Py-GC/MS applied to the analysis of synthetic organic

Analytical and Bioanalytical Chemistry
Electronic Supplementary Material
Py-GC/MS applied to the analysis of synthetic organic pigments:
Characterization and identification in paint samples
Elisa Ghelardi, Ilaria Degano, Maria Perla Colombini, Joy Mazurek, Michael Schilling,
Tom Learner
1
Table S1 List of all the pigments analysed with Py-GC/MS. The * symbol near the Colour Index
name indicate the ones presented in this work
C.I.
name
PR1
PR3
PR4
PR5
PR6
PR7*
PR8
PR12
CI
number
12070
12120
12085
12490
12090
12420
12335
12385
12380
Common name
Class
β-naphthol
β-naphthol
β-naphthol
Naphthol AS
β-naphthol
Naphthol AS
Naphthol AS
Naphthol AS
Naphthol AS
Cu-Phthalogreen
PO16
PO46
PY3
PY12
PY100
15602
11710
21090
19140:1
β-naphthol
Hansa Scarlet RNC
Hansa Red R
Monolite Red CB
Pigment Red 6
Monolite Red 4RH
3149 Fast Red F4R-Y
Monolite Rubine 2R
Permanent Bordeaux
FGR
Sunbrite Red 17
1523 Naphthol Red 23
Symuler Fast Red 4085
Suimei Dianisidine Red
R
Cortone Scarlet 2BBT
Rubine Toner 2BO
Eljon Rubine 2BRC
Sunbrite Red 49:1
Sunbrite Red 49:2
Sunbrite Red 52:1
BR-522 Bon Maroon
1320 Red Lake C
Irgalite Rubine 4BP
Cortone Rubine 4BCT
Sunbrite Red 63:1
Alizarin Crimson
Cogilor Almandine
90110
Naphthol Red Light
Cromopthal Red BRN
Cromophtal Red RN
Napathol Red Medium
Novoperm Red HFT
Pigment Red 176
Novoperm Carmine
HF4C
Pigment Orange 5
Spectra Pac E Orange
16
Sunbrite Orange 46
Hansa Yellow Light
Sunbrite Yellow 12
Tartrazine yellow
PGr7
74260
Pigment Green 7
PR14
PR17
PR23
PR31
PR41*
PR48:1*
PR48:2*
PR48:2*
PR49:1*
PR49:2*
PR52:1*
PR52:2*
PR53:1*
PR57*
PR57:1*
PR63:1*
PR83*
PR90:1*
PR112
PR144
PR166
PR170
PR175
PR176
PR185
PO5
12390
12355
12360
21200
15865:1
15865:2
15865:2
15630:1
15630:2
15860:1
15860:2
15585:1
15850
15850:1
15880:1
58000:1
45380
12370
20735
20730
12475
12513
12515
12516
12075
21160
Naphthol AS
Naphthol AS
Naphthol AS
Disazopyrazolone
BONA, Ba
BONA, Ca
BONA, Ca
β-naphthol, Ba
β-naphthol, Ca
BONA, Ca
BONA, Mn
β-naphthol, Ba
BONA
BONA, Ca
BONA, Ca
Anthraquinone, Ca
Eosine
Naphthol AS
Disazo condensation
Disazo condensation
Naphthol AS
Benzimidazolone
Benzimidazolone
Benzimidazolone
β-naphthol
Diarylide yellow
β-naphthol, Ba
Monoazo yellow
Diarylide yellow
Monoazopyrazolone,
Al
2
Manufacturer or
Supplier
Clariant
Clariant
Clariant
ICI (Avecia)
Kremer
ICI
HY pigments
Avecia
Year
nd
2002
2002
2002
nd
1996
2002
2002
Clariant
Clariant
Lansco
Dainippon
2002
nd
2002
2002
Sansui
EC pigments
Avecia
EC pigments
Sun
Sun
Sun
Lansco
Lansco
Ciba
EC pigments
Sun
W&N
2003
nd
2002
2002
2002
2002
2002
2002
2002
2002
2002
2002
nd
Anstead
Golden
Ciba
Ciba
W&N
Clariant
Royal Talens
nd
1996
2002
2002
1996
2002
2002
Sun
W&N
nd
1996
Sun
Sun
Golden
Sun
H. Kohnstamm & Co.,
Inc. 83-93 Park Place,
NY, NY Tartrazine 640
F.D&C Yellow Certified
W&N
2002
2002
1996
2002
nd
1996
PGr8*
