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
HO N HO
O
HO N HO
H O
HO N HO
H
O
O HO H
O
HO HO
O
HO N HO
H
N H H
m/z 72
HO HO
O H
HO
HO m/z 165
- CO
HO HO
S-4 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
HO N CH3O
O
HO N CH3O
H
O
HO N CH3O
H
O
O CH3O H
O
HO CH3O
O
HO N 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
HO N 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
HO N HO
OH
H H
m/z 260
O
HO N HO
O
N H
O
O
HO N HO
H
O
N O O N H
H N H
O O
HO N HO
H O
N H
H O
S-6
O
HO NH CH3O
H
O HO O
HO NH CH3O
O HO
m/z 292 M5
m/z 140 m/z 140
m/z 98
N O O N H
H N H
O - N
H O m/z 310
O HO m/z 87
- H2O
m/z 310
NH
O HO m/z 158 O
NH2 HO
CH3O
O HO
O
HO N CH3O
H O
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
O HO m/z 87
- NH3 m/z 104
O HO
NH3
O
HO NH CH3O
O HO
NH2 O
NH O
NH
O OH O
N O
O HO
CH3O
N O
H
HO CH3O
NH
O OH
HO CH3O
NH OH
O OH HO
CH3O
NH OH
O OH O
HO NH CH3O
H
O HO M5
- H2O
m/z 310 m/z 310 m/z 310
- H2O
m/z 292
O O
-
- H2CO
O O
- - 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 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 274
N H
O
N O O N H
H N H
O N
H H O
m/z 137
O
CH3O N HO
O
O
CH3O N HO
H
O
O
CH3O N HO
H O
O
CH3O O H O
CH3O N HO
OH
H H
O
CH3O N 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 274
N H
O
N O O N H
H N H
O N
H H O
m/z 137 HO CH3O
O
HO N CH3O
O
O
HO N CH3O
H
O
O
HO N CH3O
H O
O
O CH3O H HO
CH3O
O H O
HO N CH3O
OH
H H
O
HO N CH3O
S-10 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 H H
m/z 72
OH
O N O
OH2
O N O
m/z 278
O N O
- H2O OH
O N O
H
OH
O
O H
- CH3OH
- H2CO
O N 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
HO N CH3O
H
m/z 205
m/z 173
M9
- H2CO
- N
H
m/z 294
m/z 142
m/z 205
m/z 137 HO CH3O
O
HO N CH3O
OH O
HO N CH3O
H OH
N OH m/z 294
- H2O O
HO N CH3O
H OH
- CH3CH=CH2
O
O CH3O
H
m/z 151 O
HO CH3O m/z 276
- N
H
O
HO N 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
HO N CH3O
OH
m/z 294 O
HO N CH3O
H OH
- H2O
m/z 276 - CO
N H
m/z 98 m/z 248
- CH4
H N
HO CH3O
m/z 232 - CH3OH
O
H N
m/z 200 - CH≡CH
N H H
m/z 72
O
CH3O N
H
H
H O
HO N CH3O
H
S-12 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
HO N CH3O
H
OH
N OH HO N H
H N H
OH N
H
OH O
HO N CH3O
H OH
N H H
OH
m/z 88 - H2O
m/z 70 N H
H O
HO N CH3O
OH
- H2O O
HO N CH3O
H m/z 251
O
HO N CH3O
H OH
m/z 248 CH3O N H
HO