO

O

O

scopoletinH3CO

gluc-O

O

O

scopolin

gluc-O

O

O

CH3O

CH3O

isofraxidin-7-glucoside

peroxidase

BAHD acyltransferases are involved with incorporation of ferulate into suberin

suberization-asociated anionic peroxidaseenhances deposition of lignin and suberinin cell walls

peroxidaseperoxidase

CH2CHO

OH

CH3

phenylacetaldehyde

p-cresol

(phosphatidic acid) lysophosphatidic acid

bisphosphatidic acid

phosphatidic acid has been reported to bind to a numberof proteins eg PEPC, HSP90, tubulin, PP2A regulatorysubunit, GTP-binding like, SNF1-related kinase, and 14-3-3, in Arabidopsis

diacylglycerolpyrophosphate (DGPP)

cytidine diphosphate1,2-diacylglycerol

(opens Ca2+ channels)

adenine

Pathogenesis-related proteinsB-1,3-glucanases (PR-2) There are acidic (gluA) and basic (gluB) gene families Basic glucanases: 36 and 36.2 kDachitinases (PR-3, -4, -8, -11) acidic (ChtA) and basic (ChtB) chitinases are induced in leaves by infection and elicitor treatment whereas a glycosylated chitinase (ChtC) is constitutively expressed in leaves. Basic endochitinases: 32.2, 32.6, 33.2, 34.3, 38 and 38.7 KDa

ATP ADP ADPATP ATP

1-deoxyxylulose-5-P(DOXP)

pyruvate + glyceraldehyde-3-phosphate

ADP + Pi + CO2

OPP

Comments and additional information should be sent to: [email protected] can be viewed on the internet at www.potatometabolicpathways.webs.com

Metabolic pathways of the diseased potato

PPi

NADP + PPi

Phosphoinositide cascade (poorly described in plants;though some information from Arabidopsis. Someof the detail shown here is from animal and yeast systems. The potato scheme may therefore di�er slightlyand some biosynthetic routes will be more strongly favouredthan others).

protein farnesylation

proteinfarnesyltransferase(FTase)

Isoprenylation is a post-translational modi�cation of proteins involving covalent attachment of an isoprenyl moiety (either farnesyl or geranylgeranyl)to the cysteine residue at the C-terminus of proteins.Prenylated proteins can be further modi�ed by palmitoylation, COOH-terminal proteolysis and methylation. Most prenylated proteins are associated with signal transduction cascades.

GGTase

ent-kaurenesynthase

ent-kaureneoxidase

ent-kaurenoicacid oxidase

copalyldiphosphatesynthase

phytoenesynthase

O2

Transcription of protein-coding genes in eukaryotesoccurs through a co-ordinated group of general transcription factors (eg TFIIA, TFIIB, TFIID, etc). For example, TFIID is composed of TATA box-binding protein (TBP) and TBP-associated factors (TAFs).TFIID may have histone acetyltransferase activity.Cellular localization of histone deacetylases may be regulated by 14-3-3 proteins.

NADH

tyrosine ammonia-lyase (only occursin monocots ?)

O2

NADP+

NADPH

mevalonic acidkinase

mevalonic acid5-phosphate kinase

mevalonate5-pyrophosphatedecarboxylase

isopentenylpyrophosphateisomerase

geranylgeranylpyrophosphatesynthase

geranylgeranylpyrophosphatesynthase

COOH

OH

OH

HO

O

Oumbelliferone

Linolenic and linoleic acids are the two mainsubstrates for lipoxygenase in plants. Potatohas 9-LOX activity with linoleic acid but 5-LOXactivity with arachidonic acid. Arachidonic acidis present in Phytophthora infestans but isreported to be absent in higher plants.

3-kinase

tyrosine

laminarin, a B-1,3-glucooligosaccharide, inducesthe accumulation of N-p-coumaroyloctopamine andincreases THT, PAL, 4CL and tyrosine decarboxylaseactivity (presumably through up-regulation of the genes)

?

cycloartenolmethyltransferase(sterol methyltransferase; SMT1)

sterol methyltransferase; SMT2

24-methylene cycloartenol

24-methylene lophenol

24-ethylidene lophenol

isofucosterol

sitosterol

OCH3

CH3

OH

O

O2 + NADPH NADP

OCH3

CH2OH

OH

O

acetovanillone a-hydroxyacetovanillone

acetovanillonea-hydroxylase: a P450-dependentmonooxygenase

present in Solanumkhasianum

EIN3EIL1-3(nuclear)

ADP-ribosylation factors (ARFs) are small GTP-bindingproteins that function in the assembly of coated vesiclesthat transport proteins between intracellular organelles.

Some lipid peroxidation products:4-hydroxy-2-nonenal (HNE)4-hydroxy-2-hexenalmalondialdehyde (MDA)

HNE originates from peroxidation of arachidonicacid and linoleic acids in eukaryotes. HNE reactswith thiols eg GSH, cysteine, and proteins containingthiol groups to form thioether adducts which undergocyclization to form hemiacetals. HNE also reacts withother amino acids in proteins to form stable adducts.HNE can inhibit alternative oxidase.

UDP-glucose

UDP-glucose:solanidineglucosyltransferase(SGT2)

p-coumaryl-CoA

p-coumaryl-CoA

decarboxylated S-adenosylmethionine

S-adenosylmethioninedecarboxylase (SAMDC)

spermidine

spermine

Spermine and spermidine have beenreported to activate nonspeci�c acid phosphatase(EC 3.1.3.2) by lowering the K(m) value.

Binding of polyamines to 14-3-3proteins may be involved in regulation of growth and devlopment.

putrescine

N-methylputrescine

N-methylpyrrolinium

N-methylaminobutanal

delta1-pyrroline

1,3-diaminopropane

1-(3-aminopropyl)-pyrroline

agmatine

N-carbamoylputrescine

arginine

ornithine

ornithinepyrroline-2-carboxylate

proline

spontaneous

hydroxyproline

alpha-keto-delta-aminovalerate

arginine decarboxylase

agmatine iminohydrolase(agmatine deiminase)

N-carbamoylputrescineamidohydrolaseornithine

decarboxylase

arginase

spermidinesynthase

sperminesynthase

w-feruloyloxypalmitic acid

C

OH

OCH3

O O(CH2)15

COOH

suberininvolved inwound healing

OHCOOH

O C COOH

CH2

isochorismic acid

OH

Mg2+

anthraquinonesphylloquinones

isochorismatesynthase

Mg2+

In Arabidopsis isochorismate synthase gene ACS1is transcriptionally regulated by AtWRKY28.

ACC synthase and ACC oxidaseactivity may be controlled by kinases andphosphatases in mung bean (noexperimental evidence yet for potato)

C

OH

OCH3

O O

(CH2)n

CH3

CH2

n=14 : hexadecyl ferulaten=16 : octadecyl ferulaten=18 : eicosyl ferulaten=20 : docosyl ferulaten=22 : tetracosyl ferulaten=24 : hexacosyl ferulaten=26 : octacosyl ferulate

Mevalonatepathway

Enzyme activity and subcellular localization is oftencontrolled through post-translational modi�cationinvolving proteolysis, phosphorylation, prenylation,glycosylation, acylation, methylation, sulphation,hydroxylation and carboxylation. Some Eukaryotic cellular proteins have a covalentlyattached myristoyl group at the amino terminus - suchproteins may be involved in controlling calcium-sensitive processes: (calcium-myristoyl switches).Myristoyl CoA:protein N-myristyltransferase is the enzymeinvolved in protein myristoylation.

HMG-CoAsynthase

thiolase(acetyl-CoA acetyltransferase)

pyruvate decarboxylase

phosphoenolpyruvatecarboxykinase

rhamnogalacturonan O-acetyl-transferase

NADPHNADP+

HMGR encoded by three genes. Hmg1 isstrongly induced by wounding leading toaccumulation of glycoalkaloids, whereashmg2 and hmg3 are enhanced by arachidonicacid and P. infestans.