PGr10*
PGr13*
PGr36
PB15:0*
10006
12775
74200
74265
74160
PB15:1*
PB15:2*
PB15:3*
PB15:4*
PB15:6*
PB16*
74160
74160
74160
74160
74160
74100
74180
PB17*
PB60*
PB62*
PB63
PB76*
PV1*
PV3*
PV5
PV19*
PV23*
PV27*
PV29*
PV32*
PV36*
PV37*
PV39*
PV42*
PV44*
PV51*
PV52*
PV53*
PBr23
PBr25
PBr38*
PBr41
PBr42
69800
44084
73015:x
45170:2
42535:2
58055
73900
51319
42535:3
71129
12517
73385
51345
42555:2
20060
12510
561660
-
Bricofor Green L5837
Nickel Azo Yellow
Phthalochrome Green
Monastral Green 6Y-C
5561 Cu
Phthalocyanine Blue
Monastral Blue LBX
Monastral Blue FBN
Monastral Blue BG
Monastral Blue FGX
Heliogen Blue
Heliogen Blau D7490
4230 Fast Sky Blue
Lake
Monolite Blue 3R
Eljon Blue FR
Indigo Carmine
Aluminium Lake
Fastogen Blue 10GN
Rhodamine B PTMA
1903 PTM Violet
Alizarine Violet
Monolite Violet 4R
Monolite Violet RN
Eljon Violet CMW
CI Pigment Violet 29
Novoperm Bordeaux
HF3R
Thio Violet
Cromophtal Violet B
Crystal Violet
Quinacridone Violet
Symuler Fast Violet
4142
1120 Rightfit Violet
1118 Rightfit Pink
1117 Engeltone Red 4B
Cromophtal Brown 5R
Hostaperm Brown HFR
01
Pigment Brown 38
Translucent Brown
Azo Golden Brown
Metal complex
Metal complex
Cu-Phthalogreen
Cu-Phthalogreen
Cu Phthaloblue
Albion / Hays
Avecia
Avecia
Lansco
2002
nd
nd
2002
2002
Cu Phthaloblue
Cu Phthaloblue
Cu Phthaloblue
Cu Phthaloblue
Cu Phthaloblue
Phthaloblue metal
free
Cu Phthaloblue
Avecia / Zeneca
Avecia / Zeneca
Avecia
Avecia
Kremer
BASF
2002
2002
nd
2002
2002
2002
HY pigs
Avecia / Zeneca
EC pigments
KKK
2002
2002
2002
2003
Dianippon
Magruder
Lansco
Kremer
Avecia
Avecia
EC pigments
Bayer
2002
2002
2002
2002
2002
2002
2002
2002
2002
Indanthrone
Triarylcarbonium
Indigo, sulphonic
acid, Al
Cu Phthaloblue
Triarylcarbonium
Triarylcarbonium
Anthraquinone
Quinacridone
Dioxazin
Triarylcarbonium
Perylene
Benzimidazolone
Clariant
Thioindigo
Dioxazine
Triarylcarbonium
Quinacridone
Naphthol AS
Monoazo
Monoazo
Disazo condensation
Benzimidazolone
Isoindoline
Disazo condensation
Disazo condensation
3
Ciba
Sigma Aldrich
nd
2002
nd
nd
Dianippon
Engelhard
Engelhard
Engelhard
Ciba
2002
2003
2003
2003
nd
Clariant
2002
nd
nd
nd
Mass spectra of unknown pyrolysis products
231
107
77
170
122
92
51
135
152
63
202
20
40
60
80
100
120
140
160
180
200
220
Fig. S1 Unknown product (231, 170, 107) at 13.7 min found in PV32
246
231
168
122
52
0
20
40
66
60
79
80
94
100
138
109
120
140
202
154
160
180
Fig. S2 Unknown product (246, 231, 168, 202) at 15.5 min found in PV32
4
200
220
240
160
188
57
130
41
204
71
20
40
60
104
80
100
174
120
140
160
180
317
200
220
240
260
280
300
320
Fig. S3 Unknown product (160, 188, 189) at 15.6 min found in PB15:6
233
262
117
20
40
60
80
100
120
175 189
140
160
180
Fig. S4 Unknown product (233, 262) at 12.3 min found in PV19
5
200
247
220
240
260
280
195
167
139
83
0
50
100
150
450
200
250
300
350
400
450
Fig. S5 Unknown product (195, 167, 139) at 15.7 min found in PV42
