1. protein kinase
Phosphorylated
enzyme
MAP kinase kinase
(MAPKK or MEK)
activation of protein
kinase p51-PK
WRKY transcription factor
14-3-3 protein may bind
to phosphorylated enzyme
MAP kinase
(MAPK or ERK extracellular
signal-regulated
kinase)
O-linked N-acetylglucosamine (O-GlcNac) is
present in all eukaryotes and may be involved
in posttranslational modification of some proteins
O-GlcNac
protein
O-GlcNac
transferase
protein
possible
regulatory
mechanism
PO4
serine/threonine
phosphatase
protein
MAP kinase phosphatases
involved in
dephosphorylation of MAPKs.
Act by negative feedback
regulation of MAPK activity.
O-GlcNAcase
resistance responses
(includes basic chitinase, phytoalexin and
protease inhibitor accumulation)
sphingolipids
OH
(sphingosine is a potent
inhibitor of protein
kinase C in animals)
sphingosine
kinase
SEBF
PR10a
acylsphingosine
deacylase
NH2
OH
sphingosineacetyl
transferase
NO
H2C
StCDPK5 directly involved with regulating
the oxidative burst via phosphorylation of
the NADPH oxidase StRBOHB
HR ?
OH
R1
O
C
O
HC
O
C
O
O
P
OH
O
PtdIns(3,5)P2
O
ceramide
1-phosphate
NH2
X
regulation of specific
protein kinases ?
OH
OH
4,8-sphingadienine
phospholipase D
NH2
inositol-phosphorylceramide(IPC)
OH
IPC synthase
OH
4-hydroxy-8-sphingenine
OH
In plants PtdIns(4)P is 10-20 fold
higher than PtdIns(4,5)P2 (in animals
the ratio is 1:1).
mannose-inositol-P-ceramide (MIPC)
phosphatidylinositol
M(IP)2C synthase
OH
3-phosphatase
mannose-(inositol-P)2-ceramide (M(IP)2C)
O
2(E)-nonen-1-ol
OH
4-hydroxy-2(E)-nonenal (HNE)
2(E),6(Z)-nonadien-1-ol
Ins(1,2,4,5,6)P5
2(E)-nonenal
COOH
2(E),6(Z)-nonadienal
COOH
O
COOH
9-oxononanoic acid
O
O
colneleic acid
9-[1'(E),3'(Z)-nonadienyloxy]-8(E)-nonenoic acid
3(Z),6(Z)-nonadienal
InsP7 kinase
OH
OH
OH
OH
OH
COOH
9
-desaturase
oleic acid (C18:1)
-desaturase
epoxygenase
O OH
COOH
COOH
epoxide
hydrolase
9(S),10-epoxy-10,12(Z)-octadecadienoic acid
(an allene oxide)
Cyt.-P450
HO
COOH
HO
C5H11
monomers of cutin
a macrolactone
O
O
O
O
OH
(allene oxide
synthase)
HO
hydroperoxide
dehydratase
hexanal
HOOC
9-hydroxy-hexadecan-1,16-dioic acid
g -ketol
9-hydroxy-13-oxo-10(E)-octadecenoic acid
COOH
HOOC
HO
COOH
lipoxygenase
COOH
O
HOOC
9-hydroxy-16-oxo-hexadecanoic acid
NADPH + H+
dinor-oxo-phytodienoic acid
(dnOPDA) (increases in wounded
tissues)
NADP+
H
H
COOH
COOH
O
Lipoxygenase
R
H
H
R
R
LH
H
H
R
R
H
H
R
.
Lipoxygenase - Fe++ - LOO
COOH
O
3-oxo-2-(2'-pentyl)cyclopentanebutanoic acid
(DH-OPC-4:0)
R
malondialdehyde
+
NH3
PROTEIN
lysyl
residue
Michael adducts
PROTEIN
N
OH
H
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.
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
COOH
.
(+)-7-epi-dihydrojasmonic acid
epi-jasmonic acid
((-)-7-epi-jasmonic acid)
OH
COOH
R peroxide
OH radical
hydroxyalkenals
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.
COOH
O
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.
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.
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.
COOCH3
receptor
O
methyl (-)-jasmonate
COR
O
amino acid conjugates of (-)-jasmonic acid
(R=leucine, isoleucine, valine)
epi-jasmonic acid
((+)-7-epi-jasmonic acid)
COOH
O
OH
O
COOH
HO
OH
CHO
F1-phytoprostanes
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.
O-beta-gluc
O
methyl tuberonate glucoside (MeTAG)
arachidonic acid (20:4)
from P. infestans
HO
OH
N
OH
COOH
CH3
NH
CH3
HO
CH3
HO
H
CH3
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 infestans but is
reported to be absent in higher plants.
rishitinol
COOH
rishitin
H
CH3
eicosapentaenoic acid
from P. infestans
H
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)
StPRp27 reported to contribute
to race-nonspecific resistance to
P. infestans.
In tobacco, basic PR proteins accumulate in the
vacuole whilst acidic PR proteins accumulate
extracellularly.
P. infestans induces 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.
CH3
HO
OH
hydroxyglutinosone
H
HO
HO
O
leptine I
leptine II
CH3
N
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 calciumsensitive processes: (calcium-myristoyl switches).
Myristoyl CoA:protein N-myristyltransferase is the enzyme
involved in protein myristoylation.
rham
beta-solanine
O
rham
CH3
CH3
CH3
alpha-chaconine
O
H
O
gluc
H
gal
gluc
O
NH
CH3
H
CH2
O
rham
rham
O
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.
O
nicotianamine
synthase
CH2
O
OH OH
CH3
malonyl-ACC
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.
ERF1 interacts with the GCC box
of ethylene response genes
rham
Responses
(eg induction
of stress response
genes including Eca
response gene-1)
CH3
gluc
gluc
CH3
CH3
H
N
CH3
CH3
H
N
CH3
CH3
CH3
CH3
xyl
CH3
gal
dehydrodemissine
dehydrocommersonine
O
gluc
gluc
gluc
gluc
rham
rham
The relative amounts of glycoalkaloids
and their aglycones vary between
different Solanum species.
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.
ADP-ribosylation factors (ARFs) are small GTP-binding
proteins that function in the assembly of coated vesicles
that transport proteins between intracellular organelles.
HMGR encoded by three genes. Hmg1 is
strongly induced by wounding leading to
accumulation of glycoalkaloids, whereas
hmg2 and hmg3 are enhanced by arachidonic
acid and P. infestans.
H
O
N
ERFs
PK12 ?
ERN
EIN3
EIL1-3
(nuclear)
EIN2
MAPK
(eg SIMK, MMK3
MPK6 (MPK13))
ERFs are a family of ethylene-responsive
transcription factors.
(Previously called ethylene-responsive
element-binding proteins or ERBPs).
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.
There is evidence that PAL can be phosphorylated
and hence activity may be controlled, in part, by
phosphorylation.
ACC synthase and ACC oxidase
activity may be controlled by kinases and
phosphatases in mung bean (no
experimental evidence yet for potato)
ETR1
ETR2
ERS1
CTR1
MAPKK
ERS2
(a MAPKKK)
(eg SIMKK)
EIN4
C
arginine
ACC
arginase
ACC oxidase
(cofactors iron and ascorbate
Gene up-regulated by salicylic
acid or IAA application)
O2
CH2
CH2
CH3-S-CH2-CH2-CH2-NH2
ethylene
CH2
O
delta-pyrroline
-5-carboxylate
proline
dehydrogenase
proline
P5C
reductase
pyrroline-2carboxylate
alpha-keto-deltaaminovalerate
spontaneous
hydroxyproline
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.
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.
ornithine
ornithine-alphaaminotransferase
putrescine
NH2(CH2)4NH2
NH2(CH2)4NH(CH2)3NH2
spermidine
spermine
synthase
Pectin methyltransferases are the main enzymes
involved in the control of methylesterification of
pectin.
