SUPPORTING INFORMATION
Biomimetic design of amphiphilic polycations and surface grafting onto
polycarbonate urethane film as effective antibacterial agents with controlled
hemocompatibility
Musammir Khan1, Yakai Feng1,2,3*, Dazhi Yang1, Wei Zhou1, Hong Tian1, Ying Han1, Li
Zhang1, Wenjie Yuan1, Jin Zhang1, Jintang Guo1,3, Wencheng Zhang4
1
2
School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072, China
Key Laboratory of Systems Bioengineering, Ministry of Education, Tianjin University, Tianjin
300072, China
3
Tianjin University- Helmholtz-Zentrum Geesthacht, Joint Laboratory for Biomaterials and
Regenerative Medicine, Weijin Road 92, 300072 Tianjin, China, Kantstr. 55, 14513 Teltow,
Germany
4
Department of Physiology and Pathophysiology, Longistics University of Chinese People’s
Armed Police Force, Tianjin 300072, China
*
To whom correspondence should be addressed: e-mail: yakaifeng@hotmail.com, tel.: +86-22-
27401447, fax: +86-022-27408829.
1
1.
Gel permeation chromatography (GPC)
1400
A
B
C
1200
RI response (mV)
1000
800
600
400
200
20.0
20.5
21.0
21.5
22.0
22.5
23.0
Retention volume (mL)
Figure S1. GPC chromatogram (in THF) of PTBAEMA homopolymer Mn = 21.0 kDa (A), (PTBAEMA-bPEGMA) diblock Mn = 28.0 kDa (B) and (PTBAEMA-co-PEGMA) random Mn = 37.0 kDa (C), copolymers.
2
1
H NMR analysis of different synthesized polymers:
a)
b
CH3
a
CH2 C
O
C
c H2C
n
O
CH2 d
e
HN
e H3C
CH3 e
C
d
CH3
e
c
4.5
4.0
b
a
3.5
3.0
2.5
2.0
1.5
1.0
0.5
ppm
Figure S2. (PTBAEMA)-(a) homopolymer
3
b
CH 3
b)
a
CH2 C
O
C
n
O
c H2C
e
CH 2 d
f H3C
N
I
CH 3 f
e H3C
C
CH 3 e
b
CH 3
e
f
c
d
5.0
4.5
4.0
a
3.5
3.0
2.5
2.0
1.5
1.0
ppm
Figure S2.1. Iodomethane-quaternized homopolymer (H1)-(b-1)
4
b
CH3
c)
a
CH2 C
O
C
c H2C
f
x
n
O
CH2d
x
f
Br
g
N
g
e H3C
C
CH3 e
CH3
e
g
5.0
4.5
4.0
f
c
d
3.5
3.0
b, x
a
2.5
2.0
1.5
1.0
0.5
0.0
ppm
Figure S2.2. Bromohexane quaternized homopolymer (H2)-(c-1)
5
b
CH 3
a
H2 C
a)
HO
d H2 C
c
C
H2
C
C
O
a
CH 2
b
n
O
C
O
m
f H 2C
g
x
C
O
CH 2 e
HN
c
g H 3C
C
CH3 g
CH3
g
f
a
d
b
CH 3
b
e
5.5
5.0
4.5
4.0
3.5
3.0
2.5
2.0
1.5
1.0
0.5
/ppm
Figure S3. Diblock copolymer (PEGMA)-b-(PTBAEMA)-(a)
6
b)
b
CH 3
a
H2C
HO
C
d H2C
c
C
H2
n
C
O
b
a
CH2
O
m
e
H2C
g
H3C
N
f H3C
C
f
e
C
O
g
d
b
CH 3
x
C
O
c
CH 2
I g
CH3
CH3 f
CH3
f
b
c
a
6.0
5.5
5.0
4.5
4.0
3.5
3.0
2.5
2.0
1.5
1.0
0.5
0.0
/ppm
Figure S3.1. Iodomethane-quaternized block copolymer (B1)-(b-2)
7
b
CH3
a
H2C
C)
HO
e
d H2C
c
C
H2
C
C
O
a
CH2
b
n
b
CH3
C
x
C O
O c
e CH2
H2C
O
m
x
Br
g
f
x
d
c
5.0
4.5
4.0
g
C
CH3 h
x
g
5.5
h H3C
N
f
3.5
3.0
a
2.5
2.0
CH3
h
b,f,h
1.5
1.0
0.5
0.0
ppm
Figure S3.2. Bromohexane quaternized block copolymer (B2)-(c-2)
8
b
CH3
a)
a
H2C
HO
d H2Cc
C
H2
C
b
CH3
n
C
O
a
CH2
co
O
C
O
m
e
H2C
x
C
O
c
CH2
HN
f
H3C
f
c
b
a
5.5
5.0
4.5
4.0
3.5
3.0
2.5
2.0
f
CH3
CH3
f
e
d
C
1.5
1.0
0.5
/ppm
Figure S4. Random copolymer (PEGMA-co-PTBAEMA)-(a)
9
b
CH 3
a
H2C
b)
HO
c
d
d H2C
c
C
H2
C
n
C
O
a
CH 2
co
O
C
O
m
e
H2C
g
H3C
N
f H3C
C
g
h
b
CH 3
x
C
O
c
CH 2
I g
C H3
C H3 f
C H3
f
f
5.5
5.0
4.5
4.0
e
b
a
3.5
3.0
2.5
2.0
1.5
1.0
ppm
Figure S4.1. Iodomethane-quaternized random copolymer (R1)-(b-3)
10
c)
b
CH3
a
H2C
d` H2C
c
C
H2
HO
C
C
O
a
CH2
co
n
x
C O
O c
d CH2
H2C
O
m
f
d`
e H3C
x
d
4.5