There is evidence that PAL can be phosphorylatedand hence activity may be controlled, in part, byphosphorylation.

In tobacco, basic PR proteins accumulate in thevacuole whilst acidic PR proteins accumulateextracellularly.P. infestans induces accumulation of osmotin-likeproteins in potato. These proteins may have a dual function in osmotic stress and disease resistance.A silencing element binding factor (SEBF) has been shown to bind to the promoter sequence of a numberof PR proteins - this may be involved in downregulation of genes.

Phosphorylated enzymes may, in speci�c cases, bemore active or less active than the unphosphorylatedenzyme. A variation on this theme is where an enzymemay be controlled by an inhibitor protein whose activityis controlled by phosphorylation.

3-dehydroquinatedehydratase

NADPH oxidase

glycosyltransferase

catechin oxidase (from fungi and bacteria)

glycosyltransferase

5-enolpyruvylshikimate3-phosphate (EPSP)synthase

Pectin methyltransferases are the main enzymesinvolved in the control of methylesteri�cation ofpectin.

SAM synthetase

After ATP, SAM is the major high energy intermediatein the cell and is the major methyl donor of a wide rangeof compounds including proteins, nucleic acids, sugars,pectin and chlorophyll.

(in nahGtransformed plants)

hydroperoxidelyase (a cytochrome P450;CYP74B)

IF

arogenatedehydrogenase

glutamine 2-oxoglutaric acid

glutamic acid

reduced ferredoxin

oxidisedferredoxin

glutamine

NH4+

from PAL

GOGAT = glutamine: 2-oxo-glutarateamidotransferase)

homocysteine +adenosine

homocysteine

homocysteine

cystathione

threonine

isoleucine

cysteine

cysteine plays an important rolein the immune response ofArabidopsis

O-acetylserine serine

homoserine

aspartateO-phosphohomoserine

S-adenosyl-Lhomocysteine(SAHc)

CH3

activated CH3

Methylation reactions eg for pectin methylation,norepinephrine to normetanephrine, and to COOH-terminal S-farnesylatedcysteine of prenylated proteins (prenylprotein-speci�c methyltransferase; PPSEP)

adenine

inosine

adenosinenucleosidase

adeninephosphoribosyl-transferase

methioninesynthase

adenosinedeaminase

adenosinekinase

cystathionegamma-synthase

O-acetylserine(thiol) lyase(OASTL)

cystathionebeta-lyase

threoninesynthase

SAH hydrolase

COOHO

hydroperoxidecyclase

hydroperoxide dehydratase

allene oxide

COOH

O HO

COOH

OHO

alpha-ketol

gamma-ketol

COOH

COOH

OOH

cholesterol

HO

HCH3CH3

CH3

CH3CH3

HO

HCH3CH3

CH3

CH3CH3

cholesteranol

HO

H

CH3

CH3

CH3HO

CH3

HO

H

CH3

CH3

CH3H2N

CH3

HO

H

CH3

CH3

CH3 H2N

CH3HO

HO

H

CH3

CH3

CH3CH3

N

CH3NH

H

CH3

CH3solasodine

HO

CH3

HO

H

CH3

CH3

CH3CH3

HO

HO

H

CH3

CH3

CH3CH3

H2N

O

H

CH3

CH3

CH3

NO

NHCH3

HO

soladulcidine

H

CH3

CH3

CH3

CH3

HO

NH

tomatidenol

NH4+

HO

H

CH3

CH3

CH3CH3

HO

HO

dormantinol

HO

H

CH3

CH3

CH3CH3

HO

O

dormantinone

HO

H

CH3

CH3

CH3

CH3

solanidine

HO

H

CH3

CH3

CH3CH3

N

verazineHO

H

CH3

CH3

CH3CH3

N

OH

etioline

Possible biosynthetic pathwaysfrom cholesterol andcholesteranol to aglycones.

L-arginine has been reportedto be the most likely N sourcein glycoalkaloid biosynthesis

OCCH3

acetyldehydrorishitinolO

OH

OHrishitinol

polyphenoloxidase(tyrosinase)

dopadecarboxylase

OH

OH

RO O

chlorogenic acidO

O

RO O

chlorogenic acidquinone

O

O

RO O

H

H

HP-X

OH

O

RO O

HP-X

OH

O

RO O

H

X-P

R = quinic acidP-X = proteinX = NH2, OH, SH

polyphenoloxidase H+

OH

O-gluc

arbutin

vanillic acid glucoside(vanillate glucoside)

COOH

O-glucp-hydroxybenzoic acidglucoside

OH

OCH3

O NH-CH-CH2-COOH

feruloylaspartate

COOH

C NH

OOHHO

C NH

OOHHO

OCH3

COO-gluc

OHp-coumaroyl-D-glucose

COO-gluc

OH

OH

ca�eoyl-D-glucose

COO-gluc

t-cinnamoyl-D-glucose

UDPG:cinnamateglucosyltransferase

O-gluc

COOH

OCH3

COOCH3

Omethyl (+)-jasmonate

COR

Oamino acid conjugates of (-)-jasmonic acid(R=leucine, isoleucine, valine)

11,12-epoxycyclolubimin

Potato lectin is a hydroxyproline-rich glycoprotein (HRGP) which can bind oligomers of N-acetylglucosamine.Extensin and PAL mRNA levels as well as cell wallhydroxyproline increase in response to woundingand subsequent aerobic incubation but not underanaerobic conditions.

NH2(CH2)4NH(CH2)3NH2

CH3-S-CH2-CH2-CH2-NH2

CH2

OHOH

AdeO

NH2(CH2)3NH(CH2)4NH(CH2)3NH2

H-γ-Glu-Cys-Gly-OH

(g-Glu-Cys-Gly)2

HC N

OOHHO

OCH3

OH

protein adducts

(allene oxidesynthase: A cytochrome P450 ; CYP74A)

(allene oxidecyclase)

3-dehydroquinatesynthase

ornithine

delta-pyrroline-5-carboxylate

malonyl-ACC

jasmonic acid-ACC

malonyltransferase

quinatedehydrogenase

R

OH OH

OH

R

O

O

R

cresolase catecholase complex brownpolymers

Reaction scheme of tyrosinase

Sulfhydryl (SH or thiol) compounds such as cysteine,N-acetyl-L-cysteine, and reduced glutathione, as wellas ascorbic and citric acids, are good inhibitors of PPOwhich catalyzes enzymic browning.

ERFsPK12 ?ERN

ERFs are a family of ethylene-responsivetranscription factors.(Previously called ethylene-responsiveelement-binding proteins or ERBPs).

In Arabidopsis, F box proteins EBF1 and EBF2 interact with EIN3/EIL transcription factors. EIN3 is degraded through a ubiquitin/proteasomepathway mediated by EBF1 and EBF2.

L-tyrosinetyrosinedecarboxylase

chorismatesynthase

pyruvate lyase?

indole-3-glycerol-phosphatesynthase

tryptophan synthase a

tryptophan synthase b

inositol-1,4,5-trisphosphate5-phosphataseIns PolyP

2-kinase

phosphatidylinositol-3-phosphatase

inositol-3,4-bisphosphate4-phosphatase

inositol-1,4-bisphosphate1-phosphatase

InsP6 kinase

InsP7 kinase

A number of derivatives of jasmonic acid have been detected in other plants includingamino acid conjugates (JA-Ile, JA-Val, JA-LeuJA-Phe; possibly synthesised via a JA-aminosynthetase), JA conjugated to the ethyleneprecursor ACC, and hydroxylated forms. F boxproteins are involved in JA-Ile perception inArabidopsis. In Arabidopsis JA-Ile signals throughthe COI1-JAZ coreceptor complex and AtCYP94B3is involved in JA-Ile turnover providing negativefeedback of JA-Ile levels. 12-hydroxy-JA-Ile hasbeen identi�ed in Arabidopsis.

