10.1007:s00216-015-9088-1 (1).pdf
TRANSCRIPT
S-1
ELECTRONIC SUPPLEMENTARY MATERIAL
ANALYTICAL STRATEGY TO INVESTIGATE 3,4-
METHYLENEDIOXYPYROVALERONE (MDPV) METABOLITES IN
CONSUMERS’ URINE BY HIGH RESOLUTION MASS
SPECTROMETRY
María Ibáñez1*, Óscar J. Pozo2, Juan V Sancho1, Teresa Orengo3, Gonzalo Haro4,5,Félix
Hernández1
1Research Institute for Pesticides and Water, University Jaume I, Avda. SosBaynat, E-
12071 Castellón, Spain.
2Bioanalysis Research Group, IMIM, Hospital del Mar Medical Research Institute,
Doctor Aiguader 88, 08003 Barcelona, Spain
3Addictions Treatment Unit Grao-Clínico, Valencia, Spain
4School of Medicine, University CEU-Cardenal Herrera, Castellón
5Psychiatry Department, Consorcio Hospitalario Provincial de Castellón
* Corresponding author [email protected], Tel +34 964 387339, Fax +34 964 387368
S-2
Fig S.1. Extracted Ion Chromatograms (XICs) for all detected metabolites.
S-3
Metabolite M1
Figure S.2. Product ion spectrum of M1 (20 eV) and proposed fragmentation pathway.
m/z 193
m/z 264
m/z 175
M1
- H2O
-
- CH3CH2CH2•
N
H
O
O
m/z 137
m/z 221
N
m/z 264
m/z 126
N H
m/z 126
H
N
H
m/z 84
m/z 193
m/z 123
O
NHO
HO
O
NHO
HO
H
O
NHO
HO
H
O
O
HO
H
O
HO
HO
O
NHO
HO
H
N
HH
m/z 72
HO
HO
O
H
HO
HOm/z 165
- CO
HO
HO
S-4
Metabolite M2
Figure S.3. Product ion spectrum of M2 (20 eV) and proposed fragmentation pathway.
m/z 207
m/z 278
m/z 175
M2
- H2CO
-
- CH3CH2CH2•
N
H
O
O
m/z 151
m/z 235
N
m/z 278
m/z 126
N H
m/z 126
H
N
H
m/z 84
m/z 207
m/z 137
O
NHO
CH3O
O
NHO
CH3O
H
O
NHO
CH3O
H
O
O
CH3O
H
O
HO
CH3O
O
NHO
CH3O
H
HO
CH3O
O
H
HO
CH3O
S-5
Metabolite M3
Figure S.4. Product ion spectrum of M3 (20 eV) and proposed fragmentation pathway.
O
NHO
HO
m/z 193
m/z 278
m/z 175
M3
- H2O
-
- H2O
O
O
m/z 137
m/z 278
m/z 140 m/z 140
m/z 98
m/z 193
m/z 123
O
O
HO
H
O
HO
HO
m/z 86
HO
HO
O
H
HO
HO
m/z 278
O
NHO
HO
OH
H H
m/z 260
O
NHO
HO
O
N
H
O
O
NHO
HO
H
O
NO N HO
H
N
H
O
O
NHO
HO
HO
N
HH
O
S-6
Metabolite M5
O
NHHO
CH3O
H
OHO
O
NHHO
CH3O
OHO
m/z 292
M5
m/z 140 m/z 140
m/z 98
NO N HO
H
N
H
O
-N
H
O
m/z 310
OHO
m/z 87
- H2O
m/z 310
NH
OHO
m/z 158
O
NH2HO
CH3O
OHO
O
NHO
CH3O
HO
m/z 207
m/z 175
- H2CO
O
O
m/z 151
m/z 207
m/z 137
O
O
CH3O
H
O
HO
CH3O
HO
CH3O
O
H
HO
CH3O
OHO
m/z 87
- NH3
m/z 104
OHO
NH3
O
NHHO
CH3O
OHO
NH2
O
NHO
NH
O
OH
O
NO
O
HO
CH3O
N
O
H
HO
CH3O
NH
O
OH
HO
CH3O
NH
OH
O
OH
HO
CH3O
NH
OH
O
OH
O
NHHO
CH3O
H
OHO
M5
- H2O
m/z 310 m/z 310 m/z 310
- H2O
m/z 292
OO-
- H2CO
OO-
- H2CO
- H2O
m/z 206
m/z 260- H2CO
m/z 242
m/z 274
m/z 174
- HCOOH
m/z 214
m/z 232
-
HO
CH3O
NH2
HO
CH3O
N
O
HO
CH3O
NH
m/z 205
S-7
Figure S.5. Product ion spectrum of M5 (20 eV) and proposed fragmentation pathway.
