Supporting Information
Self-Assembly of A New Class of Amphiphilic PAMAM Dendrimers And Their
Electrochemical Properties
Bing-Bing Wang, Xin Zhang, Xin-Ru Jia*, Zi-Chen Li, Yan Ji
Department of Polymer Science & Engineering, College of Chemistry & Molecular Engineering
Peking University, Beijing 100871, China
Yen Wei*
Department of Chemistry, Drexel University, Philadelphia, PA 19104, USA
Measurements. UV-vis spectra were acquired on a UV-Visible scanning spectrophotometer
(Schimaduza UV-2101 PC) at room temperature. 1H-NMR spectra were obtained on Varian Mercury
300 Hz NMR spectra using chloroform-d as solvent and tetrametylsilane as an internal standard.
Elementary analyses were performed on a Carlo ERBA elementary analyzer. FT-IR spectra were taken
on a Nicolet Magna IR-750 spectrometer in a KBr pellet form. The fluorescence emission
measurements were carried out at room temperature in water using a Hitachi F-4500 fluorescence
spectrophotometer. The slit width of both monochromators was 5.0nm. Matrix-assisted laser
desorption/ ionization time-of-flight (MALDI-TOF) mass spectra were recorded on a BIFLE XIII
time-of-flight MALDI mass spectrometer. Ditranol (DI) and 2, 5-dihydroxybenzoic acid (DHB) were
chosen as the matrixes, which can give the best resolution. The analytic sample was prepared by
mixing the solution (1 L, 1 mg/mL) of dendrimer and the matrix solution (1 L, 10 mg/mL) on a
stainedless steel probe tip, followed by drying at room temperature prior to measurement.
Synthesis and Characterizations
S1
PAMAM Dendrimers Modified with 5-dimethyamino-naphthalene-1-sulfonyl-chloride (DNS)
Groups
PAMAM-DNS G1: A methanol solution (20 ml) of PAMAM G1 (0.1000 g, 0.007 mmol) was added
dropwise to the aqueous solution of 5-dimethyamino-naphthalene-1-sulfonyl-chloride (DNS) (0.1510 g,
0.5603 mmol) at room temperature for 40 min. The pH value of the reaction solution was controlled
between 10 and 12 by a proper addition of NaOH (20%) solution. Then the solution was heated to 35 0C
with stirring for 1 h. After evaporated the solvent under 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, which was then dissolved in methanol and dialyzed by
a dialysis bag (MW 5,000) using methanol as a solvent at room temperature for 24 h. After evaporating
solvent under reduced pressure, a pale yellow powder was obtained, and then dried in a vacuum at
400C for 24 h.
1
H NMR: (CDCl3,) δ=6.984-8.528 (48H, aromatic rings), δ=2.763, (56H,
-CH2-N(-CH2-)-CH2-CH2-),δ=3.481 (24H, 12-CH2-NH-SO2-),δ=3.185 (48H, 8-N(CH3)2), δ=2.534,
(28H, -CH2-CO-). FT-IR (KBr): 3078, 3480, 3360, 2849, 1647, 1542, 1456, 1318, 1324, 790.
MALDI-TOF MS (matrix: 2,5-dihydroxybenzoic acid): Calcd for C159H220N34O28S8 [M]: 3302.4, found:
3302 (M) +.
PAMAM-DNS G0, G2-5 were synthesized in a same manner as PAMAM-DNS G1.
PAMAM-DNS G0: 1H NMR: (CDCl3) δ=6.984-8.528 (24H, 4aromatic ring), δ=2.763 (24H, 4- N
(CH3)2), δ=3.481, (8H, 4-CH2-NH-SO2-), δ=3.185 (8H, 4-CH2-N(-CH2-)-CH2), δ=2.534 (8H,4-CH2CO-). FT-IR (KBr): 3052, 3358, 2850, 1642, 1555, 1461, 1320, 1143, 787.