H

CH3

CH3

CH3

CH3

NN

gluc

glucxyl

dehydrodemissinegal

H

CH3

CH3

CH3

CH3

NN

gluc

glucgluc

dehydrocommersoninegal

The relative amounts of glycoalkaloidsand their aglycones vary betweendi�erent Solanum species.

O

O

OH

COOH

HO

HO

COOHHOOC

traumatic acid(implicated in woundsignalling)

H

CH3

CH3

CH3

NO

tomatidineHO

CH3

NH

H

CH3

CH3

CH3

CH3

NN

gal

gluc

gluc

xyl

demissineO

H

CH3

CH3

CH3

CH3

NN

gal

gluc

gluc

gluc

commersonine

A feruloytyramine trimer has beenisolated from scab lesions.

O

H

CH3

CH3

CH3

NO

gal

glucgluc

tomatine

NHCH3

xyl

O

H

CH3

CH3

CH3

NO

gal

rhamgluc

solasonine

NHCH3

O

OH

elicitor-activeoligogalacturonides

plant pectin

AtSNI1 is a negative regulator of SAR and HRin Arabidopsis. AtBRCA2 is downstream of AtNPR1and is a major regulator of defense-related genetranscription. The BRCA2-RAD51 complex isinvolved with HR and in plant immune responses.

WRKY transcription factor

pectic enzymes fromplant pathogens

phosphorylation of anapprox 34 kDa protein(pp34)

resistance responses(includes basic chitinase, phytoalexin andprotease inhibitor accumulation)

Why1

Pti4

SEBF

PR10a

COOH

COOHNH2 NH2

OH

O

COOH

COOH

HOOC

COOH NH2H2NNH2 H2N

OH

OO

OH

isodityrosine

di-isodityrosine

proteinkinase C

triacylglycerol(triglyceride)

Ca2+ mobilisation

C NH

OOHHO

OH

4-coumaroyloctopamine

C NH

OOH

OH

HO

OH

4-coumaroylnoradrenaline

C NH

OOH

OH

cinnamomyloctopamine

+ cinnamic acid

C NH

OOH

+ cinnamic acid

cinnamomyltyramine

receptor receptor

resistance responsesincluding StLTPa7, PR proteins,erg-1, and StrbohB (anNADPH oxidase)

resistance responsesincluding PR proteins(reported to be di�erentfrom those inducedby salicylic acid)

receptorMany induced responses includinginduction of aspartic proteinase inhibitorepoxide hydrolase, threonine deaminase,leucine aminopeptidase, and StLTPa7Increases lipoxygenase activity.Does not induce sesquiterpenephytoalexin accumulation nor PR protein P4.Induces putrescine N-methyltransferase intobacco, Acetyl-CoA carboxylase in bean,and multicystatin in tomato. SuppressesStCPK2 gene transcription.

OH

HO

H

CH3

CH3

CH3

CH3

hydroxy-solanidine

OOCH3

HO

H

CH3

CH3

CH3

CH3

acetyl-solanidine(in S. chacoense)

acetylase

hydroxylase

leptinine Ileptinine II

leptine Ileptine II

UDP-galactose:solanidinegalactosyltransferase (SGT1)

UDP-galactose

Extracellular signal

receptor

MAP kinase kinase kinase(MAPKKK)

MAP kinase kinase(MAPKK or MEK)

MAP kinase(MAPK or ERK -extracellularsignal-regulatedkinase)MAP kinase phosphatases

involved in dephosphorylation of MAPKs.Act by negative feedbackregulation of MAPK activity.

Responses NADPH oxidase gene

S-nitrosylation of NADPH oxidaseassociated with cell death inplant immunity in Arabidopsis

ROS production

Programmed cell death also involves reorganisation of theplant cytoskeleton involving microtubules and micro�laments.

StCDPK5 directly involved with regulatingthe oxidative burst via phosphorylation ofthe NADPH oxidase StRBOHB

NO

Alternaric acid (from Alternaria solani) stimulates in vitro phosphorylation ofHis-tagged RiCDPK1 from potato cv Rishiri)

NO associated (NOA gene)

HR ?

P. infestans hyphalwall components,salicylic acid,arachidonic acid.

activation of protein kinase p51-PK

phosphorylation andactivation of nuclearand cytoplasmic elements

stigmasterol

6-deoxoteasterone

6-deoxotyphasterol

6-deoxocastasterone

castasterone

brassinolide

campesterol

H

CH3

CH3

CH3

NO

gal

rhamgluc

alpha-solamarine

NHCH3

O

H

CH3

CH3

CH3

NO

gluc

rhamrham

beta-solamarine

NHCH3

O

pulcherosine(in tomato)

PtdIns(3,4,5)P3

PI3K

3-phosphatase

4-phosphatase

phosphatidylinositol 4-phosphate (PtdIns(4)P)

PIP5K(PtdIns-4-phosphate 5-kinase)

(inositol 1,4-bisphosphate) IP3 5-

phosphatase

Ca2+ regulation

HQT

glutathioneS-transferase

COOH

Odinor-oxo-phytodienoic acid(dnOPDA) (increases in woundedtissues)

7,10,13-hexadecatrienoic acid (16:3)

woundsignalling ?

Ubiquitin may serve as a marker for targeting proteinsfor their subsequent degradation. Ubiquitin may also attach to stable proteins, eg some cell surface receptors,where ubiquitination in response to ligand binding actsas an internalisation signal. Genes for ubiquitin carrier protein and ubiquitin-ribosomal fusion protein have beenreported to be up-regulated in response to infection.

arginine

citrulline

sesquiterpene phytoalexininduction eg rishitin

lipid peroxidation, DNA damage

NADPH

NADP+

NO.

NO2-

NO+

nitrosatedproteins (nitrosylation)

R-NO

NO-

ONOO-

RCH2NH2 + O2 + H20 RCHO + NH3 + H2O2

ONOOH

H+

NO synthase ? nitrate reductase?NAD(P)H-dependentnitrate reductase ornitrite reductase

peroxynitriteanion

peroxynitrousacid

1,3,-IP2

1-IPphytate 1,3,4,6-IP4

1,2,5,6-IP4

diphosphoinositoltetrakisphosphate(5-PP-Ins(1,3,4,6)P4)

5,6-bis-PP-Ins(1,2,3,4)P4

1,2,3,6-IP4

1,3,4,5,6-IP5

1,2,3,5,6-IP5

diphosphoinositolpentakisphosphate(5-PP-Ins(1,2,3,4,6)P5)

IP6

3,4,5,6-IP4

IP3 receptor

IP2 1-phosphatase

IP3 6-kinaseIP4 5-kinase

4-phosphatase

PtdIns-4 kinase

CDP-diacylglycerol-inositol3-phosphatidyltransferase(phosphatidylinositol synthase)

diacylglycerol-3-P

OH

OH

catechol

asparaginesynthetase

glutamine + aspartate

asparagine + glutamate

anthranilate1,2 dioxygenase

dehydroshikimic aciddehydratase ?

protocatechuic acidamine oxidase

indole-3-pyruvicacid decarboxylase

indole-3-acetaldehydeoxidase

COO-gluc

OH

glucosyl salicylate(salicyloyl-glucose ester)

salicylic acidcarboxylglucosyltransferase

?

?

OH

methyl salicylate

methyl salicylate is anSAR signal in potato.

salicylic acidmethyl-transferase

COOCH3

SAM-dependentmethylase

PI3KPtdIns(3,4)P2

PtdIns(3,4)P2

regulation of speci�cprotein kinases ?