Br
4.0
c
3.5
3.0
2.0
g
C
CH3 e
f
f,b
a
2.5
N
x
CH3
e
x
5.0
C
g
g
5.5
b
CH3
1.5
1.0
0.5
0.0
ppm
Figure S4.2. Bromohexane quaternized random copolymer (R2)-(c-3)
5.
Casting of polycarbonate urethane (PCU) film
Here we prepared a crosslinked polycarbonate urethane (PCU) film as a grafting substrate for our
synthesized polymers. A homogeneous solution of PCU was prepared in DMF (10 %, w/w) and
kept in a shaker at 37 oC for about one week. Then 30.0 g of this solution was added 0.74±0.01 g
hexamethylene-1,6-diisocynate homopolymer crosslinker and vigorously shaken until the
mixture becomes homogeneous, and then kept until no bubble remains inside. The mixture was
casted onto a glass plate and heated at 70 oC until all solvent evaporate, then raised the
temperature to 90 oC and kept constant for about 7 h. Finally the film was cleaned ultrasonically
with ethanol and dried in vacuum dry box at 50 oC for three days.
11
5.1.
Covalent
immobilization/grafting
of
different
amphiphilic
polycations
onto
polycarbonate urethane (PCU) surfaces using surface initiated atom transfer radical
polymerization (si-ATRP):
Preparation of amino-group terminated PCU surfaces: In a typical grafting experiment, the
PCU was cut into small pieces (3 × 3 cm2), cleaned with ethanol and dried in vacuum at 30 oC
overnight. The film was then treated with HDI in presence of DBTDL catalyst for 90 min at 50
o
C, immersed in water overnight to create amino group terminated surfaces and dried in vacuum
at 30 oC.
Immobilization of BIBB initiator: The BIBB initiator was immobilized onto PCU surfaces
using dry n-hexane solvent and pyridine as catalyst for 6 h at room temperature. The films were
cleaned ultrasonically with n-hexane, then ethanol and dried in vacuum box at 50 oC overnight (a
detailed grafting mechanism is shown in Scheme S 4.1). These PCU surfaces are termed as Brterminated surfaces now.
Grafting different polycations onto Br-terminated PCU surfaces: The different amphiphilic
polycations were then grafted onto PCU surfaces using surface initiated single-electron transfer
living radical polymerization (si-SET-LRP). All the conditions of grafting of homo, random and
diblock copolymers were similar to the solution polymerization reactions, except in case of
diblock copolymer the first block was TBAEMA and the second one PEGMA. The
quaternization reactions were carried out under the same conditions, except using dimethyl
sulfoxide (DMSO) as a solvent. Finally the film was ultrasonically cleaned with the solvent
being used and then rinsed with DI water to remove the loosely adhered reagents and spent
catalyst from the surfaces.
12
Scheme S 5.1. Mechanistic illustration showing the sequential grafting of PTBAEMA and PEGMA from
polycarbonate urethane (PCU) surface to synthesize PCU modified surface, [PCU-(PTBAEMA-b-PEGMA)], by
surface initiated single-electron transfer living radical polymerization (si-SET-LRP). The subsequent
postquaternization reaction resulted in surface bound quaternized polymers. The homo and random copolymers also
follow the same grafting and quaternization pattern. Where R-X stands for quaternizing reagents (CH3I and
C6H13Br) being used.
13