metabolic pathways of_diseased_potato

Halliwell-Asada enzyme pathway

gamma-solanine

Shikimate pathwayPhenylpropanoidbiosynthesis

Polyaminebiosysnthesis

Glycoalkaloids

Ethylenebiosynthesis

SAM cycle

Sesquiterpenephytoalexinbiosynthesis

Fatty acid degradation

Phosphoinositide cascade

COO-gluc

COSCoA

COOH COOH COOH COOH

COS-CoA

OH OH OH OH

OH OCH3 OCH3 OCH3HO H3CO

C4Hphenylalaninehydroxylase

F5H COMT

4CL 4CL 4CL 4CL 4CL

putrescine hydroxycinnamoyl transferase

UDP-glucose: sinapic acidglucosyltransferase (SGT)

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

COS-CoA

OCH3HO

COS-CoA

OCH3H3CO

CCoA3H CCoAOMT

CCoAOMT

p-coumaryl-CoA ca�eoyl-CoA

ca�eoyl aldehyde

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

OCH3HO

OHconiferyl alcohol

OCH3H3CO

5-hydroxyferulyl alcohol(5-hydroxyconiferylalcohol)

sinapyl alcohol

CCR CCR CCR CCR

CAD CAD CAD CAD

p-coumaryl alcohol

o-hydroxycinnamic acid(o-coumaric acid)

PAL(multipleisozymes)

CoA ligase

coumarin

guaiacyl lignin syringyl ligninp-hydroxyphenyl lignin

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

arogenic acid

arogenate dehydratase

phenylalanine

OHtyrosine

tyramine

p-hydroxy-phenylpyruvicacid

isodityrosine intramolecularcross-link between HRGPs

peroxidase

tyrosineaminotransferase

tyrosinedecarboxylase

glutaminesynthetase

phenol oxidase

Dopaquinone

tyrosine3-monooxygenase(phenol oxidase)

HOOC CH2

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

protein

NADPH NADP+

shikimatedehydrogenase

3-dehydroshikimic acid

dopaminenorepinephrine

normetanephrine

3-dehydroquinic acid

3-phosphoquinic acidOH

quinic acid

hemiterpenes

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

O NH(CH2)4NH2

NH2(CH2)4NH2

NH2(CH2)4NHCH3

O NH(CH2)4NH2

feruloylputrescine

putrescine

putrescine-N-methyltransferase

pyrrolinedehydrogenase

N-methylputrescine oxidase (MPO)

polyamine oxidase

diamine oxidase

polyamine oxidase

N-ca�eoylputrescineOH

COO-gluc

O-gluc

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

COOHHO

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

chlorogenic acid(4 ca�eoylquinic acid)

chlorogenic acid(3 ca�eoylquinic acid)

COOHHO

isochlorogenic acid(4,5 ca�eoylquinic acid)

isochlorogenic acid(3,5 ca�eoylquinic acid)

quinic acid

melanin

Gary D. Lyon

CH2CH(NH2)COOH

skatole

pyruvate + L-glutamate

L-glutamine

COO-Glu

OCH3H3CO

coniferyl aldehyde(coniferaldehyde)

OCH3HO

5-hydroxyferuloyl aldehyde(5-hydroxyconiferaldehyde)

OCH3H3CO

OHsinapyl aldehyde(sinapaldehyde)

p-coumaryl aldehyde

protocatechualdehyde

a-hydroxyacetosyringonesyringic acid

vanillinOH

vanillic acid

catechincatechin has beendetected in potato

O2 + NADPH2 HCHO + NADP

CHOHCH2NH2

OHoctopamine

feruloyl-CoA

CH2CH2NH2

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.

C3' hydroxylaseCYP98A3CST

brassinosteroid-6-oxidase 2 (P450)

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

vanilloside(glucovanillin)

OHHOOC

acetoacetyl-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

OHHOOC

mevalonic acid5-pyrophosphate(5-pyrophosphomevalonate)

OPP OPP

dimethylallyl pyrophosphate(DMAPP)

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)

neryl pyrophosphate

monoterpenes

geranylgeranylpyrophosphate(GGPP)

squalene

squalene 2,3-epoxide

secologanin synthase(a P450)

7-deoxyloganin7-hydroxylase(a P450)

squalene 2,3-epoxidase cycloartenol cyclasecycloartenol

chlorophylls

diterpenescarotenoids

geranylgeranylpyrophosphatesynthetase

isopentylpyrophosphate+ NADPH

glucgamma-chaconine H

solanthrene

demissidine

rhamrham

solamargine

solasodiene

vetispiradiene

vetispiradiene synthaseHO

OH OCOCH3OH OCOCH3

OH OCOCH3

OCOCH3

phytuberin

OCOCH3O

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

solavetivone

O CH2OH

oxysolavetivone

O CH2OH

isolubimin

fungal degradation

HO CH2OH

15-dihydrolubimin

HO CHO

lubimin

3-hydroxylubimin

rishitin

13-hydroxyrishitin(rishitin-M-1)

