SUPPORTING INFORMATION
Controlled loop and graft formations of water-soluble polymers on SAM for the design
of biomaterials surfaces
Ko Yamada, Ryo Katoono, and Nobuhiko Yui
Experimental details of new compound preparation
Scheme S1. Preparation of 3 and 5.
Reagents (a) NaH, TBAI, DMF (85%); (b) TBAF, THF (92%); (c) p-TsCl, Et3N, DMAP, CH2Cl2 (96%); (d) NaH, Z-Tyr-OMe, TBAI,
DMF (78%); (e) LiOH, Ac2O, THF, water (79%).
Preparation of 11.
To an ice-cooled solution of 91 (4.27 g, 16.4 mmol) in DMF (160 mL) was added 60% NaH in oil (723 mg,
18.1 mmol), the mixture was stirred at room temperature for 2 hours, and then cooled down again in an ice bath.
To the ice-cooled mixture was added a solution of 102 (6.41 g, 22.6 mmol) and tetrabutylammonium iodide (71
mg, 0.19 mmol) in DMF (6 mL). The mixture was stirred at room temperature for 3 days, and then diluted with
diethyl ether, and washed with 0.1 N HCl aq. and brine. The organic layer was dried over MgSO 4. After
1
evaporation of the solvent, chromatographic separation on SiO2 (5-10% ethyl acetate/hexane) gave 11 (7.08 g) as
a colorless oil in 85% yield.
Data of 11. 1H NMR H(400 MHz; CDCl3; TMS)/ppm 4.05 (2H, t, J = 6.8 Hz), 3.77 (2H, t, J = 5.2 Hz),
3.67-3.60 (6H, m), 3.56 (2H, t, J = 5.2 Hz), 2.71 (2H, t, J = 7.2 Hz), 2.54 (2H, t, J = 7.2 Hz), 2.04 (3H,
s), 1.67-1.51 (4H, m), 1.44-1.20 (16H, m), 0.90 (9H, s), 0.07 (6H, s);
C NMR C(100 MHz;
13
CDCl3)/ppm 171.1, 72.7, 71.0, 70.7, 70.3, 64.6, 62.7, 32.5, 31.3, 29.8, 29.5, 29.5, 29.4, 29.2, 28.8,
28.6, 25.9, 25.9, 21.0, 18.3, -5.3; IR (NaCl) 3459, 2956, 2930, 2884, 2859, 1737, 1473, 1463, 1363,
1109 cm-1; EI-MS m/z 506 (M+, 15%), 449 ([M–(C4H9)]+, 52), 287 ([M–(C9H20SiO2S)]+, BP); EI-HRMS
Calcd. for C26H54SiO5S 506.3461, Found 506.3461.
Preparation of 3.
To an ice-cooled solution of 11 (7.08 g, 14.0 mmol) in THF (130 mL) was added a 1M solution of
tetrabutylammonium fluoride in THF (14.2 mL, 14.2 mmol), and the mixture was stirred at room temperature for
2 hours, and then diluted with diethyl ether and 0.1 N HCl aq. The organic layer was washed with brine and
dried over MgSO4.
After evaporation of the solvent, chromatographic separation on SiO 2 (50% ethyl
acetate/hexane) gave 3 (5.02 g) as a white solid in 92% yield.
Data of 3. mp 24-25 °C; 1H NMR H(400 MHz; CDCl3; TMS)/ppm 4.05 (2H, t, J = 6.8 Hz), 3.74 (2H,
dt, J = 3.6, 5.6 Hz), 3.69-3.61 (8H, m), 2.72 (2H, t, J = 7.2 Hz), 2.55 (2H, t, J = 7.2 Hz), 2.32 (1H, t, J =
5.6 Hz), 2.05 (3H, s), 1.65-1.54 (4H, m), 1.43-1.20 (16H, m);
13C
NMR C(100 MHz; CDCl3)/ppm 171.2,
72.5, 71.0, 70.4, 70.3, 64.6, 61.8, 32.6, 31.4, 29.8, 29.5, 29.5, 29.5, 29.2, 28.8, 28.6, 25.9, 21.0; IR
(KBr) 3456, 2927, 2855, 1740, 1466, 1366, 1112 cm-1; EI-MS m/z 392 (M+, 0.2%), 331 ([M–(C2H5O2)]+,
14), 287 ([M–C3H6O2S]+, BP); EI-HRMS Calcd. for C20H40O5S 392.2596, Found 392.2594.
