Electronic Supplementary Material

Electronic Supplementary Material PAMAM Dendrimers Bearing Electron-Donating Chromophores: Fluorescence and Electrochemical Properties Bing-BingWang a, Xin Zhang a, Ling Yang a, Xin-Ru Jia* a, Yan Ji a, Wu-Song Li a, Yen Wei* b a Department of Polymer Science & Engineering, College of Chemistry & Molecular Engineering, Peking University, Beijing 100871 China, Fax: 86-10-62751708; Tel: 86-10-62885490; E- mail: xrjia@pku.edu.cn b Department of Chemistry, Drexel University, Philadelphia, PA 19104 USA Tel. 215-895- 2650; Fax 215-895-1265; E-mail: weiyen@drexel.edu PAMAM-P G1. 10 ml of benzaldehyde (0.037 g, 3.08 mmol) was added to a methanol solution (50 ml) of the first generation PAMAM dendrimer G1 (0.50 g, 0.35 mmol) in the presence of anhydrous sodium sulfate (2.0g). After the reaction at 60 for 12 h under stirring, the system was cooled to room temperature and the solvent was removed under a reduced pressure. The residue was dissolved again in chloroform (5 ml). The solvent and excess benzaldehyde were removed under reduced pressure. The resulting yellow semi-solid crude product was purified by repeated dissolution in methanol (5 ml) and precipitation in anhydrous diethyl ether (100 ml) with vigorously stirring. The precipitate was collected and further purified by dialysis using a dialysis membrane (M W =1000) to afford final product (0.1g). Yield: 39%. FT-IR: (KBr pellet, cm -1 ) 3278, 3061, 2936, 2841, 1645, 1552, 1450, 1378, 1254, 757, 720, 695. 1 H-NMR (CDCl 3, TMS, ppm): δ7.36-7.66 (40H, aromatic ring), 8.25 (8H, s, 8-CH=N-), 3.67 (16H, 8-CH 2 -CH 2 -N=CH-), 3.50 (16H, 8-NH-CH 2 -CH 2 -N=C-), 3.18 (8H, 4-NH-CH 2 -CH 2 -N(-CH 2 -)-CH 2 -), 2.65 (22H, 11-CH 2 -N(- CH 2 -)-CH 2 -CH 2 -), 2.46(12H, 6-CH 2 -N(-CH 2 -)-CH 2 -), 2.25 (24H, 12-CH 2 -CO-). 13 C-NMR (CDCl 3, ppm): 172.49, 162.91, 135.69, 130.83, 128.56, 128.07, 60.24, 50.13, 40.13, and 33.95. MALDI- S1

