1
Supporting Information
Synthesis and Characterization of Thermo-responsive Polypeptoid Bottlebrushes
Samuel H. Lahasky, Lu Lu, Wayne A. Huberty, Jinbao Cao, Li Guo, Jayne C. Garno and Donghui Zhang*
Department of Chemistry and Macromolecular Studies Group, Louisiana State University, Baton Rouge,
Louisiana 70803, United States.
Corresponds to: [email protected]
Electronic Supplementary Material (ESI) for Polymer ChemistryThis journal is © The Royal Society of Chemistry 2013
Figure S1.
toluene-d8
(A) 1H NM
and (B) the
(B)
(A)
MR spectra o
e Nor-P(NE
of the Nor-P
G37-r-NBG
P(NEG27-r-N
16) macromo
NBG21) ma
onomer (En
acromonome
ntry 2, Table
er (Entry 1,
e S1) in CD
Table S1) i
Cl3.
2
in
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3
1000 2000 3000 4000 5000 6000
0
10000
20000
30000
m/z
Inte
nsi
ty (
a.u.
)
(A)
Figure S2. (A) Full and (B) expanded MALDI-TOF MS spectra of a norbornenyl-terminated poly(N-
ethyl glycine)-ran-poly(N-butyl glycine) random copolymer [Nor-P(NEG43-r-NBG32)] (Mn = 2.2
kg·mol-1, PDI = 1.40 from MS analysis).
Table S1. The molecular weight and composition of the polypeptoid macromonomers [Nor-
P(NEGn-r-NBGm)n+m]
Entry [M1]0:[M2]0:[I]0 Macromonomer composition a Mn (kg·mol-1) a Mn (kg·mol-1) b PDI
1 33:17:1 Nor-P(NEG27-r-NBG21) 4.7 10.4 1.05
2 38:12:1 Nor-P(NEG37-r-NBG16) 5.0 10.4 1.04
3 42:8:1 Nor-P(NEG36-r-NBG12) 4.4 9.8 1.05
4 45:5:1 Nor-P(NEG40-r-NBG9) 4.4 9.7 1.05
a. Determined by integration of the ethyl and butyl methyl peaks relative to the norbornenyl methylene peaks in their respective 1H NMR spectra in toluene-d8;
b. determined from SEC-MALS-DRI chromatography in 0.1 M LiBr/DMF using polystyrene standards (flow rate = 0.5 mL·min-1).
4340 4360 4380
0
10000
20000
30000
40000
B2
. 4
381
.5
A2
. 4
36
6.0
B1
. 4
354
.0
A1
. 4
338
.1
Inte
nsi
ty (
a.u
.)
m/z
(B)
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40 45 50 55 60
0.0
0.5
1.0
No
rma
lize
d D
RI
Re
spo
nse
Elution time (min)
Nor-P(NEG27
-r-NBG21
)
Nor-P(NEG37
-r-NBG16
)
Nor-P(NEG36
-r-NBG12
)
Nor-P(NEG40
-r-NBG9)
Figure S3. SEC-DRI chromatograms of the polypeptoid macromonomers [Nor-P(NEGn-r-NBGm)n+m]
(Entry 1-4, Table S1).
Figure S4. Plots of Mn and PDI versus time for the ROMP reaction of Nor-P(NEG40-r-NBG9) (conditions: [Nor]0/[Ru]0=150:1, [Nor]0= 0.01M, 40 °C, CH2Cl2).
0 50 100 150 200 250
4.0x104
8.0x104
1.2x105
1.6x105
2.0x105 Mn PDI
reaction time(h)
Mn(
g/m
ol)
1.2
1.4
1.6
1.8
2.0
2.2
PD
I
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Figure S5
P(NEG37-r
purification
Figure S6.
Table 1) in
. Represen
r-NBG16), -
n by centrifu
1H NMR
n CDCl3.