Preparation of 12.
To an ice-cooled solution of 3 (7.20 g, 18.3 mmol), triethylamine (6.20 mL, 44.5 mmol), and N,Ndimethylaminopyridine (229 mg, 1.87 mmol) in CH2Cl2 (110 mL) was added a solution of p-toluenesulfonyl
chloride (6.96 g, 36.5 mmol) in CH2Cl2 (60 mL), and the mixture was stirred at room temperature for 12 hours.
After addition of water to the reaction mixture, the organic layer was separated and washed with brine. The
organic layer was dried over MgSO4. After evaporation of the solvent, chromatographic separation on SiO2 (2040% ethyl acetate/hexane) gave 12 (9.58 g) as a colorless oil in 96% yield.
Data of 12. 1H NMR H(400 MHz; CDCl3; TMS)/ppm 7.80 (2H, d, J = 8.4 Hz), 7.34 (2H, d, J = 8.4
Hz), 4.17 (2H, t, J = 4.8 Hz), 4.05 (2H, t, J = 6.8 Hz), 3.70 (2H, t, J = 4.8 Hz), 3.62-3.54 (6H, m), 2.68
(2H, t, J = 7.2 Hz), 2.53 (2H, t, J = 7.2 Hz), 2.45 (3H, s), 2.05 (3H, s), 1.66-1.52 (4H, m), 1.40-1.20
(16H, m);
13C
NMR C(100 MHz; CDCl3)/ppm 171.2, 144.7, 133.0, 129.8, 127.9, 71.0, 70.7, 70.2, 69.2,
2
68.7, 64.6, 32.6, 31.4, 29.8, 29.5, 29.5, 29.5, 29.4, 29.2, 28.8, 28.6, 25.9, 21.6, 21.0; IR (NaCl) 3436,
2927, 2855, 1738, 1599, 1465, 1365, 1217, 1135 cm-1; EI-MS m/z 546 (M+, 0.4%), 331 ([M–C9H11O4S]+,
14), 287 ([M–C10H12O4S2]+, BP); EI-HRMS Calcd. for C27H46S2O7 546.2685, Found 546.2686.
Preparation of 13.
To an ice-cooled solution of Z-Tyr-OMe (2.63 g, 7.97 mmol) in DMF (60 mL) was added 60% NaH in oil
(339 mg, 8.48 mmol), the mixture was stirred at the temperature for 1 hour, and then were added a solution of 12
(5.21 g, 9.54 mmol) in DMF (10 mL) and tetrabutylammonium iodide (295 mg, 0.799 mmol), and the mixture
was stirred at room temperature for 1 week. The reaction mixture was diluted with diethyl ether, and then
washed with 0.1 N HCl aq. and brine. The organic layer was dried over MgSO4. After evaporation of the
solvent, chromatographic separation on SiO2 (30% ethyl acetate/hexane) and gel permeation chromatography
(CHCl3, detected by UV 254 nm) gave 13 (4.37 g) as a white solid in 78% yield.