THT stimulated by Mg2+ or Ca2+

4,5-PIP2 also regulates actin regulatory proteins,activation of phospholipase D, an ADP-ribosylationfactor, and proteins containing the pleckstrin homologydomain (involved in signal transduction) in animals.

regulation of speci�cprotein kinases ?

rearrangementof actin cytoskeleton(in animal cells)

PtdIns(3)P

PIP4K

PtdIns(3,5)P2 PIP5K

PIP5Kinositol(poly)phosphate5-phosphatase (SHIP)

oxidisedglutathione(GSSG)

phospholipid hydroperoxideglutathione peroxidase (PHGPX; E.C. 1.11.1.9)

L-OOH

L-OH

may conjugatewith HNE

Glutathione is said to bea scavenger of activeoxygen species. Glutathionecan conjugate with electrophilessuch as Dopaquinone.

oxidativephosphorylation

inactivation ofproteinphosphatase

palmitoyl-CoA + serine

3-ketosphinganine

sphinganine 1-phosphate

serinepalmitoytransferase

hexadecanal

3-ketosphinganinereductase

(sphingosine is a potentinhibitor of proteinkinase C in animals)

sphinganine 1-phosphatelyase

sphinganine 1-phosphatephosphatase

glycerolipids

COOH

COOH

OOH

COOHO

13-lipoxygenase

O2

hydroperoxide dehydratase

(allene oxidesynthase)

13(S)-hydroperoxy-9(Z),11(E)-octadecadienoic acid(13(S)-HPOD or 13(S)-HPODE)

COOH

O

12-oxo-phytodienoic acid

COOH

O

12-oxo-phytodienoic acidreductase

COOH

O

3-oxo-2-(2'-pentenyl)cyclopentaneoctanoic acid(OPC-8:0)

NADPH + H+

NADP+

beta-oxidation

3-oxo-2-(2'-pentenyl)cyclopentanehexanoic acid(OPC-6:0)

COOH

O

COOH

O

3-oxo-2-(2'-pentenyl)-cyclopentanebutanoic acid(OPC-4:0)

epi-jasmonic acid((-)-7-epi-jasmonic acid)

beta-oxidation

beta-oxidation

jasmonic acid carboxylmethyltransferase

hydroperoxidecyclase(allene oxidecyclase)

COOH

O

COOH

O

12-oxo-phytodienoic acidreductase

NADPH + H+

NADP+

12-oxo-phytodienoic acidreductase

NADPH + H+

NADP+

COOH

O

COOH

O3-oxo-2-(2'-pentyl)cyclopentaneoctanoic acid(DH-OPC-8:0)

b-oxidationbeta-oxidation

COOH

O

COOH

O

b-oxidationbeta-oxidation

COOH

O

COOH

O

b-oxidationbeta-oxidation

COOH

O

COOH

O(+)-7-epi-dihydrojasmonic acid(-)-7-epi-dihydrojasmonic acid

COOH

O(-)-9,10-dihydrojasmonic acid

15,16-dihydro-12-oxo-phytoenoic acid(DH-12-oxo-PDA)

3-oxo-2-(2'-pentyl)cyclopentanehexanoic acid(DH-OPC-6:0)

3-oxo-2-(2'-pentyl)cyclopentanebutanoic acid(DH-OPC-4:0)

3-oxo-2-(2'-pentenyl)cyclopentaneoctanoic acid(OPC-8:0)

3-oxo-2-(2'-pentenyl)cyclopentanehexanoic acid(OPC-6:0)

3-oxo-2-(2'-pentenyl)-cyclopentanebutanoic acid(OPC-4:0)

3-oxo-2-(2'-pentyl)cyclopentanehexanoic acid(DH-OPC-6:0)

3-oxo-2-(2'-pentyl)cyclopentanebutanoic acid(DH-OPC-4:0)

Oxylipinpathway

3-oxo-2-(2'-pentyl)cyclopentaneoctanoic acid(DH-OPC-8:0)

linoleic acid (C18:2)

Ceramidesignalling

13-KOD

12,13(S)-epoxy-9(Z),11-octadecadienoic acid (13(S)EOD) 12,13(S)-epoxy-9(Z),11,15(Z)-octadecatrienoic acid

(13(S)EOT)

(12-oxo-10,15(Z)-phytodienoic acid)12-oxo-phytodienoic acid

(12-oxo-10,15(Z)-phytodienoic acid)

ceramidekinase(acylsphingosinekinase)

ceramidase

In plants PtdIns(4)P is 10-20 foldhigher than PtdIns(4,5)P2 (in animalsthe ratio is 1:1).

COOHO

O

OOH

lipoxygenase

O2

O

OH

9-hydroxy-traumatin(4-hydroxy-2(Z)-dodecenal)

12-oxo-9(Z)-dodecenoic acid(9(Z)-traumatin)

peroxygenase

hydroperoxidelyase

hydroperoxidelyase

hexanal

3(Z)-hexenal

3(E)-hexenal

O

O

O2

4-hydroxy-2(E)-hexenal

lipoxygenase

peroxygenase

peroxygenase

O

OOH

O

OH

(steps for traumatin shown in soybean and alfalfa)

COOH

O

(13-keto-9(Z),11(E)-octadecadienoic acid)

COOH

O HO

g -ketol

O

COOH

HO

a -ketol

OH

OH

NH2

sphinganine(dihydrosphingosine)

OH

OH

NH2OHphytosphingosine

sphingosine

O

OH

NH2

cerebroside is the most abundant classof sphingolipid in plants, consisting of8-unsaturated sphingoid bases, 2-hydroxyfattyacids (potato= 16:0, 20:0, 22:0, 23:0, 24:0,25:0, and 26:0) and glucose.

dihydroceramide

In Arabidopsis several WRKY proteins are SUMO1 targets, and each of themcan be phosphorylated by MAPK kinases.

ceramideglucosylceramide

ceramide can stimulatePP2A and MAP kinase

ceramide1-phosphate

sphingosineacetyltransferase

phytoceramide

acylsphingosinedeacylase

inositol-phosphorylceramide(IPC)

mannose-inositol-P-ceramide (MIPC)

mannose-(inositol-P)2-ceramide (M(IP)2C)

M(IP)2C synthase

phosphatidylinositol

phosphatidylinositol

IPC synthase

OH

OH

NH2OH

OH

O

COOH

HO

OH

NH

COOH

NH2

HO

OH COOH

NH2

S

cysteinyldopa

leucodopachrome

+ cysteine

(COOH)

HO

OH

NH

eumelanin

polymerization

(COOH)

COOH

NH2

HO

N

S

benzothiazinederivative

COOH

NH2

HO

(COOH)

N

S

phaeomelanin

polymerization

O2

NADPH + H+

NADP+

ceramide synthase (sphinganineacyltransferase)

N-acyl sphinganinedehydrogenase

sphingosinekinase

sphingosine-1-phosphatephosphatase(SPPase)

glutathione synthetase

γ-glutamylcysteine synthetase

γ-glutamylcysteine

sphingolipids

unsaturated analogues

unsaturated analogues

The unsaturated analogues 4E and 8Eof sphinganine are the most abundant cerebroside base.

Ceramides are thought to be involved in apoptosis (programmed cell death)MAP kinases are downstream of these long chain bases in PCD.

Di�erent LOX isoforms are encoded in complex multigenefamilies. Three LOX gene families occur in potato:-9-LOX expressed mainly in tubers and roots13-LOX (2 families) expressed in leaves in response towounding.