PAMAM-DNS G2: 1H NMR: (CDCl3) δ=7.0891-δ8.512 (96H, 16aromatic ring), δ=2.794 (96H,
16N(CH3)2), δ=3.348 (56H, 28-CH2-NH-SO2-), δ=3.088 (56H, 28-N(-CH2-)-CH2), δ=2.127 (56H,
28-CH2- CO-). FT-IR (KBr): 3086, 3359, 2926, 1639, 1571, 1411, 1324, 1102, 781.
S2
PAMAM-DNS G3: 1H NMR: (CDCl3) δ=6.966-δ8.551 (192H, 32aromatic ring), δ=2.792 (192H,
32N(CH3)2, δ=3.167 (118H, 59-CH2-NH-SO2-), δ=3.047 (116H, 58N(-CH2-)-CH2), δ=2.184 (122H, 61CH2-CO-). FT-IR: (KBr): 3059, 3452, 2990, 2880, 1643, 1536, 1407, 1327, 1121, 778.
PAMAM-DNS G4: 1H NMR: (CDCl3) δ=6.954-δ8.440 (384H, 64aromatic ring), δ=2.765 (384H,
64N(CH3)2, δ=3.495 (242H, 121-CH2-NH-SO2-), δ=3.216 (252H, 126N(-CH2-)-CH2), δ=2.190 (246H,
123- CH2-CO-). FT-IR (KBr): 3075, 3417, 3373, 2926, 2853, 1644, 1540, 1460, 1323, 781.
PAMAM-DNS G5: 1H NMR: (CDCl3) δ=6.984-8.528 (768H, 128aromatic ring), δ=2.763 (768H,
128-N(CH3)2,δ=3.481
(764H,
382-CH2-NH-SO2-),
δ=3.185
(768H,
382-CH2-N(-CH2-)-CH2),
δ=2.534(758H, 379-CH2-CO-). FT-IR (KBr): 3078, 3480, 3360, 2849, 1647, 1542, 1456, 1318, 1324,
790.
S3
Scheme S-1. Representative synthetic routes for PAMAM-DNS G2 and PAMAM-NPD G2
H2N
NH2
O
NH
O
NH
H2N
H2N
NH
O
NH
N
O
N
NH2
NH
H2N
O
O NH
NH
O
N
N
NH
N
NH
O
O
O
O
HN
HN
N
O
N
O
HN
O
HN
O
HN
2
N
HN
O
N
H
N
H
O
N
O
HN
NH2
N
N
H
N
O
HN
NH
NH
O
H2N
NH
N
N
H
O
O
HN
H2N
O
O
NH2
H2N
N
N
O
O
NH
HN
HN
H2N
H2N
HN
O
O
NH2
H2N
PAMAM G2
(¢¡)
(¢¢)
N
N
N
N
N
N
N
N
O
NH
N
NH
O
HN
SO2
NH
N
O
HN
N
H
O
N
HN
HN
HN
O
N
S
O2
N
N
SO2
HN
O
O
SO2
O
N N
N
HN
O
O
NH
HN
NH
N
HN
N
O
O
O
N
HN
O
N
N
N
HN
O
O
O2S
O
O
NH
HN
O
N
N
HN
O2S
O
HN
O
N
O2S
N
HN
O2S
N
O
N
N
NH
HN
HN
O
O
N
HN
HN
O
NH
HN
N
HN
O
N N
H
N
N
H
O
N
HN
O
O
O
HN
N
O
HN
N
NH
O
O
O
H
N
N
O
HN
O
O
N
N
NH
O
O
N
N
H
N
HN
H
N
N
N
NH
NH
NH
O
N
O
O
O
O
H
N
HN
HN
N
NH
O
N
HN
O
N
HN
NH
N
O
N
N
O
NH
O
O
N
O
HN
O
N
HN
O
O
N
HN
O
H
N
O
N
O
O NH
NH
O
N N
N
N
HN
HN
N
H
N
O
O
NH
O
O2
S
O
NH
NH
O
N
H
NH
N
N
H
N
N