Data of 13. mp 46-47 °C; 1H NMR H(400 MHz; CDCl3; TMS)/ppm 7.40-7.28 (5H, m), 6.99 (2H, d, J
= 8.8 Hz), 6.81 (2H, d, J = 8.8 Hz), 5.19 (1H, d, J = 8.0 Hz), 5.11 (1H, d, J = 12.4 Hz), 5.07 (1H, d, J =
12.4 Hz), 4.61 (1H, dt, J = 5.6, 8.0 Hz), 4.10 (2H, t, J = 4.4 Hz), 4.05 (2H, t, J = 6.8 Hz), 3.85 (2H, t, J =
4.8 Hz), 3.73-3.63 (9H, m), 3.07 (1H, dd, J = 5.6, 14.0 Hz), 3.02 (1H, dd, J = 5.6, 14.0 Hz), 2.71 (2H, t,
J = 7.2 Hz), 2.53 (2H, t, J = 7.6/7.2 Hz), 2.04 (3H, s), 1.65-1.53 (4H, m), 1.42-1.20 (16H, m);
13C
NMR
C(100 MHz; CDCl3)/ppm 172.0, 171.2, 157.9, 155.6, 136.3, 130.2, 128.5, 128.2, 128.1, 127.8, 114.7,
71.0, 70.8, 70.3, 69.8, 67.4, 66.9, 64.6, 54.9, 52.3, 37.4, 32.6, 31.4, 29.8, 29.5, 29.5, 29.5, 29.2, 28.9,
28.6, 25.9, 21.0; IR (KBr) 3342, 2917, 2850, 1725, 1690, 1538, 1473, 1461, 1374, 1126 cm-1; FAB-MS
m/z 704 ([M+H]+, 21%), 287 ([M–C21H23NO6S]+, BP), 91 ([M–C31H50NO9S]+, 95); FAB-HRMS Calcd. for
C38H57SO9N+H 704.3832, Found 704.3835.
Preparation of 5.
To an ice-cooled solution of 13 (2.00 g, 2.84 mmol) in THF (83 mL) was added a solution of LiOH (598 mg,
14.2 mmol) in water (45 mL), and the mixture was stirred at the temperature for 20 minutes. After addition of
acetic anhydride (1.34 mL, 14.2 mmol), and the mixture was stirred at the temperature for 30 minutes. The
reaction mixture was diluted with 2 N HCl aq., and then extracted with ethyl acetate. The organic layer was
washed with brine, and dried over MgSO4. After evaporation of the solvent, chromatographic separation on SiO2
(1:5:15-1:4:4 acetic acid/ethyl acetate/hexane) gave 5 (1.55 g) as a white solid in 79% yield.
Data of 5. mp 55-56 °C; 1H NMR H(400 MHz; CD3OD)/ppm 7.35-7.24 (5H, m), 7.11 (2H, d, J = 8.8
Hz), 6.83 (2H, d, J = 8.8 Hz), 5.05 (1H, d, J = 12.4 Hz), 4.99 (1H, d, J = 12.4 Hz), 4.37 (1H, dd, J = 5.2,
9.2 Hz), 4.09-4.07 (2H, m), 4.03 (2H, t, J = 6.8 Hz), 3.83-3.81 (2H, m), 3.71-3.59 (6H, m), 3.12 (1H, dd,
3
J = 5.2, 14.0 Hz), 2.86 (1H, dd, J = 9.2, 14.0 Hz), 2.66 (2H, t, J = 6.8 Hz), 2.53 (2H, t, J = 7.6 Hz), 2.00
(3H, s), 1.64-1.49 (4H, m), 1.41-1.21 (16H, m);
C NMR C(100 MHz; CD3OD)/ppm 173.1, 159.2,
13
158.3, 138.3, 131.3, 130.7, 129.4, 128.9, 128.6, 115.6, 72.3, 71.8, 71.3, 70.9, 68.6, 67.4, 65.7, 37.8,
33.3, 32.3, 30.9, 30.6, 30.6, 30.3, 30.3, 29.8, 29.7, 27.0, 20.8; IR (KBr) 3442, 3310, 2920, 28520, 1730,
1697, 1539, 1467, 1455, 1367, 1129 cm-1; FAB-MS m/z 690 ([M+H]+, 10%), 287 ([M–C20H21NO6S]+,
BP), 91 ([M–C30H48NO9S]+, 80); FAB-HRMS Calcd. for C37H55SO9N+H 690.3676, Found 690.3675.
4
Scheme S2. Preparation of PEG 1l/g.
