Thermoresponsive dynamic covalent dendronized polymers · 2016. 4. 28. · Thermoresponsive dynamic...
18
S1 Supplementary Information Thermoresponsive dynamic covalent dendronized polymers Xiacong Zhang, Jiatao Yan, Wen Li, Afang Zhang Laboratory of Polymer Chemistry, Department of Polymer Materials, College of Materials Science and Engineering, Shanghai University, Nanchen Street 333, Materials Building Room 447, Shanghai 200444, China. Phone: +86-21-66138053. Fax: +86-21-66131720. E-mail: [email protected] (W.L.), [email protected] (A.Z.). Electronic Supplementary Material (ESI) for RSC Advances. This journal is © The Royal Society of Chemistry 2016
Transcript of Thermoresponsive dynamic covalent dendronized polymers · 2016. 4. 28. · Thermoresponsive dynamic...
S1
Supplementary Information
Thermoresponsive dynamic covalent dendronized polymers
Xiacong Zhang, Jiatao Yan, Wen Li, Afang Zhang
Laboratory of Polymer Chemistry, Department of Polymer Materials, College of Materials
Science and Engineering, Shanghai University, Nanchen Street 333, Materials Building
Room 447, Shanghai 200444, China. Phone: +86-21-66138053. Fax: +86-21-66131720.
E-mail: [email protected] (W.L.), [email protected] (A.Z.).
Electronic Supplementary Material (ESI) for RSC Advances.This journal is © The Royal Society of Chemistry 2016
S2
Table of Contents
Scheme S1 Synthetic procedures for the model compounds. Reagents and conditions: (a) Methyl 3-hydroxybenzoate, KI, K2CO3, DMF, 80 oC (2e: 66%); (b)LiAlH4, THF, -5 oC to 25 oC (2f: > 99%);(c) PCC, DCM, 0 oC to 25 oC (5: 65%); (d) hydrazine hydrate, MeOH (6: > 99%)..................................................................S2
Scheme S2 Dimerization reaction of model system between 5 and 6. .......................S3
Fig. S1 Plots of transmittance vs temperature for 0.25 wt % buffer solutions (pH = 1.6) of a) PG1MeHMeA after addition of G1EtH, b) PG1EtHEtA after addition of G1MeH and c) PG2EtHEtA after addition of G1MeH. Heating rate = 0.2 oC/min.........................................................................................................................................S4
Fig. S2 UV/vis spectra of aqueous solutions of PG1EtHEtA at different temperatures, [PG1EtHEtA]. ...............................................................................................................S4
Fig. S3 UV/vis spectra of aqueous solutions of PG2EtHEtA and CuSO4 at different temperatures, [-C=N-]: [Cu2+] = 1:1, [PG2EtHEtA] = 25.5 μg/mL. ........................S5
Fig. S4 1H NMR spectrum of 2a in CDCl3. .......................................................................S7Fig. S5 13C NMR spectrum of 2a in CDCl3.......................................................................S7Fig. S6 13C NMR spectrum of 2b in CDCl3. .....................................................................S8Fig. S7 1H NMR spectrum of G1MeA in CDCl3. ..............................................................S8Fig. S8 13C NMR spectrum of G1MeA in CDCl3. ............................................................S9Fig. S9 1H NMR spectrum of G1MeH in DMSO-d6. ........................................................S9Fig. S10 13C NMR spectrum of G1MeH in CDCl3. ........................................................S10Fig. S11 1H NMR spectrum of 2c in CDCl3. ...................................................................S10Fig. S12 13C NMR spectrum of 2c in