450
225
0
50
100
150
200
250
300
Fig. S6 Unknown product (450, 452, 225) at 23 min found in PV42
6
350
400
450
183
154
196
211
127
77
91
63
0
20
40
167
60
80
100
120
140
160
180
200
220
Fig. S7 Unknown product (183, 154, 196) at 14.9 min found in PV23
182
195
210
154
127
91
77
0
20
40
60
80
167
100
120
140
160
Fig. S8 Unknown product (182, 195, 210) at 15.2 min found in PV23
7
180
200
220
240
222
235
250
153
126
111
0
20
40
60
80
100
139
120
140
160
180
200
220
240
260
Fig. S9 Unknown product (222, 235, 250) at 15.7 min found in PV23
211
104
52
77
183
0
20
40
60
80
100
120
140
160
180
Fig. S10 Unknown product (211, 104) at 14.7 min found in PV37
8
200
220
240
260
135
107
121
149
220
20
40
60
80
100
120
140
160
180
200
220
240
Fig. S11 Unknown product (135, 121, 107, 149) at 12.5 min found in PR90:1
251
145
221
236
107
0
20
40
60
80
100
207
120
140
160
180
200
220
Fig. S12 Unknown product (251, 145, 221, 236) at 16.99 min found in PV27
9
240
260
280
265
221
159
144
235
120
0
20
40
60
80
100
120
140
160
180
200
220
240
260
280
Fig. S13 Unknown product (265, 221,159, 144) at 17.05 min found in PV27
279
235
158
120
0
20
40
60
80
100
120
143
262
140
160
180
200
220
Fig. S14 Unknown product (279, 235, 158, 143) at 17.11 min found in PV27
10
240
260
280
Pyrograms of the paint samples analysed
Jackson Pollock
1
4
2
2.00
4.00
6.00
8.00
10.00
3
12.00
14.00
16.00
18.00
Fig. S15 Pyrogram of Jackson Pollock paint sample #8, from Mural (1943). 1. n-buthyl
methacrylate; 2. 2-naphthol; 3. diethyl phthalate; 4. unknown characteristic PR3 product
(m/z 275, 246, 128)
11
Clyfford Still
7
2
3
5 6 7
4
8
1
4.00
6.00
8.00
4
2.00
10.00
12.00
14.00
16.00
18.00
20.00
7
2
3
5 6 7
8
1
2.00
4.00
6.00
8.00
10.00
12.00
14.00
16.00
18.00
20.00
Fig. S16 Pyrograms of samples #18 (top) and #21 (bottom), two pigments found in Still’ studio. 1.
naphthalene; 2. 2-naphthol; 3. 2-naphthalenamine; 4. 1-propene 1,2,3-tricarboxylic acid,
tributyl ester; 5. 2,2’-dinaphthyl ether; 6. naphthalene, 1-(2-naphthalenyloxy)-; 7.
dinaphtho[2,1b:1,2-d]furan and dinaphtho[2,1b:1’2’-d]furan; 8. benzo[f]naphtho[2,1c]cinnoline
12
4
11
2
12
3
10
11
6
1
8
5
2.00
4.00
6.00
8.00
10.00
12.00
9
7
14.00
16.00
18.00
20.00
Fig. S17 Pyrogram of sample #38, a pigment found in Still’ studio. 1. Naphthalene; 2. 2-naphthol;
3. 1-naphthalenamine; 4. 2-naphthalenamine; 5. Cyclododecane; 6. 1-hexadecanol; 7.
Cyclotetradecane; 8. 1,13-tetradecadiene; 9. 2,2’-dinaphthyl ether; 10. naphthalene, 1-(2naphthalenyloxy)-; 11. dinaphtho[2,1b:1,2-d]furan and dinaphtho[2,1b:1’2’-d]furan; 12.
benzo[f]naphtho[2,1-c]cinnoline
13
9
3
4
7
5
1
2.00
4.00
6.00
8.00
8
9
6
10
2
10.00
12.00
14.00
16.00
18.00
20.00
Fig. S18 Pyrogram of sample #40a, a pigment found in Still’ studio. 1. Naphthalene; 2. phthalic
anhydride; 3. 2-naphthol; 4. 2-naphthalenamine; 5. 2-naphthol, 1-amino; 6.