Post-translational covalent linkage of polyamines
to proteins is catalysed by transglutaminases.
delta1-pyrroline
H2O2 +NH3
methyl jasmonate
induction
pyrroline
dehydrogenase
gamma-aminobutyric acid
(GABA)
polyamine oxidase
O2 + H2O
O2 + H2O
NH2(CH2)3NH(CH2)4NH(CH2)3NH2
spermine
Binding of polyamines to 14-3-3
proteins may be involved in
regulation of growth and devlopment.
(S)-scopolamine
NH2(CH2)4NHCH3
N-methylputrescine
putrescine-Nmethyltransferase
diamine oxidase
O2 + H2O
phenyllactic acid
(S)-hyoscyamine
N-methylputrescine
oxidase (MPO)
agmatine
agmatine iminohydrolase
(agmatine deiminase)
N-carbamoylputrescine
amidohydrolase
spermidine
synthase
Ade
decarboxylated
S-adenosylmethionine
ornithine
N-methylpyrrolinium
N-methylaminobutanal
N-carbamoylputrescine
ornithine
ornithine
decarboxylase
OH
N
HO
tropine forming
tropinone reductase
tropine
arginine
decarboxylase
OH OH
ornithinedeltaaminotransferase
pseudotropine forming
tropinone reductase
tropinone
Polyamine
biosysnthesis
COOH
H2C
malonyl
transferase
Cu co-factor
S-adenosylmethionine
decarboxylase
(SAMDC)
NH2
OH
N
OH
calystegine B3
OH
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)
ACC synthase
H2C
OH
calystegine A3
S-adenosyl-L
homocysteine
(SAHc)
SAM-dependent
methylase
OH
OH
OH
pseudotropine
Ade
SAM
OH
N
inosine
SAH
hydrolase
PPi + Pi
CH3-S-CH2-CH2-CH-COOH
nicotianamine
Adenine
jasmonic acid-ACC
NH
adenosine
nucleosidase
adenosine
deaminase
OH
OH
N
adenine
homocysteine
+
adenosine
SAM synthetase
SAM cycle
OH
OH
calystegine B4
OH
NH2
CH2
O
N
H
methionine
synthase
ATP
OH
N
OH
calystegine B2
AMP
adenine
phosphoribosyltransferase
adenosine
kinase
CH3
methionine
5'-methylthioadenosine
nucleosidase
ACC: 1-aminocyclopropane-1-carboxylic acid
SAM: S-adenosylmethionine
beta-solamarine
OH
isoleucine
homocysteine
CH3-S-CH2-CH2-CH-COOH
OH OH
5'-methylthioadenosine
(MTA)
CH3
CH3
gluc
threonine
synthase
threonine
homocysteine
NH2
Ethylene
biosynthesis
OH
CH3
Polyhydroxylated tropane
alkaloids (calystegines) are
potent inhibitors of glycosidases
and found in potato but no
direct evidence that they
are associated with resistance.
aspartate
CHLOROPLAST
OH OH
5-methylthioribose
(MTR)
alpha-solamarine
CH3
2-
SO4
serine
homoserine
cystathione
beta-lyase
R-CO-COOH
O
N
CH3
N
2-
SO4
O-phosphohomoserine
cystathione
R-CH-COOH
complex brown
polymers
O-acetylserine
CYTOSOL
rham
CH3
CH3
O
N
NH2
CH3-S-CH2-CH2-CO-COOH
2-keto-4-methylthiobutyric acid
(KMB)
OPO3H
MTR kinase
CH3-S
solanthrene
gal
rham
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).
O
tyrosine
OH
octopamine
CH3
CH3
solasonine
CH3
CH3
N
alpha-solanine
gal
rham
?
OH
H
2-
O-acetylserine
(thiol) lyase
(OASTL)
cysteine
cystathione
gamma-synthase
OH OH
5-methylthioribose
1-phosphate (MTR-1-P)
ATP
CHOHCH2NH2
+ cinnamic acid
OH
CH3
solamargine
CH3
N
CH2
ADP
O
R
S
CH3-S
OH
O
OH catecholase
R
cysteine plays an important role
in the immune response of
Arabidopsis
HPO4 + HCOOH
O2
feruloyl-CoA
OH
CH3
cresolase
w-feruloyloxypalmitic acid
OH
O
N
rham
CH3
CH3
H
OH
Reaction scheme of tyrosinase
OH
OH
R
BAHD acyltransferases are involved with
incorporation of ferulate into suberin
THT stimulated by Mg2+ or Ca2+
OH
CH3
CH3
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.
CH3
CH3
= chacotriose
= solatriose
gal
gluc
NH
CH3
O
rham
gal
gluc
H
CH3
tomatine
gluc
gal
beta-chaconine
OH
tyramine
THT
OCH3
OH
L-tyrosine
tyrosine
decarboxylase
THT
suberin
involved in
wound healing
xyl
CH3
gluc
CH3
rham
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)
O
gluc
N
OOCH3
acetyl-solanidine
(in S. chacoense)
HO
H
O
gamma-chaconine
O
+ cinnamic acid
OH
HO
NH
CH3
CH3
a-hydroxyacetovanillone
(CH2)n
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
C
OCH3
CH2CH2NH2
OH
N
C
H
4-coumaroyloctopamine
CH3
O
N
gal
CH3
CH3
CH3
gluc
acetylase
CH3
thromboxanes
N
gamma-solanine
HO
OH
leptinine I
leptinine II
H
CH3
hydroxy-solanidine
HO
13-hydroxyrishitin
(rishitin-M-1)
Products of cyclooxygenase have not yet
been isolated from potato.
CH3
CH3
H
CH3
OCH3
OH
CH2
O
O
CH3-S
NH
CH3
tomatidenol
UDP-galactose:
solanidine
galactosyltransferase (SGT1)
UDP-glucose:
solanidine
glucosyltransferase
(SGT2)
CH3
N
O
OH
NADP
present in Solanum
khasianum
(CH2)15
C
HHT
N
H
cinnamomyloctopamine
O
H
acetovanillone
syringyl lignin
CH2OH
O
acetovanillone
a-hydroxylase:
a P450-dependent
monooxygenase
OH
HS-CoA
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)
HO
gluc
Pathogenesis-related proteins
CH3
UDP-galactose
UDP-glucose
hydroxylase
OH
CH3
CH3
CH3
gluc
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
N
HO
rishitinone
monooxygenase
O
5,6-leukotriene A4 ?
diHETE products ?
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.
CH3
CH3
CH3
solasodine
OCH3
O
O
HO-(CH2)15-COOH
w-hydroxypalmitic acid
C
OH
OH
OH
a-hydroxyacetosyringone
O2 + NADPH
sinapyl alcohol
suberization-asociated anionic peroxidase
enhances deposition of lignin and suberin
in cell walls
guaiacyl lignin
adenine
CH3
CH3
O
HO
COOH
O
O-beta-gluc
11-hydroxyjasmonic acid glucoside
O
OCH3
CH2OH
O
CH3O
OCH3
OH
syringic acid
CH3
O
peroxidase
THT
N
H
feruloyloctopamine
(both N-trans and N-cis detected)
CH3
NH
solanidine
HO
11,12-epoxyrishitin
COOH
O
OH
epi-4'-hydroxyjasmonic acid
(epi-4'-OHJA)
O
CH3
OCH3
OH
5-hydroxyferulyl alcohol
(5-hydroxyconiferyl
alcohol)
C
N
C
H
4-coumaroylnoradrenaline
verazine
HO
Glycoalkaloids
O
OH
HO
prostaglandins
O
OH
HO
etioline
HO
H3CO
OCH3
OH
OH
H
CH3O
CH3
N
H
feruloyltyramine
(both N-trans and N-cis detected)
OH
CH3
N
p-hydroxyphenyl lignin
p-coumaryl-CoA
N
C
H
cinnamomyltyramine
OCH3
OCH3
N
H
feruloyl-3'-methoxyoctopamine
CH3
OH
H
CH3
CHO
CH3
COOH
5(S)-hydroxy-6E,8Z,11Z,14Z-eicosatetraen-1-oic acid
(5-S-HETE)
gluc
CH3
CH3
3-hydroxylubimin
OH
COOH
OH
feruloyltyramine-feruloyltyramine
dimer (grossamide) and
feruloyltyramine-feruloyloctopamine dimers
have been isolated.