Reagents (a) 5, DMT-MM, DMF (29%); (b) DMT-MM, MeOH (47%); (c) BOP, HOBt, DIEA, DMF (46%).
Preparation of 1l.
To a solution of 5 (207 mg, 300 mol) and 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium
chloride (DMT-MM) (83 mg, 0.30 mmol) in DMF (3 mL) was added 4 (300 mg, 100 mol), and the reaction
mixture was stirred at room temperature for 24 hours. After evaporation of the solvent, the remaining solid was
dissolved in CH2Cl2, and washed with 0.1 N HCl aq. and brine, and then dried over MgSO4. After evaporation of
the solvent, chromatographic separation on SiO2 (5% MeOH/CH2Cl2) gave 1l (120 mg) as a yellowish solid in
29% yield.
Data of 1l. mp 32-33 °C; 1H NMR H(400 MHz; CDCl3; TMS)/ppm 7.39-7.29 (10H, m), 7.08 (4H, d, J
= 8.4 Hz), 6.81 (4H, d, J = 8.4 Hz), 6.46 (2H, br. t), 5.48 (2H, br. d), 5.09 (2H, d, J = 12.4 Hz), 5.05 (2H,
d, J = 12.4 Hz), 4.35 (2H, d, J = 6.0 Hz), 4.09 (4H, t, J = 4.7 Hz), 4.05 (4H, t, J = 6.8 Hz), 3.86-3.35
(272H, m), 3.00 (4H, d, J = 6.8 Hz), 2.71 (4H, t, J = 7.2 Hz), 2.53 (4H, t, J = 7.2 Hz), 2.04 (6H,s), 1.651.53 (8H,m), 1.41-1.22 (32H, m); 13C NMR C(100 MHz; CDCl3)/ppm 171.2, 170.8, 157.7, 155.7, 136.3,
130.3, 128.7, 128.5, 128.1, 127.9, 114.6, 71.0, 70.9-69.5 (4 signals from PEG, and 3 signals from
TEGDT), 67.3, 66.8, 64.6, 56.3, 39.2, 32.6, 31.3, 29.7, 29.5, 29.5, 29.4, 29.2, 28.8, 28.5, 25.9, 21.0; IR
(KBr) 2969, 2883, 2922, 1737, 1649, 1514, 1473, 1456, 1363, 1103 cm-1; MALDI-TOF MS (n; number
of -CH2CH2O- units in 1l) m/z 3893 ([M(n = 54)+Na]+, 31%), 3937 ([M(n = 55)+Na]+, 43), 3981 ([M(n =
56)+Na]+, 54), 4025 ([M(n = 57)+Na]+, 60), 4069 ([M(n = 58)+Na]+, 68), 4113 ([M(n = 59)+Na]+, 76),
4158 ([M(n = 60)+Na]+, 88), 4201 ([M(n = 61)+Na]+, 92), 4246 ([M(n = 62)+Na]+, 100), 4290 ([M(n =
63)+Na]+, 95), 4334 ([M(n = 64)+Na]+, 90), 4377 ([M(n = 65)+Na]+, 88), 4421 ([M(n = 66)+Na]+, 82),
4465 ([M(n = 67)+Na]+, 73), 4510 ([M(n = 68)+Na]+, 62), 4554 ([M(n = 69)+Na]+, 52), 4598 ([M(n =
70)+Na]+, 43), 4642 ([M(n = 71)+Na]+, 31).
5
Preparation of 6.
To a solution of 5 (0.29 g, 0.42 mmol) and DMT-MM (0.12 g, 0.42 mmol) in MeOH (80 mL) was added 4 (2.5
g, 0.83 mmol), and the reaction mixture was stirred at room temperature for 18 hours. After evaporation of the
solvent, the remaining solid was dissolved in CH2Cl2, and washed with 0.1 N HCl aq. and brine, and then dried
over MgSO4. After evaporation of the solvent, chromatographic separation on SiO2 (10% MeOH/CH2Cl2) gave 6
(1.4 g) as a white solid in 47% yield.