CDCl3. .................................................................S11Fig. S13 1H NMR spectrum of 2d in CDCl3....................................................................S11Fig. S14 1H NMR spectrum of G1EtA in CDCl3. ...........................................................S12Fig. S15 1H NMR spectrum of G1EtA in D2O................................................................S12Fig. S16 13C NMR spectrum of G1EtA in CDCl3...........................................................S13Fig. S17 1H NMR spectrum of G1EtH in DMSO-d6. .....................................................S13Fig. S18 1H NMR spectrum of G1EtH in D2O................................................................S14Fig. S19 13C NMR spectrum of G1EtH in CDCl3...........................................................S14Fig. S20 1H NMR spectrum of 4a in CDCl3. ...................................................................S15Fig. S21 13C NMR spectrum of 4a in CDCl3. .................................................................S15Fig. S22 1H NMR spectrum of G2EtA in CDCl3. ...........................................................S16Fig. S23 13C NMR spectrum of G2EtA in CDCl3...........................................................S16Fig. S24 1H NMR spectrum of G2EtH in DMSO-d6. .....................................................S17Fig. S25 13C NMR spectrum of G2EtH in CDCl3...........................................................S17Fig. S26 1H NMR spectrum of 2e in CDCl3. ...................................................................S18Fig. S27 1H NMR spectrum of 5 in CDCl3. .....................................................................S18Fig. S28 1H NMR spectrum of 6 in DMSO-d6. ...............................................................S19
S3
O
OEt
O
O
OEt
O
EtO
O
OO
OO
O
Z
O
OEt
O
O
OEt
O
EtO
O
OO
OO
Cl
2e: Z = COOMe
2f: Z = CH2OH
5: Z = CHO
6: Z = CONHNH2
b
c
a
d
1b
Scheme S1 Synthetic procedures for the model compounds. Reagents and conditions: (a) Methyl 3-hydroxybenzoate, KI, K2CO3, DMF, 80 oC (2e: 66%); (b)LiAlH4, THF, -5 oC to 25 oC (2f: > 99%);(c) PCC, DCM, 0 oC to 25 oC (5: 65%); (d) hydrazine hydrate, MeOH (6: > 99%).
OEt
O
O
OO
O
O
EtO
O
O
O
OEt
O
OEt
O
O
OO
O
O
EtO
O
O
O
OEt
O
OEt
O
O
OO
O
O
EtO
O
O
O
OEt
O
EtO
O
O
OO
O
O
OEt
O
O
O
EtO
O
O
HN
ONH2
HN
ON+
5 6 7
Scheme S2 Dimerization reaction of model system between 5 and 6.
S4
52 56 60 64 68 72 76 80
0
20
40
60
80
100Tr
ansm
ittanc
e (%
)
Temperature (oC)
PMeG1 PMeG1/G1EtH PMeG1/G1EtH 1d PMeG1/G1EtH 2d PMeG1/G1EtH 3d PMeG1/G1EtH 4d PMeG1/G1EtH 5d
32 34 36 38 40 42 440
20
40
60
80
100
Tran
smitt
ance
(%)
Temperature (oC)
PEtG1 PEtG1/G1MeH 1d PEtG1/G1MeH 3d PEtG1/G1MeH 5d
40 42 440
20
40
60
80
100
Tran
smitt
ance
(%)
Temperature (oC)
PEtG2 PEtG2/G1MeH PEtG2/G1MeH 1d PEtG2/G1MeH 2d PEtG2/G1MeH 3d
Fig. S1 Plots of transmittance vs temperature for 0.25 wt % buffer solutions (pH = 1.6) of a) PMeG1 after addition of G1EtH, b) PEtG1 after addition of G1MeH and c) PEtG2 after addition of G1MeH. Heating rate = 0.2 oC·min-1.
200 300 400 5000.0
0.5
1.0
1.5
2.0
Abso
rban
ce
Wavelength (nm)
25 oC 35 oC 45 oC 55 oC 65 oC 75 oC 90 oC
Fig. S2 UV/vis spectra of aqueous solutions of PEtG1 at different temperatures, [PEtG1] = 39 μg·mL-1.
S5
200 300 400 5000.0
0.5
1.0
1.5
2.0
Abso
rban
ce
Wavelength (nm)
25 oC 35 oC 45 oC 55 oC 65 oC 75 oC 85 oC 90 oC
Fig. S3 UV/vis spectra of aqueous solutions of PEtG2 and CuSO4 at different temperatures, [-C=N-]: [Cu2+] = 1:1, [PEtG2] = 25.5 μg·mL-1.
