Supporting Information. for. Advanced Functional Materials, adfm Wiley-VCH 2006
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1 Supporting Information for Advanced Functional Materials, adfm Wiley-VCH Weinheim, Germany
2 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 ghhsiue@mx.nthu.edu.tw 1
3 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
4 Block I m o m p CH 3 x-1 n q H n H 2 p n o DMS-d6 q 3
5 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
6 2. CMC of each copolymer Graft I I /I E E-5 1E-4 1E Concentration (mg/ml) Block I I /I E-2 1E-4 1E Concentration (mg/ml) Block II 1.2 I /I E-3 1E-4 1E Concentration (mg/ml) 5
7 3. The effects of the composition of diblock copolymers on the preparation of mixed micelles. (A) Average diameter (nm) Average diameter Polydispersity index molar ratios of mpeg-pla Polydispersity index (B) Average diameter (nm) Average diameter Polydispersity index Molar ratios of PEz-PLA 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
8 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
9 (D) Mixed micelle from Graft I, Block I, and 54 mol % of Block II. 5. Phase Transition Determination at 25 C. Transmittance (%) mixed micelle with 10 mol % of Block II mixed micelle with 54 mol % of Block II ph 8
10 6. Structural Change Evaluation. I 1 / I mixed micelles buffer solution Temperature ( o C) 9
11 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: ) m/z (CH 5 N 5-6, Block II): Intensity = 187; Resolution = m/z (C 8 H 7-5, Block I): Intensity = 342; Resolution = Mixed micelles after structural change. (Total intensity: ) m/z (CH 5 N 5-6, Block II): Intensity = 320; Resolution = m/z (C 8 H 7-5, Block I): Intensity = 230; Resolution =
12 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: ) m/z (C 14 H 7 +, Graft I): Intensity = ; Resolution = 867. Mixed micelles after structural change. (Total intensity: ) m/z (C 14 H 7 +, Graft I): Intensity = ; Resolution =
13 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 (%) Micelle concentration (µg/ml) 12
14 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
15 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
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