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Solid‐phase synthesis of the aged‐nonapeptide‐nerve‐agent adduct of butyrylcholinesterase as reference materials for analytical verification

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SUPPORTING INFORMATION

Solid-phase Synthesis of the

Aged-Nonapeptide-Nerve-Agent Adduct of Butyrylcholinesterase as

Reference Materials for Analytical Verification

Andreas Bielmann

†,‡

, Christophe Curty

†

, Christian G. Bochet

‡

†

Spiez Laboratory, Austrasse, CH-3700 Spiez, Switzerland

‡

Department of Chemistry, University of Fribourg, Chemin du Musée 9, CH-1700 Fribourg,

Switzerland

christian.bochet@unifr.ch

Table of Contents

1

H NMR,

13

C NMR and IR spectra of 6

S2

1

H NMR,

13

C NMR,

31

P NMR and IR spectra of 9

S5

1

H NMR,

13

C NMR,

31

P NMR and IR spectra of 3

S9

1

H NMR,

13

C NMR,

31

P NMR and IR spectra of 11

S13

1

H NMR,

13

C NMR,

31

P NMR and IR spectra of 12

S17

1

H NMR,

13

C NMR,

31

P NMR and IR spectra of 13

S21

1

H NMR,

13

C NMR,

31

P NMR and IR spectra of 4

S25

1

H NMR,

13

C NMR and IR spectra of 1

S29

1

H NMR and

31

P NMR spectra and the chromatogram of 2 (route A)

S32

1

(2)

9.5

9.0

8.5

8.0

7.5

7.0

6.5

6.0

5.5

5.0

4.5

4.0

3.5

3.0

2.5

2.0

1.5

1.0

0.5

ppm

0.88 1.26 2.18 3.90 3.92 3.99 3.99 4.01 4.02 4.18 4.19 4.21 4.38 4.40 4.42 4.44 4.47 4.48 4.49 5.20 5.78 5.80 7.24 7.29 7.31 7.33 7.37 7.38 7.57 7.59 7.74 7.76

0.16

0.24

1.01

1.84

1.20

2.96

1.94

0.88

8.62

2.10

2.00

(3)

210

200

190

180

170

160

150

140

130

120

110

100

90

80

70

60

50

40

30

20

10

0

ppm

-0.00 14.12 22.65 31.58 42.02 47.00 47.10 53.70 56.15 62.85 63.27 65.14 67.21 67.36 67.53 67.95 76.71 77.03 77.23 77.34 119.68 119.98 120.00 125.08 126.12 127.07 127.09 127.73 128.17 128.31 128.45 128.54 128.65 128.74 128.94 134.78 135.08 141.27 141.32 143.64 143.80 156.25 169.25 170.37

(4)
(5)

9.5

9.0

8.5

8.0

7.5

7.0

6.5

6.0

5.5

5.0

4.5

4.0

3.5

3.0

2.5

2.0

1.5

1.0

0.5

ppm

1.39 1.44 2.98 3.09 4.20 4.21 4.30 4.32 4.32 4.34 4.36 4.38 4.39 4.41 4.41 4.42 4.44 4.44 4.63 5.29 5.99 7.25 7.28 7.30 7.31 7.32 7.36 7.38 7.58 7.60 7.73 7.75

2.97

5.01

0.86

1.88

0.84

9.12

2.00

1.90

(6)

210 200 190 180 170 160 150 140 130 120 110 100

90

80

70

60

50

40

30

20

10

0

ppm

-0.00 10.44 11.90 39.71 42.01 43.34 47.01 53.46 54.47 54.54 55.09 64.73 64.79 65.23 65.58 67.39 67.71 76.72 77.03 77.24 77.35 77.73 119.73 119.95 124.33 124.79 125.17 125.20 125.67 126.10 126.77 127.09 127.39 127.71 128.02 128.16 128.33 128.41 128.51 128.60 128.91 129.07 135.02 135.30 139.72 140.92 141.23 143.71 143.80 155.53 155.99 168.78 169.11

(7)

160

150

140

130

120

110

100

90

80

70

60

50

40

30

20

10

ppm

34.43

35.21

13.49

(8)
(9)

11

10

9

8

7

6

5

4

3

2

1

ppm

-0.15 -0.00 0.07 0.15 1.19 1.21 1.22 1.25 1.27 1.28 1.33 1.40 1.43 1.46 1.50 1.51 1.53 1.59 1.66 1.67 1.69 1.72 2.27 2.87 2.94 3.36 3.43 3.47 3.64 3.66 3.69 3.71 3.76 3.88 3.91 3.93 3.95 3.97 3.99 4.04 4.14 4.15 4.17 4.22 4.32 4.33 4.37 4.43 4.53 4.58 4.61 4.70 5.20 6.20 6.67 6.82 6.84 6.98 6.99 7.14 7.16 7.17 7.19 7.23 7.24 7.25 7.26 7.30 7.32 7.33 7.35 7.38 7.45 7.50 7.52 7.53 7.55 7.57 7.69 7.71 7.74 7.75 7.77 8.01 8.07 9.99 10.34 10.71