30
0.0
0.1
0.2
0.3
0.4
DR
I R
esp
on
se (
a.u
.)
ntative SEC
-·-] and the
fugal dialysi
spectrum o
0 35
C-DRI chro
e correspon
s.
of the PNor
40 45
Elution time (
MacromBottlebrBottlebr
omatograms
nding bottle
r25-g-P(NEG
5 50
(min)
monomerrush before purificrush after purificat
s of the p
ebrush copo
G37-r-NBG1
55
cation tion
polypeptoid
olymer befo
6) bottlebru
macromon
ore (---) an
ush copolym
nomer [No
nd after (—
mer (Entry 2
5
r-
—)
2,
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30 35 40 45 50
0.00
0.25
0.50
0.75
1.00
Nor
ma
lized
DR
I R
esp
onse
(a.
u.)
Elution time (min)
PNor25
-g-P(NEG27
-r-NBG21
)
PNor25
-g-P(NEG37
-r-NBG16
)
PNor25
-g-P(NEG36
-r-NBG12
)
PNor25
-g-P(NEG40
-r-NBG9)
Figure S7. SEC-DRI chromatograms of the polypeptoid bottlebrushes having the same backbone
length and various side chain compositions (Entries 1-3 and 5, Table 1).
30 40 50 60 70 80
0
25
50
75
100
Tra
nsm
itta
nce
(%
)
Temperature (oC)
as-prepared thermally annealed
(A)
30 40 50 60 70 80
0
25
50
75
100
Tra
nsm
ittan
ce (
%)
Temperature (oC)
as-prepared thermally annealed
(B)
Figure S8. (A) Transmittance versus temperature plots for the as-prepared (---) and thermally annealed
aqueous solutions (—) of the bottlebrush copolypeptoid PNor25-g-P(NEG27-r-NBG21) (Entry 1, Table 1)
and (B) PNor25-g-P(NEG36-r-NBG12) (Entry 3, Table 1).
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0.1 1 10 100 1000 10000
0
1
2
3
4
5
6
7 As-prepared Annealed
Inte
nsity
(%
)
Apparent hydrodynamic diameter (nm)
Figure S9. Dynamic light scattering (DLS) analysis of aqueous solutions (1.0 mg·ml-1) containing as-
prepared (—) or thermally-annealed PNor25-g-P(NEG27-r-NBG21) sample (—) (Entry 1, Table 1) at 25
°C.
25 30 35 40 45 50 55
0
25
50
75
100
Tra
nsm
itta
nce
(%
)
Temperature (oC)
[NaCl]=0 M [NaCl]=0.05 M [NaCl]=0.25 M [NaCl]=0.50 M
Figure S10. Transmittance versus temperature plots of the polypeptoid macromonomer [Nor-
P(NEG27-r-NBG21)] (Entry 1, Table S1) in aqueous solutions with varying NaCl concentrations.
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30 40 50 60 70 80 90
0
25
50
75
100
Tra
nsm
itta
nce
(%)
Temperature (oC)
[NaCl]=0.0 M (as-prepared) [NaCl]=0.05 M (as-prepared) [NaCl]=0.10 M (as-prepared) [NaCl]=0.25 M (as-prepared)
Figure S11. Transmittance versus temperature plot of the polypeptoid bottlebrush [PNor25-g-P(NEG27-
r-NBG21)] (Entry 1, Table 1) in aqueous solutions with varying NaCl concentrations.
30 40 50 60 70 80
0
25
50
75
100
Tra
nsm
itta
nce
(%
)
Temperature (oC)
[NaCl]=0 M [NaCl]=0.25 M [NaCl]=0.50 M
Figure S12. Transmittance versus temperature plots of the polypeptoid macromonomer [Nor-
P(NEG37-r-NBG16)] (Entry 2, Table S1) in aqueous solutions with varying NaCl concentrations.
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30 40 50 60 70 80 90
0
25
50
75
100
Tra
nsm
ittan
ce (
%)
Temperature (oC)
[NaCl]=0 M (thermally annealed) [NaCl]=0 M (as-prepared) [NaCl]=0.25 M (as-prepared) [NaCl]=0.50 M (as-prepared)
Figure S13. Transmittance versus temperature plots of the polypeptoid bottlebrush [PNor25-g-
P(NEG37-r-NBG16)] (Entry 2, Table 1) in aqueous solutions with varying NaCl concentrations. The
solutions are either subjected to the turbidity measurement directly (as-prepared) or thermally annealed
at 75 °C for 10 min followed by cooling at 4 °C overnight prior to the turbidity measurement.
