1. A Dual-Responsive Supra-Amphiphilic Polypseudorotaxane
Constructed from a Water-Soluble Pillararene and an Azobenzene-Containing Random
Xiaodong Chi, Xiaofan Ji, Danyu Xia, and Feihe Huang*
J. Am. Chem. Soc., 2015, 137 (4), pp 1440–1443

2. Macromolecular amphiphiles
sensor
system
biomedical
material
drug
delivery
Macromolecular
amphiphiles
potential applications in many fields

3. ・ easily obtained in a facile
Macromolecular
supra-amphiphiles
hydrophlic and hydrophobic parts are connected by noncovalent forces
・ easily obtained in a facile
　 and dynamic manner
・ abundant stimuli
　responsiveness

4. + azobenzene + pillararene ・ easily obtained in a facile
Macromolecular
supra-amphiphiles
hydrophlic and hydrophobic parts are connected by noncovalent forces
・ easily obtained in a facile
　 and dynamic manner
guest 1
host
+ azobenzene
+ pillararene
・ abundant stimuli
　responsiveness ↓
photoresponsive ↓
thermoresponsive

5. Function & Units
memo: LCST = Lower Critical Solution Temperature

6. Function & Units
memo: LCST = Lower Critical Solution Temperature

7. Function & Units
memo: LCST = Lower Critical Solution Temperature

8. PHOTOresponsive & THERMOresponsive

9. Function & Units
memo: LCST = Lower Critical Solution Temperature

10. Observe the host−guest complexation
between WP7 and the azobenzene unit
① 1H NMR (400 MHz, D2O, 298 K):
2.00 mM trans-1;
(b) 2.00 mM trans-1 and 2.00 mM WP7;
(c) 2.00 mM trans-1 and 2.00 mM WP7 after irradiation at 365 nm for 10 min;
(d) 2.00 mM trans-1 after irradiation at 365 nm for 10 min;
(e) 2.00 mM trans-1 and 2.00mMWP7 after further irradiation at 435 nm for 10 min.

11. ② -1 dynamic light scattering (DLS) &
Observe the self-assembly behavior of the supra-amphiphilic polypseudorotaxane
in water
② -1 dynamic light scattering (DLS) &
transmission electron microscopy (TEM)
Characterizations of vesicles formed by the supra-amphiphilic
polypseudorotaxane WP7⊃3:
DLS data;
TEM image;
enlarged TEM image of a partially collapsed vesicle.

12. ② -2 DLS &TEM + PHOTOresponsive
Observe the self-assembly behavior of the supra-amphiphilic polypseudorotaxane
in water
② -2 DLS &TEM + PHOTOresponsive
(a) TEM image of an aqueous solution of 7.00 mM WP7 and
1.00 mM 3 after irradiation with UV light at 365 nm;
(b) DLS result of (a);
(c) TEM image of aqueous solution of WP7 and 3 after further irradiation with visible light at 435 nm;
(d) DLS result of (c).

13. ② -3 DLS &TEM + THERMOresponsive
Observe the self-assembly behavior of the supra-amphiphilic polypseudorotaxane
in water
② -3 DLS &TEM + THERMOresponsive
(a) TEM image of an aqueous solution of 7.00 mM WP7 and
1.00 mM 3 upon heating to 60 °C;
(b) DLS result of (a);
(c) TEM
image of aqueous solution of WP7 and 3 after further cooling to 25 °C;
(d) DLS result of (c).

14. ②a new recognition motif to construct a dual-responsive
Conclusion
① a new molecular
recognition motif
(guest 1 & host)
which has
dual-responsivity　　
guest 1
host
②a new recognition motif to
construct a dual-responsive
supra-amphiphilic
polypseudorotaxane in water.
　(polymer 3 & host) 　
This work offered a new way to
combine polymer science with pillararene supramolecular
chemistry to construct functional supramolecular materials.