TOF MS (matrix: dithranol/silver trifluoroacetate =1:1/w:w): Calcd for C 118 H 160 N 26 O 12 [M]: 2132, found: 2133 (M+H + ), 2155 (M+Na + ). PAMAM-P G2 to G5 were synthesized in a same manner as PAMAM-Ph G1. PAMAM-P G2: 1 H-NMR (CDCl 3, TMS, ppm): δ 7.71, 7.97 (90H, 16aromatic ring), 8.27 (16H, s, 16-CH=N-), 3.59 (32H, 16-CH 2 -CH 2 -N=CH-), 3.36 (32H, 16-NH-CH 2 -CH 2 -N=CH-), 3.06 (24H, 12-NHCH 2 -CH 2 -N(-CH 2 -)-CH 2 -), 2.60 (56H, 28-CH 2 -N(-CH 2 -)-CH 2 -CH 2 -), 2.39 (24H, 12-CH 2 - N(-CH 2 -)-CH 2 -), 2.16 (56H, 28-CH 2 -CO-). FT-IR: (KBr pellet, cm -1 ): 1695 (C=N), 1640, 1553 (- NH-CO-), 1451, 756, 696 (phenyl ring). PAMAM-P G3: 1 H-NMR (CDCl 3, TMS, ppm): δ 7.31, 7.68 (160H, 32aromatic ring), 8.25 (32H, 32-CH=N-), 3.66 (64H, 32-CH 2 -CH 2 -N=CH-), 3.46 (64H, 32-NH-CH 2 -CH 2 -N=CH-), 3.10 (54H, 27-NHCH 2 -CH 2 -N(-CH 2 -)-CH 2 -), 2.64 (124H, 62-CH 2 -N(-CH 2 -)-CH 2 -CH 2 -), 2.32 (54H, 27-CH 2 - N(-CH 2 -)-CH 2 -), 2.24 (122H, 61-CH 2 -CO-). FT-IR: (KBr pellet, cm -1 ): 1695 (C=N), 1645, 1556 (- NH-CO-), 1456,756, 695 (phenyl ring). PAMAM-P G4: 1 H-NMR (CDCl 3, TMS, ppm): δ 7.36, 7.66 (320H, 64aromatic ring), 8.25 (64H, s, 64-CH=N-), 3.67 (126H, 63-CH 2 -CH 2 -N=CH-), 3.50 (130H, 65-NH-CH 2 -CH 2 -N=CH-), 3.18 (122H, 61-NH-CH 2 -CH 2 -N(-CH 2 -)-CH 2 -), 2.65 (252H, 126-CH 2 -N(-CH 2 -)-CH 2 -CH 2 -), 2.46(118H, 59-CH 2 -N(-CH 2 -)-CH 2 -), 2.25 (246H, 123-CH 2 -CO-). FT-IR: (KBr pellet, cm -1 ): 1688 (C=N), 1649,1558 (-NH-CO-), 1456, 779, 691 (phenyl ring). PAMAM-P G5: 1 H-NMR (CDCl 3, TMS, ppm): δ 7.36-7.66 (640H, 128aromatic ring), 8.25 (128H,s, 128-CH=N-), 3.67 (252H, 126-CH 2 -CH 2 -N=CH-), 3.50 (252H, 126-NH-CH 2 -CH 2 -N=CH- ), 3.18 (244H, 122-NH-CH 2 -CH 2 -N(-CH 2 -)-CH 2 -), 2.65 (502H, 251-CH 2 -N(-CH 2 -)-CH 2 -CH 2 -), 2.46(250H,125-CH 2 -N(-CH 2 -)-CH 2 -), 2.25 (508H, 259-CH 2 -CO-). FT-IR: (KBr pellet, cm -1 ) 3278, 3061, 2936, 2841, 1645, 1552, 1450, 1378, 1254, 757, 720, 695. PAMAM-PA G1: 1 H-NMR(CDCl 3, TMS, ppm): δ 6.65-6.69 (16H, 8aromatic ring), 7.54 (16H, 8aromatic ring), 8.11 (8H, s, 8-CH=N-), 3.62 (16H, 8-CH 2 -CH 2 -N=CH-), 3.51 (16H, 8-NH-CH 2 - CH 2 -N=C-), 3.23 (8H, 4-CO-NH-CH 2 -CH2-N(-CH 2 -)-CH 2 -), 3.00 (48H, 8-N-(CH 3 ) 2 ), 2.80 (8H, 4 -CH 2 -N(-CH 2 -)-CH 2 -), 2.64 (24H, 12-CH 2 -N(-CH 2 -)-CH 2 -CH 2 -), 2.45 (4H, -CH 2 -(-CH 2 -)-N-CH 2 - S2

