Supporting Information for Advanced Functional Materials, adfm.200500627 Wiley-VCH 2006 69451 Weinheim, Germany
Supporting information for: Self-assembly of a Novel Micelle Structure from Graft and Diblock Copolymers: an Example of vercoming the Limitations of Polyions in Drug Delivery. Chun-Liang Lo, Ko-Min Lin, Chun-Kai Huang and Ging-Ho Hsiue* Department of Chemical Engineering, National Tsing Hua University, 101, Section 2 Kuang Fu Road, Hsinchu, 300 Taiwan, RC E-mail: ghhsiue@mx.nthu.edu.tw 1
1. 1 H-NMR of Copolymers. Graft I b h c d e g mpeg (Mw 2000) as a standard to evaluate Mn of Graft I a x NH i a H y l z CH 2 CH 2 j f k H n H 2 DMS-d6 b-f a l k j i g, h 2
Block I m o m p CH 3 x-1 n q H n H 2 p n o DMS-d6 q 3
Block II u t H 3 CH 2 C v w H 3 C N s x N CH 2 CH 3 z H y s u t w z v 4
2. CMC of each copolymer. 1.4 1.3 1.2 Graft I I 335.5 /I 337.5 1.1 1.0 0.9 0.8 1.27E-3 0.7 1E-5 1E-4 1E-3 0.01 0.1 Concentration (mg/ml) 1.3 1.2 Block I I 335.5 /I 337.5 1.1 1.0 0.9 0.8 8.393E-2 1E-4 1E-3 0.01 0.1 1 10 Concentration (mg/ml) 1.4 1.3 Block II 1.2 I 337.5 /I 335.5 1.1 1.0 0.9 0.8 0.7 1.7E-3 1E-4 1E-3 0.01 0.1 1 Concentration (mg/ml) 5
3. The effects of the composition of diblock copolymers on the preparation of mixed micelles. (A) Average diameter (nm) 350 300 250 200 150 100 50 0 Average diameter Polydispersity index 0.0 0.2 0.4 0.6 0.8 1.0 molar ratios of mpeg-pla 0.5 0.4 0.3 0.2 0.1 0.0 Polydispersity index (B) Average diameter (nm) 350 300 250 200 150 100 50 0 Average diameter Polydispersity index 0.0 0.1 0.2 0.3 0.4 0.5 1 Molar ratios of PEz-PLA 0.5 0.4 0.3 0.2 0.1 0.0 Polydispersity index A) Average diameters and polydispersity indexes of mixed micelles as a function of the molar ratio of Block I at a fixed concentration of Graft I (10.0 mg/l). B) Average diameters and polydispersity indexes of mixed micelles as a function of the molar ratio of Block II at a fixed concentration of Graft I (10.0 mg/l) and Block I (5.625 mg/l). 6
4. AFM Images of Mixed Micelles. (A) Mixed micelle from Graft I and 50 mol % of Block I. (B) Mixed micelle from Graft I, Block I, and 10 mol % of Block II. (C) Mixed micelle from Graft I, Block I, and 31 mol % of Block II. 7
(D) Mixed micelle from Graft I, Block I, and 54 mol % of Block II. 5. Phase Transition Determination at 25 C. Transmittance (%) 100 90 80 70 60 50 40 30 20 10 0 mixed micelle with 10 mol % of Block II mixed micelle with 54 mol % of Block II 3 4 5 6 7 8 ph 8
6. Structural Change Evaluation. I 1 / I 3 2.0 1.9 1.8 1.7 1.6 1.5 1.4 1.3 1.2 1.1 1.0 mixed micelles buffer solution 24 26 28 30 32 34 36 38 40 42 44 Temperature ( o C) 9
7. The Negative TF-SIMS Spectra. Mixed micelles before structural change Mixed micelles after structural change Graft I Block I Block II Mixed micelles before structural change. (Total intensity: 3733281) m/z 183.026 (CH 5 N 5-6, Block II): Intensity = 187; Resolution = 50429. m/z 183.0439 (C 8 H 7-5, Block I): Intensity = 342; Resolution = 7243. Mixed micelles after structural change. (Total intensity: 4785491) m/z 183.026 (CH 5 N 5-6, Block II): Intensity = 320; Resolution = 6218. m/z 183.0439 (C 8 H 7-5, Block I): Intensity = 230; Resolution = 12316. 10
8. The Positive TF-SIMS Spectra. Mixed micelles before structural change Mixed micelles after structural change Graft I Block I Block II Mixed micelles before structural change. (Total intensity: 2466044) m/z 191.0068 (C 14 H 7 +, Graft I): Intensity = 218.16; Resolution = 867. Mixed micelles after structural change. (Total intensity: 2480599) m/z 191.0068 (C 14 H 7 +, Graft I): Intensity = 416.67; Resolution = 1088. 11
9. TEM Images of Mixed Micelles Before and After Structural Change (Scale bar = 200 nm). Before structural change. After structural change. 10. Cytotoxicities of Micelles. 120 Graft Ι micelle Mixed micelle Cell viability (%) 100 80 60 40 20 0 100 1000 10000 Micelle concentration (µg/ml) 12
11. Phase contrast images of HepG2 cells (Corresponding to the fluorescence images in main text, Fig. 5). (A) 1 h 8 h (B) 1 h 8 h (A) Phase contrast images of HepG2 cells incubated with free Dox (10µg ml-1), and (B) Phase contrast images of HepG2 cells incubated with Dox-mixed micelles (50µg ml-1). 13
12. Internalization of Chinese hamster ovary (CH-K1) cells treated with free Dox and Dox-mixed micelles. (B) (C) Superimpose Phase contrast Confocal image (A) Phase contrast and confocal images of CH-K1 cells incubated with free Dox (10µg ml-1) and Doxmixed micelles (50µg ml-1). (A) Free Dox after 1 h of exposure, (B) Dox-mixed micelles after 1 h of exposure, (C) Dox-mixed micelles after 6 h of exposure. (Scale bar = 10 µm) 14