COOH

O

COOH

O

9-lipoxygenase 9-lipoxygenase

possible modulation ofDAG kinase by arachidonic acidin mammalsannexin (from pepper) inhibits

phospholipase A2

phosphatidylcholine

thaumatin-like (PR-5)proteinase inhibitors (PR-6)proteinase (PR-7)peroxidases (PR-9)ribonuclease-like (PR-10)plant defensins (PR-12)thionins (PR-13)lipid transfer proteins (PR-14)

phospholipase A2

phospholipase D

phosphatidatekinase

DGPPphosphatase

phosphatidicacidphosphatase

copalylpyrophosphate

ent-kaurene

AMP

OOH

COOH

OH

O

COOH

OHO

COOH

OHOHOH

COOH

OH

OH OH

COOH

9(S)-hydroperoxy-10(E),12(Z),15(Z)-octadecatrienoic acid(9(S)-HPOT or 9(S)-HPOTE)

10(S),11(S)-epoxy-9(S)-hydroxy-12(Z),15(Z)-octadecadienoic acid

9(S),10(S),11(R)-trihydroxy-12(Z),15(Z)-octadecadienoic acid

12(R),13(S)-epoxy-9(S)-hydroxy-10(E),15(Z)-octadecadienoic acid

9(S),12(S),13(S)-trihydroxy-10(E),15(Z)-octadecadienoic acid

epoxy alcohol synthase

epoxy alcohol synthase

epoxide hydrolaseepoxide hydrolase

spontaneoushydrolysis

Sesquiterpenes

H

H

H

O

sesquisabinenealpha-cadinol alpha-zingiberene

alpha-humulene

beta-sesquiphellandrene

(+)-germacrene

germacrenes

2-(1',2'-dihydroxy-1'-methylethyl)-6,10-dimethylspiro

[4,5]dec-6,9-dien-8-one

bicyclogermacrene(-)-germacrene(germacrene D)

HO

ledol

caryophyllene oxide

cedrol

H

H

beta-caryophyllene

trans-beta-bergamotene

trans-apha-bergamotene

HH

germacrene D-4-olOH

A transcriptional coadaptor or coactivator, themultiprotein bridging factor 1 (MBF1), is up-regulatedby fungal infection and wounding. Some pathogenresponse genes are regulated by WRKY transcriptionfactors.

inositol-1 (or 4)-phosphatase

methyl jasmonate induction

gene up-regulated by MeJ in bean

COOH

arachidonic acid (20:4)

COOH

eicosapentaenoic acidfrom P. infestans

5-lipoxygenase (inhibited byalpha-tocopherol in vitro)

peroxygenase

protein kinase Chomolog

5(S)-hydroperoxy-6E,8Z,11Z,14Z-eicosatetraen-1-oic acid(5-S-HPETE)

5(S)-hydroxy-6E,8Z,11Z,14Z-eicosatetraen-1-oic acid(5-S-HETE)

from P. infestans

Induced responses including necrosis, LOX,sesquiterpene phytoalexin induction, peroxidase,NADPH oxidase, and increased PAL activity. Alsoinduces systemic resistance. SAR not induced againstP. infestans in nahG plants. Induces local but notsystemic induction of a PR1-like protein.Increases GAPDH (glyceraldehyde-3-phosphatedehydrogenase), alcohol dehydrogenase (ADH) and ferritin gene transcripts. [GAPDH is involved in glycolysis]. Induces PR proteins P4 and PR-10abut not wound-inducible proteinase inhibitor PINII.Induces cystatin in tomato.

5,6-leukotriene A4 ?

cyclooxygenase (detected in tobaccobut not yet in potato. There is now some doubt as to whether this is a true cyclooxygenaseor is an alpha-dioxygenase)

thromboxanesprostaglandins

Products of cyclooxygenase have not yetbeen isolated from potato.

diHETE products ?

StPRp27 reported to contributeto race-nonspeci�c resistance toP. infestans.

Cu co-factor

Post-translational covalent linkage of polyaminesto proteins is catalysed by transglutaminases.

ERF1 interacts with the GCC boxof ethylene response genes

OH

CH2OH

OH

O

CH3O

OH

OH

O

CH3O OCH3

'high energy' diphosphorylatedinositol polyphosphates

?

COOH

OH

Phosphatidylinositol transfer protein (PI-TP) and the non-speci�c transfer protein (nsL-TP) belong to a largeand diverse family of lipid-binding proteins. 135 nsLtps(non-speci�c lipid transfer proteins) have been identi�edin the Solanaceae.

The reduced form of ubiquinone, ubiquinol, functions as an antioxidant,protecting membrane phospholipids from peroxidation, and mitochondrialDNA and membrane proteins from free-radical-induced oxidative damage.

AbbreviationsC3H: coumarate-3-hydroxylaseC4H: cinnamate-4-hydroxylase4CL: hydroxycinnamate:CoA ligase (4-coumaroyl:CoA ligase)CAD: cinnamyl alcohol reductaseCCoA3H: coumaroyl-CoA-3-hydroxylaseCCoAOMT: ca�eoyl-CoA 3-O-methyltransferaseCCR: cinnamyl:CoA reductaseCOMT: ca�eic acid 3-O-methyltransferaseDAHP: 3-deoxy-D-arabino-heptulosonate-7-phosphate

DMAPP: dimethylallyl pyrophosphateF5H: ferululate-5-hydroxylaseFHT: fatty w-hydroxy acid /fatty alcohol hydroxycinnamoyl transferaseFPP: farnesyl pyrophosphateGGTase: protein geranylgeranyltransferaseGTase: UDP-glucose:salicylic acid 3-O-glucosyltransferaseHHT: hydroxycinnamomyl-CoA:w-hydroxypalmitic acid- -O-hydroxycinnamomyltransferaseHMGR: 3-hydroxy-3-methylglutaryl-CoA reductaseHQT: hydroxycinnamoyl-CoA quinate transferasePAL: phenylalanine ammonia-lyasePEP: phosphoenolpyruvateTHT: tyraminehydroxycinnamomyl transferase

PPO

malondialdehyde

O O

PLASTID

CYTOSOL

Elicitor-induced activation of the potato pathogenesis-related gene PR-10a requires a 30-bp promoter sequence termed the ERE(elicitor response element) that is bound by the nuclear factor PBF-2 (PR-10a binding factor 2)

DOXP pathway (in plants in general)

pseudotropine formingtropinone reductase

tropine formingtropinone reductase

tropinone

tropine

phenyl-lactic acid

(S)-hyoscyamine

(S)-scopolamine

pseudotropine

N

OH OH

OH

calystegine A3

N

OH

HO

OH

OH

calystegine B1

N

OH OH

OH

OHcalystegine B2

N

OH OH

OH

OHcalystegine B3

N

OH OH

OH

OHcalystegine B4

Polyhydroxylated tropanealkaloids (calystegines) arepotent inhibitors of glycosidasesand found in potato but no direct evidence that theyare associated with resistance.

gamma-aminobutyric acid(GABA)

beta-alanine

Some oxidised polyamines have been reportedto possess antimicrobial activity - but not yetproven in potatoes.

1,5-diazabicylononane

H2O2

H2O2 +NH3

H2O2

O2 + H2O

O2 + H2O

O2 + H2O

chorismate mutaseis activated by tryptophan

high levels of phenylalanineand tyrosine inhibit chorismate mutase(feedback mechanism)

OH

OH

NH

CR O

OH

OH

NH2

4,8-sphingadienine

OH

OH

OH

NH24-hydroxy-8-sphingenine

CH2CHCOOH

O

NH

Cu2+Cu2+

p-coumaroyl tyramineferuloyl tyramine

COOH

COO-glucbenzoic acid

benzoyl-glucose

benzoyl-CoA

Two pathways leadingto benzoic acid have been proposed in plants though the"non-oxidative" route viabenzaldehyde now seems to be unlikely or ofminor importance.

B-oxidation route

"non-oxidative" route

O

3(Z)-hexenal

OCOOH

12-oxo-10(E)-dodecenoic acid

O

divinyl ether synthase

O

COOH

alpha-ketol)

(a cyclopentenone)Both 9(R),13(R) and 9(S),13(S)enantiomers are produced.

OHO

COOH

Acetyl-CoACOOH

OH

COOH

OHO

13-OH-9(Z),11(E),15(Z)-octadecatrienoic acid (13-HOT)

15,16-epoxy-13-OH-9(Z),11(E)-octadecadienoic acid

peroxygenase

hydroperoxidereductase

COOH

O

13-keto-9(Z),11(E),15(Z)-octadecatrienoic acid

lipoxygenase

b-oxidation

O

COOH

allene oxide synthase

glutathione peroxidase(from P. infestans)

COOH

O

?non-enzymiccyclization

non-enzymiccyclization

9-hydroxy-10-oxo-12(Z)-octadecenoic acid

a macrolactone

a macrolactone

?

?