CH 2 -N(-CH 2 -)-CH 2 -), 2.28 (24H, 12-CH 2 -CO-). FT-IR: (KBr pellet, cm -1 ): 3289; 3075; 2924; 2851; 1645; 1608; 1556; 1524; 1446; 1359; 1228; 1182; 1166. PAMAM-PA G2: 1 H-NMR(CDCl 3, TMS, ppm): δ 6.66-6.69 (32H, 16aromatic ring), 7.58 (32H, 16aromatic ring), 8.115 (16H, s, 16-CH=N-), 3.62 (32H, 16-CH 2 -CH 2 -N=CH-), 3.51 (32H, 16-NH- CH 2 -CH 2 -N=C-), 3.23 (24H, 12-CO-NH-CH 2 -CH2-N(-CH 2 -)-CH 2 -), 3.00 (96H, 16-N-(CH 3 ) 2 ), 2.80 (24H, 12 -CH 2 -N(-CH 2 -)-CH 2 -), 2.64 (56H, 28-CH 2 -N(-CH 2 -)-CH 2 -CH 2 -), 2.45 (4H, -CH 2 -(-CH 2 - )-N-CH 2 -CH 2 -N(-CH 2 -)-CH 2 -), 2.28 (56H, 28-CH 2 -CO-). FT-IR (KBr pellet, cm -1 ): 3287; 3072; 2925; 2852; 1649; 1614; 1552; 1523; 1446; 1353; 1226; 1182; 1165. PAMAM-PA G3: 1 H-NMR(CDCl 3, TMS, ppm): δ 6.65-6.69 (64H, 32aromatic ring), 7.54-7.58 (64H, 32aromatic ring), 8.12 (32H, s, 32-CH=N-), 3.63 (64H, 32-CH 2 -CH 2 -N=CH-), 3.50 (64H, 32- NH-CH 2 -CH 2 -N=C-), 3.26 (56H, 28-CO-NH-CH 2 -CH2-N(-CH 2 -)-CH 2 -), 3.00 (192H, 32-N- (CH 3 ) 2 ), 2.81 (56H, 28 -CH 2 -N(-CH 2 -)-CH 2 -), 2.66 (120H, 60-CH 2 -N(-CH 2 -)-CH 2 -CH 2 -), 2.45 (4H, -CH 2 -(-CH 2 -)-N-CH 2 -CH 2 -N(-CH 2 -)-CH 2 -), 2.28 (120H, 60-CH 2 -CO-). FT-IR (KBr pellet, cm - 1 ): 3287; 3072; 2925; 2852; 1649; 1614; 1552; 1523; 1446; 1353; 1226; 1182; 1165. PAMAM-PA G4: 1 H-NMR(CDCl 3, TMS, ppm): δ 6.65 (128H, 64aromatic ring), 7.55 (128H, 64aromatic ring), 8.11 (64H, s, 64-CH=N-), 3.63 (128H, 64-CH 2 -CH 2 -N=CH-), 3.50 (128H, 64- NH-CH 2 -CH 2 -N=C-), 3.23 (120H, 60-CO-NH-CH 2 -CH2-N(-CH 2 -)-CH 2 -), 3.00 (384H, 64-N- (CH 3 ) 2 ), 2.81 (120H, 60 -CH 2 -N(-CH 2 -)-CH 2 -), 2.66 (248H, 124-CH 2 -N(-CH 2 -)-CH 2 -CH 2 -), 2.45 (4H, -CH 2 -(-CH 2 -)-N-CH 2 -CH 2 -N(-CH 2 -)-CH 2 -), 2.28 (248H, 124-CH 2 -CO-). FT-IR (KBr pellet, cm -1 ): 3287; 3072; 2925; 2852; 1649; 1614; 1552; 1523; 1446; 1353; 1226; 1182; 1165. PAMAM-PA G5: 1 H-NMR(CDCl 3, TMS, ppm): δ 6.61-6.65 (256H, 128aromatic ring), 7.51-7.55 (256H, 128aromatic ring), 8.10 (128H, s, 128-CH=N-), 3.61 (256H, 128-CH 2 -CH 2 -N=CH-), 3.48 (256H, 128-NH-CH 2 -CH 2 -N=C-), 3.21 (248H, 124-CO-NH-CH 2 -CH2-N(-CH 2 -)-CH 2 -), 3.00 (768H, 128-N-(CH 3 ) 2 ), 2.81 (248H, 124 -CH 2 -N(-CH 2 -)-CH 2 -), 2.66 (504H, 252-CH 2 -N(-CH 2 -)-CH 2 -CH 2 - ), 2.45(4H, -CH 2 -(-CH 2 -)-N-CH 2 -CH 2 -N(-CH 2 -)-CH 2 -), 2.28 (504H, 252-CH 2 -CO-). FT-IR (KBr S3

