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1
Supplementary information to “Trifluoroacetylazobenzene for optical and electrochemical
detection of amines” by Jhih-Fong Lin et al.
1H-NMR and 13C-NMR spectroscopy analyses
The dye amine adduct were characterized using nuclear magnetic resonance spectroscopy (NMR) Bruker
AV 400. 1H NMR and 13C NMR spectra were recorded on a Bruker DRX-400 and calibrated using the residual
peak of solvents as an internal standard [CDCl3 (CHCl3 δH 7.26 ppm, CDCl3 δC 77.0 ppm). The dye was
dissolved in CDCl3 and different concentration of amine was added. Spectrum was taken 20 min after
addition.
Scheme S1
The reaction of dye with different amines (cadaverine, putrescine, ethylamine and ammonia) was also Ha (δ
ppm 8.16 ), Hb and Hc (δ ppm 7.87-7.92) protons of dye undergoes upfield shift upon reaction with the
amine (for 1H-NMR and 13C-NMR spectra see data 1.1-1.25). New Ha’, Hb’ and Hc’ in the dye amine adduct
appeared in the range δ ppm 7.78-7.40.1
Imine or carbinolamine or aminal are the three possible products in the reaction of dye with amine. The
study of 13C-NMR of the dye and dye adduct indicates the carbinolamine formation. The quartet of carbonyl
carbon at 180 ppm in the dye disappeared in the dye adduct and replaced by new quartet at 86 ppm for
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7
9
110
3
2
4
6
5
12
3
457
6
89
10
11
12
13
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15
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19
20
21
22
23
24
11
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1718
Electronic Supplementary Material (ESI) for Journal of Materials Chemistry A.This journal is © The Royal Society of Chemistry 2015
2
carbinolamine in the adduct spectrum. This corroborates with the results reported by Mertz et al. (Table
2).1 The imine carbon is expected to give quartet around 150 ppm.2
We determined the percentage of product (dye and amine adducts, amines: cadaverine, putrescine and
ethylamine) and dye in the reaction mixture from integration values of hydrogens of the dye and product
(Table 1).
Note, that product formation during the reaction of dye with ammonia even at high concentration of
ammonia could not be detected.
Table S1 Peak and integration values
Peak 8.16 (d, J= 8Hz) Expected
integration : 2 hydrogens (Ha
protons)
7.87-7.92 Expected
integration : 4 hydrogens (Hb and Hc
protons)
7.78-7.40 Expected integration
: 6 hydrogens (Ha’, Hb’, Hc’
protons)
Compound
Dye 2 4 0
Dye + cadaverine (1:0.5 molar eqv.) 1.79(89.64%) 3.56(89.02%) 0.75 (12.48%)
Dye + cadaverine (1:1 molar eqv.) 1.50 (74.92%) 3.02 (75.41%) 1.42 (23.63%)
Dye + cadaverine (1:1.5 molar eqv.) 1.26 (63.00% 2.53 (63.25%) 2.19 (36.50%)
Dye + cadaverine (1:2 molar eqv.) 1.04 (52.00%) 2.13 (53.25%) 2.75 (45.83%)
Dye + cadaverine (1:3 molar eqv.) 0.91 (45.50%) 1.89 (47.25%) 3.15 (52.50%)
Dye + cadaverine (1:4 molar eqv.) 0.72 (36.00%) 1.49 (37.25%) 3.75 (62.50%)
Dye + cadaverine (1:8 molar eqv.) 0 0 6 (100 %)
Dye + putrescine (1:0.5 molar eqv.) 1.76 (88.00%)
Two peaks are not separated
Dye + putrescine (1:1 molar eqv.) 1.56 (78.00%)
Dye + putrescine (1:2 molar eqv.) 0.47 (23.5 %)
Dye + putrescine (1:2.5 molar eqv.) 0.35 (17.50%)
Dye + putrescine (1:3 molar eqv.) 0.34 (17.00%)
Dye + putrescine (1:8 molar eqv.) 0 0 6 (100%)
Dye + ethyl amine (1:0.5 molar eqv.) 1.96 (98.00%) 3.91 (97.75) 0.13 (21.70%)
Dye + ethyl amine (1:1 molar eqv.) 1.91 (95.50%) 3.79 (94.75%) 0.27 (4.50%)
Dye + ethyl amine (1:2 molar eqv.) 1.80 (90.00%) 3.57 (89.25) 0.64 (10.66)
Dye + ethyl amine (1:3 molar eqv.) 1.74 (87.00%) 3.47 (86.75) 0.76 (12.67)
