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. 2018 Jun 20;8(40):22530-22535.
doi: 10.1039/c8ra02146e. eCollection 2018 Jun 19.

A fluorescent calixarene-based dimeric capsule constructed via a MII-terpyridine interaction: cage structure, inclusion properties and drug release

Jun-Fang Wang  1 , Li-Yuan Huang  2 , Jian-Hua Bu  3 , Shao-Yong Li  4 , Su Qin  2 , Yao-Wei Xu  2 , Jun-Min Liu  2 , Cheng-Yong Su  2
Affiliations

A fluorescent calixarene-based dimeric capsule constructed via a MII-terpyridine interaction: cage structure, inclusion properties and drug release

Jun-Fang Wang et al. RSC Adv. .

Abstract

Two analogues of capsule-like fluorescent cages have been constructed by dimerization of terpyridine-containing calixarene derivatives utilizing a MII-terpyridine (M = Zn and Cd) interaction. 1H NMR spectral studies show that the self-assembled molecular capsules Zn4L12 and Cd4L12 have a highly symmetrical D 4h-structure. The encapsulation of the anticancer drug mercaptopurine in their cavities has been documented by NMR, ESI-TOF-MS, fluorescence switching, and molecular simulation, indicating that strong S-π and π-π interactions between drug and cage are of importance for the host-guest binding. The nanoscale cages exhibit excellent behaviors to control the release of mercaptopurine in phosphate buffered saline solution (pH = 7.4). These results further highlight the potential of self-assembled Zn4L12 cages for drug-carrier applications.

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Conflict of interest statement

We have no competing interests.

Figures

Scheme 1
Scheme 1. The synthesis of calix[4]arene based nanocapsules.
Fig. 1
Fig. 1. 1H NMR spectra (400 MHz, 298 K) of (a) ligand L1 (CDCl3) and (b) Cd4(L1)2(PF6)8 MOC (CD3CN).
Fig. 2
Fig. 2. 1H DOSY spectrum (400 MHz, CD3CN, 298 K) of Cd4(L1)2(PF6)8 MOC.
Fig. 3
Fig. 3. ESI-MS spectrum of Cd4(L1)2(PF6)8 MOC.
Fig. 4
Fig. 4. The optimized structures of Zn4L12 (a) and 4(mercaptopurine)@Zn4L12 (b). The interactions are colored in dotted lines: coordination bond in gray, S–π interaction in green, S–H–π interaction in yellow and π–π interaction in pink. All hydrogens are omitted for clarity.
Fig. 5
Fig. 5. (a) UV-Vis and (b) fluorescent titrations of Zn4L12 (1.23 × 10−6 mol L−1) with mercaptopurine in MeCN and H2O (2 : 1 v/v). From a to u: 0, 0.5, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 5.5, 6.0, 6.5 equiv.; from a to h: 0, 0.5, 1.0, 1.5, 2.0, 3.0, 4.0, 5.0, 6.0, 7.0, 8.0, 9.0, 10.0, 11.0, 15.0, 19.0, 23.0, 28.0, 38.0, 48.0, 58.0 equiv.
Fig. 6
Fig. 6. The release of mercaptopurine from control (red circle) and mercaptopurine@Zn4L12 (black square).
See this image and copyright information in PMC

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