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Fig. S1. Further glucosinolates Those coded structures in brackets with numbering <200 are already know and have been covered earlier, those with number codes >200 are extrapolations, to complete each new homologous series.
A. Sulfur containing side-chains
Methyl-thio- Methyl-thio- Methyl-thio- Methyl-sulfinyl- Methyl-sulfinyl- Methyl-sulfinyl- Methyl-sulfony- Methyl-sulfonyl- alkene hydroxy-alkyl oxo-alkyl alkene hydroxy-alkyl oxo-alkyl alkene hydroxy-alkyl
n 1 201 210 218 225 234 242 250 259 2 [83] 211 219 [63] 235 243 [75] [260*] 3 202 212 220 226 236 244 251 261 4 203 [37] 221 227 [33] 245 252 [35] 5 204 [36] [91] 228 [32] 246 253 [34] 6 205 213 [90] 229 237 [70] 254 262 7 206 214 [93] 230 238 [71] 255 263 8 207 215 222 231 239 247 256 264 9 208 216 223 232 240 248 257 265 10 209 217 224 233 241 249 258 266
XS S XOH
S XO
XS
O
S XO
OH
S XO
OXS
O
O
S XO
OH
S XO
O
O
O
nn n
nn n n
n
n
Methyl-sulfonyl- Butenyl-thio- Benzyl-sulfonyl- Glucosyl- Dimer Cysteinyl- Glycinyl- oxo-alkyl alkene alkene disulfanyl-alkyl mercapto thio-alkyl thio-alkyl
n 1 267 277 286 295 304 313 322 2 268 278 287 296 305 314 [323*] 3 269 279 [181] 297 306 315 324 4 270 280 288 [135] [136] [121] 325 5 271 281 289 298 307 316 326 6 272 282 290 299 308 317 327 7 273 283 291 300 309 318 328 8 274 284 292 301 310 319 329 9 275 [182] 293 302 311 320 330 10 276 285 294 303 312 321 331
XS nXS n
XSS
OHO
HOOH
OH
n XS2n XHO
NH2
O
nXS nNH2
O
HO
Mercapto- Cysteinyl- Glutathione- Methylsulfonyl- Aspartyl-cysteinyl- alkyl disulfanyl-alkyl disulfanyl-alkyl hydroxy-alkene disulfanyl-alkyl
n 1 332 341 350 359 369 2 333 342 351 360 370 3 334 343 352 361 371 4 [185] [186] [187] 362 372 5 335 344 353 363 373 6 336 345 354 364 374 7 337 346 355 365 375 8 338 347 356 366 376 9 339 348 357 367 37710 340 349 358 368 378
n XHS XSS
n
NH2
O
HO SS
HN
NH
HOO
O
ONH2
O
HO Xn XS n
OH
O
O SS
HN
NH
HO
HO
O
O
O XO
NH2
Supplementary Material (ESI) for Analytical MethodsThis journal is (C) The Royal Society of Chemistry 2010
Fig. S2. Screening for cinnamoyl and benzoyl esters
Cinnamoyl acid Formulae Acid
Folmulae Ester
Mass gain Mono-ester
Mass gain Di-ester
Cinnamic acid C9H8O2 C9H6O 130.04186 260.08372Coumaric acid C9H8O3 C9H6O2 146.03678 292.07356Caffeic acid C9H8O4 C9H6O3 162.03169 324.06338Ferulic acid C10H10O4 C10H8O3 176.04734 352.09468Isoferulic acid C10H10O4 C10H8O3 176.04734 352.09468Sinapic acid C11H12O5 C11H10O4 206.05791 412.11582
O OHOH
HOS
NOSO3HOH
O
O
OCH3
OH
O OHOHS
O
N
O
OH
OCH3
O
O
OH
OCH3
OSO3HOH
(2R)-Glucobarbarin 2'-O-isoferuloyl-b-D-thioglucoside Aglycone + C10H8O3 m/z = GLS + 176.04734
(2R)-Glucobarbarin 2',6'-di-O-isoferuloyl-b-D-thioglucoside Aglycone + C20H16O6 m/z = GLS + 2 x 176.04734 = + 352.09468
O OHOH
HOS
NOSO3HOH
HO
C15H21NO10S2Exact Mass: 439.0607
(2R)-Glucobarbarin
C25H29NO13S2Exact Mass: 615.1080
C35H37NO16S2Exact Mass: 791.1554
HO
O
OCH3
OH
C10H10O4Exact Mass: 194.0579
[-H2O]
HO
O
OCH3
OH
C10H10O4Exact Mass: 194.0579
[-H2O] C10H8O3 = 176.04734
O
GLS
R2
R1
R4
R3
R1 R2 R3 R4Cinnamic acid H H H HCoumeric acid OH H H Hm-Coumaric acid H OH H Hp-Coumaric acid H H OH HCaffeic acid H OH OH HFerulic acid H OCH3 OH HIsoferulic acid H OH OCH3 HSinapic acid H OCH3 OH OCH3
HO
O
C9H8O2Exact Mass: 148.0524
HO
O
OH
HO
O
OH
OH
HO
O
OH
OCH3
HO
O
OH
OCH3
OCH3
C11H12O5Exact Mass: 224.0685
C9H8O3Exact Mass: 164.0473
C9H8O4Exact Mass: 180.0423
C10H10O4Exact Mass: 194.0579
O
GLS
O
OHC7H6O2
Exact Mass: 122.0368
Benzyl ester
Benzoic acid
[-H2O]
Aglycone + C7H4O m/z = GLS +104.02621
Supplementary Material (ESI) for Analytical MethodsThis journal is (C) The Royal Society of Chemistry 2010
Tab
le S
1. S
ome
sour
ces o
f Bra
ssic
ale
seed
s in
the
UK
.