H
O
O
O
N
O
O
N
NH
N
O2
S
N
O
O NH
N
O
NH
N
NH
NH
NH
N
N N
O
O
N
O
HN
N
O2S
HN
N
HN
O
NH
NH
NH
O
SO2
H
N
O
N
HN
O
O
N
O
NH
HN
HN
O
O
N
N
HN
SO2
O
N
O
O2S
SHO2
HN
SO2
N
O
N
N
N
N
N
N
O
O
N
N
N
N
N
N
PAMAM-NPD G2
PAMAM-DNS G2
Reagents and Conditions: (¢¡ ) 5-dimethyamino-naphthalene-1-sulfonyl-chloride, NaOH (20%), CH3OH, room temperature,
24 h; (¢¢) N- (1-(naphthalenyl)-2-phenyldiazene )maleimine, CH3OH, room temperature, 24 h
S4
Scheme S-2. Synthetic route toward N- (1-(naphthalenyl)-2-phenyldiazene )maleimide
1
O
NH2
ethylether
N
N
+
O
O
O
1h
2
3
NaAcO, (AcO)2O, 800C
N
30min
10
9
N
O
4
N
7
8
6
5
.
PAMAM Dendrimers Modified with N-1-(naphthalenyl)-2-phenyldiazene Groups
PAMAM-NPD G1: 1H NMR: (CDCl3): δ=8.952-7.548 (88H, aromatic rings), δ=3.742 (8H, -CH2-CH
-CO-NH-),
δ=3.411
(16H,
8-CH2-CH2-NH-CH-CO-CH2-),
δ=3.238
(8H,
4-NH-CH2-CH2-NH-CH-),δ=2.629 (32H, 16-CH2-N(-CH2-)-CH2-CH2-),δ=2.207 (24H, 12-CH2-CO-).
FT-IR (KBr): 3314, 1719, 1644, 1540, 1400, 1179, 1110, 757, 692.
PAMAM-NPD G2: 1H NMR: (CDCl3): δ=8.960-7.555 (176H, aromatic rings), δ=3.673 (16H,
16-CH2-CH-CO-NH-),
δ=3.304
(56H,
28-NH-CH2-CH2-NH-CH-),
δ=2.900
(32H,
16-CH2-NH-CH-CH2), δ=2.647 (56H, 28-CH2-CH2-NH-CH-CO-CH2-), δ=2.246 (56H, 28-CH2-CO-).
FT- IR (KBr):
3047, 3135, 2975, 1644, 1551, 1443, 1327, 782, 701.
PAMAM-NPD G3:
1
H NMR: (CDCl3) δ=8.957-7.553 (352H, aromatic ring), δ=3.671 (32H,
32-CH2-CH-CO-NH-),
δ=3.265
32-CH2-NH-CH-CH2),
δ=2.619
(116H,
(118H,
58-NH-CH2-CH2-NH-CH),
59-CH2-CH2-NH-CH-CO-CH2-),
δ=2.915
(64H,
δ=2.243(122H,
61-CH2-CO-). FT- IR (KBr): 3026, 1700, 1648, 1563, 1415, 1320, 765.
PAMAM-NPD G4: 1H NMR: (CDCl3) δ=8.964-7.551 (704, aromatic ring), δ=3.701 (64H, 64-CH2-CH
-CO-NH-), δ=3.250 (252H, 126-NH-CH2-CH2-NH-CH), δ=2.934 (128H, 64-CH2-NH-CH-CH2),
S5
δ=2.653 (242H, 121-CH2-CH2-NH-CH-CO-CH2-), δ=2.265(246H, 123-CH2-CO-). FT- IR (KBr):
3030, 1714, 1643, 1540, 1408, 1324, 777, 691.