Compound 2e. According to general procedure A from Methyl 3-hydroxybenzoate (0.30
g, 1.97 mmol), 1b (1.1 g, 1.79 mmol), KI (0.20 g, 1.20 mmol), K2CO3 (0.74 g, 5.35 mmol)
and dry DMF, 2e was yielded as a yellow oil (0.86 g, 66%). 1H NMR (CDCl3): δ = 1.21-1.24
(m, 9H, CH3), 3.51-3.56 (m, 6H, CH2), 3.59-3.62 (m, 6H, CH2), 3.66-3.69 (m, 12H, CH2),
3.80 (br, 6H, CH2), 3.82 (br, 2H, CH2), 3.88 (br, 4H, CH2), 3.94 (s, 3H, OCH3), 4.16-4.19
(m, 6H, CH2), 5.01 (s, 2H, CH2), 6.70 (s, 2H, CH), 7.16-7.18 (d, 1H, CH), 7.37 (t, 1H, CH),
7.65-7.68 (m, 2H, CH).
Compound 2f. According to general procedure B from LiAlH4 (0.04 g, 1.05 mmol), 2e (0.59
g, 0.81 mmol) and dry THF, 2f was yielded as a bright yellow oil (0.57 g, > 99%).
Compound 5. According to general procedure C from PCC (0.23 g, 1.07 mmol), 2b (0.57
g, 0.81 mmol) and dry DCM, 5 was yielded as a bright yellow oil (0.37 g, 65%). 1H NMR
(CDCl3): δ = 1.20-1.24 (m, 9H, CH3), 3.51-3.57 (m, 6H, CH2), 3.59-3.62 (m, 6H, CH2), 3.66-
3.69 (m, 12H, CH2), 3.74-3.76 (m, 6H, CH2), 3.82 (t, 2H, CH2), 3.87 (t, 4H, CH2), 4.16-4.20
(m, 6H, CH2), 5.03 (s, 2H, CH2), 6.70 (s, 2H, CH), 7.25-7.27 (m, 1H, CH), 7.47-7.52 (m,
3H, CH), 10.00 (s,1H, HC=O).
Compound 6. According to general procedure D from 2e (0.29 g, 0.40 mmol), hydrazine
hydrate (0.90 mL, 22.04 mmol) and anhydrous MeOH, 6 was yielded as a bright yellow
solid (0.29 g, > 99%). 1H NMR (DMSO-d6): δ = 1.01-1.08 (m, 9H, CH3), 3.36-3.40 (m, 6H,
CH2), 3.42-3.45 (m, 6H, CH2), 3.48-3.52 (m, 12H, CH2), 3.55-3.58 (m, 6H, CH2), 3.65 (t,
2H, CH2), 3.72 (t, 4H, CH2) , 4.00 (t, 2H, CH2), 4.08 (t, 4H, CH2), 4.57 (br, 2H, NH2), 5.03
(s, 2H, CH2), 6.79 (s, 2H, CH), 7.13-7.16 (m, 1H, CH), 7.35-7.38 (m, 1H, CH), 7.41-7.43
(m, 1H, CH), 7.46-7.47 (m, 1H, CH), 9.77 (s, 1H, NH).
S6
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 ppm
1.90
3.38
3.39
3.55
3.55
3.56
3.56
3.57
3.65
3.65
3.66
3.66
3.67
3.68
3.68
3.69
3.73
3.74
3.75
3.75
3.76
3.80
3.81
3.82
3.86
3.87
3.88
3.96
4.16
4.17
4.18
4.19
4.20
5.04
6.69
7.29
7.83
7.84
8.31
8.31
8.32
8.74
6.23
12.2
16.
112.
154.
025.
806.