O

C5H11

O

O

O

C5H11

O

O

(an

10-oxo-11-phytoenoic acid(2-oxo-5-pentyl-3-cyclopentene-1-octanoic acid)

OOH

COOH

O

3(E)-hexen-1-ol

O

3(Z)-nonenal

COOHO9-oxononanoic acid

O3(Z),6(Z)-nonadienal

3(Z)-nonen-1-ol

4-hydroxy-2(E)-nonenal (HNE)

2(E)-nonenal

2(E)-nonen-1-ol

2(E),6(Z)-nonadienal

2(E),6(Z)-nonadien-1-ol

3(Z),6(Z)-nonadien-1-ol

OH

O

COOH

OHO

COOH

OHOHOH

COOH

OH

OH OH

COOH

In plants, calcium-dependent protein kinases (CDPK's),are modulated by changes in Ca2+ concentration.

Proteinphosphorylation

ADP

Dephosphorylatedenzyme

Phosphorylatedenzyme

ATPPi

H2O

protein kinasephosphatase

Enzyme control by phosphorylation and/or 14-3-3 proteins

14-3-3 protein may bindto phosphorylated enzyme

14-3-3

Calmodulin-binding protein binds to calmodulinwhich is involved in calcium regulation.

Bakker et al. (2011) identi�ed 280 TIR-NB-LRR and 448 CC-NB-LRR sequences in S. tuberosum ssp. tuberosum.

O-linked N-acetylglucosamine (O-GlcNac) is present in all eukaryotes and may be involved in posttranslational modi�cation of some proteins

protein

protein protein

protein

O-GlcNac

PO4

O-GlcNAcase

serine/threoninekinaseserine/threonine

phosphatase

O-GlcNac transferase

possible regulatorymechanism

4-hydroperoxy-2(Z)-dodecenal

9-hydroxy-13-oxo-10(E)-octadecenoic acid

12-oxo,13-hydroxy-9(Z)-octadecenoic acid

autoxidation

HO

COOH

epoxidehydrolase

epoxidehydrolase

non-speci�c lipid transfer protein (PR-14)may be involved in biosynthesis of epicuticular wax or cutin.

9,10-epoxystearic acid(9R,10S ; 9S,10R)

18-hydroxy-9,10-epoxystearic acid 9,10-dihydroxystearic acid

9,10,18-trihydroxystearic acid

monomers of cutin

oleic acid (C18:1)

azelaic acid(reported to increase salicylicacid in Arabidopsis)

stearic acid (C18:0)

Cyt.-P450

Cyt.-P450

epoxygenase

-desaturase

COOHO

COOH

OH

O COOHHO

HO

COOHHO

HO OH

10-hydroxy-hexadecan-1,16-dioic acid

9-hydroxy-hexadecan-1,16-dioic acid

OH

COOHHOOC

OH

COOHHOOC

10-hydroxy-16-oxo-hexadecanoic acid

9-hydroxy-16-oxo-hexadecanoic acid

OH

CHOHOOC

OH

CHOHOOC

9,16-dihydroxypalmitic acid

10,16-dihydroxypalmitic acid

OH

OHHOOC

OH

OHHOOC

protein methionine S-oxide + reduced thioredoxinprotein methionine + oxidized thioredoxin

peptide methioninesulfoxide reductase

= chacotriose

= solatriose

gluc

rhamrham

gal

rham

Type-2 nuclear histone deacetylases (HDACs) act as negative regulatorsof elicitor-induced cell death in tobacco suggesting that HR is controlledby post-translational modi�cations including (de)acetylation of nuclearproteins (Bourque et al., 2011).

gluc

R. = non oxygen free radical

RO.= alcoxyl radical

ROO. = peroxyl radical

OH. = hydroxyl radical

ONOO- = peroxynitriteGS-NO = nitrosoglutathione

O-acetylation of plant cell wall polysaccharides(e.g. pectin)

OHHOOH

COOH

OHHO OH

COOH

HO HO OH

COOH

Lipid peroxidation

Lipoxygenase

e-

Lipoxygenase - Fe+++

Lipoxygenase - Fe++ - L.

Lipoxygenase - Fe++ - LOO.O2

LOOH

H+

LH

H+

LH = fatty acidsLOOH = hydroperoxy fatty acids

(active enzyme)

Lipoxygenase (LOX) catalyses the hydroperoxidationof unsaturated fatty acids which have a cis-1,4-pentadiene moiety within their structure.

RR

OOH

HH

RR

HH

O.

RR

HH

O

RR

HH

OH

RR

H

OH

.

RR

OH.

RR

OHOO.

hydroxyalkenals

O2

LH L.

peroxideradical

cutin

HOOH

NPROTEIN

lysylresidue

NH3PROTEIN

lysylresidue

+

HNE

N

OHO

PROTEINMichael adducts

OH

O

linolenic acid (C18:3)

2(R)-hydroperoxy-9(Z),12(Z),15(Z)-octadecatrienoic acid

2(R)-hydroxy-9(Z),12(Z),15(Z)-octadecatrienoic acid

8(Z),11(Z),14(Z)-heptadecatrienal

8(Z),11(Z),14(Z)-heptadecatrienoic acid

COOH

linolenic acid (C18:3)

dinor isoprostane E1type II

PPD1type II

dinor isoprostane E1type I

PPD1type I

F1-phytoprostanes

COOH

OOH

O

OCOOH

OOH

O

O

COOH

OH

O

HO

COOH

OHO

HO

COOH

OH

O

HO

COOH

OH

HO

O

COOH

OHHO

HO

COOH

OH

HO

HO

free radical catalysedautoxidation to form phytoprostanes

OHHO HO

COOH

OH OHHO

COOH

Fe(II)

Fe(II) Fe(III)

Fe(III)

sphingosine

sphingosine transfer protein acceleratesthe transfer of sphingosine between membranes.

OH

OH

NH2

COOH

OH

linoleyl alcohol

9- and 13-hydroperoxyoctadecadien-1-olsIn the presence of a free radical scavenger the followingare the major products formed:-9(S)-hydroperoxy-10E,12Z-octadecadien-1-ol13(S)-hydroxy-9Z,11E-octadecadien-1-ol

lipoxygenase

1-monolinoleoyl-rac-glycerol

1-[9-hydroxy-10E,12Z-octadecadienoyl]-rac-glycerol (9-(E,Z)HODE-GE)

O

OOH

OH

O

O

OH

OH

OH

other products of lipoxygenase degradation of 1-monolinoleoyl-rac-glycerol include :-1-[13-hydroxy-9Z,11E-octadecadienoyl]-rac-glycerol (13-(Z,E)-HODE-GE)1-[13-hydroxy-9E,11E-octadecadienoyl]-rac-glycerol (13-(E,E)HODE-GE)1-[9-hydroxy-10E,12E-octadecadienoyl]-rac-glycerol (9-(E,E)HODE-GE)

lipoxygenase

COOH

O O-beta-gluc

tuberonic acid-12-O-beta-D-glucoside (TAG)(O- -D-glucopyranosyltuberonic acid) β

COOCH3

O O-beta-gluc

methyl tuberonate glucoside (MeTAG)

O-beta-gluc

COOH

O

11-hydroxyjasmonic acid glucosideOH

COOH

O

epi-4'-hydroxyjasmonic acid (epi-4'-OHJA)

threonine dehydratase(threonine deaminase)

L-threonine

2-oxobutanoate

gene up-regulated by MeJANH3

H2O

NH2

OH

Snakin-1 is an antimicrobial peptide. Cystatin (a cysteine protease inhibitor) is induced in tomato by arachidonic acidand gamma linolenic acid.