3.78

1.11

0.20

0.37

5.79

0.03

0.66

0.17

0.04

4.60

2.07

2.00

0.35

2.12

(10)

210

200

190

180

170

160

150

140

130

120

110

100

90

80

70

60

50

40

30

20

10

0

ppm

-0.00 10.34 11.78 46.99 50.77 54.57 65.54 67.47 76.70 77.02 77.22 77.33 119.98 124.74 125.15 127.10 127.75 141.25 143.61 143.75 156.22 172.56

(11)

160

150

140

130

120

110

100

90

80

70

60

50

40

30

20

10

ppm

32.57

34.17

12.71

(12)
(13)

9.5

9.0

8.5

8.0

7.5

7.0

6.5

6.0

5.5

5.0

4.5

4.0

3.5

3.0

2.5

2.0

1.5

1.0

0.5 ppm

1.45 1.49 4.70 4.94 4.96 4.97 4.99 5.03 5.05 5.06 5.08 7.34 7.36 7.36 7.37

3.00

0.87

3.95

12.05

(14)

190

180

170

160

150

140

130

120

110

100

90

80

70

60

50

40

30

20

10

ppm

10.97 12.40 65.23 67.07 67.13 76.72 77.04 77.36 126.95 127.53 127.90 128.41 128.51 128.60 129.70 129.75 136.29 136.35 141.11

(15)

160

150

140

130

120

110

100

90

80

70

60

50

40

30

20

10

ppm

23.18 23.40 31.74

0.35

0.32

99.33

(16)
(17)

9.5

9.0

8.5

8.0

7.5

7.0

6.5

6.0

5.5

5.0

4.5

4.0

3.5

3.0

2.5

2.0

1.5

1.0

0.5

ppm

1.49 1.54 2.09 4.70 5.03 5.05 7.32 7.33 7.33 7.34 7.34 7.35 7.35 7.36 7.37 7.39

3.00

1.69

0.86

1.89

1.66

1.22

7.29

(18)

210 200 190 180 170 160 150 140 130 120 110 100

90

80

70

60

50

40

30

20

10

0

ppm

11.15 12.61 20.81 65.35 66.49 66.55 127.01 127.67 127.81 128.38 128.58 136.11 136.18 140.78 176.57

(19)

160

150

140

130

120

110

100

90

80

70

60

50

40

30

20

10

ppm

31.97

34.65

1.74

(20)
(21)

9.5

9.0

8.5

8.0

7.5

7.0

6.5

6.0

5.5

5.0

4.5

4.0

3.5

3.0

2.5

2.0

1.5

1.0

0.5

ppm

1.26 1.46 1.47 1.49 1.50 2.04 4.11 4.13 4.22 4.23 4.35 4.39 4.41 4.42 4.43 4.43 4.45 4.94 4.96 4.97 4.99 5.04 5.06 5.07 5.09 5.80 5.82 5.92 5.94 7.34 7.35 7.36 7.61 7.61 7.75 7.77

0.32

14.43

1.21

0.21

2.26

0.93

2.45

5.34

0.86

17.12

1.99

2.00

(22)

190

180

170

160

150

140

130

120

110

100

90

80

70

60

50

40

30

20

10 ppm

-0.00 10.53 10.57 11.96 12.01 14.20 21.06 27.94 27.96 47.09 54.86 60.40 65.73 67.07 67.13 67.23 67.29 67.45 67.51 83.15 119.98 125.16 127.09 127.72 127.91 127.98 128.05 128.41 128.59 128.61 128.63 128.68 128.70 136.09 141.29 143.75 143.85 155.85 168.06 171.16

(23)

160

150

140

130

120

110

100

90

80

70

60

50

40

30

20

10

ppm

31.71 32.18 32.27

10.11

50.72

39.17

(24)
(25)

11

10

9

8

7

6

5

4

3

2

1

ppm

1.45 1.47 1.50 1.51 1.95 4.16 4.17 4.19 4.27 4.29 4.30 4.33 4.34 4.36 4.39 4.52 4.54 4.56 5.00 5.02 5.04 5.07 5.09 5.99 6.01 6.13 6.15 7.25 7.27 7.28 7.30 7.32 7.36 7.55 7.57 7.60 7.71 7.73 10.48

0.49

3.05

0.14

1.66

2.22

2.06

2.15

1.00

9.40

2.13

2.00

1.35

(26)