10
2.00
2.00
1.94
0.91
OMe
O
O
O
O
O
O
MeO
O
O
O
OMe
O
O
O
O
O
Fig. S4 1H NMR spectrum of 2a in CDCl3.
170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 ppm
52.37
58.90
68.78
69.63
70.41
70.43
70.48
70.58
70.71
71.83
71.86
72.25
76.96
77.22
77.47
107.05
120.07
123.18
131.41
131.75
152.74
158.58
165.95
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
OO
Fig. S5 13C NMR spectrum of 2a in CDCl3.
S7
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
2.01
3.38
3.39
3.54
3.55
3.55
3.55
3.56
3.56
3.57
3.64
3.64
3.65
3.65
3.65
3.66
3.67
3.67
3.72
3.72
3.73
3.73
3.74
3.79
3.80
3.81
3.84
3.85
3.86
4.14
4.16
4.16
4.17
4.18
4.65
5.00
6.68
6.92
6.93
7.29
8.73
5.96
12.0
15.
882.
164.
055.
92
3.94
1.95
2.00
1.88
0.99
OMe
O
O
O
O
O
O
MeO
O
O
O
OMe
OH OH
O
Fig. S6 13C NMR spectrum of 2b in CDCl3.
10 9 8 7 6 5 4 3 2 1 ppm
1.82
3.38
3.39
3.55
3.56
3.56
3.57
3.65
3.66
3.67
3.68
3.68
3.69
3.73
3.74
3.75
3.76
3.80
3.81
3.82
3.86
3.87
3.88
4.16
4.17
4.18
4.19
4.20
5.09
6.70
7.28
7.74
8.00
10.07
8.73
6.24
12.0
66.
402.
364.
185.
95
2.00
2.00
1.96
0.98
1.98
OMe
O
O
O
O
O
O
MeO
O
O
O
OMe
O O
O
Fig. S7 1H NMR spectrum of G1MeA in CDCl3.
S8
180 160 140 120 100 80 60 40 20 ppm
58.90
68.85
69.62
70.42
70.44
70.46
70.59
70.62
70.71
71.83
71.86
72.26
77.01
77.26
77.52
107.17
120.12
124.27
130.92
138.32
138.37
152.83
159.70
190.79
O
O
O
O
O
O
O
O
O
O O
O
O
OO
Fig. S8 13C NMR spectrum of G1MeA in CDCl3.
10 9 8 7 6 5 4 3 2 1 ppm
2.52
3.22
3.24
3.43
3.50
3.50
3.50
3.51
3.51
3.51
3.52
3.53
3.53
3.57
3.57
3.58
3.58
3.59
3.60
3.60
3.66
3.67
3.68
3.73
3.74
3.75
4.01
4.02
4.03
4.10
4.11
4.11
4.53
5.07
6.80
7.56
7.57
7.87
9.81
9.00
12.6
66.
271.
914.
062.
054.
093.
38
1.76
1.78
1.78
0.87
1.80
OMe
O
O
O
O
O
O
MeO
O
O
O
OMe
NH
O
HN
O
H2N NH2
O
Fig. S9 1H NMR spectrum of G1MeH in DMSO-d6.
S9
160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 ppm
58.06
58.86
58.91
58.96
68.61
68.68
69.66
70.07
70.35
70.38
70.43
70.49
70.52
70.53
70.60
70.62
70.66
70.73
71.80
71.83
71.88
72.21
74.60
76.85
77.11
77.36
106.60
106.99
117.06
131.86
137.59
152.48
152.52
158.78
O
O
O
O
O
O
O
O
O
NH
O
HN
O
H2N NH2
O
O
OO
Fig. S10 13C NMR spectrum of G1MeH in CDCl3.
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 ppm
1.20
1.21
1.21
1.22
1.23
1.24
1.90
3.51
3.52
3.52
3.53
3.54
3.54
3.55
3.59
3.59
3.60
3.60
3.60
3.61
3.65
3.66
3.66
3.67
3.68
3.68
3.69
3.69
3.73
3.74
3.74
3.75
3.76
3.81
3.86
3.87
3.88
3.96
4.16
4.17
4.18
4.19
4.20
5.04
6.69
7.29
7.83
7.84
8.31
8.99
6.09
6.18
12.2
16.