A harpin binding protein (HrBP1) has beenidenti�ed in potato

A number of authors have shown 2-oxoglutarate-dependentdioxygenase (2-ODD) genes to be up-regulated in responseto infection. But, as 2-ODD exists as a family of genes it is notclear which enzyme activity these proteins possess.

isopropylmalate dehydrogenase

3-methyl-2-oxobutanoatedehydrogenase

isovaleryl-CoAdehydrogenase

3-methyl-glutaconyl-CoAhydratase

branched chainamino acidtransaminase

2-oxo-isocaproate leucine

isovalery-CoA

methylcrotonyl-CoA

methyl-crotonyl-CoAcarboxylase gene up-regulated in Arabidopsis by MeJ

3-methyl-glutaconyl-CoA

3-isopropylmalate

H2C

HC

H2C

O

O R1

R2

O X

O

C

C

PO

O-

phospholipase Dphospholipase C

phospholipase A1

phospholipase A2

O

O

NH2

OH

OH

HO

NH2

OH

HO

OCH3

ascorbate

dehydroascorbate

SAM-dependentmethylase

O

OH OH

O

OH

HO

OH

salicylic acid

pyruvate

WRKY?

pathway proposed inArabidopsis but not yetproven in potato

COOH

OH

SO42-SO4

2-S2-

CHLOROPLAST

CYTOSOLCOOH

COOH

OOH

COOH

OH

CHO

COOH

9

-desaturase12

-desaturase15

Membrane lipids

acyl hydrolaselipase

O

N

O

H

CH3

CH3

CH3

CH3

gal

rhamgluc

alpha-solanine

N

beta-chaconine beta-solanine

O

H

CH3

CH3

CH3

CH3

gluc

rhamrham

alpha-chaconine

N

N

N

O N

N

CHO

OH

OH

C3' hydroxylaseCYP98A3

feruloyl-3'-methoxyoctopamineH

C N

OOHHO

OCH3

OCH3

OH

NADH

NAD

Hsp70-likechaperone

dehydratase

glucose-6-phosphateisomerase

phosphomannoseisomerase

glucosamine-6-phosphate synthase

phosphomannomutase

GDP-mannosepyrophosphorylase

galactosedehydrogenase

oxidase/dehydrogenasegalactono-1,4 lactone

dehydrogenase

GDP-mannose3",5"-epimerase

epimerase/reductase

GDP-fucoseNADPH

GDP-gulose

gulose

stress

gulono-1,4-lactone

GDP-galactose

phosphateGMP

GDP-4-keto,6-deoxy-mannose GDP-mannose

mannose-1-phosphate

mannose-6-phosphate

ascorbic acid

fructose-6-phosphate

glucosamine-6-phosphate

fructose-1,6-bisphosphate

NADP

NADPH

NADPH

NADP(+)

ATP

chloroplast G6PDH issubject to phosphorylation

di�erential transcription of G6PDH genes in parsley by fungal elicitorsPi

T6P is considered as a key regulatory molecule

glucose-6-phosphate

trehalose-6-phosphate (T6P) trehalose In Arabidopsis bZIP11 is involvedwith carbohydrate metabolism includingT6P and SnRK1

UDP-glucosetrehalose-6-phosphate synthasegene upregulated by P. infestans

glucono-1,5-lactone 6-phosphate(6-phosphogluconolactone)

6-phosphogluconate

ribulose-5-phosphate

glyceraldehyde-3-phosphate

dihydroxyacetonephosphate

glycerol-3-phosphate (G3P)

glycerol-3-phosphate interacts with the lipidtransfer protein DIR1 to induce SAR in plants.

phosphatidicacid

diacylglycerol

acyl-G3P(lyso-phosphatidicacid)

glyceraldehyde-3-phosphate

1,3-bisphosphoglycerate

3-phosphoglycerate

2-phosphoglycerate

phosphoenolpyruvateoxaloacetateGlyoxylatecycle

erythrose-4-phosphate

plastid enzymes of G6PDHare redox regulated

phosphoglucomutase

trehalose-6-phosphate synthase

trehalose-6-phosphate phosphatase

triosephosphateisomerase

phosphofructokinase

fructose 1,6-bisphosphatealdolase

glycerol-3-phosphatedehydrogenase

glyceraldehyde-3-phosphatedehydrogenase

phosphoglyceratekinase

phosphoglyceratemutase

pyruvate kinase

enolase

glucose-6-phosphatedehydrogenase (G6PDH)

6-phosphogluconolactonase

6-phosphogluconatedehydrogenase

glucose-1-phosphate glucose-1-phosphate + ATP diphosphate + ADP-glucose

galactono-1,4-lactone

galactose

Pathway suggested from workon Arabidopsis. No con�rmationyet that this pathway is correctfor potato

ferricytochrome c

ferrocytochrome c

p-hydroxyphenylpyruvate dioxygenase

homogentisatephytyltransferase p-hydroxy-

phenylpyruvicacid

homogentisatetocopherol 2-methyl-6-phytyl-benzoquinol

glucose-6-phosphate

myo-inositol-1-phosphatesynthase (MIPS)

(pathway from tobacco)

ABC transporteracid phosphatase likeactin depolymerizing factor 6alcohol:NADP+ oxidoreductaseallantoinaseankyrin-likeallene oxide synthase (AOS3) likeamino acid transporteraspartic proteinase 2ATP/ADP transporterauxin induced (e.g. GH3)biotic cell death associatedbromo-adjacent homology (BAH) domainCAAX prenyl proteasecalcineurincalcium binding proteincalmodulincalnexincatechol oxidaseCf-likechalcone reductasecitrate binding proteincopper amine oxidasecyclophilincysteine protease (cathepsin B like)cysteine protease inhibitorcytochrome fcytokinin oxidasedecarboxylate carrier proteindehydration responsive element-binding proteinDnaJ likeDND1 likeDOF transcription factorenhanced disease susceptibility (EDS1) likeenhanced disease susceptibility (EDS5) likeelongation factor 1-alphaErwinia-induced protein (ei1)Erwinia-induced protein (ei2)esteraseexocyst subunitexostosin likeextensinF box familyferredoxinferritin�brillin/CDSP34 protein (plastid lipid-associated)formin homology 2 domain-containing proteinglycogenin glucosyltrasferase likeHcr-likeheat shock proteinhexose transporterHIN1 likejasmonic acid 2lipaselipid transfer proteinlipid desaturaseluminal binding proteinmetal transportermetalothioneinmetallocarboxypeptidase inhibitorMRP-likeMYB transcription factorNa/K proton exchangerNAC (N-acetylcysteine) domain proteinNADP-dependent malic enzymeNADP(H) oxidoreductaseNam-likeNDR1 likenectarin 5 likeNPR1 likeNtPRp27-like2-oxoglutarate dehydrogenaseoxysterol-binding proteinPAD4PEN1PEN2 likePEP carboxylase kinaseperoxyredoxinphosphate transporter (StPT3)pleiotropic drug resistant (PDR1, PDR2, PDR3, PDR4)poly(A) binding proteinporin (mitochondrial)26S proteasome AAA-ATPaseprp1protein kinase (shaggy-like)proteinase inhibitor (pinII)protein synthesis initiation factor 4GpSTH-2pSTH-21PUB17R1 geneRAR1 likerespiratory burst oxidaseRING box likeripening regulated proteinsenescence-associated protein 5sesquiterpene synthaseSGT1 likeSudD-likethaumatin likethaumatine like receptor kinasetransducin family / WD40 repeat proteinubiquinol-cytochrome C reductase complexUPA16 (MTN3 like)vacuolar processing enzymeWD-40 repeat proteinwin1win2WIZZ (WRKY family)WRKY transcription factorswun1wun2xylosidase beta-1,4yippee-likeZFP1ZIKzinc �nger proteins

Other genes or proteins up-regulated by wounding or infection but not yet included in 'pathways'

Dehydroascorbate has been shown toinhibit some kinases in HeLa cells andmay therefore do the same in plants.

