Electronic Supplementary Material (ESI) for Polymer Chemistry This journal is © The Royal Society of Chemistry 2012

Supporting Information

Thiol and pH Dual-Responsive Dynamic Covalent Shell Cross-Linked

Micelles for Triggered Release of Chemotherapeutic Drugs†

Xianglong Hu,a Hui Li,a Shizhong Luo,*b Tao Liu,a Yanyan Jianga and Shiyong Liu*a

CAS Key Laboratory of Soft Matter Chemistry, Department of Polymer Science and Engineering, National Laboratory for Physical Sciences at the Microscale, University of Science and Technology of , Hefei, 230026, China; Anhui Key Laboratory of Functional Molecular Solids and Anhui Key Laboratory of Molecule-based Materials, College of Chemistry and Materials Science, Anhui Normal University, , Anhui 241000, China

* To whom correspondence should be addressed. E-mail: [email protected], [email protected]

a University of Science and Technology of China b Anhui Normal University

Electronic Supplementary Material (ESI) for Polymer Chemistry This journal is © The Royal Society of Chemistry 2012

PCL -Br PCL43-b-P(OEGMA0.67-co-MAEBA0.33)73 43 M = 4.89 kDa, Mn = 32.6 kDa, Mw/Mn = 1.19 n

Mw/Mn = 1.15

16 20 24 28 32 36 Elution Time / min 

Fig. S1. DMF GPC traces recorded for PCL43-Br and PCL43-b-P(OEGMA0.67-co-

MAEBA0.33)73 diblock copolymer. Electronic Supplementary Material (ESI) for Polymer Chemistry This journal is © The Royal Society of Chemistry 2012

1200

900

600

-3 CMC = 9.6*10 g/L 300

0 Fluorescence Intensity 1E-4 1E-3 0.01 0.1

logCpolymer/ (g/L)

Fig. S2. Plot of emission intensity of Nile red at the emission maxima 615 nm (Ȝex = 550 nm;

slit widths: Ex. 5 nm, Em. 5 nm) as a function of concentration of PCL43-b-

P(OEGMA0.67-co-MAEBA0.33)73 diblock copolymer. Nile red concentration was fixed to be 1.0 u 10-6 M. Electronic Supplementary Material (ESI) for Polymer Chemistry This journal is © The Royal Society of Chemistry 2012



1.0

0.8

0.6 

0.4

0.2 0 50 100 150 200 250 Relative Scattering Intensity Time / min

Fig. S3. Time dependence of relative light scattering intensities recorded for 0.05 g/L aqueous solution of (ż) Non-crosslinked (NCL) micelles and (Ƒ) Shell cross-linked (SCL)

micelles fabricated from PCL43-b-P(OEGMA0.67-co-MAEBA0.33)73 diblock copolymer upon treating with 0.1 g/L lipase at 37 oC.