Photo-induced Dynamic Association of
Coumarin Pendants within Amphiphilic Random
Copolymer Micelles
Huan Chang, Yan Liu, Mei Shi, Zhaotie Liu, Zhongwen Liu and Jinqiang Jiang *
Key Laboratory of Applied Surface and Colloid Chemistry, Ministry of Education.
School of Chemistry & Chemical Engineering, Shaanxi Normal University, Xi’an,
Shaanxi, 710062, China.
Tel: 86-29-81530784 Fax: 86-29-81530784 E-mail: jiangjq@snnu.edu.cn
1H-NMR
spectrum of P(DMA-co-VBC)
From the 1H-NMR spectrum, comparing the integrals of CO-CH (6.14 ppm, 1H) in the
coumarin structure and N-CH (4.05 ppm, 2H) in the DMAEMA structure led to the estimation of
100/4 unit ratio of DMAEMA/VBC in the copolymer structure. The composition of the polymer
was also analyzed according to the calibration curve of the coumarin in dioxane.
S1.The 1H-NMR spectrum of P(DMA-co-VBC) in CDCl3.
S2. The GPC chromatogram of P(DMA-co-VBC) with THF as eluent.
Calibration curve of the coumarin pendants
A standard solution of VBC in dioxane was prepared at the concentration of 1.0 mg/mL. Then,
the solution was diluted to 2.00×10-2, 1.50×10-2, 1.00×10-2, 8.00×10-3 and 4.00×10-3 mg/mL with
dioxane and scanned by the UV-vis instrument. And the polymer of P(DMA-co-VBC) was also
dissolved in dioxane (1.80×10-1 mg/mL) and checked by UV-vis instrument, as shown in S3a.
S3. a) UV spectra of VBC and polymer in dioxane. b) The standard line of VBC fit according to absorbance
intensities at 320 nm and the estimated coumarin content in P(DMA-co-VBC).
As shown in S3b, the absorbance intensity of coumarin at 320 nm decreased as a function of
VBC concentration and its displayed a good linearity in dioxane, resulted in a standard line of A =
56.1067B and the estimation of 4 units of VBC in P(DMA-co-VBC).
The photo-dimerization procedure upon 320 nm irradiation
S4. UV-vis spectra of polymer aqueous solution (0.25 mg/mL×1 mL) upon 320 nm irradiations (a: 0.44 mW/cm2 ,
b: 0.64 mW/cm2 and c: 0.86 mW/cm2).
S5. Fluorescence spectra of polymer aqueous solution (0.25 mg/mL×1 mL) upon 320 nm irradiations (a: 0.44
mW/cm2, b: 0.64 mW/cm2 and c: 0.86 mW/cm2) and the dependence of I2/I1 as a function of irradiation time (d).
The photo-reaction procedure upon 254 nm irradiations
S6. UV-vis spectra of photo-crosslinked polymer aqueous solution (0.25 mg/mL×1 mL, PD(0) = 88.31%) upon 254
nm irradiations (a: 0.16 mW/cm2, b: 0.24 mW/cm2, c: 0.28 mW/cm2 and d: 0.32 mW/cm2).
S7. Fluorescence spectra of photo-crosslinked polymer aqueous solution (0.25 mg/mL×1 mL, PD(0) = 88.31%)
upon 254 nm irradiations (a: 0.16 mW/cm2, b: 0.24 mW/cm2, c: 0.28 mW/cm2 and d: 0.32 mW/cm2).
The reversible photo-dimerization cycles upon alternative irradiations
S8. UV-vis spectra of polymer aqueous solution (0.25 mg/mL×1 mL) upon the first alternative irradiation cycle of
320 nm (a: 0.86 mW/cm2) and 254 nm (b: 0.24 mW/cm2).
S9. AFM image (2×2 μm2) (a) and the cumulative distribution of particle size (b) and height (c) for polymer
micelles before photo-dimerization.
S10. AFM image (2×2 μm2) (a) and the cumulative distribution of particle size (b) and height (c) for polymer
micelles after photo-dimerization.
S11. AFM image (2×2 μm2) (a) and the cumulative distribution of particle size (b) and height (c) for polymer
micelles after photo-cleavage in the first irradiation cycle.
S12. UV-vis spectra of polymer aqueous solution (0.25 mg/mL×1 mL) upon the second alternative irradiation
cycle of 320 nm (a: 0.86 mW/cm2) and 254 nm (b: 0.24 mW/cm2).
S13. UV-vis spectra of polymer aqueous solution (0.25 mg/mL×1 mL) upon the third alternative irradiation cycle
of 320 nm (a: 0.86 mW/cm2) and 254 nm (b: 0.24 mW/cm2).
S14. UV-vis spectra of polymer aqueous solution (0.25 mg/mL×1 mL) upon the fourth alternative irradiation cycle
of 320 nm (a: 0.86 mW/cm2) and 254 nm (b: 0.24 mW/cm2).
S15. Fluorescence spectra of polymer aqueous solution (0.25 mg/mL×1 mL) upon the first alternative irradiation
cycle of 320 nm (a: 0.86 mW/cm2) and 254 nm (b: 0.24 mW/cm2).
S16. Fluorescence spectra of polymer aqueous solution (0.25 mg/mL×1 mL) upon the second alternative
irradiation cycle of 320 nm (a: 0.86 mW/cm2) and 254 nm (b: 0.24 mW/cm2).
S17. Fluorescence spectra of polymer aqueous solution (0.25 mg/mL×1 mL) upon the third alternative irradiation
cycle of 320 nm (a: 0.86 mW/cm2) and 254 nm (b: 0.24 mW/cm2).
S18. Fluorescence spectra of polymer aqueous solution (0.25 mg/mL×1 mL) upon the fourth alternative irradiation
cycle of 320 nm (a: 0.86 mW/cm2) and 254 nm (b: 0.24 mW/cm2).