Supporting Information for
Multiple Morphologies of the Aggregates from Self-Assembly of
Diblock Copolymer with Relatively Long Corona-Forming Block
in Dilute Aqueous Solution
Fabao Zhao, Jianpin Sun, Zhilei Liu, Liang Feng, and Jiwen Hu
Guangzhou Institute of Chemistry, Chinese Academy of Sciences, Guangzhou, People’s Republic
of China, 510650. Email: hjw@gic.ac.cn

Corresponding author, email: hjw@gic.ac.cn (Dr. Jwen Hu), fax: 86-20-85232307
1
S-1 Experimental Section
Materials and Reagents
L-leucine (98+%) was purchased from Chinese Huixing biochemistry reagent Co.,
LTD. N-(3-dimethylaminopropyl)-N-ethylconbodiimide (EDC·HCl, 98+%) was
purchased from Acros. Thionyl chloride (99%), formaldehyde (36 wt%) and formic
acid (88 wt%) were all from Guangzhou chemical reagent company in China and used
as received. Methacrylic acid (98+%), which was purchased from Tianjin Yongda
chemical reagent research center in China, was distilled just before use. N,NDiethylethanamine (99+%), also purchased from Tianjin Yongda chemical reagent
research center, was distilled over calcium hydride. Tris(2-aminoethyl) amine
(97%), calcium hydride (99.9%), and poly (ethylene glycol) methyl ether (MPEG,
Mw=5000g/mol, 98%, Aldrich) were all purchased from Aldrich and used as received.
CuBr (98+%, Fluka) was washed with acetic acid 10X and then ethanol 3X before
drying under vacuum to remove any volatiles. 2-Bromopropionyl bromide (BPB,
99+%, Acros) was distilled prior to use. Toluene was purified by distilling over
sodium. Tetrahydrofuran (99.0+%) and DMF (99.0+%) were distilled before use.
Water was purified using a home-made double-distilled pure water generator. Other
reagents employed are all in experimental grade and were treated using normal
procedures if needed before use.
Preparation of Macroinitiator MPEG-Br
15.0g of MPEG (or 3.0 mmol) and 200 ml of anhydrous toluene were charged to a
single-necked round-bottomed flask with a stir bar and sealed with a rubber septum.
The mixture was heated at 40 ºC with stirring to have MPEG fully dissolved in
toluene, and cooled down to room temperature before 1.26 ml of (or 9 mmol)
anhydrous N, N-diethylethanamine was added through a dry syringe. After the
solution was stirred for 5 min, 0.94 ml (or 9 mmol) of 2-Bromopropionyl bromide
was further added drop wise over 30 min. The reaction proceeded under stirring at
45 °C for 5 h under N2 atmosphere. Finally, the reaction mixture was filtered to
remove the salt, and the filtrate was concentrated under vacuum before precipitated
out over ice-cooled diethyl ether. The crude product was further purified by
dissolving in dry dichloromethane and then precipitated out again over ice-cooled
diethyl ether, the dissolving-precipitation process was repeated 3 times before dried
under vacuum. 13.1 g (or 83.7% yield) of white product was obtained.
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H-NMR was recorded at 30 ºC in CDCl3, δ=1.73 (3H, CHBr-CH3), δ=3.36 (3H,
CH3-O), δ=3.62 (4n-4H, -(CH2-CH2-O)n-1-), δ=4.30 (2H, -CH2-O-CO-), δ=4.54 (1H,
CHBr-CH3).
Synthesis of MALM and Me6TREN
The synthesis of MALM (  D =+5.3°, c= 10.0 g/dl in chloroform) and Me6TREN
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have been reported in our previous paper.[1]
Preparation of MPEG-PMALM via ATRP[2]
In a sample run, the MPEG macroinitiator (1.03 g, 0.21 mmol), CuBr (0.03 g, or
0.21 mmol), MALM (5.25 g, or 0.025 mmol) and a magnetic stirring bar were added
to a single necked round bottomed flask. The flask was then sealed with a rubber
2
septum. After being subjected to high vacuum for 30 min, the flask was filled with
argon, and toluene (4.5 mL) was added. The system was frozen by liquid nitrogen,
and subjected again to high vacuum for 10min. The solution was then thawed and
the flask filled with argon at the same time. The process of: freeze-vacuum-thaw
was repeated three times. The solution was further stirred for 5 min before the
addition of 58.3μL（0.21 mmol） of Me6TREN via a degassed and dried syringe.