S-8
Metabolite M6
Figure S.6. Product ion spectrum of M6 (20 eV) and proposed fragmentation pathway.
m/z 207
m/z 292
m/z 175
M6
- CH3OH
-
- H2O
O
O
m/z 292
m/z 140 m/z 140
m/z 98
m/z 207
m/z 86
m/z 292
m/z 274N
H
O
NO N HO
H
N
H
O
N
HH
O
m/z 137
O
NCH3O
HO
O
O
NCH3O
HO
H
O
O
NCH3O
HO
HO
O
CH3O
O
H
O
NCH3O
HO
OH
H H
O
NCH3O
HO
CH3O
HO
O
H
CH3O
HO
S-9
Metabolite M7
Figure S.7. Product ion spectrum of M7 (20 eV) and proposed fragmentation pathway.
m/z 207
m/z 292
m/z 175
M7
- CH3OH
-
- H2O
O
O
m/z 292
m/z 140 m/z 140
m/z 98
m/z 207
m/z 86
m/z 292
m/z 274N
H
O
NO N HO
H
N
H
O
N
HH
O
m/z 137
HO
CH3O
O
NHO
CH3O
O
O
NHO
CH3O
H
O
O
NHO
CH3O
HO
O
O
CH3O
H
HO
CH3O
O
H
O
NHO
CH3O
OH
H H
O
NHO
CH3O
S-10
Metabolite M8
Figure S.8. Product ion spectrum of M8 (20 eV) and proposed fragmentation pathway.
m/z 189 m/z 217
m/z 175
M8
- H2O
-
- CH3CH2CH2•
N
H
m/z 159
m/z 278
m/z 260
m/z 207
N
HH
m/z 72
OH
NO
O
OH2
NO
O
m/z 278
NO
O
- H2O
OH
NO
O
H
OH
O
O H
- CH3OH
- H2CO
NO
O
O
O
O
O
O
N
m/z 126
N H
m/z 126
H
N
H
m/z 84
S-11
Metabolite M9
HO
CH3O
O
H
O
NHO
CH3O
H
m/z 205
m/z 173
M9
- H2CO
- N
Hm/z 294
m/z 142
m/z 205
m/z 137
HO
CH3O
O
NHO
CH3O
OH O
NHO
CH3O
H OH
N
OH
m/z 294 - H2O
O
NHO
CH3O
H
OH
- CH3CH=CH2
O
O
CH3O
H
m/z 151
O
HO
CH3O
m/z 276
- N
H
O
NHO
CH3O
m/z 234
O
O
CH3O
H
m/z 205
O
CH3O
H
O
m/z 205
- CH2=CH2 O
CH3O
H
O
m/z 177
- H2O
O
HO
CH3O
OH
m/z 223
- H2O
m/z 216
O
N
O
O
O
M9
O
NHO
CH3O
OH
m/z 294
O
NHO
CH3O
H
OH
- H2O
m/z 276
- CO
N H
m/z 98 m/z 248
- CH4
HN
HO
CH3O
m/z 232
- CH3OH
O
H
N
m/z 200
- CH≡CHN
HH
m/z 72
O
CH3O N
H
H
H
O
NHO
CH3O
H
S-12
Figure S.9. Product ion spectrum of M9 (20 eV) and proposed fragmentation pathway. Only fragmentation corresponding to one of the two possible candidates (concretely, 1-(4-hydroxy-3-methoxyphenyl)-3-hydroxy-2-(1-pyrrolidinyl)pentan-1-one) is shown, but the implied pathways for both candidates will be “identical”.
S-13
Metabolite M10
Figure S.10. Product ion spectrum of M10 (20 eV) and proposed fragmentation pathway. Only fragmentation corresponding to the most feasible candidate (concretely 1-(4-hydroxy-3-methoxyphenyl)-2-(2-hydroxypyrrolidinyl)pentan-1-one is shown, but the implied pathways for both candidates will be “identical”.
m/z 207
m/z 294
m/z 175
M10
- H2CO
-
- CH3CH2CH2•
O
O
m/z 151
m/z 276
m/z 294
m/z 142 m/z 142
m/z 100
m/z 207
m/z 137
O
O
CH3O
H
O
HO
CH3O
HO
CH3O
O
H
HO
CH3O
O
NHO
CH3O
H
OH
NOH
N HHO
H
N
H
OH
N
H
OH
O
NHO
CH3O
HOH
N
HH
OH
m/z 88
- H2O
m/z 70
N
HH
O
NHO
CH3O
OH
- H2O
O
NHO
CH3O
H
m/z 251
O
NHO
CH3O
HOH
m/z 248
N HCH3O
HO