Supporting Information for

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Cameron Alexander d. ,. Kevin M. Shakesheff d. , and Brian R. Saunders a,. * a. Biomaterials Research Group, The School of Materials, The University of ...

Supporting Information for: Thermally-triggered

assembly

of

cationic

graft

copolymers

containing 2-(2-methoxyethoxy)ethyl methacrylate side chains Nabilah Shahidana, Ruixue Liua,b, Francesco Cellesic, Cameron Alexanderd, Kevin M. Shakesheffd, and Brian R. Saundersa,* a

Biomaterials Research Group, The School of Materials, The University of Manchester, b

Grosvenor Street, M13 9PL, UK.

School of Material and Chemical Engineering, Zhengzhou

University of Light Industry, Zhengzhou, 450002, P.R. China.

c

School of Pharmacy, The

University of Manchester, Oxford Road, M13 9PT, U.K. d School of Pharmacy, The University of

Hydrodynamic diameter / nm

Nottingham, University Park, Nottingham, NG7 2 RD, UK.

200

Precipitation

150 100 0.05M 50

0.001M 0

0 0

10

20

30

40

50

Temperature / oC Fig. 1S. Variation of hydrodynamic diameter with temperature for M1-PMA101 in the presence of different concentrations of NaCl (shown). The dispersion precipitated in the presence of 0.05 M NaCl when the temperature exceeded 20 oC.

Hydrodynamic diameter / nm

180 160 140 120 100 80 60 40 20 0

MI1-PMA101 M1-PMA52

0

20

45

10

20

20

20

45

30 40 50 Time / min

60

45

70

Fig. 2S. Variation of hydrodynamic diameter for M1-PMA52 and M1-PMA101 with temperature cycling. The measurements commenced at 20 oC and increased to 45 oC and then returned to 20 oC.

(b)

(a) 50 nm

50 nm

(c)

200 nm

Fig. 3S. TEM images of stained micellar aggregates of (a) M1-PMA29, (b) M1-PMA101 and (c) a lower magnification image of M1-PMA52. The samples were deposited and stained using phosphotungstic acid. The small white particles in (a) and (b) originate from the phosphotungstic acid which acts as a positive stain for the micellar aggregates. Aggregates are highlighted with arrows.

Table 1S. Measured and calculated sizes for unimolecular micelles at approximately 20 oC.

Code

d20 / nma

(dm(uni) + Lm(uni))b / nm

d20/(dm(uni) + Lm(uni))

M1-PMA18

26

20

1.3

M1-PMA29

54

25

2.1

M1-PMA52

49

36

1.4

M1-PMA101

110

60

1.8

M3-PMA69

77

45

1.7

Hydrodynamic diameter measured at 20 oC, b dm(uni) and Lm(uni) are the calculated diameters and lengths, respectively, for cylinders of the M(x/y)-PMAn copolymers considered. The calculations for these values were based on the compositions (Table 1) and also a repeat unit length of 0.24 nm. a