HNE has been shown to activate some MAP kinasesin animal cells. No evidence yet for plants.

nicotinamideCONH2

N

nicotinic acid

SAM SAHc

nicotinic acid betaine(trigonelline)

COOH

N

COOH

N

CH3

nicotinic acidN-methyltransferase

OH

(E)-beta-farnesene(Z-beta-farnesene also detected)

delta-cadinene

germacrene A

beta-elemene

HOHO

alpha-cadinol delta-cadinene

beta-bisabolene

beta-sesquiphellandrenealpha-cubebenebeta-cubebenealpha-copaene

alpha-gurjunene

cross-linkedN-trans-feruloyltyramine dimerandN-cis-feruloyltyramine dimer

(down-regulated by compatible P. infestansinfection)

CO2 + H2O

carbonic anhydrase

H2CO3

GTP

guanylylcyclase

cGMP

ATP

adenylatecyclase

cAMP

OH

CHO

4-hydroxyhexenalOH

CHO

OH4-hydroxynonenal (HNE)

N1,N12-Bis(dihydroca�eoyl)spermine (kukoamine A) and N1,N8-bis(dihydroca�eoyl)spermidine havebeen isolated from potato.

OH

COOH

9(S)-HOT

compounds which induce (some) resistance-relatedresponses when applied exogenously to potato

metabolic conversion

signal transduction

StMBF1 is up-regulated in response to oxidative stress andinteracts with the TATA-box binding protein (Arce et al., 2006).

nuclear factor PBF-2(DNA binding protein p24)

PR-10a

CaPR10 interacts with CaLRR1 (in Capsicum annuum)

The "Whirly" DNA binding proteinStWhy1 protein is a transcriptionalactivator of genes containing thePBF2 binding PB promoter element.

kunzeaoOH

SGT3 SGT3

Glutaminyl cyclase (an acyltransferase) catalyzes theconversion of N-terminal glutaminyl residues intopyroglutamic acid e.g. on pathogenesis-related proteins.

The substrate for sesquiterpene synthase is farnesyl diphosphate.

N-acylphosphatidylethanolamine (NAPE)

phosphatidylethanolamine (PE) acylated sterolglycosides (ASG) increasein tobacco after elicitation

N-acylethanolamine (NAE)

elicitor stimulationin tobacco

(e.g. N-lauroylethanolamine andN-myristoylethanolamine)

phospholipase D

NAPE synthase

lipoxygenase

ethanolaminekinase

phosphoethanolamineN-methyltransferase

phosphoethanolamineN-methyltransferase

phosphoethanolamineN-methyltransferase

cytidyltriphosphate-phosphocholinecytidyltansferase

aminoalcohol-phosphotransferase

cholinekinase

cytidyltriphosphate-phosphoethanolaminecytidyltransferase

ethanolamine

phosphoethanolaminephosphomonomethylethanolaminephosphodimethylethanolamine

phosphatidyldimethylethanolamine phosphatidylmonomethylethanolamine

phosphocholine

cytidine 5'-diphosphatecholine

phosphatidylcholine

Choline and phosphatidylcholine biosynthesis

choline

cytidyldiphosphate (CDP)ethanolamine

(CH3)3N-CH2-CH2-OH

(CH3)3N-CH2-CH2-O-P-OH

O

O

free fatty acids

NAPEsynthase fatty acid

amidehydrolase

A leucine-rich repeatreceptor-like protein kinaseStLRPK1 is induced by P. infestans.

A RING-H2 �nger protein, StRFP1,is constitutivel expressed but isup-regulated by P. infestans

A lectin receptor kinase has been shownto bind to the Phytophthora RXLR-dEERe�ector IPI-O in vitro.

IPC synthase

StMES1

hyoscyamine 6-hydroxylase (a 2-oxoglutarate-dependentdioxygenase)

Thioredoxin catalyzes the SA-induced release of NPR1 monomerswhich translocate to the nucleus where they interact with TGA transcriptionfactors. S-nitrosylation of NPR1 is mediated by S-nitrosoglutathione.

strictosidine synthase (up-regulatedby P. infestans)

secologanin

3-alpha(S)-strictosidine

7-deoxyloganin loganin secologanin

4-coumaroyl-CoA

malonyl-CoA

tetrahydroxychalcone(naringenin chalcone)

naringenin

eriodictyol

rutin (quercetin-3-rutinoside)

nicoti�orin (kaempferol-3-O-rutinoside) ?

chalconesynthase

chalconeisomerase

�avonoid 3’hydroxylase

dihydroquercetinquercetin

conversion byV. dahliae

2-protocatechuoylphloroglucinolcarboxylicacid

a �avanone and a �avonol-glucoside have been detected in potato in response to P. infestans. 4-methyl-umbelliferyl-β-glucoronide has been detected.

�avonone 3hydroxylase

�avanolsynthase

quercetinase

activation of phospholipase D

phytosphingosine-1-phosphate

mobilisation of Ca2+ ?programmed cell death

sphinganine induces a calcium-dependentprogrammed cell death in tobacco BY-2 cells,and also triggers production of H2O2 via activation of NADPH oxidases, and inductionof NO. OH

O

O

OH

OH

P

NH2OH

gallic acid

OH

OH

O

HO OH

Mono-ubiquitination has di�erent consequencesto polyubiquitination. Further, depending on whichamino acid is ubiquitinated may also a�ect thesubsequent role of the protein. Some ubiquitinatedproteins may therefore be involved in a proteasome-independent function such as signal transduction.

The protein Star encodes a RING�nger protein and is a putativeE3 ubiquitin ligase.

Sumoylation

PROTEIN

PROTEIN

protease

ligase

SUMOSUMOprecursor

E1, E2, E3

AVR3a(from P.infestans)

CMPG1(an E3 ligase)

R3a, R2,Rx PCD (independent of CMPG1)

PCD

E1 = ubiquitin activating enzymeE2 = ubiquitin conjugating enzymeE3 = ubiquitin ligase

PROTEIN PROTEIN

UbUb

Ub

Ub

UbProtein ubiquitination

26S proteasome(ATP dependent)

peptides

deubiquitinating enzymes may be involved insuppressing plant cell death, ie a negativeregulator of HR.

The COP9 signalosome (CSN) is a multi-protein complex that regulates the activities of cullin-RING E3 ubiquitin ligases (CRLs). CSN is involved with plant defense responses such as jasmonate-dependent responses.

Ub

Multiple isoforms of SUMO (small ubiquitin-related modi�er)exists in plants. SUMO conjugation (sumoylation) of someproteins can regulate their activity and is associated withstress response. Enzymes include SUMO activating enzyme (SAE),SUMO-conjugating enzyme (SCE), SUMO ligase complex, andSUMO-speci�c proteases. SUMO conjugation plays a role insuppressing defence signalling in non-infected plants.

NO3-

nitrate reductase

nitrotyrosine (peroxynitrite mediatednitration of protein tyrosine residues)

cysteineS-nitrosylation

GSH

S-nitrosoglutathione(GSNO)

PIP2

AVR3a from P. infestans interacts withand stabilizes potato E3 ubiquitin ligaseCMPG1.

P. infestans

P. infestans

Avr3a

Avr3a inhibits cell death triggeredby the INF1 elicitor from P. infestans

R3a

RanGAP2 interacts with R proteins

Avr3b

cystatin-like e�ector proteins (EPICseg EPIC1, EPIC2B)(produced by P. infestans) inhibitpotato proteases eg papain-likecysteine protease C14

R3b

P. infestans

PiAVR2

P. infestans

SNE1 (suppressor of necrosis 1)is expressed during biotrophicgrowth stage and suppressesaction of necrosis-inducinge�ectors (Nep1-like proteins)eg PiNPP1.1R2

BSL1(BSU-likeprotein1)

C14 / EPIC complex

R3b does not recognise Avr3a

glucose-1-phosphateadenylyltransferase

allyl alcoholacrolein (propenalor ethylene aldehyde)

allyl-alcoholdehydrogenase

+ NADPH + H+H

H2C

OOH + NADP+

sucrose-phosphatesynthase

SPS regulated by SnRK1 in ArabidopsisSPS down-regulated in potatoin response to P. infestans

fructose 6-phosphate + UDP glucose UDP + sucrose 6-phosphate

2-keto acids(S)-2-hydroxy acids

H2O2O2

glycolate oxidase

glutamic-gamma-semialdehyde

OH

OO

HO

R3a relocated to vesicles in endocytic pathway

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