Dye + ethyl amine (1:4 molar eqv.) 1.62 (81.00%) 3.26 (81.50%) 1.03 (17.16%)
Dye + ethyl amine (1:8 molar eqv.) 1.54 (77.00%) 3.08 (77.00%) 1.35 (22.50%)
Percentage of dye in reaction mixture= (integration of Ha peak/2)* 100 Percentage of dye in reaction mixture = (integration of Hb and Hc peak/4)* 100
Percentage of product in reaction mixture = (integration of Ha’, Hb’ and Hc’ peak/6)* 100
3
Table S2 13C chemical shifts of dye and dye adduct
Carbon δppm of carbon
Dye Dye cadaverine adduct
1 111.39, 115.56, 118.46, 122.65 121.25, 125.09, 128.79, 142.85
2 179.5, 179.85, 180.20, 180.54 85.90, 86.19, 86.47, 86.76
3 131.53 137.37
4 131.52 125.09
5 129.33 121.25
6 151.83 150.40
7 143.57 142.85
8 126.65 125.09
9 111.39 110.78
10 157.79 153.24
11 51.51 50.89
12 31.99 31.57
13 29.62 29.22
14 29.47 29.06
15 27.47 26.87
16 27.27 26.87
17 22.83 22.41
18 14.28 13.87
19 -- 41.37
20 --
23.97 21 --
22 --
23 --
24 -- 33.46
4
-2-1
15
14
13
12
11
10
98
76
54
32
10
ppm
0.877
0.894
0.911
1.291
1.317
1.342
1.351
1.630
1.648
2.007
3.359
3.379
3.398
6.684
6.707
7.260
7.875
7.898
7.906
7.911
7.924
7.928
8.161
8.181
6.13
20.59
4.03
4.01
2.00
4.00
2.02
Current Data Parameters
NAME Dye
EXPNO 1
PROCNO 1
F2 - Acquisition Parameters
Date_ 20141216
Time 17.41
INSTRUM spect
PROBHD 5 mm PABBO BB/
PULPROG zg30
TD 65536
SOLVENT CDCl3
NS 8
DS 2
SWH 7978.724 Hz
FIDRES 0.121746 Hz
AQ 4.1069226 sec
RG 137.88
DW 62.667 usec
DE 6.50 usec
TE 298.0 K
D1 1.00000000 sec
TD0 1
======== CHANNEL f1 ========
SFO1 399.6024677 MHz
NUC1 1H
P1 10.25 usec
PLW1 16.00000000 W
F2 - Processing parameters
SI 65536
SF 399.6000096 MHz
WDW EM
SSB 0
LB 0.30 Hz
GB 0
PC 1.00
Dye
7.8
7.9
8.0
8.1
8.2
8.3
ppm
1.1 1H NMR Spectrum of Dye
5
210200190180170160150140130120110100
90
80
70
60
50
40
30
20
10
0ppm
14.28
22.83
27.27
27.56
29.47
29.62
31.99
51.51
76.89
77.20
77.52
111.39
115.56
118.46
122.65
126.54
129.33
131.52
131.53
143.57
151.83
157.72
179.50
179.85
180.20
180.54
Current Data Parameters
NAME Dye 2
EXPNO 1
PROCNO 1
F2 - Acquisition Parameters
Date_ 20141220
Time 8.57
INSTRUM spect
PROBHD 5 mm PABBO BB/
PULPROG zgpg30
TD 65536
SOLVENT CDCl3
NS 2048
DS 4
SWH 24038.461 Hz
FIDRES 0.366798 Hz
AQ 1.3631488 sec
RG 191.21
DW 20.800 usec
DE 6.50 usec
TE 298.0 K
D1 2.00000000 sec
D11 0.03000000 sec
TD0 1
======== CHANNEL f1 ========
SFO1 100.4895474 MHz
NUC1 13C
P1 9.75 usec
PLW1 78.00000000 W
======== CHANNEL f2 ========
SFO2 399.6015984 MHz
NUC2 1H
CPDPRG[2 waltz16
PCPD2 90.00 usec
PLW2 16.00000000 W
PLW12 0.17827000 W
PLW13 0.08952800 W
F2 - Processing parameters
SI 32768
SF 100.4794824 MHz
WDW EM
SSB 0
LB 1.00 Hz
GB 0
PC 1.40
Dye 2
178
179
180
181
182
ppm
1.2 13C NMR Spectrum of Dye
6
-2-1
15
14
13
12
11
10
98
76
54
32
10
ppm
0.714
1.036
1.111
1.129
1.136
1.147
1.158
1.169
1.186
1.195
1.204
1.239
1.256
1.274
1.291
1.309
1.450
2.489
2.506
2.523
3.150
3.169
3.188
6.487
6.510
7.260
7.620
7.649
7.671
8.18
101.11
66.56
5.69
58.08
4.00
2.02
6.06
Current Data Parameters
NAME Dye+cadaverine 8.0_11mg
EXPNO 1
PROCNO 1
F2 - Acquisition Parameters
Date_ 20150106
Time 18.19
INSTRUM spect
PROBHD 5 mm PABBO BB/
PULPROG zg30
TD 65536
SOLVENT CDCl3
NS 8
DS 2
SWH 7978.724 Hz
FIDRES 0.121746 Hz
AQ 4.1069226 sec
RG 15.82
DW 62.667 usec
DE 6.50 usec
TE 298.0 K
D1 1.00000000 sec
TD0 1
======== CHANNEL f1 ========
SFO1 399.6024677 MHz
NUC1 1H
P1 10.25 usec
PLW1 16.00000000 W
F2 - Processing parameters
SI 65536
SF 399.6000104 MHz
WDW EM
SSB 0
LB 0.30 Hz
GB 0
PC 1.00
Dye+cadaverine 8.0_11mg
6.6
6.8
7.0
7.2
7.4
7.6
7.8
ppm
1.3 1H NMR Spectrum of Dye + cadaverine (1:8 eqv.) (spectrum taken after 20 min)