Data of 6. mp 48-49 °C; 1H NMR H(400 MHz; CDCl3; TMS)/ppm 7.39-7.25 (5H, m), 7.08 (2H, d, J =
8.6 Hz), 6.81 (2H, d, J = 8.6 Hz), 6.34 (1H, br. t), 5.44 (1H, br. d), 5.08 (2H, d, J = 3.5 Hz), 4.33 (1H, d,
J = 6.8 Hz), 4.09 (2H, t, J = 4.7 Hz), 4.05 (2H, t, J = 6.8 Hz), 3.91-3.31 (272H, m), 3.00 (2H, d, J = 6.8
Hz), 2.71 (2H, t, J = 7.2 Hz), 2.53 (2H, t, J = 7.2 Hz), 2.04 (3H,s), 1.69-1.51 (4H,m), 1.42-1.19 (16H,
m);
13C
NMR C(100 MHz; CDCl3)/ppm 170.8, 157.8, 136.6, 130.4, 128.7, 128.5, 128.2, 128.0, 114.6,
71.0, 70.9-69.5 (4 signals from PEG, and 3 signals from TEGDT), 67.0, 66.7, 64.7, 56.3, 41.1, 32.6,
31.4, 30.8, 29.5, 29.4, 29.2, 28.9, 28.6, 25.9, 21.0; IR (KBr) 2973, 2880, 2921, 1735, 1643, 1517,
1468, 1455, 1361, 1101 cm-1; MALDI-TOF MS (n; number of -CH2CH2O- units in 6) m/z 3350 ([M(n =
58)+Na]+, 55), 3394 ([M(n = 59)+Na]+, 67), 3437 ([M(n = 60)+Na]+, 68), 3480 ([M(n = 61)+Na]+, 75),
3525 ([M(n = 62)+Na]+, 72), 3569 ([M(n = 63)+Na]+, 92), 3613 ([M(n = 64)+Na]+, 87), 3657 ([M(n =
65)+Na]+, 98), 3701 ([M(n = 66)+Na]+, 100), 3745 ([M(n = 67)+Na]+, 85), 3789 ([M(n = 68)+Na]+, 79),
3833 ([M(n = 69)+Na]+, 76), 3877 ([M(n = 70)+Na]+, 75), 3921 ([M(n = 71)+Na]+, 68), 3966 ([M(n =
71)+Na]+, 66).
Preparation of 1g.
To a solution of Z-Phe-OH 7 (33 mg, 0.11 mmol), Benzotriazole-1-yloxytris(dimethylamino)phosphonium
hexafluorophosphate (BOP) (49 mg, 0.11 mmol), N-Hydroxybenzotriazole (HOBt) (15 mg, 0.11 mmol) and
diisopropylethylamine (14 mg, 0.11 mmol) in DMF (1 mL) was added 6 (0.20 g, 55 mol), and the reaction
mixture was stirred at room temperature for 15 hours. After evaporation of the solvent, the remaining solid was
dissolved in CH2Cl2, and washed with 0.1 N HCl aq. and brine, and then dried over MgSO4. After evaporation of
the solvent, chromatographic separation on SiO2 (6% MeOH/CH2Cl2) gave 1g (99 mg) as a yellowish solid in
46% yield.