11,12-epoxyrishitin

rishitinone

hydroxyglutinosoneOH

mono-oxygenase

tyramine

OHp-hydroxybenzoic acid

p-hydroxybenzaldehydedehydrogenase

2-dehydrolubimin

O11,12-epoxycyclodehydro-isolubimin

2-dihydrocyclodehydro-isolubimin (cyclolubimin)

cyclodehydroisolubimin

O CH2OH

HO CH2OH

HO CHO

3,4-dehydroisolubimin

15-dihydro-10-epilubimin

10-epilubimin

OHO-gluc

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

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)

12-oxo-9(Z)-dodecenoic acid

12-oxo-phytodienoic acidreductase

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

COOCH3

Omethyl (-)-jasmonate

tuberonic acid12-hydroxy-jasmonate sulphate

O OSO3H

alcoholdehydrogenase

3Z-hexen-1-ol

2E-hexenal

3(E)-hexenal

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

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

CH3-S-CH2-CH2-CH-COOH

methionine

CH3-S-CH2-CH2-CH-COOH

AdenineO

OPO3HO

H2C COOH

ACC synthase

nicotianaminesynthase

5'-methylthioadenosinenucleosidase

MTR kinase

CH2 CH2

ethylene

ETR1ETR2ERS1ERS2EIN4

CTR1(a MAPKKK)

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

PPi + Pi

HPO4 + HCOOHO2

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

nicotianamine

5'-methylthioadenosine(MTA)

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

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

epoxide hydrolaseepoxide hydrolase

divinyl ether synthase(P450, CYP74D)

NADPH + H+

beta-oxidation

alpha-dioxygenase(a pathogen inducibleoxygenase (PIOX)

beta-oxidation

hydroxy-jasmonatesulphotransferase

anthranilatesynthase

phosphoribosyl-anthranilatetransferase

phosphoribosyl-anthranilateisomerase

tryptamine

tryptophandecarboxylase

tryptophanaminotransferase

CH2CH2NH2

salicylatehydroxylase

catechol

NADPH + H+

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

2H2OO2

dehydroascorbate

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

photosynthesis

O2- HO2.

superoxide

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

superoxide dismutase

photorespirationfatty acid oxidationphotosynthesisoxidative phosphorylation

catalase

H2O + O2

peroxidase(includesE.C. 1.11.1.12)

RH + H2O

Fe+++(Cu++)

Fe++(Cu+)

Fenton reaction(non-enzymic)

superoxide

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

hydroperoxylradical

HO- + HO.

NADPH + O2

geosmin

FPP synthase

geranylgeranylated proteins

gibberellins

inactive HMGRkinase

PP1PP2A

exogenous fatty acid

O C COOH

Last modi�ed 24 December 2012

squalenesynthase

O2 monooxygenase

HMGR kinase is notAMP-activated in potato

O-gluc

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

benzaldehyde

benzaldehydedehydrogenase

2,5-dihydroxybenzoicacid (gentisic acid)

2,3-dihydroxybenzoicacidCOOH

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

esculetinO-gluc

esculin

scopoletinH3CO

gluc-O

scopolin

gluc-O

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

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

Comments and additional information should be sent to: GaryDavidLyon@gmail.comChart can be viewed on the internet at www.potatometabolicpathways.webs.com

Metabolic pathways of the diseased potato

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

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.

tyrosine ammonia-lyase (only occursin monocots ?)

mevalonic acidkinase

mevalonic acid5-phosphate kinase

mevalonate5-pyrophosphatedecarboxylase

isopentenylpyrophosphateisomerase

geranylgeranylpyrophosphatesynthase

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

O2 + NADPH NADP

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

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

O O(CH2)15

suberininvolved inwound healing

OHCOOH

O C COOH

isochorismic acid

anthraquinonesphylloquinones

isochorismatesynthase

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)

(CH2)n

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)

arogenatedehydrogenase

glutamine 2-oxoglutaric acid

glutamic acid

reduced ferredoxin

oxidisedferredoxin

glutamine

from PAL

GOGAT = glutamine: 2-oxo-glutarateamidotransferase)

homocysteine +adenosine

homocysteine

cystathione

threonine

isoleucine

cysteine

cysteine plays an important rolein the immune response ofArabidopsis

O-acetylserine serine

homoserine

aspartateO-phosphohomoserine

S-adenosyl-Lhomocysteine(SAHc)

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

hydroperoxidecyclase

hydroperoxide dehydratase

allene oxide

alpha-ketol

gamma-ketol

cholesterol

HCH3CH3

CH3CH3

HCH3CH3

CH3CH3

cholesteranol

CH3H2N

CH3 H2N

CH3CH3

CH3solasodine

CH3CH3

soladulcidine

tomatidenol

CH3CH3

dormantinol

CH3CH3

dormantinone

solanidine

CH3CH3

verazineHO

CH3CH3

etioline

Possible biosynthetic pathwaysfrom cholesterol andcholesteranol to aglycones.

