1
Photo and redox-responsive vesicles assembled from
Bola-Type superamphiphiles
Tao Sun,a Lan Shu,a Jian Shen,b Chunhui Ruan,a Zhifeng Zhao,a Chen Jiang*a
aKey Laboratory of Smart Drug Delivery (Ministry of Education), State Key Laboratory of
Medical Neurobiology, Department of Pharmaceutics, School of Pharmacy, Fudan University,
Shanghai 201203, PR China
bSchool of Chemistry and Chemical Engineering, Weifang University, Weifang 261061, PR China
Supporting InformationTable of Contents
1. Characterizations of all compounds..........................................................................Page S2
2. Supporting information for the mechanism study ..................................................Page S11
3. Photo- and redox-responsive properties .................................................................Page S15
4. Drug loading and release ........................................................................................Page S17
5. References of supporting information ....................................................................Page S20
Electronic Supplementary Material (ESI) for RSC Advances.This journal is © The Royal Society of Chemistry 2016
2
1. Characterizations of all compounds
NN
OBr
1
2
34
5
6
78
910, 11
12, 13
14, 15
16, 17
2
Figure S1. 1H NMR spectrum of 2 in CDCl3 at ambient temperature.
Figure S2. 13C NMR spectrum of 2 in CDCl3 at ambient temperature.
3
Figure S3. MS-ESI spectrum of 2 in CDCl3 at ambient temperature.
4000 3500 3000 2500 2000 1500 1000 500
0
20
40
60
80
100
Tran
smitt
ance
/%
Wavelength/cm-1
Figure S4. FT-IR spectrum of 3 in KBr tablet at ambient temperature.
4
NN
OSH
1
2
34
5
6
78
910, 11
12, 13
14, 15
16, 17
3
18
Figure S5. 1H NMR spectrum of 3 in CDCl3 at ambient temperature.
Figure S6. 13C NMR spectrum of 3 in CDCl3 at ambient temperature.
5
Fi
gure S7. MS-ESI spectrum of 3 in CDCl3 at ambient temperature.
4000 3500 3000 2500 2000 1500 1000 500
8
10
12
14
16
18
20
Tran
smitt
ance
/%
Wavelength/cm-1
Figure S8. FT-IR spectrum of 3 in KBr tablet at ambient temperature.
6
NN
OS
1
2
34
5
6
78
910, 11
12, 13
14, 15
16, 17
4
S N
1819
20
21
Figure S9. 1H NMR spectrum of 4 in CDCl3 at ambient temperature.
7
Figure S10. 13C NMR spectrum of 4 in CDCl3 at ambient temperature.
8
Figure S11. MS-ESI spectrum of 4 in CDCl3 at ambient temperature.
9
4000 3500 3000 2500 2000 1500 1000 500
0
20
40
60
80
100
Tran
smitt
ance
/%
Wavelength/cm-1
Figure S12. FT-IR spectrum of 4 in KBr tablet at ambient temperature.
10
NN
OS
1
2
34
5
6
78
910, 11
12, 13
14, 15
16, 17
1
S18, 19
NN
O20, 21
22, 23
24, 2526
2728
2930
3132
3334
Figure S13. 1H NMR spectrum of 1 in CDCl3 at ambient temperature.
11
Figure S14. 13C NMR spectrum of 1 in CDCl3 at ambient temperature.
12
Figure S15. MS-ESI spectrum of 1 in CDCl3 at ambient temperature.
Figure S16. HR-Ms result of 1 at ambient temperature.
13
4000 3500 3000 2500 2000 1500 1000 50050
100
150
200
250
300
Tran
smitt
ance
/%
Wavelength/cm-1Figure S17. FT-IR spectrum of 1 in KBr tablet at ambient temperature.
14
2. Supporting information for the mechanism study
Figure S18. Different phenomenon of β-CD in aqueous solution (0.1 mM), β-CD/1 vesicular
solution (0.1 mM) and 1 aqueous dispersion in water (0.1 mM) illuminated by a laser pointer.
Figure S19. Cryo-TEM images of β-CD/1 vesicular sample in water.
15
Figure S20. The molecular status after MM2 energy minimize calculation and corresponding
calculated molecular sizes.1
Figure S21. TEM micromorphology images of only β-CD in water after a 20 min sonication.
Phosphotungstic acid was employed as the negative staining agent.
16
Figure S22. TEM micromorphology images of only compound 1 in water after a 20 min
sonication. Phosphotungstic acid was employed as the negative staining agent.
Figure S23. 1H NMR spectra of β-CD and β-CD/1 in D2O at ambient temperature.