7
1.413 C NMR Spectrum of Dye + cadaverine (1:8 eqv.) (spectrum taken after 4 h).
210
200
190
180
170
160
150
140
130
120
110
100
90
80
70
60
50
40
30
20
10
0ppm
13.88
22.41
23.97
26.87
29.06
29.22
31.58
33.46
41.97
50.99
76.86
77.18
77.50
86.19
86.47
86.76
110.78
121.25
125.09
128.79
137.37
142.85
150.40
153.24
Current Data Parameters
NAME Dye+cadaverine 8.0_11mg
EXPNO 2
PROCNO 1
F2 - Acquisition Parameters
Date_ 20150106
Time 22.04
INSTRUM spect
PROBHD 5 mm PABBO BB/
PULPROG zgpg30
TD 65536
SOLVENT CDCl3
NS 3072
DS 4
SWH 24038.461 Hz
FIDRES 0.366798 Hz
AQ 1.3631488 sec
RG 191.21
DW 20.800 usec
DE 6.50 usec
TE 298.0 K
D1 2.00000000 sec
D11 0.03000000 sec
TD0 1
======== CHANNEL f1 ========
SFO1 100.4895474 MHz
NUC1 13C
P1 9.75 usec
PLW1 78.00000000 W
======== CHANNEL f2 ========
SFO2 399.6015984 MHz
NUC2 1H
CPDPRG[2 waltz16
PCPD2 90.00 usec
PLW2 16.00000000 W
PLW12 0.17827000 W
PLW13 0.08952800 W
F2 - Processing parameters
SI 32768
SF 100.4795072 MHz
WDW EM
SSB 0
LB 1.00 Hz
GB 0
PC 1.40
Dye+cadaverine 8.0_11mg
86
87
ppm
100
120
140
ppm
8
-2-1
15
14
13
12
11
10
98
76
54
32
10
ppm
1.250
1.287
1.311
1.329
1.335
1.339
1.349
1.360
1.367
1.377
1.386
1.398
1.415
1.423
1.440
1.457
1.474
1.492
1.495
1.526
1.542
1.643
2.003
2.675
2.692
2.709
3.330
3.355
3.375
3.394
6.680
6.703
6.996
7.260
7.519
7.776
7.803
7.827
7.851
7.871
7.894
7.902
7.920
7.924
8.156
8.177
7.02
41.69
14.00
4.98
12.13
4.00
2.02
0.75
3.56
1.79
Current Data Parameters
NAME Dye+cadaverine 0.5
EXPNO 1
PROCNO 1
F2 - Acquisition Parameters
Date_ 20141216
Time 17.47
INSTRUM spect
PROBHD 5 mm PABBO BB/
PULPROG zg30
TD 65536
SOLVENT CDCl3
NS 8
DS 2
SWH 7978.724 Hz
FIDRES 0.121746 Hz
AQ 4.1069226 sec
RG 123.45
DW 62.667 usec
DE 6.50 usec
TE 298.0 K
D1 1.00000000 sec
TD0 1
======== CHANNEL f1 ========
SFO1 399.6024677 MHz
NUC1 1H
P1 10.25 usec
PLW1 16.00000000 W
F2 - Processing parameters
SI 65536
SF 399.6000096 MHz
WDW EM
SSB 0
LB 0.30 Hz
GB 0
PC 1.00
Dye+cadaverine 0.5
7.8
7.9
8.0
8.1
8.2
ppm
1.5 1H NMR Spectrum of Dye + cadaverine (1:0.5 eqv.) (spectrum taken after 20 min)
9
-2-1
15
14
13
12
11
10
98
76
54
32
10
ppm
0.869
0.886
0.903
1.246
1.283
1.307
1.313
1.325
1.331
1.336
1.346
1.358
1.364
1.373
1.382
1.395
1.412
1.419
1.436
1.454
1.471
1.489
1.492
1.638
2.671
2.689
2.706
3.352
3.371
3.391
6.676
6.699
7.260
7.777
7.797
7.825
7.848
7.867
7.890
7.899
7.921
8.153
8.173
7.41
55.23
24.29
4.94
22.12
4.00
1.97
1.42
3.02
1.50
Current Data Parameters
NAME Dye+cadaverine
EXPNO 1
PROCNO 1
F2 - Acquisition Parameters
Date_ 20141216
Time 18.24
INSTRUM spect
PROBHD 5 mm PABBO BB/
PULPROG zg30
TD 65536
SOLVENT CDCl3
NS 8
DS 2
SWH 7978.724 Hz
FIDRES 0.121746 Hz
AQ 4.1069226 sec
RG 107.6
DW 62.667 usec
DE 6.50 usec
TE 298.0 K
D1 1.00000000 sec
TD0 1
======== CHANNEL f1 ========
SFO1 399.6024677 MHz
NUC1 1H
P1 10.25 usec
PLW1 16.00000000 W
F2 - Processing parameters
SI 65536
SF 399.6000096 MHz
WDW EM
SSB 0
LB 0.30 Hz
GB 0
PC 1.00
Dye+cadaverine
7.8
7.9
8.0
8.1
8.2
8.3
ppm
1.6 1H NMR Spectrum of Dye + cadaverine (1:1 eqv.) (spectrum taken after 20 min)
10
1.7 1H NMR Spectrum of Dye + cadaverine (1:1.5 eqv.) (spectrum taken after 20 min)
-2-1
15
14
13
12
11
10
98
76
54
32
10
ppm
0.865
0.882
0.899
1.230
1.242
1.279
1.303
1.309
1.321
1.327
1.332
1.343
1.354
1.360
1.369
1.378
1.432
1.450
1.623
1.631
2.667
2.684
2.702
3.347
3.366
3.387
6.672
6.695
7.260
7.776
7.790
7.821
7.843
7.863
7.886
7.895
7.917
8.149
8.169
71.25
39.01
4.99
33.72
4.00
2.00
2.19
2.53
1.26
Current Data Parameters
NAME Dye+cadaverine 1.5
EXPNO 1
PROCNO 1
F2 - Acquisition Parameters
Date_ 20141219
Time 12.31
INSTRUM spect
PROBHD 5 mm PABBO BB/
PULPROG zg30
TD 65536
SOLVENT CDCl3
NS 8