Gen
us a
nd sp
ecie
s C
omm
on n
ame
Su
pplie
r Al
liari
a pe
tiola
ta
Gar
lic m
usta
rd
Po
yntz
field
her
b nu
rser
y Ar
mor
acia
rust
ican
a
Hor
sera
dish
(R
oots
) H
orse
radi
sh
Tayl
ors b
ulbs
Au
brie
ta d
elto
idea
R
ock
cres
s H
ende
rson
ii C
hilte
rn se
eds
Barb
area
ver
na
Cre
ss
Am
eric
an la
nd c
ress
Jo
hnso
ns
Barb
area
vul
gari
s var
. var
iega
ta
Cre
ss
Var
iega
ted
win
ter l
and
cres
s C
N se
eds
Buni
as o
rien
talis
Tu
rkis
h ro
cket
CN
seed
s Br
assi
ca c
arin
ata
Et
hiop
ian
mus
tard
Te
xsel
gre
ens
CN
seed
s Br
assi
ca ju
ncea
In
dian
mus
tard
G
reen
gia
nt
CN
seed
s Br
assi
ca ju
ncea
var
. int
eglif
olia
R
ed g
iant
mus
tard
C
hine
se m
usta
rd re
d gi
ant
John
sons
seed
s Br
assi
ca n
apob
rass
ica
Rut
abag
a (S
wed
e)
Bro
ra
Thom
pson
& M
orga
n
Bras
sica
ole
race
a va
r. ac
epha
la
Kal
e
Ref
lex
F1
Thom
pson
& M
orga
n
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ole
race
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epha
la
Bor
ecol
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urly
kal
e)
Ner
o di
tosc
ana
(Bla
ck R
ussi
an)
Kin
gs se
eds
Bras
sica
ole
race
a va
r. al
bogl
abra
K
ai-la
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hine
se b
rocc
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C
N se
eds
Bras
sica
ole
race
a va
r. bo
tryt
is
Cau
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ipsy
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pson
& M
orga
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race
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p. ro
man
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Rom
anes
co b
rocc
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Bro
ccol
i rom
anes
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Thom
pson
& M
orga
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race
a va
r. ca
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ta
Whi
te c
abba
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rum
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rigad
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1 Th
omps
on &
Mor
gan
Br
assi
ca o
lera
cea
var.
capi
tata
gp.