pellet, cm -1 ): 3287; 3072; 2925; 2852; 1649; 1614; 1552; 1523; 1446; 1353; 1226; 1182; 1165. PAMAM-Cz G0: 1 H-NMR(CDCl 3, TMS, ppm): δ 7.17-7.48 (64H, 8carbazole), 4.23 (16H, 8-CH 2 - CH 2 -CH 2 -N-), 3.37-3.40 (8H, 4-CO-NH-CH 2 -), 3.10 (8H, 4 -N(-CH 2 -)-CH 2 -), 2.78 (8H, 4-CH 2 -N(- CH 2 -)- CH 2 -), 2.56 (8H, 4-CH 2 -CO-), 2.43 (16H, 8-CH 2 -CH 2 -CH 2 -N-), 1.87 (16H, 8-CH 2 -CH 2 - CH 2 -N-). FT-IR: (KBr pellet, cm -1 ): 3361; 3259; 3051; 2924; 2852; 1658; 1597; 1548; 1463; 1454; 1348; 1327; 1234; 1216. PAMAM-Cz G1: 1 H-NMR(CDCl 3, TMS, ppm): δ 7.17-7.49 (128H, 16carbazole), 4.12-4.20 (32H, 16-CH 2 -CH 2 -CH 2 -N-), 3.37-3.41 (24H, 12-CO-NH-CH 2 -), 3.10 (24H, 12 -N(-CH 2 -)-CH 2 -), 2.77 (32H, 12-CH 2 -N(-CH 2 -)- CH 2 -), 2.52 (24H, 12-CH 2 -CO-), 2.42-2.44 (32H, 16-CH 2 -CH 2 -CH 2 -N-), 1.82 (32H, 16-CH 2 -CH 2 - CH 2 -N-). FT-IR: (KBr pellet, cm -1 ): 3361; 3258; 3049; 2929; 2853; 1661; 1596; 1548; 1484; 1454; 1348; 1327; 1233; 1218. PAMAM-Cz G2: 1 H-NMR(CDCl 3, TMS, ppm): δ 7.16-7.48 (256H, 32carbazole), 4.11 (64H, 32- CH 2 -CH 2 -CH 2 -N-), 3.37-3.40 (56H, 28-CO-NH-CH 2 -), 3.10 (56H, 28-N(-CH 2 -)-CH 2 -), 2.78 (56H, 28-CH 2 -N(-CH 2 -)- CH 2 -), 2.42-2.44 (56H, 28-CH 2 - CO-), 2.23-2.26 (64H, 32-CH 2 -CH 2 -CH 2 -N-), 1.83 (64H, 32-CH 2 -CH 2 -CH 2 -N-). FT-IR: (KBr pellet, cm -1 ): 3402; 3249; 3049; 2937; 2853; 1660; 1596; 1548; 1484; 1454; 1348; 1327; 1234; 1216. PAMAM-Cz G3: 1 H-NMR(CDCl 3, TMS, ppm): δ 7.12-7.44 (512H, 64carbazole), 4.14 (128H, 64- CH 2 -CH 2 -CH 2 -N-), 3.37-3.40 (120H, 60-CO-NH-CH 2 -), 3.12 (120H, 60 -N(-CH 2 -)-CH 2 -), 2.78 (120H, 60-CH 2 -N(-CH 2 -)-CH 2 -), 2.57 (120H, 60-CH 2 - CO-), 2.40-2.47 (128H, 64-CH 2 -CH 2 -CH 2 - N-), 1.81 (128H, 64-CH 2 -CH 2 -CH 2 -N-). FT-IR: (KBr pellet, cm -1 ): 3398; 3262; 3050; 2927; 2853; 1661; 1597; 1548; 1484; 1454; 1348; 1327; 1233; 1216. PAMAM-Cz G4: 1 H-NMR(CDCl 3, TMS, ppm): δ 7.17-7.48 (1024H, 128carbazole), 4.23 (256H, 128-CH 2 -CH 2 -CH 2 -N-), 3.37-3.40 (248H, 124-CO-NH-CH 2 -), 3.10 (248H, 124-N(-CH 2 -)-CH 2 -), 2.78 (248H, 124-CH 2 -N(-CH 2 -)- CH 2 -), 2.56 (248H, 124-CH 2 -CO-), 2.43 (256H, 128-CH 2 -CH 2 - CH 2 -N-), 1.87 (256H, 128-CH 2 -CH 2 - CH 2 -N-). FT-IR: (KBr pellet, cm -1 ): 3390; 3250; 3050; 2931; S4