DS 2
SWH 7978.724 Hz
FIDRES 0.121746 Hz
AQ 4.1069226 sec
RG 95.01
DW 62.667 usec
DE 6.50 usec
TE 298.0 K
D1 1.00000000 sec
TD0 1
======== CHANNEL f1 ========
SFO1 399.6024677 MHz
NUC1 1H
P1 10.25 usec
PLW1 16.00000000 W
F2 - Processing parameters
SI 65536
SF 399.6000096 MHz
WDW EM
SSB 0
LB 0.30 Hz
GB 0
PC 1.00
Dye+cadaverine 1.5
7.8
8.0
8.2
ppm
11
-2-1
15
14
13
12
11
10
98
76
54
32
10
ppm0.861
0.878
0.895
1.216
1.238
1.275
1.300
1.306
1.317
1.323
1.328
1.339
1.350
1.356
1.366
1.375
1.411
1.428
1.446
1.463
1.481
1.484
2.663
2.681
2.698
3.343
3.359
3.383
6.657
6.669
6.675
6.691
7.260
7.774
7.785
7.816
7.839
7.859
7.882
7.891
7.913
8.145
8.165
7.21
93.92
47.62
5.22
45.76
4.00
2.00
2.75
2.13
1.04
Current Data Parameters
NAME Dye+cadaverine 2.0
EXPNO 1
PROCNO 1
F2 - Acquisition Parameters
Date_ 20141219
Time 13.25
INSTRUM spect
PROBHD 5 mm PABBO BB/
PULPROG zg30
TD 65536
SOLVENT CDCl3
NS 8
DS 2
SWH 7978.724 Hz
FIDRES 0.121746 Hz
AQ 4.1069226 sec
RG 84.69
DW 62.667 usec
DE 6.50 usec
TE 298.0 K
D1 1.00000000 sec
TD0 1
======== CHANNEL f1 ========
SFO1 399.6024677 MHz
NUC1 1H
P1 10.25 usec
PLW1 16.00000000 W
F2 - Processing parameters
SI 65536
SF 399.6000096 MHz
WDW EM
SSB 0
LB 0.30 Hz
GB 0
PC 1.00
Dye+cadaverine 2.0
7.8
7.9
8.0
8.1
8.2
8.3
ppm
1.8 1H NMR Spectrum of Dye + cadaverine (1:2 eqv.) (spectrum taken after 20 min)
12
-2-1
15
14
13
12
11
10
98
76
54
32
10
ppm
0.051
0.875
1.208
1.235
1.272
1.296
1.314
1.320
1.325
1.336
1.347
1.353
1.362
1.371
1.408
1.425
1.443
1.460
1.989
2.660
2.677
3.314
3.338
3.354
3.379
6.653
6.666
6.673
6.687
7.260
7.773
7.781
7.813
7.835
7.856
7.880
7.888
7.910
8.143
8.162
4.00
1.98
3.15
1.89
0.91
Current Data Parameters
NAME Dye+cadaverine 3.0
EXPNO 1
PROCNO 1
F2 - Acquisition Parameters
Date_ 20141219
Time 14.30
INSTRUM spect
PROBHD 5 mm PABBO BB/
PULPROG zg30
TD 65536
SOLVENT CDCl3
NS 8
DS 2
SWH 7978.724 Hz
FIDRES 0.121746 Hz
AQ 4.1069226 sec
RG 84.69
DW 62.667 usec
DE 6.50 usec
TE 298.0 K
D1 1.00000000 sec
TD0 1
======== CHANNEL f1 ========
SFO1 399.6024677 MHz
NUC1 1H
P1 10.25 usec
PLW1 16.00000000 W
F2 - Processing parameters
SI 65536
SF 399.6000096 MHz
WDW EM
SSB 0
LB 0.30 Hz
GB 0
PC 1.00
Dye+cadaverine 3.0
7.8
7.9
8.0
8.1
8.2
8.3
ppm
1.9 1H NMR Spectrum of Dye + cadaverine (1:3 eqv.) (spectrum taken after 20 min)
13
-2-1
15
14
13
12
11
10
98
76
54
32
10
ppm
0.870
1.197
1.231
1.267
1.292
1.298
1.310
1.315
1.321
1.331
1.343
1.348
1.358
1.367
1.404
1.421
1.438
1.455
1.473
1.476
1.592
1.610
1.985
2.655
2.673
2.690
3.309
3.331
3.349
6.647
6.669
7.260
7.775
7.808
7.830
7.851
7.875
7.883
7.905
8.137
8.158
8.47
99.44
39.09
66.44
5.33
75.18
4.00
2.04
3.75
1.49
0.72
Current Data Parameters
NAME Dye+cadaverine 4.0
EXPNO 1
PROCNO 1
F2 - Acquisition Parameters
Date_ 20141219
Time 15.30
INSTRUM spect
PROBHD 5 mm PABBO BB/
PULPROG zg30
TD 65536
SOLVENT CDCl3
NS 8
DS 2
SWH 7978.724 Hz
FIDRES 0.121746 Hz
AQ 4.1069226 sec
RG 76.32
DW 62.667 usec
DE 6.50 usec
TE 298.0 K
D1 1.00000000 sec
TD0 1
======== CHANNEL f1 ========
SFO1 399.6024677 MHz
NUC1 1H
P1 10.25 usec
PLW1 16.00000000 W
F2 - Processing parameters
SI 65536
SF 399.6000097 MHz
WDW EM
SSB 0
LB 0.30 Hz
GB 0
PC 1.00
Dye+cadaverine 4.0 7.8
8.0
8.2
ppm
1.10 1H NMR Spectrum of Dye + cadaverine (1:4 eqv.) (spectrum taken after 20 min)
15
-2-1
15
14
13
12
11
10
98
76
54
32
10
ppm
0.066
0.873
0.891
0.908
1.288
1.314
1.338
1.347
1.458
1.467
1.475
1.482
1.491
1.643
2.691
2.708
2.724
3.355
3.374
3.393
6.680
6.703
7.260
7.870
7.893
7.902
7.924
8.157
8.177
7.08
31.50
13.08
5.52
10.66
4.00
2.00
4.07
1.77
Current Data Parameters
NAME Dye+Putrescine 0.5
EXPNO 1
PROCNO 1
F2 - Acquisition Parameters
Date_ 20141216
Time 17.53
