supplementary information ne for optical and ...supplementary information to...

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

8

7

9

110

3

2

4

6

5

12

3

457

6

89

10

11

12

13

14

15

16

1718

19

20

21

22

23

24

11

12

13

14

15

16

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 (1:8 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)



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


NAME Dye 2

EXPNO 1

PROCNO 1


Date_ 20141220

Time 8.57

INSTRUM spect


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


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


NAME Dye+cadaverine 8.0_11mg

EXPNO 1

PROCNO 1


Date_ 20150106

Time 18.19

INSTRUM spect


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


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



EXPNO 2

PROCNO 1


Date_ 20150106

Time 22.04

INSTRUM spect


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


SI 32768

SF 100.4795072 MHz

WDW EM

SSB 0

LB 1.00 Hz

GB 0

PC 1.40


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


NAME Dye+cadaverine 0.5

EXPNO 1

PROCNO 1


Date_ 20141216

Time 17.47

INSTRUM spect


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


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


NAME Dye+cadaverine

EXPNO 1

PROCNO 1


Date_ 20141216

Time 18.24

INSTRUM spect


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


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


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



EXPNO 1

PROCNO 1


Date_ 20141219

Time 12.31

INSTRUM spect


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


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



EXPNO 1

PROCNO 1


Date_ 20141219

Time 13.25

INSTRUM spect


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


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


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



EXPNO 1

PROCNO 1


Date_ 20141219

Time 14.30

INSTRUM spect


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


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


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



EXPNO 1

PROCNO 1


Date_ 20141219

Time 15.30

INSTRUM spect


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


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


14

1.11 Comparison of spectra (dye and dye-cadaverine adduct at different concentrations):

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


NAME Dye+Putrescine 0.5

EXPNO 1

PROCNO 1


Date_ 20141216

Time 17.53

INSTRUM spect


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


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


NAME Dye-Putrescine2

EXPNO 1

PROCNO 1


Date_ 20141217

Time 10.44

INSTRUM spect


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


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


NAME Dye+putrescine 2.0

EXPNO 1

PROCNO 1


Date_ 20150108

Time 11.36

INSTRUM spect


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


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


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



EXPNO 1

PROCNO 1


Date_ 20150108

Time 12.43

INSTRUM spect


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


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


NAME Dye+Putrescine 3.0

EXPNO 1

PROCNO 1


Date_ 20150108

Time 14.46

INSTRUM spect


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


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


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



EXPNO 1

PROCNO 1


Date_ 20150106

Time 18.25

INSTRUM spect


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


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


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


NAME Dye+Ethylamine 0.5

EXPNO 1

PROCNO 1


Date_ 20141216

Time 17.58

INSTRUM spect


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


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


NAME Dye+Ethylamine2

EXPNO 1

PROCNO 1


Date_ 20141217

Time 10.49

INSTRUM spect


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


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


NAME Dye+ethylamine 2.0

EXPNO 1

PROCNO 1


Date_ 20150108

Time 11.42

INSTRUM spect


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


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


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



EXPNO 1

PROCNO 1


Date_ 20150106

Time 16.38

INSTRUM spect


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


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


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



EXPNO 1

PROCNO 1


Date_ 20150108

Time 12.49

INSTRUM spect


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


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



EXPNO 1

PROCNO 1


Date_ 20150106

Time 18.31

INSTRUM spect


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


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


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


NAME Dye+Ammonia2

EXPNO 1

PROCNO 1


Date_ 20141217

Time 10.54

INSTRUM spect


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


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



EXPNO 2

PROCNO 1


Date_ 20150106

Time 22.04

INSTRUM spect


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


SI 32768

SF 100.4795072 MHz

WDW EM

SSB 0

LB 1.00 Hz

GB 0

PC 1.40


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.

31

Chemical selectivity and cross-sensitivity of the electrochemical sensors

Figure S1 Cyclic voltammetry curves measured with the composite electrodes using electrolytes consisting

of only one (a)-(c) or two different types of amines (d) and (e) in the presence of KCl.

supplementary information ne for optical and ...supplementary information to...

Documents