2852; 1662; 1596; 1548; 1484; 1454; 1348; 1327; 1234; 1216. PAMAM-Py G1. A methanol solution (25 ml) of PAMAM G1 (0.0136 g, 0.00952 mmol) was added dropwise to an acetone solution (30 ml) of N-(1-pyrenyl)maleimide (0.050 g, 0.168 mmol) at 0 C. The resultant solution was kept at 30 C with stirring for 48 h. After evaporating the solvent under a reduced pressure, the residue was dissolved in methanol (5 ml), which was then dropped into anhydrous diethyl ether (100 ml) with stirring. A white precipitation was collected by suction filtration, then dissolved again in methanol (10 ml) and dialyzed with a dialysis bag (M W =3500) using methanol as a solvent at room temperature for 24 h. After evaporating methanol under a reduced pressure and drying in a vacuum oven at 40 C for 24 h, a pale yellow powder (0.0070 g) was obtained. Yield: 30%. FT-IR (KBr pellet, cm-1): 3021, 3116, 2925, 1641, 1504, 1411, 1326, 781, 735. 1 H NMR: (CDCl 3, ppm) δ 7.597-8.235 (72H, aromatic ring), 3.700 (8H, 8-CH 2 -CH (-CO- )-NH-), 2.873 (16H, 8-NH-CH 2 -CH 2 -N(-CH 2 -)-CH 2 -), 3.483 (16H, 8-CH 2 -CH 2 -NH-CH(-CO-)- CH 2 -), 3.323 (8H, 4-NH-CH 2 -CH 2 -NH-CH- ), 2.654 (32H,16-CH 2 -N(-CH 2 -)-CH 2 -CH 2 -), 2.366 (24H, 12- CH 2 -CO-). MALDI-TOF MS (matrix: 2, 5-dihydroxybenzoic acid) Calcd for C 223 H 220 N 34 O 28 [M]: 3821.7. Found: 3846 (M + Na) +. PAMAM-Py G0: 1 H-NMR: (CDCl 3, ppm) δ 7.954 (36H, 4aromatic ring), 3.678(4H, 4-CH 2 -CH(- CO-)-NH-), 2.695(8H, 4-CH 2 -N(-CH 2 -)-CH 2 -CH 2 -), 3.230 (8H, 4-CH 2 -CH 2 -NH-CH(-CO-)-CH 2 -), 2.862 (8H, 4-NHCH 2 -CH 2 -NH-CH-), 2.234 (8H, 4-CH 2 -CO-). FT-IR (KBr pellet, cm -1 ): 3016, 3220, 2924, 1642, 1519,1403, 1325, 778, 742. MALDI-TOF MS (matrix: DI): Calcd for C102H92N14O12 [M]: 1704.7, found:[m+h + ] 1706. PAMAM-Py G2: 1 H-NMR: (CDCl 3, ppm) δ 7.999 (288H,16aromatic ring), 3.492(16H, 16-CH 2 - CH-(-CO-)-NH-), 2.657(32H, 16-CH 2 -NH-CH 2 -CH 2 ), 3.219 (56H,284-CH 2 -CH 2 -NH-CH(-CO-)- CH 2 -), 2.450 (56H,28-NHCH 2 -CH 2 -NH-CH-), 2.218 (56H, 28-CH 2 -CO-). FT- IR (KBr pellet, cm - 1 ): 3047, 3135,2975, 1644, 1551, 1443, 1327, 782, 711. PAMAM-Py G3: 1 H-NMR: (CDCl 3, ppm) δ 7.963 (576H,32aromatic ring), 3.665(32H, 32-CH 2 - CH-(-CO-)-NH-), 2.780(64H, 32-CH 2 -NH-CH 2 -CH 2 ), 3.484 (58H, 58-CH 2 -CH-(-CO-)-NH-), 2.591(118H, 59-NHCH 2 -CH 2 -NH-CH-), 2.312(122H, 61-CH 2 -CO-). FT- IR (KBr pellet, cm - S5