INSTRUM spect
PROBHD 5 mm PABBO BB/
PULPROG zg30
TD 65536
SOLVENT CDCl3
NS 8
DS 2
SWH 7978.724 Hz
FIDRES 0.121746 Hz
AQ 4.1069226 sec
RG 137.88
DW 62.667 usec
DE 6.50 usec
TE 298.0 K
D1 1.00000000 sec
TD0 1
======== CHANNEL f1 ========
SFO1 399.6024677 MHz
NUC1 1H
P1 10.25 usec
PLW1 16.00000000 W
F2 - Processing parameters
SI 65536
SF 399.6000096 MHz
WDW EM
SSB 0
LB 0.30 Hz
GB 0
PC 1.00
Dye+Putrescine 0.5
1.12 1H NMR Spectrum of Dye + Putrescine (1:0.5 eqv.) (spectrum taken after 20 min)
16
-2-1
15
14
13
12
11
10
98
76
54
32
10
ppm
0.887
1.284
1.310
1.333
1.342
1.454
1.463
1.471
1.479
1.488
2.704
3.349
3.367
3.387
6.674
6.697
7.260
7.864
7.887
7.919
8.153
8.173
7.42
43.27
26.62
5.32
23.46
4.00
2.00
0.70
3.75
1.46
Current Data Parameters
NAME Dye-Putrescine2
EXPNO 1
PROCNO 1
F2 - Acquisition Parameters
Date_ 20141217
Time 10.44
INSTRUM spect
PROBHD 5 mm PABBO BB/
PULPROG zg30
TD 65536
SOLVENT CDCl3
NS 8
DS 2
SWH 7978.724 Hz
FIDRES 0.121746 Hz
AQ 4.1069226 sec
RG 123.45
DW 62.667 usec
DE 6.50 usec
TE 298.0 K
D1 1.00000000 sec
TD0 1
======== CHANNEL f1 ========
SFO1 399.6024677 MHz
NUC1 1H
P1 10.25 usec
PLW1 16.00000000 W
F2 - Processing parameters
SI 65536
SF 399.6000096 MHz
WDW EM
SSB 0
LB 0.30 Hz
GB 0
PC 1.00
Dye-Putrescine2
7.7
7.8
7.9
8.0
8.1
8.2
8.3
ppm
1.13 1H NMR Spectrum of Dye + Putrescine (1:1 eqv.) (spectrum taken after 20 min)
17
11
10
98
76
54
32
10ppm
0.863
1.260
1.286
1.307
1.314
1.422
1.429
1.432
1.438
1.446
1.454
1.460
1.463
1.470
2.662
2.679
2.692
2.695
3.309
3.327
3.346
6.643
6.665
7.774
7.810
7.831
8.130
9.98
61.81
58.72
5.75
51.55
4.00
1.97
5.45
0.47
Current Data Parameters
NAME Dye+putrescine 2.0
EXPNO 1
PROCNO 1
F2 - Acquisition Parameters
Date_ 20150108
Time 11.36
INSTRUM spect
PROBHD 5 mm PABBO BB/
PULPROG zg30
TD 65536
SOLVENT CDCl3
NS 8
DS 2
SWH 7978.724 Hz
FIDRES 0.121746 Hz
AQ 4.1069226 sec
RG 69.1
DW 62.667 usec
DE 6.50 usec
TE 298.0 K
D1 1.00000000 sec
TD0 1
======== CHANNEL f1 ========
SFO1 399.6024677 MHz
NUC1 1H
P1 10.25 usec
PLW1 16.00000000 W
F2 - Processing parameters
SI 65536
SF 399.6000096 MHz
WDW EM
SSB 0
LB 0.30 Hz
GB 0
PC 1.00
Dye+putrescine 2.0
8.0
ppm
1.14 1H NMR Spectrum of Dye + Putrescine (1:2 eqv.) (spectrum taken after 20 min)
18
11
10
98
76
54
32
10ppm
0.841
0.859
0.875
1.219
1.256
1.282
1.302
1.309
1.396
1.406
1.417
1.428
1.466
1.477
1.487
1.600
2.674
3.304
3.322
3.341
6.638
6.661
7.260
7.769
7.805
7.826
8.088
8.125
8.136
8.148
9.61
139.96
6.96
61.04
4.00
1.97
5.51
0.35
Current Data Parameters
NAME Dye+putrescine 2.5
EXPNO 1
PROCNO 1
F2 - Acquisition Parameters
Date_ 20150108
Time 12.43
INSTRUM spect
PROBHD 5 mm PABBO BB/
PULPROG zg30
TD 65536
SOLVENT CDCl3
NS 8
DS 2
SWH 7978.724 Hz
FIDRES 0.121746 Hz
AQ 4.1069226 sec
RG 61.96
DW 62.667 usec
DE 6.50 usec
TE 298.0 K
D1 1.00000000 sec
TD0 1
======== CHANNEL f1 ========
SFO1 399.6024677 MHz
NUC1 1H
P1 10.25 usec
PLW1 16.00000000 W
F2 - Processing parameters
SI 65536
SF 399.6000097 MHz
WDW EM
SSB 0
LB 0.30 Hz
GB 0
PC 1.00
Dye+putrescine 2.5
8.0
ppm
1.15 1H NMR Spectrum of Dye + Putrescine (1:2.5 eqv.) (spectrum taken after 20 min)
19
11
10
98
76
54
32
1ppm0.029
0.852
1.213
1.250
1.255
1.264
1.276
1.296
1.303
1.400
1.411
1.460
1.470
1.576
1.594
1.609
2.667
3.296
3.315
3.334
6.631
6.654
7.260
7.763
7.797
7.819
10.50
178.57
7.36
77.80
4.00
1.99
5.72
0.34
Current Data Parameters
NAME Dye+Putrescine 3.0
EXPNO 1
PROCNO 1
F2 - Acquisition Parameters
Date_ 20150108
Time 14.46
INSTRUM spect
PROBHD 5 mm PABBO BB/
PULPROG zg30
TD 65536
SOLVENT CDCl3
NS 8
DS 2
SWH 7978.724 Hz
FIDRES 0.121746 Hz
AQ 4.1069226 sec
RG 61.96
DW 62.667 usec
DE 6.50 usec
TE 298.0 K
D1 1.00000000 sec
TD0 1
======== CHANNEL f1 ========
