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100 100 100 2: Rosaniline b. Standards mixture 40 20 40 60 80 20 60 80 20 40 60 80 100 100 20 40 60 80 20 40 60 80 a. Historical sample 20 40 60 80 20 40 60 80 14 20 40 60 80 20 40 60 80 20 40 60 80 o b a n e o b a n e o b a n e 10 20 30 100 100 100 o b a n e o b a n e 20 40 60 80 20 40 60 80 CA o b a n e 275 221 453 331 281 s c s c s c Abundance s c s c 20 40 60 80 20 40 60 80 20 40 60 80 s c Absorbance 275 0 0 0 0 0 Wavelength (nm) 0 dcII 100 100 0 0 0 5 1 2 5 Relative Relative 4 1 7 6 3 7 6
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14 16 18 20 22 24 26
0
20
40
60
80
100
4
32
Re
lative
Ab
so
rba
nce
1
Historical sample
250 300 350 4000
20
40
60
80
100
NH2
NH2
NH2
+
Cl-
Re
lative
Ab
un
da
nce
m/z
288
250 300 350 4000
20
40
60
80
100
NH2
NH2
NH2
+
CH3
CH3 CH3
Cl-
Re
lative
Ab
un
da
nce
m/z
250 300 350 4000
20
40
60
80
100
NH2
NH2
NH2
+
CH3
Cl-
4: New Fuchsin3: Magenta II
2: Rosaniline
330316
Re
lative
Ab
un
da
nce
m/z
3021: Pararosaniline
250 300 350 4000
20
40
60
80
100
NH2
NH2
NH2
+
CH3
CH3
Cl-
Re
lative
Ab
un
da
nce
m/z
Time (min)
1Rhodamine B
4Fuchsin compounds
1Indigo carmine
4Haematoxylum campechianum L.Logwood
16Isatis tinctoria L./Indigofera tinctoria L.and other
Indigo/woad
1Rhamnus treesBuckthorn berries
4Genista tinctoria L.Dyer’s broom
8Reseda luteola L.Weld
11Cotinus coggygria Scop.Young fustic
3Rubia tinctorum L.Madder
12Caesalpinia treesRedwood
19Dactylopius coccus Costa (most likely)Cochineal
No of objectsBiological sourceDye
300 400 5000
20
40
60
80
100
m/z
300 400 5000
20
40
60
80
100
m/z
300 400 5000
20
40
60
80
100
dcVIIdcIV
491491
Rela
tive A
bundance
m/z
dcII
10 12 14 16 18
0
10
20
30
dcVIIdcIV
CA
Re
lative
In
ten
sity
Time (min)
dcII
275
12 14 16 18 20 22
0
20
40
60
80
100
12 14 16 18 20 22
0
20
40
60
80
100
b. Treatment with TFA
5
43
1
2
Re
lative
Ab
so
rba
nce
Time (min)
5
76
76
Re
lative
Ab
so
rba
nce
a. Treatment with HCl
18 20 22 24 26 28
0
20
40
60
80
100
18 20 22 24 26 28
0
20
40
60
80
100
b. Standards mixture
Time (min)
7
6
54
3
2
1
Rela
tive
Absorb
ance
Rela
tive
Absorb
ance
7
6
5
4
321
a. Historical sample
6 8 10 12 14 16
0
20
40
60
80
100281
m/z
c. Logwood + HCl
Time (min)
6 8 10 12 14 16
0
20
40
60
80
100
6 8 10 12 14 16
0
20
40
60
80
100
b. Haematein + HCl
Re
lative
Ab
so
rba
nce
Re
lative
Ab
so
rba
nce
Re
lative
Ab
so
rba
nce
Haematein derivative
a. Historical sample + HCl
200 300 400 500 6000
20
40
60
80
100
275
221
453
Wavelength (nm)
Re
lative
Ab
so
rba
nce
200 300 400 500 6000
20
40
60
80
100
Re
lative
Ab
un
da
nce
331
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