samuel h. lahasky, lu lu, wayne a. huberty, jinbao cao, li ... · department of chemistry and...

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


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)


4

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


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,


6

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).


7

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.


8

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.


9

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.


10

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)





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



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.


11

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



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.


12

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.


13

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


14

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.


15

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.


samuel h. lahasky, lu lu, wayne a. huberty, jinbao cao, li ... · department of chemistry and...

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