SFO1 399.6024677 MHz
NUC1 1H
P1 10.25 usec
PLW1 16.00000000 W
F2 - Processing parameters
SI 65536
SF 399.6000097 MHz
WDW EM
SSB 0
LB 0.30 Hz
GB 0
PC 1.00
Dye+putrescine 3.0
8.0
ppm
1.16 1H NMR Spectrum of Dye + Putrescine (1:3 eqv.) (spectrum taken after 20 min)
20
-2-1
15
14
13
12
11
10
98
76
54
32
10
ppm
1.050
1.166
1.177
1.180
1.191
1.202
1.222
1.230
1.314
1.407
1.498
1.516
1.534
2.574
2.577
2.580
2.585
2.588
2.591
2.594
2.597
2.601
2.605
2.608
3.219
3.239
3.258
6.555
6.578
7.260
7.686
7.715
7.738
10.17
219.62
29.98
254.75
6.33
251.54
4.00
2.09
6.08
Current Data Parameters
NAME Dye+putrescine 8.0
EXPNO 1
PROCNO 1
F2 - Acquisition Parameters
Date_ 20150106
Time 18.25
INSTRUM spect
PROBHD 5 mm PABBO BB/
PULPROG zg30
TD 65536
SOLVENT CDCl3
NS 8
DS 2
SWH 7978.724 Hz
FIDRES 0.121746 Hz
AQ 4.1069226 sec
RG 33.09
DW 62.667 usec
DE 6.50 usec
TE 298.0 K
D1 1.00000000 sec
TD0 1
======== CHANNEL f1 ========
SFO1 399.6024677 MHz
NUC1 1H
P1 10.25 usec
PLW1 16.00000000 W
F2 - Processing parameters
SI 65536
SF 399.6000101 MHz
WDW EM
SSB 0
LB 0.30 Hz
GB 0
PC 1.00
Dye+putrescine 8.0
7.70
7.75
7.80
7.85
ppm
1.17 1H NMR Spectrum of Dye + Putrescine (1:8 eqv.) (spectrum taken after 20 min)
21
-2-1
15
14
13
12
11
10
98
76
54
32
10
ppm
0.872
0.889
1.084
1.102
1.120
1.287
1.312
1.337
1.346
1.642
2.711
2.729
2.747
2.765
3.355
3.375
3.394
4.763
4.781
6.680
6.703
7.870
7.893
7.901
7.919
7.923
8.156
8.176
4.00
1.99
0.13
3.91
1.96
Current Data Parameters
NAME Dye+Ethylamine 0.5
EXPNO 1
PROCNO 1
F2 - Acquisition Parameters
Date_ 20141216
Time 17.58
INSTRUM spect
PROBHD 5 mm PABBO BB/
PULPROG zg30
TD 65536
SOLVENT CDCl3
NS 8
DS 2
SWH 7978.724 Hz
FIDRES 0.121746 Hz
AQ 4.1069226 sec
RG 84.69
DW 62.667 usec
DE 6.50 usec
TE 298.0 K
D1 1.00000000 sec
TD0 1
======== CHANNEL f1 ========
SFO1 399.6024677 MHz
NUC1 1H
P1 10.25 usec
PLW1 16.00000000 W
F2 - Processing parameters
SI 65536
SF 399.6000099 MHz
WDW EM
SSB 0
LB 0.30 Hz
GB 0
PC 1.00
Dye+Ethylamine 0.5
7.8
7.9
8.0
8.1
8.2
ppm
1.18 1H NMR Spectrum of Dye + Ethylamine (1:0.5 eqv.) (spectrum taken after 20 min).
22
-2-1
15
14
13
12
11
10
98
76
54
32
10
ppm
0.889
1.084
1.102
1.120
1.287
1.312
1.337
1.346
1.643
2.711
2.729
2.747
2.765
3.355
3.375
3.394
4.772
7.260
7.870
7.893
7.901
7.923
8.156
8.176
6.37
10.21
22.76
29.03
6.32
4.00
1.99
0.23
3.84
1.90
Current Data Parameters
NAME Dye+Ethylamine2
EXPNO 1
PROCNO 1
F2 - Acquisition Parameters
Date_ 20141217
Time 10.49
INSTRUM spect
PROBHD 5 mm PABBO BB/
PULPROG zg30
TD 65536
SOLVENT CDCl3
NS 8
DS 2
SWH 7978.724 Hz
FIDRES 0.121746 Hz
AQ 4.1069226 sec
RG 76.32
DW 62.667 usec
DE 6.50 usec
TE 298.0 K
D1 1.00000000 sec
TD0 1
======== CHANNEL f1 ========
SFO1 399.6024677 MHz
NUC1 1H
P1 10.25 usec
PLW1 16.00000000 W
F2 - Processing parameters
SI 65536
SF 399.6000096 MHz
WDW EM
SSB 0
LB 0.30 Hz
GB 0
PC 1.00
Dye+Ethylamine2
8.0
8.2
ppm
1.19 1H NMR Spectrum of Dye + Ethylamine (1:1 eqv.) (spectrum taken after 20 min)
23
11
10
98
76
54
32
1ppm
0.887
1.081
1.099
1.117
1.284
1.335
1.343
2.708
2.726
2.744
2.762
3.352
3.372
3.391
4.725
6.677
6.700
6.995
7.519
7.867
7.890
7.899
7.920
8.153
8.173
20.26
23.41
12.14
4.00
1.91
0.64
3.56
1.81
Current Data Parameters
NAME Dye+ethylamine 2.0
EXPNO 1
PROCNO 1
F2 - Acquisition Parameters
Date_ 20150108
Time 11.42
INSTRUM spect
PROBHD 5 mm PABBO BB/
PULPROG zg30
TD 65536
SOLVENT CDCl3
NS 8
DS 2
SWH 7978.724 Hz
FIDRES 0.121746 Hz
AQ 4.1069226 sec
RG 61.96
DW 62.667 usec
DE 6.50 usec
TE 298.0 K
D1 1.00000000 sec
TD0 1
======== CHANNEL f1 ========
SFO1 399.6024677 MHz
NUC1 1H
P1 10.25 usec
PLW1 16.00000000 W
F2 - Processing parameters
SI 65536
SF 399.6000095 MHz
WDW EM
SSB 0
LB 0.30 Hz