17
200 210 220 230 240
0.0
0.5
1.0
1.5
2.0
Abso
rban
ce
Wavelength/nm
G:H10:09:18:27:36:45:54:63:72:81:90:10
Figure S24. UV/vis spectra of 1/β-CD (G/H = 10:0, 9:1, 8:2, 7:3, 6:4, 5:, 4:6, 3:7, 2:8, 1:9, 0:10,
shown from top to down) for Job’s plots in water at room temperature.
Figure S25. Double reciprocal plots of 1/β-CD inclusion complex in water at 282 nm: (A) UV
absorbance of 1 in presence of β-CD with different concentrations; (B) the complex constant
calculated in 1:2 mode (G/H, r2 = 0.90).
18
3. Photo- and redox-responsive properties
Figure S26. TEM micromorphology images of β-CD/1 vesicular sample in water upon recovery
with visible light irradiation. Phosphotungstic acid was employed as the negative staining agent.
Figure S27. 1H NMR spectra (400 MHz in CD3OD/CDCl3 (2/1, v/v) at 298 K, the entire version)
19
from the same tube of 1 before (A), after (B) UV irradiation (365 nm, 60 mW·cm-2, 30 min) and
(C) visible light radiation (434 nm, 20 mW·cm-2, 5 h).
Figure S28. TEM micromorphology images of only β-CD/1 sample in water upon DTT treatment.
Phosphotungstic acid was employed as the negative staining agent.
1 10 100 1000
0
5
10
15
20
-CD in PBS 7.40 -CD/3 in water
Inte
nsity
%
Size/nmFigure S29. DLS results of the β-CD in PBS 7.40 (black, average size: 0.8 nm) and β-CD/3 (red,
average size: 1.8 nm) in water at 300 K.
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4. Drug loading and release
1000 2000 3000 40000
30
60
32673314
3450
MMC
vesicles carrying MMC
Tran
smitt
ance
/%
Wavelength/nm
freeze-dried vesicles
1729
Figure S30. FT-IR spectra comparison of β-CD/1 dried vesicles, and dried vesicles
carrying mitomycin C (MMC) in KBr capsules at 300 K.
Figure S31. Representative HPLC chromatogram of MMC and riboflavin (internal
standard)
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0.0 0.1 0.2 0.3 0.4 0.5-1
0
1
2
3
4
5
6
7
8
Area
MM
C/Are
a ribof
lavi
n
MMC concentration (mg/mL)
Figure S32. The standard curve of MMC concentration with riboflavin as the internal
standard determined by HPLC. R2=0.99393 and the values are represented as a mean
± SD (n = 3).
Figure S33. A: TEM micromorphology images (A) and DLS result (B) of pyrene-loaded β-CD/1/
vesicles in water. Phosphotungstic acid was employed as the negative staining agent.
22
4000 3500 3000 2500 2000 1500 1000 500
-100
-50
0
50
100
150
200
Tran
smitt
ance
/%
Wavelength/cm-1
dried vesicles carrying with pyrene dried vesicles
Figure S34. FT-IR spectra comparison of β-CD/1 dried vesicles, and dried vesicles
carrying pyrene in KBr capsules at 300 K.
Pyrene, with poor aqueous solubility (~10-6 mol/L) and high stability, can play the
role as the hydrophobic drug model for the drug-carrying qualification.2 We found
that upon the drug loading, the β-CD/1 vesicles’ diameter tend to increase from TEM
and DLS observations (417 nm, Figure S31). This may be due to the insertion of
hydrophobic models into the bilayers.3 The characteristic vc=c peak (1702 cm-1) of
pyrene in the FTIR spectrum demonstrates the successful carrying of pyrene to the
vesicular system (Figure S32).
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5. References of supporting information
1. T. Sun, H. Yan, G. Liu, J. Hao, J. Su, S. Li, P. Xing, A. Hao, Strategy of directly
employing paclitaxel to construct vesicles. J. Phys. Chem. B, 2012, 116,
14628−14636.
2. S. Li, T. Sun, X. Yang, B. Wang, P. Xing, Y. Hou, J. Su and A. Hao, Light-
responsive drug carrier vesicles assembled by cinnamicacid-based peptide, Colloid.
Polym. Sci., 2013, 291, 2639−2646.
3. J. Zhang, X. Li, M. Yan, L. Qiu, Y. Jin, K. Zhu, Hydrogen bonding-induced
transformation of network aggregates into vesicles-A potential method for the
preparation of composite vesicles, Macromol. Rapid Commun., 2007, 28 (6),
710−717.