HO
OH
O
CH2OH
peroxidase
OH
C
A feruloytyramine trimer has been
isolated from scab lesions.
solasodiene
HO
CAD
COMT
HO
OCH3
OH
coniferyl alcohol
p-coumaryl alcohol
OH
p-hydroxybenzoic acid
O
commersonine
O
gal
CH2OH
COOH
N
C
H
4-coumaroyltyramine
OCH3
gluc
OCH3
OH
sinapyl aldehyde
(sinapaldehyde)
CAD
CH2OH
OH
NADH
HO
CH3
CH3
O
H
H3CO
OH
5-hydroxyferuloyl aldehyde
(5-hydroxyconiferaldehyde)
CAD
COOH
HO
HO
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)
peroxygenase
HO
CH3
CH3
OCH3
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
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
CHO
F5H
p-hydroxybenzaldehyde
dehydrogenase
HO
N
H
HO
OH
p-coumaryl-CoA
CH3
O
O
5-lipoxygenase (inhibited by
alpha-tocopherol in vitro)
5(S)-hydroperoxy-6E,8Z,11Z,14Z-eicosatetraen-1-oic acid
(5-S-HPETE)
12-hydroxy-jasmonate sulphate
CH3
H2N
H
10-epilubimin
lubimin
O2
COOH
OH
CH3
CH3
NH
CH3
O
CH3
CH3
H
CH3
OCCH3
acetyldehydrorishitinol
COOH
COOCH3
O-beta-gluc
O
tuberonic acid-12-O-beta-D-glucoside (TAG)
(O-β-D-glucopyranosyltuberonic acid)
CH3
isofraxidin-7-glucoside
Abbreviations
COMT
coniferyl aldehyde
(coniferaldehyde)
OH
p-hydroxybenzaldehyde
O
CH3
gluc
CH3O
OCH3
OH
sinapoyl glucose
CCR
CHO
OCH3
OH
caffeoyl aldehyde
peroxidase
demissine
O
gal
feruloylaspartate
O
CHO
O
gluc
xyl
H3CO
OCH3
OH
sinapoyl-CoA
CCR
CHO
NAD+
C
OH
HO
HO
HO
COOH
COOCH3
O
methyl (+)-jasmonate
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.
CH3
gluc
protein kinase C
homolog
COOH
PPD1
type II
OSO3H
HO
HO
2-dehydrolubimin
OH
O
HO
hydroxy-jasmonate
sulphotransferase
tuberonic acid
CHO
HO
CH3
jasmonic acid carboxyl
methyltransferase
O
(-)-9,10-dihydrojasmonic acid
OO.
OH
dinor isoprostane E1
type II
OH
N
CH3
HO
PPD1
type I
beta-oxidation
COOH
O
N
H
demissidine
HO
N
H3CO
OCH3
OH
hydroxycinnamoyl-CoA:shikimate hydroxycinnamoyltransferase (CST)
or hydroxycinnamoyl-CoA:quinate hydroxycinnamoyltransferase (CQT)
p-coumaroyl quinic acid
CH3
H
OH
COO-Glu
COMT
COOH
C3' hydroxylase
CYP98A3
CH3
CH3
CH3
dormantinone
CH3
CHO
O
HO
COOH
HO
OH
dinor isoprostane E1
type I
O
8(Z),11(Z),14(Z)heptadecatrienoic acid
CH3
HO
H
CH3
CHO
p-coumaryl aldehyde
OH
p-coumaroyl shikimic acid
chlorogenic acid
CH3
HO
OH
Induced responses including necrosis, LOX,
sesquiterpene phytoalexin induction, peroxidase,
NADPH oxidase, and increased PAL activity. Also
induces systemic resistance. SAR not induced against
P. infestans in 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.
COOH
N
O
O
COOH
beta-oxidation
COOH
O
R
O2
R
HO
2(R)-hydroxy-9(Z),12(Z),15(Z)octadecatrienoic acid
HO
O
3-oxo-2-(2'-pentenyl)-cyclopentanebutanoic acid
(OPC-4:0)
CH3
H
15-dihydro-10-epilubimin
HO
COOH
COOH
COOH
O
3-oxo-2-(2'-pentenyl)-cyclopentanebutanoic acid
(OPC-4:0)
b-oxidation
COOH
O
(-)-7-epi-dihydrojasmonic acid
R
COOH
8(Z),11(Z),14(Z)heptadecatrienal
CH3
CH3 HO
15-dihydrolubimin
2-dihydrocyclodehydroisolubimin (cyclolubimin)
OOH
O
OH
CHO
beta-oxidation
HO
O
CH3
CH3
OOH
O
COOH
O
3-oxo-2-(2'-pentenyl)cyclopentanehexanoic acid
(OPC-6:0)
HO
caffeoyl shikimic acid
OCH3
UDP-glucose: sinapic acid
glucosyltransferase (SGT)
COS-CoA
5-hydroxyferuloyl-CoA
CCR
OH
C3' hydroxylase
CYP98A3
CST
caffeoyl CoA
HO
OCH3
OH
CAD
OH
arbutin
phenylacetaldehyde
CH3
O
N
H
H3CO
scopolin
COOH
CH3
brassinolide
tomatidine
gluc-O
H3CO
CCoAOMT
F5H
p-cresol
NH
CH3
CH3
COS-CoA
feruloyl-CoA
CH2OH
CH2CHO
stigmasterol
CH3
CH3
HO
H
dormantinol
H2N
CH3
O
COOH
R
OH
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.
HNE
COOH
CH2OH
HO
CH3
O
2(R)-hydroperoxy-9(Z),12(Z),15(Z)octadecatrienoic acid
beta-oxidation
Oxylipin
pathway
O
3-oxo-2-(2'-pentyl)cyclopentanebutanoic acid
(DH-OPC-4:0)
beta-oxidation
H
.
O
O
COOH
OH
.
L
Lipoxygenase (LOX) catalyses the hydroperoxidation
of unsaturated fatty acids which have a cis-1,4pentadiene moiety within their structure.
O
b-oxidation
CH2OH
HO
O
COOH
O
COOH
beta-oxidation
O
3-oxo-2-(2'-pentenyl)cyclopentanehexanoic acid
(OPC-6:0)
O
3-oxo-2-(2'-pentyl)cyclopentanehexanoic acid
(DH-OPC-6:0)
O
OOH
O
3-oxo-2-(2'-pentenyl)cyclopentaneoctanoic acid
(OPC-8:0)
beta-oxidation
COOH
COOH
.
O2
O
3-oxo-2-(2'-pentenyl)cyclopentaneoctanoic acid
(OPC-8:0)
3-oxo-2-(2'-pentyl)cyclopentaneoctanoic acid
(DH-OPC-8:0)
beta-oxidation
COOH
CH3
CH3
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)
free radical catalysed
autoxidation to form
phytoprostanes
linolenic acid (C18:3)
COOH
b-oxidation
O
3-oxo-2-(2'-pentyl)cyclopentanehexanoic acid
(DH-OPC-6:0)
O
.