1 ):3028, 3114, 2925, 1643, 1567, 1416, 1326, 776. PAMAM-Py G4: 1 H-NMR: (CDCl 3, ppm) δ 7.997 (1152H,64aromatic ring), 3.701(64H, 64-CH 2 - CH(-CO-)-NH-), 2.873(128H, 64-CH 2 -NH-CH 2 -CH 2 ), 3.483 (126H, 126-CH 2 -CH-(-CO-)-NH-), 2.592(242H, 121-NHCH 2 -CH 2 -NH-CH-), 2.366(246H, 123-CH 2 -CO-). FT- IR (KBr pellet, cm - 1 ):3030, 3109, 2925, 2853, 1642, 1541, 1409, 1324, 778. PAMAM-Py G5: 1 H-NMR:(CDCl 3, ppm) δ 7.597-8.235 (1152H, 128aromatic ring), 3.700 (128H,128-CH 2 -CH-(-CO-)-NH-), 2.873 (252H, 126-CH 2 -NH-CH 2 -CH 2 ), 3.483 (258H, 258-CH 2 - CH-(-CO-)-NH-), 3.323 (258H, 258-CH 2 -CH-(-CO-)-NH-), 2.654(764H, 387-NHCH 2 -CH 2 -NH- CH-), 2.366 (758H, 379-CH 2 CO-). FT-IR (KBr pellet, cm -1 ): 3021, 3116, 2925, 1641, 1504, 1411,1326, 781, 735. 9-(3-bromopropyl)-9H-carbazole: 9-(3-bromopropyl)-9H-carbazole was synthesized as shown in Scheme S-1. Hydride sodium (0.53 g, 0.02mol) was added slowly into a tetrahydrofuran solution (50 ml) of carbazole (3.34 g, 0.02 mol) in a 100 ml flask. The reaction mixture was added 1,3- dibromopropane (40.4 g, 0.20 mole) when there was no more hydrogen bubbling out. The mixture was stirred for 12 h at room temperature. Then the crude product was obtained after filtrating the solvent followed by purification by chromatography over silica using a mixed petroleum ether/dichloromethane (20:1/v:v) solvent as eluent. Yield: 52%. 1 H-NMR(CDCl3, TMS, ppm): δ 8.1 (d,2h), 7.6-7.2 (m,6h),4.5 (t,2h),3.38 (t,2h),2.43 (m,2h). Scheme S-1. Synthesis of N-(ω-bromopropyl)-carbazole NaH, THF NH Br Br room temperature N Br S6

Relative Intensity 20 80 min 70 min 60 min 50 min 40 min 10 30 min 20 min 10 min 0 360 450 540 Wavelength /nm Figure S-1. Changes in the fluorescence intensity during the reaction of PAMAM G 4 with 4- dimethylaminobenzaldehyde in methanol. [chromophore] = 5x10-6 M S7

Figure S-2. 1 H-NMR spectra during the reaction of PAMAM G 4 with p-dimethylaminobenzaldehyde. Reaction time for each spectrum (min): 2, 17, 62 (from bottom to top). S8

100 Conversion (%) 75 50 25 1000 500 0 Relative Fluorescence Intensity 0 20 40 60 80 Reaction time /min Figure S-3. Reaction of PAMAM G 4 with p-dimethylaminobenzaldehyde monitored by following the changes in fluorescence intensity and by 1 H-NMR spectroscopy. S9

1000 Relative Intensity 800 600 400 50 60 70 80 90 100 Conversion(%) Figure S-4. Correlation plot of fluorescence intensity versus reaction extent of PAMAM G 4 with p-dimethylaminobenzaldehyde 70 0.8 60 Absorbance 0.6 0.4 0.2 50 40 30 20 Relative Intensity 10 0.0 0 200 250 300 350 400 450 500 550 Wavelength /nm Figure S-5. UV-vis absorption and fluorescence spectra of PAMAM-PA G 5 in methanol. [PA]=1x10-5 M, λ ex =340 nm. S10