332.
174.
086.
066.
00
1.87
1.88
1.98
0.94
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
OO
Fig. S11 1H NMR spectrum of 2c in CDCl3.
S10
180 160 140 120 100 80 60 40 20 ppm
15.08
52.35
66.51
68.82
69.63
69.73
69.76
70.40
70.43
70.47
70.58
70.60
70.73
72.26
76.97
77.23
77.48
107.07
120.05
123.16
131.37
131.74
138.20
152.76
158.58
165.91
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
OO
Fig. S12 13C NMR spectrum of 2c in CDCl3.
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 ppm
1.17
1.18
1.19
1.19
1.20
1.21
1.95
2.36
3.48
3.49
3.50
3.50
3.51
3.52
3.52
3.55
3.56
3.57
3.57
3.57
3.58
3.61
3.62
3.62
3.63
3.64
3.65
3.69
3.69
3.70
3.71
3.76
3.77
3.78
3.81
3.82
3.83
4.12
4.13
4.14
4.15
4.16
4.62
4.62
4.96
6.65
6.89
6.90
7.26
8.85
1.93
5.96
6.10
12.1
46.
056.
206.
03
4.05
1.94
2.00
1.89
1.01
O
O
O
O
O
O
O
O
O
OH OH
O
O
OO
Fig. S13 1H NMR spectrum of 2d in CDCl3.
S11
10 9 8 7 6 5 4 3 2 1 ppm
1.20
1.21
1.22
1.23
1.23
1.24
1.75
3.51
3.52
3.53
3.54
3.54
3.55
3.56
3.59
3.60
3.60
3.61
3.62
3.65
3.66
3.66
3.67
3.67
3.68
3.68
3.69
3.69
3.73
3.74
3.75
3.75
3.76
3.81
3.82
3.83
3.87
3.88
3.89
4.18
4.19
5.09
6.70
7.29
7.74
7.74
8.00
10.08
9.21
6.22
6.26
12.6
26.
292.
134.
096.
08
2.00
2.00
2.00
1.00
1.98
O
O
O
O
O
O
O
O
O
O O
O
O
OO
Fig. S14 1H NMR spectrum of G1EtA in CDCl3.
10 9 8 7 6 5 4 3 2 1 ppm
Fig. S15 1H NMR spectrum of G1EtA in D2O.
S12
190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 ppm
15.10
66.55
68.85
69.63
69.74
69.76
70.45
70.48
70.58
70.61
70.66
70.75
72.29
76.93
77.18
77.44
107.18
120.18
124.30
130.94
138.34
138.38
152.85
159.73
190.79
O
O
O
O
O
O
O
O
O
O O
O
O
OO
Fig. S16 13C NMR spectrum of G1EtA in CDCl3.
10 9 8 7 6 5 4 3 2 1 ppm
1.07
1.08
1.10
1.11
2.51
2.51
2.51
3.35
3.39
3.40
3.41
3.42
3.43
3.44
3.45
3.45
3.46
3.47
3.47
3.48
3.48
3.50
3.50
3.51
3.51
3.52
3.52
3.53
3.54
3.54
3.58
3.59
3.59
3.60
3.60
3.61
3.68
3.74
3.75
3.76
4.10
4.11
4.12
5.07
6.80
7.57
7.57
7.89
9.80
9.22
12.8
412
.59
6.38
2.17
4.18
2.05
4.17
4.08
2.05
2.00
2.05
1.00
2.07
O
O
O
O
O
O
O
O
O
NH
O
HN
O
H2N NH2
O
O
OO
Fig. S17 1H NMR spectrum of G1EtH in DMSO-d6.
S13
10 9 8 7 6 5 4 3 2 1 ppm
Fig. S18 1H NMR spectrum of G1EtH in D2O.