Lipoxygenase - Fe++ - L
LH = fatty acids
LOOH = hydroperoxy fatty acids
H+
Lipid
peroxidation
COOH
linolenic acid (C18:3)
alpha-dioxygenase
(a pathogen inducible
oxygenase (PIOX)
CH3
CH3
L-arginine has been reported
to be the most likely N source
in glycoalkaloid biosynthesis
CH3
O
11,12-epoxycyclolubimin
O
OH
COOH
12-oxo-phytodienoic acid
reductase
CH3 HO
CH3
COOH
HO
4CL
F5H?
OH
COOH
O-gluc
p-hydroxybenzoic acid
glucoside
H
CCoAOMT
CHO
H2N
NH2
H2N
HOOC
O
N
H
COS-CoA
NH-CH-CH2-COOH
O
OCH3
OH
sinapic acid
4CL
OH
HO
H2 N
CH3
CH3
CH3
OCH3
OH
5-hydroxyferulic acid
4CL
caffeoyl-CoA
OH
brassinosteroid-6oxidase 2 (P450)
O
O
scopoletin
O
NH2
soladulcidine
gibberellins
3,4-dehydroisolubimin
OCH3
OH
ferulic acid
COOH
Possible biosynthetic pathways
from cholesterol and
cholesteranol to aglycones.
OH
1-[9-hydroxy-10E,12Z-octadecadienoyl]-rac-glycerol
(9-(E,Z)HODE-GE)
NADPH + H+
NADP+
CH3
CH3
HO
OH
O
H3CO
O
(pathway from tobacco)
OH
HO
O
CH2OH
O
CH3
HO
H
CH3
ent-kaurenoic
acid oxidase
O
lipoxygenase
gamma-ketol
12-oxo-phytodienoic acid
reductase
NADP+
R
OOH
e-
O
1-monolinoleoyl-rac-glycerol
alpha-ketol
COOH
CH3
CH3
H
COOH
COMT
COOH
castasterone
NH
CH3
CH3
HO
CH3
CH3
OH
4CL
6-deoxocastasterone
cholesteranol
HO
COOH
HO
CH3O
OH
sitosterol
CH3
NH2
isodityrosine
O-gluc
cholesterol
HO
putrescine
NH(CH2)4NH2
OCH3
OH
caffeic acid
OH
O
NH
isofucosterol
O-gluc
OH
caffeic acid 3-glucoside
gluc-O
melanin
CH3
isochlorogenic acid
(3,5 caffeoylquinic acid)
feruloylputrescine
COS-CoA
OH
di-isodityrosine
H
CH3
OH
1-caffeoyl-B-D-glucoside
O
F5H
OH
CH3
CH3
CH3
H
OH
COOH
OH
OH
N-caffeoylputrescine
O
CCoA3H
p-coumaryl-CoA
COOH
OH
COOH
COO-gluc
OH
caffeoylD-glucose
COOH
COMT
O
pulcherosine
(in tomato)
6-deoxotyphasterol
O
putrescine hydroxycinnamoyl transferase
COOH
COS-CoA
OH
NH2
Dopaquinone
NH
O
O
O
HO
HO
O-gluc
esculin
COO-gluc
OH
p-coumaroylD-glucose
CCR
OH
leucodopachrome
CH3
HO
COOH
OH
COOH
OH
OH
isochlorogenic acid
(4,5 caffeoylquinic acid)
OH
NH(CH2)4NH2
O
HO
OH
esculetin
protein
6-deoxoteasterone
CH3
CH3
CH3
HO
O
15,16-epoxy-13-OH-9(Z),11(E)-octadecadienoic acid
12-oxo-phytodienoic acid
(12-oxo-10,15(Z)-phytodienoic acid)
NADPH + H+
12-oxo-phytodienoic acid
reductase
NADP+
beta-oxidation
R
O
COOH
CH2OH
isolubimin
cyclodehydroisolubimin
HO
OH
O
CH3
CH3
ent-kaurene
oxidase
O
O
11,12-epoxycyclodehydroisolubimin
OH
COOH
O
12-oxo-phytodienoic acid
(12-oxo-10,15(Z)-phytodienoic acid)
NADPH + H+
12-oxo-phytodienoic acid
reductase
O
3-oxo-2-(2'-pentyl)cyclopentaneoctanoic acid
(DH-OPC-8:0)
LH
peroxygenase
Acetyl-CoA
COOH
wound
signalling ?
LOOH
b-oxidation
13-OH-9(Z),11(E),15(Z)-octadecatrienoic acid (13-HOT)
O
HO
spontaneous
hydrolysis
COOH
O
15,16-dihydro-12-oxo-phytoenoic acid
(DH-12-oxo-PDA)
COOH
Lipoxygenase - Fe+++
(active enzyme)
9-hydroxy-traumatin
(4-hydroxy-2(Z)-dodecenal)
COOH
O
O
CHO
O
COOH
COOH
OH
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
OH
hydroperoxide
reductase
allene oxide
12,13(S)-epoxy-9(Z),11,15(Z)-octadecatrienoic acid
(13(S)EOT)
hydroperoxide
cyclase
(allene oxide
cyclase)
peroxygenase
O
COOH
autoxidation
HOOC
OH
10-hydroxy-16-oxo-hexadecanoic acid
13-keto-9(Z),11(E),15(Z)-octadecatrienoic acid
(allene oxide
synthase: A cytochrome
P450 ; CYP74A)
secologanin
synthase
(a P450)
7-deoxyloganin
7-hydroxylase
(a P450)
ent-kaurene
synthase
fungal degradation
lipoxygenase
COOH
traumatic acid
(implicated in wound
signalling)
OH
OH
24-ethylidene lophenol
copalyl
pyrophosphate
solanoscone
O
O
linoleyl alcohol
HOOC
COOH
protein
OH
OH
chlorogenic acid
(3 caffeoylquinic acid)
O
OH
NH2
24-methylene lophenol
sterol methyltransferase;
SMT2
GGTase
CH2OH
O
cycloartenol
ent-kaurene
O
COOH
12-oxo-10(E)-dodecenoic acid
O
4-hydroperoxy-2(Z)-dodecenal
hydroperoxide
cyclase
(allene oxide
cyclase)
7,10,13-hexadecatrienoic acid (16:3)
CHO
hydroperoxide
dehydratase
O
12,13(S)-epoxy-9(Z),11-octadecadienoic acid
(13(S)EOD)
a -ketol
12-oxo,13-hydroxy-9(Z)-octadecenoic acid
OH
(steps for traumatin
shown in soybean and alfalfa)
OOH
O
COOH
OH
10-hydroxy-hexadecan-1,16-dioic acid
H+
O2
O
COOH
O
O
Cu2+
O
OH
OH
t-cinnamoylD-glucose
isodityrosine
intramolecular
cross-link
between HRGPs
COOH
NH
campesterol
24-methylene cycloartenol
cycloartenol
methyltransferase
(sterol methyltransferase; SMT1)
HO
cycloartenol cyclase
geranylgeranylated proteins
copalyl
diphosphate
synthase
chlorophylls
oxysolavetivone
O
IF
squalene 2,3-epoxide
O
COO-gluc
Phenylpropanoid
biosynthesis
OH
OH
Dopa
polyphenol
oxidase
(tyrosinase)
O
squalene
diterpenes
cedrol
lipoxygenase
dopa
decarboxylase
O2
ascorbate
(COOH)
OH
eumelanin
geranylgeranyl
pyrophosphate
(GGPP)
solavetivone
3(E)-hexenol
COOH
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
(9(Z)-traumatin)
OH
NH2
dopamine
NH2
HO
HO
CH2OH
NH2
Cu2+
phenol oxidase
OH
OH
dehydroascorbate
COOH
OH
cysteinyldopa
nerolidyl pyrophosphate
(NPP)
squalene 2,3-epoxidase
phytoene
synthase
2-(1',2'-dihydroxy-1'OH
methylethyl)-6,10-dimethylspiro OH
[4,5]dec-6,9-dien-8-one
alpha-humulene
O
12-oxo-9(Z)-dodecenoic acid
COOH
COOH
O
hydroperoxide
lyase
H
HO
N
benzothiazine
derivative
(COOH)
(COOH)
phaeomelanin
squalene
synthase
OPP
(+)-germacrene
beta-caryophyllene
S
N
CH3
OH
geosmin
NH2
OH
SAM-dependent
methylase
norepinephrine
+ cysteine
S
HO