14 Fluorescence Quantum Yields 12 10 8 6 4 2 0 G1 G2 G3 G4 G5 Figure S-6. Fluorescence quantum yields (Φ f ) of PAMAM-PA G 1-5 in methanol (MeOH) ( ), acetonitrile (AN) ( ), N, N-dimethyforamine (DMF) ( ) and dichloromethane (DCM) ( ). Figure S-7. Cyclic voltammograms of PAMAM-PA G 1-5 in acetonitrile solution at scanning rate S11

50mVs -1 (25 ) [PA]=10-2 M 40 Relative Intensity 30 20 10 88 % 82 % 78 % 42 % 0 300 350 400 450 500 550 600 Wavelength/ nm Figure S-8. Fluorescence spectra of PAMAM-PA G 2 with different modification extents from bottom to top: 42 %, 78 %, 82 %, 88 % in methanol. [chromophore] = 5x10-6 M. λ ex = 340 nm. S12

20 Relative Intensity 10 88 % 83 % 65 % 55 % 0 300 350 400 450 500 550 600 Wavelength /nm Figure S-9. Fluorescence spectra of PAMAM-PA G 4 with different modification extents from bottom to top: 55 %, 75 %, 83 %, 88 % in methanol. [chromophore] = 5x10-6 M. λ ex = 340 nm S13

Table S - 1. Fluorescence quantum yields (Φ f ) of PAMAM-PA G1-5 in methanol (MeOH), acetonitrile (AN), dichloromethane (DCM) and N, N-dimethyforamine (DMF). η(meoh)=1.3286 MeOH G1 G2 G3 G4 G5 I 3710.700 3830.900 3488.100 3265.500 4131.500 A 0.7875 0.7944 0.8033 0.8517 0.8265 Φ f (%) 1.17 1.20 1.08 0.95 1.24 η(an)=1.3441 AN G1 G2 G3 G4 G5 I 110.5 104.5 108.6 81.36 91.51 A 0.7308 0.7290 0.7103 0.7467 0.7388 Φ f (%) 2.78 2.64 2.81 2.01 2.28 η(dcm)=1.4246 DCM G1 G2 G3 G4 G5 I 6827.3 5923.1 7203.7 8213.0 8183.6 A 0.1820 0.1391 0.1910 0.2187 0.1991 Φ f (%) 10.15 11.39 10.28 10.26 11.07 η(dmf)=1.4269 DMF G1 G2 G3 G4 G5 I 2002.3 1893.5 2278.4 2893.9 3316.8 A 0.0992 0.1010 0.1144 0.1661 0.1681 Φ f (%) 6.70 6.37 6.86 6.23 6.59 S14

Table S-2. Stokes shifts of PAMAM-PA G1 in dichloromethane (DCM), N, N-dimethyforamine (DMF), acetonitrile (AN), methanol (MeOH). Solvent f Con (mol/l) λ ab (nm) ν a (10 4 cm -1 ) λ em (nm) ν f (10 4 cm -1 ) λ=λ em - λ ab (nm) ν a -ν f (10 4 cm -1 ) DCM 0.2184 3.0 10 5 335 2.985 383.8 2.606 48.8 0.379 DMF 0.2751 3.0 10 5 335 2.985 382.4 2.615 47.4 0.370 AN 0.3054 3.0 10 5 335 2.985 386 2.589 51.0 0.396 MeOH 0.3390 3.0 10 5 335 2.985 390.8 2.559 55.8 0.426 Table S-3. Fluorescence quantum yields (Φ f ) of Carbazole and PAMAM-Cz G 0 to G 4 in dichloromethane. Carbazole G0 G1 G2 G3 G4 I 7393.8 2567.2 2433.6 2816.4 5695.2 4484.3 A 0.0828 0.0649 0.0605 0.0719 0.1273 0.1068 Φ f (%) 25.49 11.29 11.48 11.18 12.77 11.98 S15