Data of 1g. 1H NMR H(400 MHz; CDCl3; TMS)/ppm 7.42-7.19 (10H, m), 7.12 (2H, d, J = 6.3 Hz),
7.09 (2H, d, J = 8.3 Hz), 6.81 (2H, d, J = 8.1 Hz), 6.43 (2H, br. t), 5.47 (2H, br. d), 5.09 (2H, d, J = 10.6
Hz), 5.07 (2H, d, J = 10.6 Hz), 4.31 (1H, d, J = 6.0 Hz), 4.09 (1H, t, J = 4.7 Hz), 4.05 (4H, t, J = 6.8
Hz), 3.98-3.27 (272H, m), 3.13 (2H, br. t), 3.01 (2H, br. d), 2.71 (2H, t, J = 7.2 Hz), 2.53 (2H, t, J = 7.2
Hz), 2.04 (3H,s), 1.65-1.51 (4H,m), 1.42-1.16 (16H, m);
13C
NMR C(100 MHz; CDCl3)/ppm 171.2,
170.8, 156.7, 155.6, 135.0, 130.1, 129.4, 128.5, 127.0, 117.1, 71.0, 70.9-69.9 (4 signals from PEG,
6
and 3 signals from TEGDT), 69.8, 66.0, 65.1, 56.3, 39.2, 32.4, 29.1, 28.8, 27.9, 26.0, 21.1; IR (KBr)
2988, 2881, 2931, 1735, 1646, 1517, 1478, 1450, 1361, 1107 cm-1; MALDI-TOF MS (n; number of CH2CH2O- units in 1g) m/z 3628 ([M(n = 58)+Na]+, 43), 3672 ([M(n = 59)+Na]+, 55), 3716 ([M(n =
60)+Na]+, 67), 3760 ([M(n = 61)+Na]+, 73), 3804 ([M(n = 62)+Na]+, 85), 3848 ([M(n = 63)+Na]+, 91),
3892 ([M(n = 64)+Na]+, 92), 3937 ([M(n = 65)+Na]+, 100), 3980 ([M(n = 66)+Na]+, 85), 4024 ([M(n =
67)+Na]+, 77), 4068 ([M(n = 68)+Na]+, 78), 4112 ([M(n = 69)+Na]+, 58), 4156 ([M(n = 70)+Na]+, 49).
Scheme S3. Preparation of water-soluble polyrotaxane 2l/g.
Reagents (a) -CD, water;3 (b) 5, DMT-MM, MeOH (6%); (c) CH3I, NaH, DMSO (14%); (d) -CD, water; (e) 7, BOP, HOBt, DIEA,
DMF (9%); (f) CH3I, NaH, DMSO (18%).
7
Preparation of polyrotaxane 8l.
To a solution of DMT-MM (601 mg, 2.17 mmol) and 5 (1.50 g, 2.17 mmol) in MeOH (11 mL) was added 4·CD3 (3.37 g, containing 109 mol of 4), and the reaction mixture was stirred at room temperature for 48 hours.
After removal of the solvent by filtration, the remaining solid was dialyzed (MWCO: 3,500) in water, and then
collected by centrifugation and lyophilization to give polyrotaxane 8l (150 mg) as a white solid in 6% yield.
Data of 8l. mp > 300 °C; 1H NMR H(400 MHz; D2O containing 1 wt% NaOD)/ppm4 7.38-6.72
(aromatic protons), 4.91-4.82 (6H, m, H1 of -CD), 3.91-3.30 (50.4H, m, H2-6 of -CD, and -CH2CH2Oof PEG), 1.38-0.95 (alkyl protons); IR (KBr) 3402, 2926, 1651, 1385, 1246, 1155, 1079, 1033 cm-1.
Preparation of water-soluble polyrotaxane 2l.
To a stirring solution of 8l (88 mg, 3.86 mol) and iodomethane (68 L, 1.10 mmol) in DMSO (8.5 mL) was
added 60% NaH in oil (5 mg × 3, 375 mol) three times at a two-hour interval at room temperature. The
reaction mixture was diluted with 1 N HCl aq. and then washed with ethyl acetate. The aqueous layer was
dialyzed (MWCO: 3,500) in water. After removal of a solid by filtration, the filtrate was concentrated and
lyophilized to give 2l (14 mg) as a white solid in 14% yield.
Data of 2l. mp > 300°C; 1H NMR H(400 MHz; D2O)/ppm4 7.39-6.71 (br. m), 5.23-4.84 (6H, br. m, H1 of
-CD), 4.06-2.88 (84.8H, br. m, H2-6 and O2,3,6CH3 of -CD, and -CH2CH2O- of PEG), 1.36-0.92 (alkyl
protons); IR (KBr) 3413, 2928, 1718, 1638, 1515, 1385, 1249, 1153, 1082, 1041 cm-1.
