Supporting Information
Synthesis
and
Poly[poly(ethylene
Self-assembly
of
Amphiphilic
glycol)
Brush-Dendritic-Linear-like
methyl
ether
methacrylate]-b-Polyamidoamine-b-Poly(ε-caprolactone) Copolymers
Xiaohua He1, Liang Zhong1, Xiaomeng Wu1, Xin Cai1, Meiran Xie1, Shaoliang Lin2*, Deyue
Yan3
1)
Department of Chemistry, East China Normal University, Shanghai 200062, China
2)
The Key Laboratory of Advanced Polymer Materials of Shanghai, School of Materials
Science and Engineering, East China University of Science and Technology, Shanghai
200237, China
3)
School of Chemistry & Chemical Engineering, Shanghai Jiao Tong University, Shanghai
200240, China
Synthesis of the propargyl focal point polyamidoamine (PAMAM) type dendrons with
2m primary amine groups [denoted as Dm (m=1, 2, and 3: generation of dendron)
The propargyl focal point PAMAM type dendrons (Dm) were synthesized according to the
similar procedure reported by Lee et al.1 Under nitrogen atmosphere, methyl acrylate (MA, 40
mL, 0.44 mol) and methanol (50 mL) were added into a 150-mL round bottom flask equipped
with magnetic stirrer bar. The flask was then immersed into an ice-water bath. A solution of
progargylamine (denoted as D0, 3.0 mL, 43.8 mmol) in methanol (25 mL) was introduced
dropwise to the flask through a dropping funnel over 30 min. The mixed solution was stirred
vigorously for another 1 h at 0 oC, and then for an additional 48 h at room temperature under a
nitrogen atmosphere. The reaction solution was evaporated on a rotary evaporator. The
residues were further purified by a silica column chromatograph using ethyl acetate/petroleum
ether (1:2 v/v) as eluent to afford 9.5 g of the methyl ester-terminated D0.5 as a colorless oil
(yield: 96%). 1H NMR (CDCl3, δ/ppm): 3.66 (s, 6H, -OCH3), 3.47 (s, 2H, CHCCH2N-), 2.81
(t, 4H, -N(CH2CH2COO)2-), 2.49 (t, 4H, -N(CH2CH2COO)2-), 2.20 (s, 1H, CHCCH2N-).
Under nitrogen atmosphere and stirring, a solution of D0.5 (6 g, 26.40 mmol) in methanol
(30 mL) was added dropwise to another solution of ethylenediamine (EDA, 28 mL, 0.12mol)
in methanol (40 mL) over 30 min at 0 oC. The reaction mixture was stirred vigorously for 1 h
1
at 0 oC and then for another 48 h at room temperature under a nitrogen atmosphere. The
reaction solution was concentrated by a rotary evaporator at 35 oC, and the excess EDA was
removed using azeotropic mixture of toluene and methanol (9:1 v:v). The remaining toluene
was removed using an azeotropic distillation using methanol under nitrogen atmosphere, and
the residue was dried in vacuo at 35 oC for 24 h to afford 6.88 g of the propargyl focal point
polyamidoamine (PAMAM) type dendron D1 with 2 primary amine groups as a pale
yellowish oil (yield: 92%). 1H NMR (CDCl3, δ/ppm): 7.32 (s, 2H, -CONH-), 3.42 (s, 2H,
CHCCH2N-), 3.30 (t, 4H, -CONHCH2CH2NH2), 2.84 (q, 4H, -CONHCH2CH2NH2; 4H,
-NCH2CH2CONH-), 2.39 (t, 4H, -NCH2CH2CONH-), 2.23 (s, 1H, CHCCH2N-), 1.45 (s, 4H,
-CONHCH2CH2NH2).
D2 and D3 was synthesized from D1 and D2, respectively, using the same method as
successive Michael addition of primary amines with MA and amidation of methyl ester
groups with a large excess of EDA.
D1.5, ethyl acetate/methanol (9:1 v/v) as eluent, a pale yellowish oil, yield: 93%. 1H NMR
(CDCl3, δ/ppm): 7.09 (s, 2H, -CONH-), 3.67 (s, 12H, -OCH3), 3.47 (s, 2H, CHCCH2-), 3.30
(q, 4H, -CONHCH2CH2N-), 2.85 (t, 4H, -NCH2CH2CONH-), 2.76 (t, 8H, -NCH2CH2COO-),
2.55 (t, 4H, -CONHCH2CH2N-), 2.44 (t, 8H, -NCH2CH2COO-), 2.39 (t, 4H,
-NCH2CH2CONH-), 2.19 (s, 1H, CHCCH2-).