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

acetyldehydrorishitinolO

OHrishitinol

polyphenoloxidase(tyrosinase)

dopadecarboxylase

chlorogenic acidO

chlorogenic acidquinone

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

polyphenoloxidase H+

O-gluc

arbutin

vanillic acid glucoside(vanillate glucoside)

O-glucp-hydroxybenzoic acidglucoside

O NH-CH-CH2-COOH

feruloylaspartate

COO-gluc

OHp-coumaroyl-D-glucose

COO-gluc

ca�eoyl-D-glucose

COO-gluc

t-cinnamoyl-D-glucose

UDPG:cinnamateglucosyltransferase

O-gluc

COOCH3

Omethyl (+)-jasmonate

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

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

H-γ-Glu-Cys-Gly-OH

(g-Glu-Cys-Gly)2

protein adducts

(allene oxidesynthase: A cytochrome P450 ; CYP74A)

(allene oxidecyclase)

3-dehydroquinatesynthase

ornithine

delta-pyrroline-5-carboxylate

malonyl-ACC

jasmonic acid-ACC

malonyltransferase

quinatedehydrogenase

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.

glucxyl

dehydrodemissinegal

glucgluc

dehydrocommersoninegal

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

COOHHOOC

traumatic acid(implicated in woundsignalling)

tomatidineHO

demissineO

commersonine

A feruloytyramine trimer has beenisolated from scab lesions.

glucgluc

tomatine

rhamgluc

solasonine

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)

COOHNH2 NH2

COOH NH2H2NNH2 H2N

isodityrosine

di-isodityrosine

proteinkinase C

triacylglycerol(triglyceride)

Ca2+ mobilisation

4-coumaroyloctopamine

4-coumaroylnoradrenaline

cinnamomyloctopamine

+ 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.

hydroxy-solanidine

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

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

NO associated (NOA gene)

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

rhamgluc

alpha-solamarine

rhamrham

beta-solamarine

pulcherosine(in tomato)

PtdIns(3,4,5)P3

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

glutathioneS-transferase

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

nitrosatedproteins (nitrosylation)

RCH2NH2 + O2 + H20 RCHO + NH3 + H2O2

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)

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

catechol

asparaginesynthetase

glutamine + aspartate

asparagine + glutamate

anthranilate1,2 dioxygenase

dehydroshikimic aciddehydratase ?

protocatechuic acidamine oxidase

indole-3-pyruvicacid decarboxylase

indole-3-acetaldehydeoxidase

COO-gluc

glucosyl salicylate(salicyloyl-glucose ester)

salicylic acidcarboxylglucosyltransferase

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

PtdIns(3,5)P2 PIP5K

PIP5Kinositol(poly)phosphate5-phosphatase (SHIP)

oxidisedglutathione(GSSG)

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

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

13-lipoxygenase

hydroperoxide dehydratase

(allene oxidesynthase)

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

12-oxo-phytodienoic acid

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

NADPH + H+

beta-oxidation

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

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

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

beta-oxidation

jasmonic acid carboxylmethyltransferase

hydroperoxidecyclase(allene oxidecyclase)

NADPH + H+

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

b-oxidationbeta-oxidation

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

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).

lipoxygenase

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

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

peroxygenase

hydroperoxidelyase

hexanal

3(Z)-hexenal

3(E)-hexenal

4-hydroxy-2(E)-hexenal

lipoxygenase

peroxygenase

(steps for traumatin shown in soybean and alfalfa)

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

g -ketol

a -ketol

sphinganine(dihydrosphingosine)

NH2OHphytosphingosine

sphingosine

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

IPC synthase

OH COOH

cysteinyldopa

leucodopachrome

+ cysteine

(COOH)

eumelanin

polymerization

(COOH)

benzothiazinederivative

(COOH)

phaeomelanin

polymerization

NADPH + H+

ceramide synthase (sphinganineacyltransferase)

N-acyl sphinganinedehydrogenase

sphingosinekinase

sphingosine-1-phosphatephosphatase(SPPase)

glutathione synthetase

γ-glutamylcysteine synthetase

γ-glutamylcysteine

sphingolipids

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.