Finally, the flask was placed in a preheated oil bath at a constant temperature of 75±1
°C for 48 h. The reaction was stopped by cooling the flask in an ice-water bath
before opening to air. Then, the reaction mixture was diluted with 50 ml of THF and
passed through a basic alumina column before it was concentrated under vacuum.
The crude product was further dissolved in 3 ml of THF before precipitated out over
hexane. The dissolving and precipitation process was repeated twice. The final
product was dried overnight at room temperature in vacuum. 2.32 g of white powder
was obtained. (conv.=44.2%, Mn.SEC=1.58 × 104 796 g / mol , Mw/Mn=1.17),  D =
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-40.2° (Chloroform, c=1.00 g/dl)
1
H-NMR was recorded at 30 0C in CDCl3, δ=0.825~0.896 (9m+3H, -CH-CH3),
δ=1.39~1.92 (5mH+1H, -CH-CH2-CH-), δ=3.36 (1H, -O-CH3), δ=3.70 (4nH,
-(CH2-CH2-O)n-), δ=4.26 (mH, CO-CH -NH) , δ=7.81 (mH, CO-NH-CH).
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S-2 Results and discussion
Preparetion of MPEG-b-PMALM
Figure s1：1H-NMR spectra of A), MPEG-Br, and B), MPEG-b-PMALM
Figure s2：Typical SEC curves of MPEG and MPEG-b-PMALM
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Micelles preparation
Table S-1 Morphological phase diagram for system of block
copolymerMPEG115-PMALM44/DMF/water
Water
content
(wt%)
Initial polymer concentration
(wt%)
0.1
0.3
0.5
1.5
3.5
5
S
V(main)+S
V
C(main) +S
C
10
15
20
30
S
V(main)+S
V
C
C
V(main)+S
V(main)+S
V
C(main) +V(a few)
C
V(main)+S
V(main)+S
V
S +V(a few)
C
V(main)+S
V(main)+S
V
S(many)+C
C
40
V(main)+S
V(main)+S
V
S(many)+C
C
50
V(main)+S
V(main)+S
V
S(many)+C
C
S-sphere; C-cylinder; V-vesicle
Table S-2 Morphological phase diagram for system of block
copolymerMPEG115-PMALM23/DMF/water
Water
content
(wt%)
Initial polymer concentration
(wt%)
0.1
0.3
0.5
1.5
3.5
5
S
V(main)+S
V(main)+S
C(main) +S+V
C
10
15
S
V(main)+S
V
C(main) +V(a few)
C
S
V(main)+S
V
C(main) +V(a few)
C
20
30
V(a few)+S
V(main)+S
V
S +V(a few)
C
V(main)+S
V(main)+S
V
S(many)+C
C
40
50
V(main)+S
V
V
S(many)+C
C
V(main)+S
V
V
S(many)+C
C
S-sphere; C-cylinder; V-vesicle
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Table S-3 Morphological phase diagram for system of block
copolymerMPEG115-PMALM9/DMF/water
Water
content
(wt%)
5
10
15
20
30
40
50
Initial polymer concentration
(wt%)
0.1
0.5
3.5
S
S
S
S
S
S
S
S
S
S(main)+ V(a few)
S
S
S(many)+ V(many)
S(many) +V(a few))
S
V
S(main)+ V (a few)
S
V
V(most)+ S (a few)
S
S-sphere; C-cylinder; V-vesicle
[1]
[2]
Reference and note
Feng, L.; Hu, J. W.; Liu, Z. L.; Zhao, F. B.; Liu, G. J. Polymer 2007, 48, 3616.
Zhao, F. B.; Liu, Z. L.; Sun, J. P.; Hu, J. W.; J. Polym. Sci., Part B 2009, 47,
1345
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