30 40 50 60 70 80 90 100
0
25
50
75
100
Tra
nsm
itta
nce
(%
)
Temperature (oC)
[NaCl]=0 M [NaCl]=0.5 M [NaCl]=1.0 M [NaCl]=2.0 M
Figure S14. Transmittance versus temperature plots of the polypeptoid macromonomer (Nor-
P(NEG36-r-NBG12) (Entry 3, Table S1) in aqueous solutions with varying NaCl concentrations.
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30 40 50 60 70 80 90 100
0
20
40
60
80
100
Tra
nsm
ittan
ce (
%)
Temperature (oC)
[NaCl]=0 M (as-prepared)
[NaCl]=0 M (thermally annealed)
[NaCl]=0.10 M (as-prepared)
[NaCl]=0.25 M (as-prepared)
[NaCl]=0.50 M (as-prepared)
[NaCl]=1.00 M (as-prepared)
[NaCl]=2.00 M (as-prepared)
Figure S15. Transmittance versus temperature plots of the polypeptoid bottlebrush [PNor25-g-P
(NEG36-r-NBG12)] (Entry 3, Table 1) in aqueous solutions with varying NaCl concentrations. The
solutions are either subjected to the turbidity measurement directly (as-prepared) or thermally annealed
at 75 °C for 10 min followed by cooling at 4 °C overnight prior to the turbidity measurement.
50 60 70 80 90 100
0
25
50
75
100
Tra
nsm
itta
nce
(%
)
Temperature (oC)
[NaCl] = 0.5 M [NaCl] = 1.0 M [NaCl] = 2.0 M
Figure S16. Transmittance versus temperature plots of the polypeptoid macromonomer (Nor-
P(NEG40-r-NBG9) (Entry 4, Table S1) in aqueous solutions with varying NaCl concentrations.
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30 40 50 60 70 80 90 100
0
25
50
75
100
[NaCl]=0 M
(thermallly annealed) [NaCl]=0.5 M
(as-prepared) [NaCl]=1.0 M
(as-prepared) [NaCl]=2.0 M
(as-prepared)T
ran
smitt
ance
(%
)
Temperature (oC)
Figure S17. Transmittance versus temperature plots of the polypeptoid bottlebrush [PNor25-g-
P(NEG40-r-NBG9)] (Entry 5, Table 1) in aqueous solutions with varying NaCl concentrations. The
solutions are either subjected to the turbidity measurement directly (as-prepared) or thermally annealed
at 75 °C for 10 min followed by cooling at 4 °C overnight prior to the turbidity measurement.
Table S2. Tcp and the Tcp transition window (TW) of polypeptoid macromonomers [Nor-P(NEGm-r-NBGn)] in aqueous solutions with varying NaCl concentrations.
Entry Macromonomer composition [NaCl] Tcp (oC) a TW (oC) b
1 Nor-P(NEG27-r-NBG21) 0.5 34.2 13.6 0.25 37.5 12.9 0.1 39.1 15.3 0.01 40.4 18.3 0.0 40.1 14.7 2 Nor-P(NEG37-r-NBG16) 0.50 47.7 16.6 0.25 54.6 21.8 0.0 62.1 11.5 3 Nor-P(NEG36-r-NBG12) 2.0 44.2 16.9 1.0 59.9 12.3 0.5 69.4 16.3 4 Nor-P(NEG40-r-NBG9) 2.0 62.4 22.7 1.0 75.5 12.0 0.5 95.8 - c
a. Determined by turbidity measurements using an optical microscope. Tcps were considered to be the temperature at 50% transmittance; b. Tcp transition window (TW) is the temperature at 10% transmittance minus the temperature at 90% transmittance; c. TW could not be accurately obtained.