PAMAM-NPD G5:
1
H NMR:(CDCl3) δ=8.981-7.550 (1408H, aromatic ring), δ=3.770 (128H,
128-CH2-CH-CO-NH-),
δ=3.501
377-NH-CH2-CH2-NH-CH-),
(7.6H,
δ=2.943
-CH2-CH2-NH-CH-CO-CH2-),
(252H,
δ=3.299
-NH-CH2-CH2-N(-CH2-)-CH2-),
(754H,
δ=2.618(764H,
387-CH2-N-CH--CH2), δ=2.242 (758H, 379-CH2-CO-). FT-IR (KBr): 3021, 1705, 1636, 1512, 1411,
1319, 779, 756.
S6
(a)
(b)
Figure S- 1. TEM images of PAMAM-DNS G1 aggregates in water (1x10-5 M) with (a) and without (b)
negative staining
S7
220
7000
180
Relative Fluorescence Intensity
Relative Fluorescence Intensity
200
160
CAC
140
120
100
80
60
6000
CAC
5000
4000
3000
2000
1000
0
40
-1000
-5
2.5x10
-5
3.0x10
-5
3.5x10
-5
4.0x10
-5
4.5x10
-5
5.0x10
5.5x10
-5
0.0
2.0x10
-5
4.0x10
Concentration/M
-5
6.0x10
-5
8.0x10
-5
1.0x10
-4
Concentration/M
(a)
(b)
Relative Fluorescence Intensity
4000
CAC
3000
2000
1000
0
-1.0x10
-7
0.0
-7
1.0x10
2.0x10
-7
3.0x10
-7
-7
4.0x10
5.0x10
-7
-7
6.0x10
-7
7.0x10
Concentration/M
(c)
Figure S-2. Changes in fluorescent intensity with increasing the concentration of dendrimer
PAMAM-DNS G1 (a), PAMAM-DNS G2 (b) and PAMAM-DNS G3 (c). The breaking points indicate
the critical aggregation concentration (CAC)
S8
0.15
0.15
Absorbance
0.10
a
0.10
0.05
b
0.05
0.00
300
0.00
400
500
600
700
Wavelength/nm
Figure S-3 Representative UV-vis spectra of PAMAM-NPD G2 in dichloromethane before (a) and
after (b) irradiation with UV light
S9
1500
1000
I/10 A
0
-6
-6
I/10 A
500
10mv/s
30mv/s
50mv/s
70mv/s
90mv/s
-500
-1000
-1500
-1000
-500
0
500
1000
1500
1600
1400
1200
1000
800
600
400
200
0
-200
-400
-600
-800
-1000
-1200
-1400
-1600
-1800
-1000
10mv/s
30mv/s
50mv/s
70mv/s
90mv/s
-500
E/mv vs. Ag/AgCl
0
500
1000
1500
E/mv vs. Ag/AgCl
(a)
(b)
500
400
0
0
200
0
10mv/s
30mv/s
50mv/s
70mv/s
90mv/s
-1
-6
-1000
-200
I/10 A
-6
I/10 A
-500
10mv/s
30mv/s
50mv/s
70mv/s
90mv/s
-400
-600
-2
-800
-1500
-1000
-2000
-1000
-3
-500
0
500
1000
1500
-1200
-1000
E/mv vs. Ag/AgCl
-500
0
500
1000
1500
E/mv vs. Ag/AgCl
(c)
(d)
400
200
-6
I/10 A
0
-200
10mv/s
30mv/s
50mv/s
70mv/s
90mv/s
-400
-600
-800
-1000
-500
0
500
1000
1500
E/mv vs. Ag/AgCl
(e)
Figure S-4 Cyclic voltammgrams of PAMAM-DNS G0 (a), G1 (b), G2 (c), G3 (d), and G4 (e) in
acetonitrile at different scanning rate of 10, 30, 50, 70, 90 mv/s respectively.
S 10