GB 0
PC 1.00
Dye+ethylamine 2.0
8.0
8.2
8.4
ppm
1.20 1H NMR Spectrum of Dye + Ethylamine (1:2 eqv.) (spectrum taken after 20 min)
24
-2-1
15
14
13
12
11
10
98
76
54
32
10
ppm
0.062
0.869
0.903
1.245
1.254
1.284
1.309
1.334
1.343
1.640
2.000
3.352
3.371
3.391
4.785
6.676
6.700
6.995
7.278
7.519
7.867
7.890
7.898
7.916
7.920
8.153
8.173
6.70
24.04
24.95
15.93
15.12
4.00
2.01
0.76
3.47
1.74
Current Data Parameters
NAME Dye+ethylamine 3.0
EXPNO 1
PROCNO 1
F2 - Acquisition Parameters
Date_ 20150106
Time 16.38
INSTRUM spect
PROBHD 5 mm PABBO BB/
PULPROG zg30
TD 65536
SOLVENT CDCl3
NS 8
DS 2
SWH 7978.724 Hz
FIDRES 0.121746 Hz
AQ 4.1069226 sec
RG 84.69
DW 62.667 usec
DE 6.50 usec
TE 298.0 K
D1 1.00000000 sec
TD0 1
======== CHANNEL f1 ========
SFO1 399.6024677 MHz
NUC1 1H
P1 10.25 usec
PLW1 16.00000000 W
F2 - Processing parameters
SI 65536
SF 399.6000096 MHz
WDW EM
SSB 0
LB 0.30 Hz
GB 0
PC 1.00
Dye+ethylamine 3.0
7.9
8.0
8.1
8.2
ppm
1.21 1H NMR Spectrum of Dye + Ethylamine (1:3 eqv.) (spectrum taken after 20 min)
25
1.22 1H NMR Spectrum of Dye + Ethylamine (1:4eqv.) (spectrum taken after 20 min)
11
10
98
76
54
32
1ppm
0.866
0.884
0.901
1.281
1.307
1.332
1.340
1.638
2.723
2.741
3.350
3.369
3.389
4.723
6.674
6.697
6.995
7.214
7.217
7.220
7.225
7.229
7.232
7.289
7.298
7.305
7.309
7.317
7.333
7.519
7.781
7.796
7.804
7.824
7.847
7.865
7.888
7.896
7.918
8.150
8.171
8.04
33.20
27.38
11.39
19.46
4.00
1.88
1.03
3.26
1.63
Current Data Parameters
NAME Dye+ethylamine 4.0
EXPNO 1
PROCNO 1
F2 - Acquisition Parameters
Date_ 20150108
Time 12.49
INSTRUM spect
PROBHD 5 mm PABBO BB/
PULPROG zg30
TD 65536
SOLVENT CDCl3
NS 8
DS 2
SWH 7978.724 Hz
FIDRES 0.121746 Hz
AQ 4.1069226 sec
RG 84.69
DW 62.667 usec
DE 6.50 usec
TE 298.0 K
D1 1.00000000 sec
TD0 1
======== CHANNEL f1 ========
SFO1 399.6024677 MHz
NUC1 1H
P1 10.25 usec
PLW1 16.00000000 W
F2 - Processing parameters
SI 65536
SF 399.6000096 MHz
WDW EM
SSB 0
LB 0.30 Hz
GB 0
PC 1.00
Dye+ethylamine 4.0
7.8
8.0
8.2
ppm
26
-2-1
15
14
13
12
11
10
98
76
54
32
10
ppm
0.058
1.077
1.095
1.113
1.636
2.721
2.739
3.348
3.367
3.387
4.784
6.673
6.696
7.863
7.886
7.894
7.916
8.149
8.169
8.47
42.34
29.50
26.14
4.00
2.00
1.35
3.08
1.54
Current Data Parameters
NAME Dye+ethylamine 8.0
EXPNO 1
PROCNO 1
F2 - Acquisition Parameters
Date_ 20150106
Time 18.31
INSTRUM spect
PROBHD 5 mm PABBO BB/
PULPROG zg30
TD 65536
SOLVENT CDCl3
NS 8
DS 2
SWH 7978.724 Hz
FIDRES 0.121746 Hz
AQ 4.1069226 sec
RG 76.32
DW 62.667 usec
DE 6.50 usec
TE 298.0 K
D1 1.00000000 sec
TD0 1
======== CHANNEL f1 ========
SFO1 399.6024677 MHz
NUC1 1H
P1 10.25 usec
PLW1 16.00000000 W
F2 - Processing parameters
SI 65536
SF 399.6000096 MHz
WDW EM
SSB 0
LB 0.30 Hz
GB 0
PC 1.00
Dye+ethylamine 8.0
7.9
8.0
8.1
8.2
ppm
1.23 1H NMR Spectrum of Dye + Ethylamine (1:8 eqv.) (spectrum taken after 20 min)
27
-2-1
15
14
13
12
11
10
98
76
54
32
10
ppm
0.873
0.891
0.908
1.288
1.303
1.314
1.339
1.348
1.636
3.357
3.376
3.395
4.723
6.681
6.705
7.260
7.872
7.895
7.903
7.907
7.920
7.925
8.158
8.178
6.40
20.97
4.00
1.98
3.95
1.98
Current Data Parameters
NAME Dye+Ammonia2
EXPNO 1
PROCNO 1
F2 - Acquisition Parameters
Date_ 20141217
Time 10.54
INSTRUM spect
PROBHD 5 mm PABBO BB/
PULPROG zg30
TD 65536
SOLVENT CDCl3
NS 8
DS 2
SWH 7978.724 Hz
FIDRES 0.121746 Hz
AQ 4.1069226 sec
RG 123.45
DW 62.667 usec
DE 6.50 usec
TE 298.0 K
D1 1.00000000 sec
TD0 1
======== CHANNEL f1 ========
SFO1 399.6024677 MHz
NUC1 1H
P1 10.25 usec
PLW1 16.00000000 W
F2 - Processing parameters
SI 65536
SF 399.6000095 MHz
WDW EM
SSB 0
LB 0.30 Hz
GB 0
PC 1.00
Dye+Ammonia2
7.8
7.9
8.0
8.1
8.2
ppm
1.24 1H NMR Spectrum of Dye + ammonia (1:1 eqv.) (spectrum taken after 20 min).