Sab
auda
W
hite
cab
bage
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oy)
Savo
y ki
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1 M
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herg
ill's
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race
a va
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ifera
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ings
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assi
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italic
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Bro
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en c
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M
r Fot
herg
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Bras
sica
ole
race
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r. ita
lica
B
rocc
oli (
Spro
utin
g)
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utin
g ea
rly p
urpl
e M
r Fot
herg
ill's
Bras
sica
ole
race
a va
r. ko
mat
suna
K
omat
suna
Sp
inac
h m
usta
rd
John
sons
seed
s Br
assi
ca ra
pa v
ar. c
hine
nsis
Pa
k ch
oi (C
anto
nese
) Sh
angh
ai
John
sons
seed
s Br
assi
ca ra
pa v
ar. j
appo
nica
M
ibun
a gr
eens
CN
seed
s Br
assi
ca ra
pa v
ar. j
appo
nica
M
izun
a gr
eens
Ja
pane
se g
reen
s Jo
hnso
ns se
eds
Bras
sica
rapa
var
. par
achi
nens
is
Cho
y su
m (F
alse
pak
cho
i) H
on ts
ai ta
i Jo
hnso
ns se
eds
Bras
sica
rapa
var
. pek
inen
sis
Chi
nese
cab
bage
John
sons
seed
s Br
assi
ca ra
pa v
ar. p
ervi
ridi
s K
omat
suna
Sp
inac
h m
usta
rd
John
sons
seed
s Br
assi
ca ra
pa v
ar. r
apife
ra
Turn
ip
Mila
n pu
rple
top
Kin
gs se
eds
Bras
sica
rapa
var
. ros
ular
is
Tats
oi (R
oset
te p
ak c
hoi)
Yuk
ina
savo
y Jo
hnso
ns se
eds
Supplementary Material (ESI) for Analytical MethodsThis journal is (C) The Royal Society of Chemistry 2010
Bras
sica
rapa
var
. ruv
o R
apin
i (B
rocc
oli r
aab)
CN
seed
s C
ram
be m
ariti
ma
Sea
kale
Li
lly w
hite
C
N se
eds
Cap
pari
s spi
nosa
var
iner
mis
C
aper
s
Chi
ltern
seed
s C
aric
a pa
paya
Pa
w P
aw
C
hilte
rn se
eds
Car
ica
cand
amer
ensi
s M
ount
ain
paw
paw
Chi
ltern
seed
s C
leom
e sp
inos
a Sp
ider
flow
er
Spar
kler
Ju
ngle
seed
s D
iplo
taxi
s mur
alis
W
ild R
ocke
t
Thom
pson
& M
orga
n
Dip
lota
xis t
enui
folia
W
ild R
ocke
t
John
sons
seed
s Eu
ruca
ves
icar
ia ss
p. sa
tiva
Roc
ket s
alad
R
ocke
t dis
cove
ry
Thom
pson
& M
orga
n
Euru
ca v
esic
aria
ssp.
sativ
a R
ocke
t sal
ad
Roc
ket a
pollo
Th
omps
on &
Mor
gan
Is
atis
tinc
tori
a W
oad
C
N se
eds
Hes
peri
s mat
rona
lis
Dam
e's v
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t Sw
eet r
ocke
t H
erita
ge w
ild fl
ower
s Le
pidi
um sa
tivum
C
ress
Po
lycr
ess
Thom
pson
& M
orga
n
Lim
nant
hes d
ougl
asii
Po
ache
d eg
g pl
ant
Th
omps
on &
Mor
gan
M
orin
ga o
leife
ra
Hor
sera
dish
tree
Jung
le se
eds
Nas
turt
ium
offi
cina
le
Wat
ercr
ess
Th
omps
on &
Mor
gan
Ph
ytol
acca
am
eric
ana
Poke
wee
d
Chi
ltern
seed
s Ph
ytol
acca
bog
oten
sis
Poke
berr
y
C
hilte
rn se
eds
Raph
anus
sativ
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Dai
kon
radi
sh
Moo
li ts
ukus
hi sp
ring
cros
s F1
Thom
pson
& M
orga
n
Raph
anus
sativ
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Rad
ish
R
udi
Thom
pson
& M
orga
n
Rese
da o
dora
ta
Mig
none
tte
Swee
t sce
nted
Su
ttons
Si
napi
s alb
a W
hite
mus
tard
W
hite
mus
tard
M
r Fot
herg
ill's
Trop
aeol
um m
ajus
N
astu
rtium
B
lack
vel
vet
Thom
pson
& M
orga
n
Was
abi j
apon
ica
W
asab
i (Po
tted)
Poyn
tzfie
ld h
erb
nurs
ery
M
ain
UK
seed
supp
lier w
ebsi
te a
ddre
sses
cnse
eds.c
o.uk
ch
ilter
nsee
ds.c
o.uk
he
ritag
ewild
flow
ers.c
o.uk
jo
hnso
n-se
eds.c
om
jung
lese
eds.c
o.uk
ki
ngss
eeds
.co.
uk
mr-
foth
ergi
lls.c
o.uk
po
yntz
field
herb
s.co.
uk
sutto
ns.c
o.uk
ta
ylor
s-bu
lbs.c
om
thom
pson
-mor
gan.
com
Supplementary Material (ESI) for Analytical MethodsThis journal is (C) The Royal Society of Chemistry 2010