210 200 190 180 170 160 150 140 130 120 110 100

90

80

70

60

50

40

30

20

10

0

ppm

8.19 8.33 9.61 9.77 45.15 45.19 52.46 52.52 63.80 63.86 64.19 64.24 65.46 65.56 65.79 65.92 65.99 66.20 66.26 118.13 118.15 123.26 123.29 123.34 123.40 125.26 125.91 126.17 126.27 126.29 126.76 126.85 126.91 126.95 133.68 133.69 133.73 133.75 139.42 139.43 141.79 141.99 154.16 154.28 168.74 168.88

(27)

160

150

140

130

120

110

100

90

80

70

60

50

40

30

20

10

ppm

32.49 32.93 33.57

4.64

41.01

54.34

(28)
(29)

9.5

9.0

8.5

8.0

7.5

7.0

6.5

6.0

5.5

5.0

4.5

4.0

3.5

3.0

2.5

2.0

1.5

1.0

0.5 ppm

1.31 1.31 1.32 1.33 1.34 1.88 1.90 1.92 1.94 2.04 2.05 2.07 2.09 2.38 2.40 2.42 3.09 3.10 3.12 3.14 3.16 3.17 3.19 3.21 3.62 3.77 3.78 3.79 3.79 3.81 3.85 3.86 3.90 3.94 4.21 4.23 4.26 4.27 4.28 4.30 4.32 4.33 4.36 4.37 4.38 7.22 7.23 7.30 7.32 7.33 7.34

9.10

2.06

2.04

2.01

1.88

8.04

6.78

5.00

(30)

210 200 190 180 170 160 150 140 130 120 110 100

90

80

70

60

50

40

30

20

10

0

ppm

16.33 16.42 16.60 26.16 29.91 36.74 42.19 42.29 49.52 49.92 52.99 54.44 54.91 55.40 60.97 61.11 128.01 129.15 129.37 133.69 169.72 170.75 171.05 171.48 173.35 174.66 174.81 175.40 177.11

(31)
(32)

9.5

9.0

8.5

8.0

7.5

7.0

6.5

6.0

5.5

5.0

4.5

4.0

3.5

3.0

2.5

2.0

1.5

1.0

0.5

ppm

0.96 1.19 1.20 1.23 1.24 1.32 1.34 2.40 2.42 2.43 3.12 3.13 3.16 3.18 3.50 3.62 3.79 3.80 3.81 3.83 3.85 3.87 3.88 3.90 3.91 3.92 3.97 4.05 4.07 4.08 4.21 4.23 4.23 4.25 4.26 4.27 4.29 4.31 4.33 4.34 4.35 4.41 4.42 4.44 4.45 7.22 7.24 7.30 7.31 7.32 7.34

0.26

2.65

10.05

1.82

0.34

1.27

2.41

2.63

1.20

9.13

7.40

5.00

(33)

160

150

140

130

120

110

100

90

80

70

60

50

40

30

20

10

ppm

27.62 27.76 27.78 27.86 28.14 37.48

9.42

78.56

3.72

6.29

2.02

(34)

1

.5

1

.8

B

G

B

G

B

G

0

.9

1

2

3

4

5

Time [min]

0

2

4

6

5

x10

Intens.

(35)

9.5

9.0

8.5

8.0

7.5

7.0

6.5

6.0

5.5

5.0

4.5

4.0

3.5

3.0

2.5

2.0

1.5

1.0

0.5

ppm

1.31 1.31 1.32 1.34 1.90 1.91 1.93 1.95 2.06 2.08 2.10 2.11 2.40 2.42 2.44 3.08 3.10 3.12 3.14 3.16 3.18 3.20 3.22 3.62 3.78 3.79 3.81 3.82 3.83 3.85 3.86 3.87 3.90 3.93 3.97 4.03 4.04 4.05 4.06 4.08 4.21 4.22 4.23 4.24 4.24 4.25 4.25 4.26 4.28 4.30 4.31 4.33 4.34 4.35 4.36 4.40 4.41 4.44 4.45 4.46 7.22 7.24 7.24 7.30 7.32 7.33 7.35 7.36 7.37

2.33

8.43

0.35

1.97

1.99

2.07

0.09

1.42

7.26

6.56

0.17

0.08

5.00

(36)

210 200 190 180 170 160 150 140 130 120 110 100

90

80

70

60

50

40

30

20

10

0

ppm

10.28 11.63 16.30 16.40 16.50 16.59 16.94 25.94 29.92 36.75 42.22 42.37 49.53 49.79 50.15 53.11 54.44 54.80 61.06 62.85 69.56 128.01 128.93 129.15 129.37 133.69 169.70 170.98 171.03 171.15 173.20 173.45 174.67 174.84 175.35 177.06

(37)

160

150

140

130

120

110

100

90

80

70

60

50

40

30

20

10

0

ppm

27.66 36.23 36.25

95.50

4.50

(38)
(39)

1

.5

B

G

B

G

B

G

1

2

3

4

5

Time [min]

1

2

3

4

5

5

x10

Intens.

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