HO
OCH3
normetanephrine
NH2
NH2
S
O
OH
OH
OH
chlorogenic acid
(4 caffeoylquinic acid)
OH
O2
OH
O
O
O
tyramine
NH
NADP + PPi
ABA
O
anhydro-beta-rotunol
((+)-spirovetiva-1(10),3,
11-trien-2-one)
OH
polymerization
HO
neryl pyrophosphate
arogenate
dehydratase
O
UDPG:cinnamate COO-gluc
glucosyl
trans-cinnamic transferase
acid
NH4+
O
O
O
OH
cinnamoyl-CoA
phenylalanine
Mg2+
COOH
COOH
CH3
OPP
CH2
HOOC
prephenate
aminotransferase
chorismate
mutase
2-3 isozymes
in potato
O
'normal'
chlorogenic acid
(5 caffeoylquinic acid)
2
COOH
isomerase
geranylgeranyl
pyrophosphate
synthetase
carotenoids
O
p-hydroxyphenylpyruvic
acid
CH2
HOOC
NH2
CH
chorismic acid
NH2
IF= isomerization factor
3(E)-hexenal
O
OOH
COOH
13(S)-hydroperoxy-9(Z),11(E)octadecadienoic acid
(13(S)-HPOD or 13(S)-HPODE)
COOH
13-KOD
(13-keto-9(Z),11(E)-octadecadienoic acid)
10,16-dihydroxypalmitic acid
hydroperoxide
lyase
3(E)-hexenal
OOH
O
monooxygenase
O
O
trans-apha-bergamotene
hydroperoxide
lyase (a cytochrome P450;
CYP74B)
monoterpenes
OPP
farnesyl diphosphate
(farnesyl pyrophosphate, FPP)
OH
germacrenes
OH
germacrene D-4-ol
2E-hexenol
O2
13-lipoxygenase
OH
trans-beta-bergamotene
caryophyllene oxide
tocopherol
geranyl
pyrophosphate
(GPP)
isopentyl
pyrophosphate
+ NADPH
O2
OH
homogentisate
p-hydroxyphenyl
phytyltransferase
pyruvate dioxygenase
2-methyl-6-phytylhomogentisate
benzoquinol
PPi
H
H
CH2OH
O
IF
geranylgeranyl
pyrophosphate
synthase
O
C
?
3-oxo-3phenylpropionyl-CoA
CoA ligase
PAL
(multiple
isozymes)
COOH
COOH
HO
OH
HO
O
COOH
NH2
COOH
O
C
phenylalanine
C4H
prephenic acid
hydroxylase
NADP+
OH
OH
high levels of phenylalanine
arogenic acid
and tyrosine inhibit chorismate mutase
2-oxoglutaric acid
NADPH
glutamine
(feedback mechanism)
GOGAT = glutamine:
isochorismate
2-oxo-glutarate
arogenate
synthase
COOH
COOH
amidotransferase)
dehydrogenase
In Arabidopsis isochorismate synthase gene ACS1
reduced
oxidised
COOH
is transcriptionally regulated by AtWRKY28.
ferredoxin
ferredoxin
NH2 tyrosine ammonia
COOH
-lyase (only occurs
COOH
pyruvate
C3H
in monocots ?)
OH
asparagine +
glutamine +
O
glutamic acid
CH2
OH
glutamine
aspartate asparagine glutamate
glutamine
tyrosine
synthetase
COOH
synthetase
pyruvate lyase?
O
C
aminotransferase
p-hydroxypathway proposed in isochorismic acid
NH4+
OH
OH
salicylic acid
phenylpyruvic
Arabidopsis but not yet
tyrosine
acid
NH4+
p-coumaric acid
proven in potato
OH
from PAL
p-coumaroyl tyramine
tyrosine
HO
feruloyl tyramine
tyrosine
NH2
decarboxylase
3-monooxygenase
anthraquinones
4CL
peroxidase
(phenol oxidase)
phylloquinones
COOH
NH
chorismate
synthase
COOH
C
OH
5-enolpyruvylshikimate
3-phosphate (EPSP)
dimethylallyl pyrophosphate
(DMAPP)
FPP synthase
O-gluc
OH
HO
O
IF
linolenic acid (C18:3)
IF
bicyclogermacrene
(-)-germacrene
(germacrene D)
H
H
2E-hexenal
3(Z)-hexenal
ledol
CH2OH
3Z-hexen-1-ol
O
COOH
OH
beta-sesquiphellandrene
alpha-zingiberene
?
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)
alcohol
dehydrogenase
-desaturase
3(Z)-hexenal
13-lipoxygenase
OH
?
9-lipoxygenase
O2
O2
C5H11
OH
OH
lysyl
residue
15
lipoxygenase
O
9,16-dihydroxypalmitic acid
PROTEIN
3(E)-hexen-1-ol
COOH
linoleic acid (C18:2)
O
OH
HOOC
HOOC
non-enzymic
cyclization
isopentenyl
pyrophosphate
(IPP)
chorismate mutase
is activated by tryptophan
tyrosine
aminotransferase
COOH
HO
HO
HQT
HO
COOH
COOH
CH2
PPO
vetispiradiene
O
H
Sesquiterpenes
sesquisabinene
HO
O
O
O
COOH
10-oxo-11-phytoenoic acid
(2-oxo-5-pentyl-3-cyclopentene-1-octanoic acid)
(a cyclopentenone)
Both 9(R),13(R) and 9(S),13(S)
enantiomers are produced.
H
OH
COOH
?
peroxygenase
9,10,18-trihydroxystearic acid
HO
OCOCH3
O
PO
phenylpyruvate
prephenate
dehydratase
NH
skatole
O
4-hydroxy- OH
benzoic acid
3-hydroxy-3phenylpropionyl-CoA
COSCoA
OH
COOH
OH
B-oxidation route
3-hydroxy-3phenylpropanoic acid
o-hydroxycinnamic acid
(o-coumaric acid)
CH3
OH
COOH
hemiterpenes
OPP
vetispiradiene
synthase
Sesquiterpene
phytoalexin
biosynthesis
OH
O
O
OOH
O
OH
4-hydroxy-2(E)-hexenal
Fatty acid degradation
9-lipoxygenase
a macrolactone
O
O
alpha-cadinol
allene oxide synthase
9(S)-hydroperoxy-10(E),12(Z),15(Z)-octadecatrienoic acid
(9(S)-HPOT or 9(S)-HPOTE)
HO
OCOCH3
OH
OCOCH3
OH
COOH
glutathione peroxidase
(from P. infestans)
COOH
OH
O
HO
peroxygenase
O
non-enzymic
cyclization
cutin
COOH
9(S)-hydroperoxy-10(E),12(Z)-octadecadienoic acid
(9(S)-HPOD or 9(S)-HPODE)
allene oxide synthase
OCOCH3
5-enolpyruvylshikimate
3-phosphate (EPSP)
synthase
OH
PO
cinnamoylglucose
protein adducts
HO
COOH
hydroxylase
COSCoA
OH
O
OH
L-glutamine
OH
3-phosphoshikimic acid
(shikimate 3-phosphate)
NH
indole-3-acetaldehyde
catechol
anthranilate
synthase
COOH
COOH
COOH
NH
tryptamine
anthranilate
1,2 dioxygenase
pyruvate + L-glutamate
Mg2+
?
amine oxidase
CH2CH2NH2
R = quinic acid
P-X = protein
X = NH2, OH, SH
O
OH
OH
O
HO
quinic acid
O
coumarin
benzaldehyde
CH2CHO
NH
indole-3-pyruvic acid
tryptophan
decarboxylase
NH
tryptophan
indole-3-acetaldehyde
oxidase
indole-3-pyruvic
acid decarboxylase
O
X-P
H
O
OH
salicyloyl-CoA
benzaldehyde
benzoyl-CoA
"non-oxidative"
route Two pathways leading
to benzoic acid have been
COOH proposed in plants though the
COSCoA
"non-oxidative" route via
benzaldehyde now seems
HO
to be unlikely or of
HO
minor importance.
