Supplementary Information
Reduction-responsive core-shell-corona micelles based on
triblock copolymer: novel synthetic strategy,
characterization, and application as tumor
microenvironment-responsive drug delivery system
Xubo Zhao and Peng Liu*
State Key Laboratory of Applied Organic Chemistry and Key Laboratory of
Nonferrous Metal Chemistry and Resources Utilization of Gansu Province, College of
Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000, China
Fax: 86 931 8912582; Tel: 86 931 8912582.
E-mail: [email protected] (P.L.)
* Corresponding author.
1
a
b
c
1735
d
1394
2100
e
1394
1241
4000 3500 3000 2500 2000 1500 1000
500
-1
Wavenumber(cm
)
Figure S1. FTIR spectra of (a) PEG42, (b) PEG42-Br, (c) PEG42-b-PtBA48, (d)
propargyl-terminated PCL53, and (e) PEG42-b-PtBA48-b-PCL53.
2
PEG43
Mn=2300
PEG43-b-PtBA48
Mn=8600
PDI=1.21
PDI=1.05
PCL53
Mn=6200
PDI=1.12
PEG43-b-PtBA48-b-B-PCL53
Mn=15600
PDI=1.27
22
23
24
25
26
27
28
Rentention time (min)
29
30
Figure S2. GPC traces of PEG42, PEG42-b-PtBA48, propargyl-terminated PCL53, and
PEG42-b-PtBA48-b-PCL53.
3
1.48
1.44
1.40
1.36
1.40
1.36
1.40
1.36
ppm
(a)
1.48
1.44
ppm
(b)
1.48
1.44
ppm
(c)
Figure S3. Fractionated gain of the signals of methyl protons on t-butyl groups before
(a) and after hydrolysis with 0.5 (b) or 2.0 equivalent NaOH (c) (in CDCl3, ppm).
4
A
B
C
D
E
F
100
Itensity (%)
80
60
40
20
0
0
40
80
120
160
200
240
Size (nm)
Figure S4. Typical Dh distributions of the micelles of the PEG42-b-PtBA48-b-PCL53
(A), PEG42-b-P(AA30-co-tBA18)-b-PCL53 (B) and crosslinked
PEG42-b-P(AA30-co-tBA18)-b-PCL53 (C) in water;
PEG42-b-P(AA30-co-tBA18)-b-PCL53 (D) and crosslinked
PEG42-b-P(AA30-co-tBA18)-b-PCL53 (E) in water/THF (v/v, 1 : 6); and crosslinked
PEG42-b-P(AA30-co-tBA18)-b-PCL53 in water/THF (v/v, 1 : 6) treated with 10 mM
GSH (F) using oscillate at 30 oC for 6 h, with PDI of 0.237, 0.137, 0.005, 0.005, 0.005
and 0.149, respectively.
5
1.6
30
NCMs 7.4
Log of cumulative release
Cumulative release(%)
25
20
15
10
5
Y=0.8214X+1.2759
2
R =0.8917
0
0
10
20
30
Sqaure root of time
NCMs 7.4
1.2
0.8
0.4
Y=0.6341X-0.3783
R2=0.9111
0.0
1.0
40
1.5
a
Log of cumulative release
CLMs 7.4
Cumulative release (%)
10
8
6
4
2
0
10
20
30
Square root of time
CLMs 7.4
0.8
0.4
0.0
Y=0.2564X+0.5941
2
R =0.9551
0
Y=0.5109X-0.5658
2
R =0.9795
1.0
40
1.5
c
CLMs 5.0
3.0
3.5
CLMs 5.0
40
30
20
10
Y=1.3299X-0.2235
2
R =0.9559
0
0
2.0
2.5
Log of tome
d
Log of cumulative release
Cumulative release (%)
50
3.0
b
1.2
12
2.0
2.5
Log of time
10
20
30
Square root of time
1.6
1.2
0.8
0.4
1.0
40
e
Y=0.5747X-0.0699
2
R =0.9847
1.5
2.0
2.5
Log of time
f
6
3.0
2.0
Log of cumulative release
Cumulative release (%)
70 CLMs 5.0 GSH
60
50
40
30
20
Y=1.6152X-0.4511
2
R =0.9746
10
0
0
10
20
30
Square of time
40
CLMs 5.0 GSH
1.6
1.2
0.8
Y=0.6602X-0.2384
2
R =0.9467
0.4
1.0
50
1.5
2.0
2.5
3.0
3.5
Log of time
g
h
Figure S5. The curves of Higuchi (cpH=7.4, epH=5.0 and gpH=5.0 GSH) and
Korsmeyer-Peppas (dpH=7.4, fpH=5.0 and hpH=5.0 GSH) models of the drug release from the
CLMs, and the Higuchi (apH=7.4,) and Korsmeyer-Peppas (bpH=7.4) models for the
NCMs.
7