180 160 140 120 100 80 60 40 20 ppm
15.02
15.06
66.54
68.60
69.63
69.66
69.69
70.09
70.34
70.48
70.50
70.53
70.64
72.21
76.92
77.17
77.43
106.66
116.94
117.81
131.82
134.03
137.62
152.48
158.73
166.67
O
O
O
O
O
O
O
O
O
NH
O
HN
O
H2N NH2
O
O
OO
Fig. S19 13C NMR spectrum of G1EtH in CDCl3.
S14
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 ppm
1.21
1.21
1.22
1.23
1.23
1.24
1.68
3.53
3.53
3.54
3.55
3.56
3.59
3.60
3.60
3.61
3.61
3.62
3.65
3.66
3.66
3.67
3.68
3.68
3.69
3.69
3.70
3.71
3.74
3.74
3.75
3.80
3.81
3.85
3.86
3.87
3.96
4.14
4.15
4.16
4.17
4.18
4.19
4.45
4.46
6.58
6.70
7.29
7.84
27.3
1
18.0
096
.79
24.9
75.
7524
.26
4.19
1.84
1.95
4.41
1.86
1.08
2.03
1.04
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
OO
O
O
O
O
O
O
O
O
O
O
O
OO
O
O
O
O
O
O
O
OO
O
O
O
O
O
O
O
O
O
O
Fig. S20 1H NMR spectrum of 4a in CDCl3.
170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 ppm
15.09
52.38
58.02
66.53
68.71
68.78
69.26
69.29
69.63
69.66
69.74
69.75
70.41
70.46
70.57
70.59
70.71
72.22
73.13
76.96
77.22
77.48
107.04
107.13
120.07
123.20
131.44
131.77
133.71
137.63
152.52
152.74
158.60
165.94
OEt
O
O
OO
O
O
EtO
O
O
O
OEt
O
O
O
O
OEt
O
O
O
O
O
OEt
OO
OEtO
O
O
O
O
O
EtO
O
O
O
O
O
EtO
OO
OOEt
O
O
O
O
O
O
O
O
O
O
Fig. S21 13C NMR spectrum of 4a in CDCl3.
S15
10 9 8 7 6 5 4 3 2 1 ppm
1.20
1.21
1.22
1.22
1.23
1.24
3.51
3.53
3.53
3.54
3.54
3.55
3.59
3.60
3.60
3.61
3.62
3.62
3.65
3.66
3.67
3.68
3.68
3.69
3.73
3.73
3.74
3.74
3.75
3.80
3.81
3.84
3.86
3.87
4.13
4.14
4.15
4.15
4.16
4.17
4.18
4.19
4.45
5.08
6.58
6.70
7.73
7.73
10.07
26.6
5
18.0
524
.45
48.3
724
.63
24.8
824
.00
5.82
1.69
5.84
1.97
1.73
0.85
1.68
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
OO
O
O
O
O
O
O
O
O
O
O
O
OO
O
O
O
O
O
O
O
OO
O
O
O
O
O
O
O O
Fig. S22 1H NMR spectrum of G2EtA in CDCl3.
180 160 140 120 100 80 60 40 20 ppm
15.10
52.71
66.54
68.71
68.84
69.26
69.29
69.64
69.66
69.74
69.76
70.42
70.46
70.55
70.57
70.60
70.63
70.72
72.23
72.29
73.14
73.15
76.94
77.20
77.45
107.04
107.27
120.16
124.30
131.02
133.70
133.72
137.64
138.34
138.38
152.53
152.82
159.71
190.82
OEt
O
O
OO
O
O
EtO
O
O
O
OEt
O
O
O
O
OEt
O
O
O
O
O
OEt
OO
OEtO
O
O
O
O
O
EtO
O
O
O
O
O
EtO
OO
OOEt
O
O
O
O
O
O O
O
Fig. S23 13C NMR spectrum of G2EtA in CDCl3.