RO
O
H
P-X
O
O
OH
HO
SCoA
O
H
H
O
chlorogenic acid
quinone
chlorogenic acid
OH
COOH
benzaldehyde
dehydrogenase
benzoyl-glucose
COO-gluc
polymerization
O2
OH
tryptophan
aminotransferase
CH2CH(NH2)COOH
WRKY?
geranylgeranyl
pyrophosphate
synthase
protein farnesylation
protein
farnesyltransferase
(FTase)
OH
CH2CHCOOH
benzoic acid
conjugate
?
RO
O
P-X
H+
HO
COOH
SCoA
OH
H
O
O
RO
O
OH
OH
HO
2,5-dihydroxybenzoic
acid (gentisic acid)
O
benzoic acid
O
IAA-aspartic acid
conjugate in Arabidopsis
CHO
(affects disease
development)
OH
?
salicylic acid glucoside
O
L-OH
phosphoribosylphosphoribosylanthranilate
anthranilate
isomerase
transferase
5-phosphoribosylanthranilate
anthranilate
1-(o-carboxyphenylamino)1-deoxyribulose 5-phosphate
COOH
OH
PO
OPP
mevalonate
5-pyrophosphate
decarboxylase
mevalonic acid
5-pyrophosphate
(5-pyrophosphomevalonate)
triglycerides
fatty acyl-CoA
fatty acid
malonyl-CoA
HO
O
OCOCH3
phytuberin
OH
HO
COOH
OOH
O
COOH
9,10-dihydroxystearic acid
HO
O
OH
phytuberol
ADP + Pi + CO2
ATP
exogenous fatty acid
12(R),13(S)-epoxy-9(S)-hydroxy
-10(E),15(Z)-octadecadienoic acid
epoxy alcohol
synthase
epoxy alcohol
synthase
OOH
HO
OH
OH
O
O
10(S),11(S)-epoxy-9(S)-hydroxy
-12(Z),15(Z)-octadecadienoic acid
12(R),13(S)-epoxy-9(S)-hydroxy
-10(E)-octadecenoic acid
epoxy alcohol
synthase
epoxy alcohol
synthase
HO
COOH
COOH
COOH
COOH
O
10(S),11(S)-epoxy-9(S)-hydroxy
-12(Z)-octadecenoic acid
epoxide
hydrolase
O
OH
OH
acetyl-Co-A
oxidised
glutathione
(GSSG)
glutamate + cysteine
ADP
OH
3-phosphoquinic acid
OPP
O
COOH
OH
OH
O
COOH
9-hydroxy-10-oxo-12(Z)-octadecenoic acid
(an alpha-ketol)
9,10-epoxystearic acid
(9R,10S ; 9S,10R)
18-hydroxy-9,10-epoxystearic acid
HO
OH
FPP synthase
O
O
O
OH
epoxide hydrolase
HMGR kinase is not
AMP-activated in potato
acetyl-CoA
carboxylase
inositol may exist in different isomers
(myo-inositol, chiro-, scyllo-, neo-).
GPI = glycosylphosphatidylinositol
COOH
9(S),12(S),13(S)-trihydroxy
-10(E),15(Z)-octadecadienoic acid
OH
9(S),10(S),11(R)-trihydroxy
-12(Z),15(Z)-octadecadienoic acid
epoxide hydrolase
epoxide hydrolase
OH
COOH
O
non-specific lipid transfer protein (PR-14)
may be involved in biosynthesis of
epicuticular wax or cutin.
2-IP
inactive ACC
γ-glutamylcysteine
CH2COOH
RO
H
umbelliferone
O
COO-conjugate
benzoic acid
2-hydroxylase
COOH
COO-gluc
NH
indole-3-acetic acid
(IAA/auxin)
O
O
COOH
NADH
salicylic acid
COOH
O-gluc
may conjugate
with HNE
Glutathione is said to be
a scavenger of active
oxygen species. Glutathione
can conjugate with electrophiles
such as Dopaquinone.
phospholipid hydroperoxide
glutathione peroxidase
(PHGPX; E.C. 1.11.1.9)
γ-glutamylcysteine
synthetase
tryptophan
synthase b
shikimate
kinase
isopentenyl
pyrophosphate
isomerase
gene up-regulated
by MeJ in bean
2-oxo-isocaproate
3-isopropylmalate
leucine
isopropylmalate
branched chain
dehydrogenase
amino acid
transaminase
glucose-6-phosphate
1-IP
1,2,3-IP3
1,2-IP2
HO
Cyt.-P450
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
he
1,2,6-IP3
OH
OH
COOH
9(S),12(S),13(S)-trihydroxy
-10(E)-octadecenoic acid
OH
9(S),10(S),11(R)-trihydroxy
-12(Z)-octadecenoic acid
epoxide hydrolase
12
acyl hydrolase
Membrane lipids
O
5,6-bis-PP
-Ins(1,2,3,4)P4
OH
COOH
COOH
stearic acid (C18:0)
OH
PP2A
PP2C
inactive HMGR
OH
shikimic acid
ATP
COOH
HO
quinic acid
CYTOSOL
Mevalonate
pathway
inactive HMGR
kinase
HMGR kinase
isovalery-CoA
3-methyl2-oxobutanoate
dehydrogenase
isopentenyl
pyrophosphate
(IPP)
OH
OPP
mevalonic acid
5-phosphate kinase
mevalonic acid
5-phosphate
(5-phosphomevalonate)
kinase kinase
PP1
PP2A
OH
HO
shikimate
dehydrogenase
OH
L-OOH
glutathione
synthetase
NH
indole
indole-3-glycerolphosphate
synthase
PLASTID
HOOC
OP
OH
O
glutathione
S-transferase
CH2
ADP
ATP
OH
HOOC
mevalonic acid
kinase
OH
HMGR
(multiple
isozymes)
ADP
ATP
mevalonic acid
OH
HOOC
glycine
tryptophan
synthase a
indole-3-glycerol
phosphate
COOH
NADP+
NADPH
3-dehydroshikimic acid
COOH
HO
dehydroascorbate
Dehydroascorbate has been shown to
inhibit some kinases in HeLa cells and
may therefore do the same in plants.
R-NO
nitrosated
proteins (nitrosylation)
dehydroshikimic acid
dehydratase ?
OH
3-dehydroquinate
dehydratase
OH
NADP+
S-CoA
HMG-CoA reductase regulated
by SnRK1 in Arabidopsis
isovaleryl-CoA
dehydrogenase
3-deoxy-D-arabino-heptulosonate
7-phosphate (DAHP)
DOXP pathway (in plants in general)
NADPH
O
HMG-CoA
methyl-crotonyl-CoA
carboxylase gene upregulated in Arabidopsis
by MeJ
myo-inositol-1-phosphate
synthase (MIPS)
?