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Table S3. Tcp and the Tcp transition window (TW) of polypeptoid bottlebrushes [PNorx-g-P(NEGm-r-NBGn)] (Entry 1-3 and 5, Table 1) in aqueous solutions with varying NaCl concentrations.
Entry Bottlebrush composition [NaCl] Tcp (oC) a TW (oC) b
1 PNor25-g-P(NEG27-r-NBG21) 0.25 32.4 4.8 0.1 34.1 4 0.01 37 16.3 0.0 37.3 24.6 2 PNor25-g-P(NEG37-r-NBG16) 1 35.3 4.3 0.5 41.5 4.6 0.25 43.2 5.1 0.0 47.2 9.2 3 PNor25-g-P(NEG36-r-NBG12) 2 35.1 6 1 47.6 8.4 0.5 53.1 4.8 0.25 57.8 4.8 0.1 63.8 5 0.0 65.6 13 4 PNor25-g-P(NEG40-r-NBG9) 1 59.5 4.7 0.5 69.9 6.3 2 44.4 6.7 0.0 78.8 18.8
a. Determined by turbidity measurements using an optical microscope. Tcps were considered to be the temperature at 50% transmittance; b. Tcp transition window (TW) is the temperature at 10% transmittance minus the temperature at 90% transmittance.
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20 40 60 80 100
0
25
50
75
100
Tra
nsm
itta
nce
(%)
Temperature (oC)
[NaF]=0.010 M [NaF]=0.050 M [NaF]=0.075 M [NaF]=0.100 M [NaF]=0.250 M [NaF]=0.500 M [NaF]=1.000 M
(A)
45 50 55 60 65 70 75
0
25
50
75
100
(C)
Tra
nsm
itta
nce
(%
)
Temperature (oC)
[NaBr]=0.050 M [NaBr]=0.075 M [NaBr]=0.100 M [NaBr]=0.250 M [NaBr]=0.500 M [NaBr]=1.000 M [NaBr]=2.000 M
Figure S18. (A) Transmittance versus temperature plots of the polypeptoid bottlebrush [PNor25-g-
P(NEG36-r-NBG12)] (Entry 3, Table 1) in aqueous solutions with varying NaF, (B) NaCl and (C) NaBr
concentrations.
Table S4. Tcp of the polypeptoid bottlebrush PNor25-g-P(NEG36-r-NBG12) (Entry 3, Table 1) in aqueous solutions with various inorganic salt concentrations
[Salt]
(M)
TcpNaCl
(oC) a
TcpNaF
(oC) a
TcpNaBr
(oC) a
0.05 -- c -- c 64 0.075 -- c 63.4 -- c 0.1 63.8 61.9 -- c
0.25 57.8 51.6 61.1 0.5 53.1 41.9 59.9 1.0 47.6 26.2 56.7 2.0 35.1 -- b 50.1
a. Determined by turbidity measurements using an optical microscope. Tcps were considered to be the temperature at 50% transmittance; b. samples were not soluble in the corresponding NaCl/H2O solution at room temperature; c. samples were not analyzed by turbidity measurements at the given salt concentration.
30 40 50 60 70 80
0
25
50
75
100
(B)
Tra
nsm
ittan
ce (
%)
Temperature (oC)
[NaCl]=0.050M [NaCl]=0.075 M [NaCl]=0.100 M [NaCl]=0.250 M [NaCl]=0.500 M [NaCl]=2.000 M
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Figure S19. (A) Full and (B) expanded SEM images of the bottlebrush copolymers [PNor25-g-P(NEG40-r-NBG9)] that precipitated from the aqueous solution after being held at 80 °C overnight. The sample used in SEM analysis was obtained by lyophilizing a 2.0 mg·mL-1 polymer suspension.
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Figure S20. The shapes and distributions of bottlebrush polypeptoids sample PNor150-g-P(NEG36-r-
NBG12) (Entry 4, Table 1) viewed with AFM. Topographs and corresponding phase images of (A) 6 ×
6 um2; (B) 4 × 4 um2; (C) 1.5 × 1.5 um2 areas.
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