D2, a pale yellowish oil, yield: 96%. 1H NMR (CDCl3, δ/ppm): 7.87 (s, 2H, -CONH-),
7.62 (s, 4H, -CONH-), 3.41 (s, 2H, CHCCH2N-), 3.26 (m, 8 H, -CONHCH2CH2NH2; 4H,
-CONHCH2CH2N-), 2.81 (m, 12H, -NCH2CH2CONH-), 2.72 (t, 8H, -CONHCH2CH2NH2),
2.52 (t, 4H, -CONHCH2CH2N-), 2.35 (t, 12H, -NCH2CH2CONH-), 2.21 (s, 1H, CHCCH2N-),
1.49 (s, 8H, -CONHCH2CH2NH2).
D2.5, ethyl acetate/methanol (1:1 v/v) as eluent, a pale yellowish viscous oil, yield: 88%.
1
H NMR (CDCl3, δ/ppm): 7.79 (s, 2H, -CONH-), 7.12 (s, 4H, -CONH-), 3.66 (s, 24H,
-OCH3), 3.47 (s, 2H, CHCCH2-), 3.32-3.27 (m, 12H, -CONHCH2CH2N-), 2.82 (t, 12H,
-NCH2CH2CONH-), 2.76 (t, 16H, -NCH2CH2COO-), 2.55 (t, 12H, -CONHCH2CH2N-), 2.44
(t, 16H, -NCH2CH2COO-), 2.39 (t, 12H, -NCH2CH2CONH-), 2.22 (s, 1H, CHCCH2-).
D3, a pale yellowish viscous oil, yield: 95%. 1H NMR (CDCl3, δ/ppm): 7.96-7.54 (m, 14H,
-CONH-), 3.45 (s, 2H, CHCCH2N-), 3.27 (m, 28H, -NCH2CH2CONH-), 2.81 (m, 12H,
2
-CONHCH2CH2N-; 16H, -CONHCH2CH2NH2), 2.75 (t, 16H, -CONHCH2CH2NH2), 2.52 (m,
12H, -CONHCH2CH2N-), 2.37 (t, 28H, -NCH2CH2CONH-), 2.24 (s, 1H, CHCCH2N-), 1.65
(s, 16H, -CONHCH2CH2NH2).
Synthesis of 2-Azidoethanol
2-azideoethanol was synthesized according to the similar procedure reported by Li et al. 2 The
procedure was as follows: 2-chloroethanol (6.0 g, 75 mmol), sodium azide (9.7g, 150 mmol),
tetrabutylammoniumiodide (3.0 g, 8 mmol) and 2-butanone (40 mL) were added into a 250
mL round-bottom flask equipped with a condenser, nitrogen inlet/outlet and a magnetic stirrer
bar. The reaction mixture was stirred at 80 oC for 24 h. After removing the insoluble solid by
a filter and evaporating the solvent by rotary evaporation, the obtained yellow oil residues
were distilled under reduced pressure to afford 4.8 g of 2-azidoethanol as a colorless oil (yield:
74%). 1H NMR (CDCl3, δ/ppm): 4.79 (2H, CH2OH), 1.97 (1H, CH2OH), 3.48 (2H, CH2N3).
Synthesis of 2-Azidoethyl-2-bromoisobutyrate (AEBIB)
2-Azidoethyl-2-bromoisobutyrate (AEBIB) was synthesized according to the similar
procedure reported by Gao et al.3 2-Azidoethanol (2.0 g, 23 mmol), anhydrous Et3N (3.9 mL,
27.8 mmol) and anhydrous methylene chloride (30 mL) were added into a 100 mL two-neck
round-bottom flask equipped with a 20-mL dropping funnel. Under nitrogen atmosphere and
magnetic stirring, a mixture of 2-bromoisobutyryl bromide (5.8 g, 25 mmol) in anhydrous
methylene chloride (15 mL) was added dropwise into the previous solution by the dropping
funnel at 0 oC. The reaction mixture was stirred for 24 h. After removal of the insoluble solid,
the solution was washed successively with distilled water (3×70 mL). The combined organic
phase was dried over anhydrous MgSO4 overnight, filtered and evaporated methylene
chloride on a rotary evaporator, and the residues were further purified by a silica column
chromatograph using CH2Cl2/petroleum ether (1:1 v/v) as eluent to afford 4.9 g of AEBIB as
a colorless oil (yield: 91%). 1H NMR (CDCl3, δ/ppm): 4.34 (t, 2H, -COOCH2CH2N3), 3.52 (t,
2H,-COOCH2CH2N3), 1.96 (s, 6H, -C(CH3)2-Br).
3
Figure S1. The micelles size distribution profiles of PPEGMEMA27-b-D2-b-(PCL90)4,
determined by DLS.
Reference
1 Lee, J. W.; Kim, B.-K.; Kim, H. J.; Han, S. C.; Shin, W. S.; Jin, S.-H. Macromolecules 2006, 39, 2418-2422.
2 Li, J.; He, W.-D.; Han, S.-c.; Sun, X.-l.; Li, L.-y.; Zhang, B.-y. J. Polym. Sci., Part A: Polym. Chem. 2009, 47,
786-796.
3 Gao, C.; He, H.; Zhou, L.; Zheng, X.; Zhang, Y. Chem. Mater. 2009, 21, 360-370.
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