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

OHOHOH

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

epoxide hydrolaseepoxide hydrolase

spontaneoushydrolysis

Sesquiterpenes

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)

caryophyllene oxide

cedrol

beta-caryophyllene

trans-beta-bergamotene

trans-apha-bergamotene

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

arachidonic acid (20:4)

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

CH3O OCH3

'high energy' diphosphorylatedinositol polyphosphates

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

malondialdehyde

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

calystegine A3

calystegine B1

OHcalystegine B2

OHcalystegine B3

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 +NH3

O2 + H2O

chorismate mutaseis activated by tryptophan

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

4,8-sphingadienine

NH24-hydroxy-8-sphingenine

CH2CHCOOH

Cu2+Cu2+

p-coumaroyl tyramineferuloyl tyramine

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

3(Z)-hexenal

12-oxo-10(E)-dodecenoic acid

divinyl ether synthase

alpha-ketol)

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

Acetyl-CoACOOH

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

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

lipoxygenase

b-oxidation

allene oxide synthase

glutathione peroxidase(from P. infestans)

?non-enzymiccyclization

non-enzymiccyclization

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

a macrolactone

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

3(E)-hexen-1-ol

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

OHOHOH

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

Proteinphosphorylation

Dephosphorylatedenzyme

Phosphorylatedenzyme

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

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

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

epoxygenase

-desaturase

O COOHHO

COOHHO

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

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

COOHHOOC

10-hydroxy-16-oxo-hexadecanoic acid

9-hydroxy-16-oxo-hexadecanoic acid

CHOHOOC

9,16-dihydroxypalmitic acid

10,16-dihydroxypalmitic acid

OHHOOC

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

peptide methioninesulfoxide reductase

= chacotriose

= solatriose

rhamrham

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).

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

OHHO OH

HO HO OH

Lipid peroxidation

Lipoxygenase

Lipoxygenase - Fe+++

Lipoxygenase - Fe++ - L.

Lipoxygenase - Fe++ - LOO.O2

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.

hydroxyalkenals

peroxideradical

NPROTEIN

lysylresidue

NH3PROTEIN

lysylresidue

PROTEINMichael adducts

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

dinor isoprostane E1type II

PPD1type II

dinor isoprostane E1type I

PPD1type I

F1-phytoprostanes

free radical catalysedautoxidation to form phytoprostanes

OHHO HO

OH OHHO

Fe(II)

Fe(II) Fe(III)

Fe(III)

sphingosine

sphingosine transfer protein acceleratesthe transfer of sphingosine between membranes.

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)

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

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

11-hydroxyjasmonic acid glucosideOH

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

threonine dehydratase(threonine deaminase)

L-threonine

2-oxobutanoate

gene up-regulated by MeJANH3

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

phospholipase Dphospholipase C

phospholipase A1

phospholipase A2

ascorbate

dehydroascorbate

SAM-dependentmethylase

salicylic acid

pyruvate

pathway proposed inArabidopsis but not yetproven in potato

SO42-SO4

CHLOROPLAST

CYTOSOLCOOH

-desaturase12

-desaturase15

Membrane lipids

acyl hydrolaselipase

rhamgluc

alpha-solanine

beta-chaconine beta-solanine

rhamrham

alpha-chaconine

C3' hydroxylaseCYP98A3

feruloyl-3'-methoxyoctopamineH

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(+)

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

nicotinic acid

SAM SAHc

nicotinic acid betaine(trigonelline)

nicotinic acidN-methyltransferase

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

delta-cadinene

germacrene A

beta-elemene

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

guanylylcyclase

adenylatecyclase

4-hydroxyhexenalOH

OH4-hydroxynonenal (HNE)

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

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

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

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

gallic acid

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

protease

ligase

SUMOSUMOprecursor

E1, E2, E3

AVR3a(from P.infestans)

CMPG1(an E3 ligase)

R3a, R2,Rx PCD (independent of CMPG1)

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

PROTEIN PROTEIN

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.

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.

nitrate reductase

nitrotyrosine (peroxynitrite mediatednitration of protein tyrosine residues)

cysteineS-nitrosylation

S-nitrosoglutathione(GSNO)

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

P. infestans

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

RanGAP2 interacts with R proteins

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

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

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

R3a relocated to vesicles in endocytic pathway

metabolic pathways of_diseased_potato

arachidonic acid

zoctadecadienoic acid

phytodienoic acid dnopda

gamma linolenic acid

loocooh o

transfer protein nsltp

desaturase oleic acid

harpin binding protein

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