S16
10 9 8 7 6 5 4 3 2 1 ppm
1.06
1.08
1.09
1.10
2.51
3.38
3.39
3.41
3.42
3.43
3.44
3.44
3.45
3.45
3.46
3.46
3.47
3.48
3.49
3.49
3.50
3.50
3.51
3.51
3.52
3.52
3.53
3.54
3.55
3.56
3.57
3.58
3.59
3.59
3.60
3.66
3.67
3.71
3.72
3.73
3.97
3.99
4.05
4.06
4.07
4.37
4.38
6.61
6.79
26.2
8
115.
078.
5015
.76
24.0
05.
783.
60
1.88
5.77
1.92
1.76
0.85
1.69
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
OO
O
O
O
O
O
O
O
O
O
O
O
OO
O
O
O
O
O
O
O
OO
O
O
O
O
O
O
NH
O
HN
O
H2N NH2
Fig. S24 1H NMR spectrum of G2EtH in DMSO-d6.
170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 ppm
15.06
15.08
66.55
68.58
68.65
68.88
69.31
69.32
69.66
69.70
69.71
69.73
69.74
70.16
70.38
70.40
70.48
70.52
70.55
70.58
70.60
70.69
70.70
72.19
72.21
73.09
73.12
76.92
77.18
77.38
77.43
106.84
106.94
107.43
117.05
117.39
131.75
133.73
133.75
134.21
137.42
137.53
138.21
152.39
152.47
152.64
158.82
166.61
Fig. S25 13C NMR spectrum of G2EtH in CDCl3.
S17
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 ppm
1.22
1.79
3.52
3.53
3.54
3.56
3.60
3.61
3.67
3.68
3.69
3.75
3.82
3.88
3.94
4.19
5.01
6.70
7.17
7.18
7.29
7.37
7.39
7.65
7.67
7.68
9.46
6.50
6.44
12.6
36.
312.
324.
103.
286.
19
2.00
1.99
1.03
1.05
2.09
O
O
O
O
O
O
O
O
OO
OO
O
OO
Fig. S26 1H NMR spectrum of 2e in CDCl3.
O
O
O
O
O
O
O
O
OO
OO
O
O
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 ppm
1.22
1.23
1.23
1.71
3.51
3.52
3.53
3.54
3.54
3.55
3.56
3.59
3.60
3.60
3.61
3.62
3.66
3.66
3.67
3.68
3.68
3.69
3.69
3.74
3.75
3.75
3.76
3.82
3.83
3.86
3.87
3.88
4.16
4.17
4.18
4.19
4.20
5.03
6.70
7.29
7.48
7.50
7.50
7.50
9.30
6.36
6.41
12.8
46.
682.
214.
196.
16
1.92
2.00
0.97
2.94
Fig. S27 1H NMR spectrum of 5 in CDCl3.
S18
10 9 8 7 6 5 4 3 2 1 ppm
1.07
1.08
1.10
1.11
2.50
2.51
2.51
3.36
3.39
3.40
3.41
3.43
3.44
3.45
3.45
3.46
3.46
3.47
3.47
3.50
3.50
3.51
3.52
3.52
3.53
3.53
3.54
3.57
3.58
3.58
3.59
3.59
3.60
3.61
3.67
3.73
3.74
3.75
4.02
4.09
4.10
4.11
5.03
6.79
9.41
6.72
6.64
12.7
56.
266.
206.
22
1.48
2.03
2.00
0.94
0.97
0.94
0.94
0.94
O
O
O
O
O
O
O
O
OO
OO
O
OHN NH2
Fig. S28 1H NMR spectrum of 6 in DMSO-d6.
![Preparation of Thermoresponsive Polymer Nanogels of Oligo ...oligo(ethylene glycol) (OEG) with thermoresponsive prop-erties has been developed [14–17]. However, PEG in water is only](https://static.fdocuments.us/doc/165x107/6121cdc39759fa2ef774e6b0/preparation-of-thermoresponsive-polymer-nanogels-of-oligo-oligoethylene-glycol.jpg)