OH
lipase
3,6-IP2
OH
HOOC
OH
1-deoxyxylulose 5-phosphate synthase
pyruvate + glyceraldehyde-3-phosphate
1-deoxyxylulose-5-P
(DOXP)
O-acetylation of plant cell wall polysaccharides
(e.g. pectin)
HMG-CoA
synthase
NO-
1-O-(indole-3-acetyl)-b-glucose
NADP+
reduced
glutathione (GSH)
H-γ-Glu-Cys-Gly-OH
NADH ubiquinone
reductase
ubiquinol + NAD(+)
ubiquinone + NAD
ubiquinol plays a role in
antioxidant defense of cells
and may prevent lipid peroxidation
lipid peroxidation,
DNA damage
OH
OH
O
ONOOH
peroxynitrous
acid
OH
protocatechuic acid
OH
3-dehydroquinic acid
HO
rhamnogalacturonan
O-acetyl-transferase
acetyl-CoA
PO3H2O
DAHP
synthase
(Inhibited by phenylalanine.
Located in chloroplasts.
May be redox regulated)
phosphoenolpyruvic acid
NO+
quinate
dehydrogenase
OH
CH2
Fe(III)
Shikimate pathway
O
Mn2+
acetyl-CoA
methyl
crotonyl-CoA
inositol
phosphatidylinositol 3-phosphate
-3-phosphatase
inositol
1,2,3,6-IP4
1,2,5,6-IP4
3-dehydroquinate
synthase
COOH
HO
D-erythrose 4-phosphate
CH3COCOOH
pyruvic acid
ONOOperoxynitrite
H+
anion
O2.
Fe(II)
Fe(II)
COOH
COOH
HO
thiolase
(acetyl-CoA acetyltransferase)
3-methylglutaconyl-CoA
3,4-IP2
inositol-3,4-bisphosphate
4-phosphatase
degradation by phytases
divinyl ether synthase
divinyl ether synthase
(P450, CYP74D)
azelaic acid
(reported to increase salicylic
acid in Arabidopsis)
Ca2+ regulation
1,2,3,5,6-IP5
diphosphoinositol
tetrakisphosphate
(5-PP-Ins(1,3,4,6)P4)
colnelenic acid
9-[1'(E),3'(Z),6'(Z)-nonatrienyloxy]-8(E)-nonenoic acid
ba
and
fungi
CHO
(from
dase
in oxi
catech
catechin
catechin has been
protocatechualdehyde
detected in potato
OH
OCH3
non-enzymatic
(by reduced ferredoxin)
.
Fe(III)
NAD(P)H
COOH
HCHO + NADP
)
cteria
transaldolase (gene upregulated in incompatible P. infestans/potato interaction)
phosphoenolpyruvate
phosphoenolpyruvate
carboxykinase
pyruvate kinase
S-CoA
3-methylglutaconyl-CoA
hydratase
IP2 1-phosphatase
3,4,5,6-IP4
O2 + NADPH2
OH
vanillic acid
sedoheptulose 7-phosphate + D-glyceraldehyde 3-phosphate
enolase
pyruvate decarboxylase
O
bisphosphatidic acid
inositol-1 (or 4)
-phosphatase
diphosphoinositol
pentakisphosphate
(5-PP-Ins(1,2,3,4,6)P5)
O
O
3(Z)-nonenal
inositol
4-phosphate
'high energy'
InsP6 kinase
diphosphorylated
inositol polyphosphates
3(Z),6(Z)-nonadien-1-ol
oxaloacetate
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
1,3,4,5,6-IP5
3,4,6-IP3
OCH3
OH
phosphoglycerate
mutase
phosphatidylcholine
1,3,4-IP3
IP4 1,3,4,6-IP
4
5-kinase
phytate
IP6
1-IP
COOH
vanillin
2-phosphoglycerate
lysophosphatidic acid
phospholipase D
IP3 5phosphatase
IP3 6-kinase
inositol-1,4-bisphosphate
1-phosphatase
CHO
glycerol-3-phosphate interacts with the lipid
transfer protein DIR1 to induce SAR in plants.
NO
sesquiterpene phytoalexin
induction eg rishitin
monodehydroascorbate
?
In Arabidopsis AtPBS3 gene is transcriptionally
regulated by AtWRKY46 affecting levels of
SA-glucoside
(in nahG
transformed
salicylate
hydroxylase plants)
catechol
OH
salicylic acid
2-O-glucosyl
-transferase
glucosyl salicylate
(salicyloyl-glucose ester)
methyl
salicylate
glucose-6-phosphate dehydrogenase
6-phosphogluconate dehydrogenase
isocitrate dehydrogenase
RO
polyphenol
oxidase
salicylic acid
carboxyl
OH
glucosyltransferase
OH
NADPH + H+
glutathione
reductase
dehydroascorbate
reductase
receptor
hydroxyl radical
COOH
COO-gluc
COOCH3
methyl salicylate is an
SAR signal in potato.
(g-Glu-Cys-Gly)2
oxidised
glutathione
(GSSG)
NAD(P)+
monodehydroascorbate
reductase
nitrate reductase?
NADP+
glycosyltransferase
glycosyltransferase
gene up-regulated by MeJA
RH2
resistance responses
including PR proteins
(reported to be different
from those induced
by salicylic acid)
OH
receptor
protein methionine S-oxide + reduced thioredoxin
peptide methionine
sulfoxide reductase
peroxidase
(includes
E.C. 1.11.1.12)
ascorbate
oxidase
2H2O
NADPH
NO synthase ?
protein methionine + oxidized thioredoxin
ascorbate
O2
ascorbate
peroxidase
O2
arginine
NAD(P)H-dependent
nitrate reductase or
NO2- nitrite reductase
citrulline
H2O + O2
Halliwell-Asada
enzyme pathway
H2O2
O-gluc
vanillic acid glucoside
(vanillate glucoside)
OH
resistance responses
including StLTPa7, PR proteins,
erg-1, and StrbohB (an
NADPH oxidase)
salicylic acid
methyltransferase
RH + H2O
superoxide dismutase
2,3-dihydroxybenzoic
acid
COOH
inactivation of
protein
phosphatase
catalase
photosynthesis
Fe++
(Cu+)
OCH3
O-gluc
2-oxobutanoate
acetyl-CoA
phospholipase A2
protein
kinase C
triacylglycerol
(triglyceride)
1,3,4,5-IP4
4-phosphatase
OCH3
H+
Fenton reaction
(non-enzymic)
COOH
vanilloside
(glucovanillin)
an acid + NADH
aldehyde
dehydrogenase
RCHO + NH3 + H2O2
amine
oxidase
photorespiration
fatty acid oxidation
photosynthesis
oxidative
phosphorylation
O2superoxide
Fe+++
(Cu++)
H2O2
threonine dehydratase
(threonine deaminase)
NH3
erythrose-4-phosphate
.
HO + HO
NADPH oxidase
superoxide
NADPH + O2
CHO
RCH2NH2 + O2 + H20
Most superoxide is probably produced by photosystem I
via the reduction of oxygen through the ferredoxin/ferredoxin
NADP+ oxidoreductase system.
oxidative
phosphorylation
O2- + H+
HO2.
superoxide
hydroperoxyl
radical
Vitamin B6 (pyridoxine) and its
derivatives are efficient singlet
oxygen quenchers.
3-phosphoglycerate
acetoacetyl-CoA
diacylglycerol (DAG)
3-kinase
Ins(1,2,3,4,5)P5
1,3,-IP2
Glyoxylate
cycle
DGPP
phosphatase
diacylglycerol-3-P
(phosphatidic acid)
phosphatidic
acid
diacylglycerol
phosphatase
kinase
phospholipase C
(receptor-triggered
activation)
IP3 receptor
Potato tuber phospholipids contain
colneleic acid in the 2-position
3(Z)-nonen-1-ol
diphosphate + ADP-glucose
L-threonine
ribulose-5-phosphate
.
R = non oxygen free radical
.
RO = alcoxyl radical
.
ROO = peroxyl radical
.