2Hphenantro[9,10b]pyran; 7. 2,2’-dinaphthyl ether; 8. naphthalene, 1-(2-naphthalenyloxy); 9. dinaphtho[2,1b:1,2-d]furan and dinaphtho[2,1b:1’2’-d]furan; 10. benzo[f]naphtho[2,1c]cinnoline
7
4
6
3
2
8
5
1
2.00
4.00
6.00
8.00
10.00
12.00
14.00
16.00
Fig. S19 Pyrogram of Clyfford Still paint sample 339_11, from Untitled (1948 a). 1. caprylic acid;
2. azelaic acid; 3. phenanthrene; 4. palmitic acid; 5. anthrone; 6. 9,10-anthracenedione,2hydroxy; 7. stearic acid, 8. squalene (anthropogenic contamination)
14
6?
2
**
3
*
4
5
1
2.00
4.00
6.00
8.00
10.00
12.00
14.00
16.00
18.00
Fig. S20 Pyrogram of Clyfford Still paint sample 322_11, from Untitled (1948 a). 1. aniline; 2. 2naphthol; 3. naphthalene, 1-isocyanato-; 4. p-nitroaniline; 5. 2-naphthol, 1-amino; 6. 4hydroxy-3methyl-beta-phenylcinnamonitrile? (m/z 235); *unknown product characteristic
of red pigments (m/z 183, 154, 114); **unknown product (m/z 263, 207, 92, 107, 281)
15
12
11
8
13
10
23 4 5
14
9 *
7
6
1
2.00
4.00
6.00
8.00
10.00
12.00
14.00
11
16.00
18.00
16.00
18.00
12
8
23 4 5
4.00
7
6
1
2.00
13
10
9 *
6.00
8.00
10.00
12.00
14.00
Fig. S21 Pyrograms of Clyfford Still paint samples 968_1 (top) and 968_2 (bottom), both from
Untitled (1951-1952). 1. toluene; 2. cyclohexanone; 3. benzene, 1-methylethyl; 4. alphamethylstirene; 5. benzene, tert-butyl-; 6. octanoic acid; 7. naphthalene: 8. 2-naphthol; 9.
naphthalene, 1-isocyanato-; 10. azelaic acid; 11. palmitic acid; 12. stearic acid; 13. linoleic
acid; 14. naphthalene, 1-(2-naphthalenyloxy)-; *unknown product characteristic of red
pigments (m/z 183, 154, 114)
16
15
12
14
16
13
5
1
2.00
4.00
23
6.00
4
9
6
7
8
8.00
11
17
*
18
10
10.00
12.00
14.00
16.00
Fig. S22 Pyrogram of Clyfford Still paint sample 969_2, from Untitled (1954). 1. toluene; 2.
ethylbenzene; 3. styrene; 4. benzene, 1-methylethyl; 5. alpha-methylstyrene; 6. benzene,
tert-butyl; 7. benzene, 2-methyl-1-propenyl; 8. octanoic acid; 9. naphthalene; 10.
naphthalene, 2-methyl-; 11. octanedioic acid; 12. 2-naphthol; 13. 2-naphthalenamine; 14.
azelaic acid; 15. palmitic acid; 16. stearic acid; 17. linoleic acid; 18. naphthalene, 1-(2naphthalenyloxy)-; *unknown product characteristic of red pigments (m/z 183, 154, 114)
17
15
16
12 13
*
17
10 11
4
12
2.00
4.00
6
7 8
14
18
9
3 5
6.00
8.00
10.00
12.00
14.00
16.00
Fig. S23 Pyrogram of Clyfford Still paint sample 693_4, from Untitled (1960). 1. toluene; 2.
cyclopentanone; 3. ethylbenzene; 4. cyclohexanone; 5. benzene, 1-methylethyl-; 6. alphamethylstyrene; 7. cycloheptanone; 8. p-aminotoluene; 9. octanoic acid; 10. naphthalene;
11. benzenamine, 3-chloro-4-methyl-; 12. 2-naphthol; 13. 2-naphthalenamine; 14. azelaic
acid; 15. palmitic acid; 16. stearic acid; 17. linoleic acid; 18. naphthalene, 1-(2naphthalenyloxy)
18