28
210
200
190
180
170
160
150
140
130
120
110
100
90
80
70
60
50
40
30
20
10
0ppm
13.88
22.41
23.97
26.87
29.06
29.22
31.58
33.46
41.97
50.99
76.86
77.18
77.50
86.19
86.47
86.76
110.78
121.25
125.09
128.79
137.37
142.85
150.40
153.24
Current Data Parameters
NAME Dye+cadaverine 8.0_11mg
EXPNO 2
PROCNO 1
F2 - Acquisition Parameters
Date_ 20150106
Time 22.04
INSTRUM spect
PROBHD 5 mm PABBO BB/
PULPROG zgpg30
TD 65536
SOLVENT CDCl3
NS 3072
DS 4
SWH 24038.461 Hz
FIDRES 0.366798 Hz
AQ 1.3631488 sec
RG 191.21
DW 20.800 usec
DE 6.50 usec
TE 298.0 K
D1 2.00000000 sec
D11 0.03000000 sec
TD0 1
======== CHANNEL f1 ========
SFO1 100.4895474 MHz
NUC1 13C
P1 9.75 usec
PLW1 78.00000000 W
======== CHANNEL f2 ========
SFO2 399.6015984 MHz
NUC2 1H
CPDPRG[2 waltz16
PCPD2 90.00 usec
PLW2 16.00000000 W
PLW12 0.17827000 W
PLW13 0.08952800 W
F2 - Processing parameters
SI 32768
SF 100.4795072 MHz
WDW EM
SSB 0
LB 1.00 Hz
GB 0
PC 1.40
Dye+cadaverine 8.0_11mg
86
87
ppm
100
120
140
ppm
1.25 Comparison of spectra
References:
1. Eric Mertz, James B. Beil, and Steven C. Zimmerman Org. Lett., 2003, 5, 3127-3130
2. Malwina Allen And John D. Roberts Can. J. Chem.,1981, 59. 451-458
29
Color transformation from RGB to Lab space
Before the image processing, four different color pattern (three reference colors patterns (red, green and
blue) and the sensor pattern) are cropped separately. The size of each input color pattern is about 25×25
pixels. Color in RGB space (r, g, b) were converted to CIELAB colorspace (L, a, b) using Matlab functions.
cform = makecform(‘srgb2lab’); lab_image = applycform(rgb_image, cform);
The average values for L*, a* and b* were then calculated for every four squares.
average_L = lab2double(mean(mean(lab_image(:,:,1)))); average_a = lab2double(mean(mean(lab_image(:,:,2)))); average_b = lab2double(mean(mean(lab_image(:,:,3))));
In mathematical form, the color transformation is done by two steps: (1) from sRGB color space to CIEXYZ
color space, (2) from CIEXYZ color space to CIELAB color space.
Before the color transformation, the color correction of input images must be taken to eliminate the
photographical error from the display on monitor. As a result, the color in sRGB space should be modified
to linear RGB space as below.[1]
Note: When images are presented on a monitor, the gamma value of color in sRGB space is 2.0 – 2.5 and it
should be transformed to 1.0 (in linear RGB space).
𝐶𝑙𝑖𝑛𝑒𝑎𝑟 = {
𝐶𝑠𝑟𝑔𝑏
12.92, 𝑖𝑓 𝐶𝑠𝑟𝑔𝑏 ≤ 0.03928
(𝐶𝑠𝑟𝑔𝑏 + 0.055
1.055)2.4, 𝑖𝑓 𝐶𝑠𝑟𝑔𝑏 > 0.03928
CsRGB is r, g and b value of each input color in sRGB space.
The color transformation from sRGB color space to CIEXYZ color space is followed by the linear equation:
[𝑋𝑌𝑍
] = [0.4124 0.3576 0.18050.2126 0.7152 0.07220.0193 0.1192 0.9505
] [
𝑅𝑙𝑖𝑛𝑒𝑎𝑟
𝐺𝑙𝑖𝑛𝑒𝑎𝑟
𝐵𝑙𝑖𝑛𝑒𝑎𝑟
]
Then, the coordinate of each color (X, Y, Z) in CIEXYZ space was subsequently transformed to (L, a, b) in Lab
color space.[2]
𝐿 = 116 × 𝑓 (𝑌
𝑌𝑛) − 16
𝑎 = 500 × [𝑓 (𝑋
𝑋𝑛) − 𝑓 (
𝑌
𝑌𝑛)]
𝑏 = 200 × [𝑓 (𝑌
𝑌𝑛) − 𝑓 (
𝑍
𝑍𝑛)]
30
𝑓(𝐼) = {𝐼1/3, 𝑖𝑓 𝐼 > (6/29)3
(841
108) 𝐼 +
4
29, 𝑖𝑓𝐼 ≤ (6/29)3
Where (Xn, Yn, Zn) is coordinate of the white point in CIEXYZ space (in our calculation, it is (0.9504, 1.0000,
1.0889) for the definition of white point in CIE Standard Illuminant D65).
[1] M. Stokes, M. Anderson, S. Chandrasekar, R. Motta, A Standard Default Color Space for the Internet –
sRGB, Version 1.10, 1996.
[2] J. Schanda, Colorimetry: Understanding the CIE system 2007, 61.