OH = hydroxyl radical
ONOO- = peroxynitrite
GS-NO = nitrosoglutathione
H2O
phosphoglycerate
kinase
phosphatidic
acid
diacylglycerol
pyrophosphate (DGPP)
phosphatidate
kinase
phosphatidate
cytidyltransferase
(cdp.dg synthase)
phosphatidylinositol
4,5-bisphosphate (PtdIns(4,5)P2)
inositol-1,4,5inositol-1,4,5trisphosphate (IP3)
trisphosphate (opens Ca2+ channels)
5-phosphatase
1,4-IP2
(inositol 1,4bisphosphate)
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).
cytidine diphosphate
1,2-diacylglycerol
PIP5K
(PtdIns-4-phosphate
5-kinase)
Phosphoinositide
cascade
Ins(1,4,5,6)-P4
Ins PolyP
2-kinase
NH2
sphingosine transfer protein accelerates
the transfer of sphingosine between
membranes.
In Arabidopsis bZIP11 is involved
with carbohydrate metabolism including
T6P and SnRK1
D-erythrose 4-phosphate + fructose 6-phosphate
possible modulation of
DAG kinase by arachidonic acid
in (from pepper) inhibits
annexin mammals
phospholipase A2
PI synthase
phosphatidylinositol
4-phosphate (PtdIns(4)P)
PI3K
PtdIns(3,4,5)P3
Ca2+ mobilisation
NH2
OH
sphingosine
regulation of specific
protein kinases ?
rearrangement
of actin cytoskeleton
(in animal cells)
PI3K
inositol
(poly)phosphate
5-phosphatase (SHIP)
PtdIns(3,4)P2
phospholipase C
NADPH
1,3-bisphosphoglycerate
diacylglycerol
CDP-diacylglycerolinositol
3-phosphatidyltransferase
(phosphatidylinositol synthase)
PtdIns4 kinase
4-phosphatase
PtdIns(3,4)P2
PIP5K
phosphatidylinositol
gulono1,4-lactone
ferricytochrome c
oxidase/
galactono-1,4 lactone
dehydrogenase
dehydrogenase
ferrocytochrome c
ascorbic acid
phosphatidylinositol (PtdIns)
PtdIns(3)P
PIP5K
PIP4K
O
OH
phytoceramide
phospholipase A2
O-
Programmed cell death also involves reorganisation of the
plant cytoskeleton involving microtubules and microfilaments.
glucosylceramide
C
R
R2
H2C
ROS production
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.
galactono1,4-lactone
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.
NH
ceramide
kinase
(acylsphingosine
kinase)
sphingosine
O
OH
ceramide
ceramidase
OH
phospholipase A1
T6P is considered as a
key regulatory molecule
trehalose-6-phosphate synthase
gene upregulated by P. infestans
glyceraldehyde-3-phosphate
dehydrogenase
NADH
OH
OH
glyceraldehyde3-phosphate
phosphate
GMP
N-acyl sphinganine
dehydrogenase
ceramide can stimulate
PP2A and MAP kinase
NADPH oxidase gene
Responses
glycerol-3phosphate (G3P)
GDP-galactose
GDP-gulose
Pathway suggested from work
on Arabidopsis. No confirmation
yet that this pathway is correct
for potato
acyl-G3P
(lyso-phosphatidic
gulose
galactose
NAD
acid)
galactose
dehydrogenase
dihydroceramide
OH ceramide synthase
(sphinganine
acyltransferase)
NH2
OH
phytosphingosine
sphingosine1-phosphate
phosphatase
(SPPase)
S-nitrosylation of NADPH oxidase
associated with cell death in
plant immunity in Arabidopsis
Alternaric acid (from Alternaria solani) stimulates in vitro phosphorylation of
His-tagged RiCDPK1 from potato cv Rishiri)
3-ketosphinganine
reductase
NADP+
unsaturated analogues
Why1
serine/threonine
kinase
GDP-fucose
OH
NH2
sphinganine
(dihydrosphingosine)
unsaturated analogues
The unsaturated analogues 4E and 8E
of sphinganine are the most abundant
cerebroside base.
phosphorylation and
activation of nuclear
and cytoplasmic elements
NO associated (NOA gene)
O
NADPH + H+
UDP-glucose
trehalose
trehalose-6phosphate
phosphatase
glucose-1-phosphate
glucose-1-phosphate + ATP
fructose-6-phosphate
glucose-6-phosphate
phosphomannose
glucose-6-phosphate
phosphoglucomutase
isomerase
isomerase
NADP
phosphomannomutase
ATP
glucose-6-phosphate
phosphofructokinase
chloroplast G6PDH is
dehydrogenase (G6PDH)
subject to phosphorylation
plastid enzymes of G6PDH
mannose-1-phosphate
are redox regulated
differential transcription of G6PDH
fructose-1,6-bisphosphate
genes in parsley by fungal elicitors
Pi
NADPH
GDP-mannose
glucono-1,5-lactone 6-phosphate
pyrophosphorylase
fructose 1,6(6-phosphogluconolactone)
epimerase/
bisphosphate
dehydratase
reductase
aldolase
6-phosphogluconolactonase
GDP-4-keto,6-deoxy-mannose
GDP-mannose
NADPH
dihydroxyacetone
glyceraldehydeGDP-mannose
phosphate
triosephosphate 3-phosphate
6-phosphogluconate
3",5"-epimerase
isomerase
glycerol-3NADP(+)
phosphate
Hsp70-like
dehydrogenase
6-phosphogluconate
stress
chaperone
an aldehyde + NAD(+) + H2O
dehydrogenase
serine
palmitoytransferase
3-ketosphinganine
Ceramides are thought to be involved in apoptosis (programmed cell death)
MAP kinases are downstream of these long chain bases in PCD.
sphinganine 1-phosphate
sphinganine 1-phosphate
phosphatase
lyase
hexadecanal
sphinganine 1-phosphate
glycerolipids
Pti4
protein
Ceramide
signalling
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.
phosphorylation of an
approx 34 kDa protein
(pp34)
ADP
trehalose-6phosphate
synthase
mannose-6-phosphate
palmitoyl-CoA + serine
P. infestans hyphal
wall components,
salicylic acid,
arachidonic acid.
MAP kinase kinase kinase
(MAPKKK)
trehalose-6-phosphate (T6P)
glucosamine-6phosphate synthase
In Arabidopsis several WRKY proteins
are SUMO1 targets, and each of them
can be phosphorylated by MAPK
kinases.
Comments and additional information should be sent to: GaryDavidLyon@gmail.com
Chart can be viewed on the internet at www.potatometabolicpathways.webs.com
elicitor-active
oligogalacturonides
Protein
phosphorylation
H2O
glucosamine-6-phosphate
OH
pectic enzymes from
plant pathogens
receptor
Enzyme control by phosphorylation and/or 14-3-3 proteins
14-3-3
Dephosphorylated
Pi
enzyme
ATP
phosphatase
Gary D. Lyon
plant pectin
O
Extracellular signal
O
Calmodulin-binding protein binds to calmodulin
which is involved in calcium regulation.
OH
Metabolic pathways of the diseased potato
Bakker et al. (2011) identified 280 TIR-NB-LRR and 448 CC-NB-LRR sequences in S. tuberosum ssp. tuberosum.
In plants, calcium-dependent protein kinases (CDPK's),
are modulated by changes in Ca2+ concentration.
H2O2 1,3-diaminopropane
beta-alanine
H2O2
polyamine oxidase
1,5-diazabicylononane
1-(3-aminopropyl)-pyrroline
Spermine and spermidine have been
Some oxidised polyamines have been reported
reported to activate nonspecific acid phosphatase
to possess antimicrobial activity - but not yet
(EC 3.1.3.2) by lowering the K(m) value.
proven in potatoes.
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.
Last modified 24 December 2012
calystegine B1
OH