Preparation of polyrotaxane 8g.
To a solution of 7 (0.16 g, 0.54 mmol), BOP (0.24 g, 0.54 mmol), HOBt (73 mg, 0.54 mmol), and
diisopropylethylamine (70 mg, 0.54 mmol) in DMF (3 mL) was added 6·-CD (1.0 g, containing 27 mol of 6),
and the reaction mixture was stirred at room temperature for 48 hours. After removal of the solvent by filtration,
the remaining solid was dialyzed (MWCO: 3,500) in water, and then collected by centrifugation and
lyophilization to give polyrotaxane 8g (70 mg) as a white solid in 9% yield.
Data of 8g. mp > 300 °C; 1H NMR H(400 MHz; D2O containing 1 wt% NaOD)/ppm4 7.37-6.75
(aromatic protons), 4.98-4.79 (6H, m, H1 of -CD), 3.98-3.21 (46.4H, m, H2-6 of -CD, and -CH2CH2Oof PEG), 1.37-1.05 (alkyl protons); IR (KBr) 3398, 2933, 1657, 1381, 1238, 1155, 1078, 1031 cm-1.
8
Preparation of water-soluble polyrotaxane 2g.
To a stirring solution of 8g (53 mg, 1.8 mol) and iodomethane (43 L, 0.69 mmol) in DMSO (5.3 mL) was
added 60% NaH in oil (9 mg × 3, 0.23 mmol) three times at a two-hour interval at room temperature. The
reaction mixture was diluted with 1 N HCl aq. and then washed with ethyl acetate. The aqueous layer was
dialyzed (MWCO: 3,500) in water. After removal of a solid by filtration, the filtrate was concentrated and
lyophilized to give 2g (11 mg) as a white solid in 18% yield.
Data of 2g. mp > 300°C; 1H NMR H(400 MHz; D2O)/ppm4 7.41-6.77 (br. m), 5.43-4.89 (6H, br. m, H1
of -CD), 4.11-2.90 (79.7H, br. m, H2-6 and O2,3,6CH3 of -CD, and -CH2CH2O- of PEG), 1.37-0.93
(alkyl protons); IR (KBr) 3408, 2924, 1715, 1636, 1535, 1372, 1243, 1150, 1076, 1035 cm-1.
9
Supplementary Figures
Figure S1. 1H NMR spectra (400 MHz) of (a) 1l, (b) 1g, measured in CDCl3, (c) 8l, (d) 8g, measured in
1 wt% NaOD/D2O, and (e) 2l, (f) 2g, measured in D2O.
10
Figure S2. GPC profiles of (a) 1l, (b) 1g, (c) 2l and (d) 2g, eluted with DMSO containing 1wt% NaNO3
with a flow rate of 0.3 mL/min at 313 K, detected by RI.
Figure S3. Amounts of HPF (
bars for a flow rate of 15 L/min,
bars for a flow rate of 1
L/min), adsorbed on substrates I2ndb, II2ndb, and III, measured by SPR (n = 3).
11
References and note
(1) Anyaogu, K. C., Fedorov, A. V., and Neckers, D. C. Synthesis, characterization, and antifouling potential
of functionalized copper nanoparticles. Langmuir 24, 4340–4346 (2008).
(2) Stavenger, R. A., and Schreiber, S. L. Asymmetric catalysis in diversity-oriented organic synthesis:
enantioselective synthesis of 4320 encoded and spatially segregated dihydropyrancarboxamides. Angew.
Chem. Int. Ed. 40, 3417–3421 (2001).
(3) Yang, D. H., Katoono, R., Yamaguchi, J., Miura, Y., and Yui, N. Immobilization of polyrotaxane on a
solid substrate as the design of dynamic surface. Polym. J. 41, 952–953 (2009).
(4) Reference is set for H2O as 4.70 ppm in 1H NMR.
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