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Nano Research

Article Title

Complex micelles with the bioactive function of reversible oxygen transfer

Authors

Liangliang Shen, State Key Laboratory of Medicinal Chemical Biology, Key Laboratory of Functional Polymer Materials, Ministry of Education, Collaborative Innovation Center of Chemical Science and Engineering(Tianjin), Institute of Polymer Chemistry, Nankai University, Tianjin, 300071, China
Lizhi Zhao, State Key Laboratory of Hollow Fiber Membrane Materials and Processes, School of Materials Science and Engineering, Tianjin Polytechnic University, Tianjin, 300387, China
Rui Qu, State Key Laboratory of Medicinal Chemical Biology, Key Laboratory of Functional Polymer Materials, Ministry of Education, Collaborative Innovation Center of Chemical Science and Engineering(Tianjin), Institute of Polymer Chemistry, Nankai University, Tianjin, 300071, China
Fan Huang, State Key Laboratory of Medicinal Chemical Biology, Key Laboratory of Functional Polymer Materials, Ministry of Education, Collaborative Innovation Center of Chemical Science and Engineering(Tianjin), Institute of Polymer Chemistry, Nankai University, Tianjin, 300071, China
Hongjun Gao, State Key Laboratory of Medicinal Chemical Biology, Key Laboratory of Functional Polymer Materials, Ministry of Education, Collaborative Innovation Center of Chemical Science and Engineering(Tianjin), Institute of Polymer Chemistry, Nankai University, Tianjin, 300071, China
Yingli An, State Key Laboratory of Medicinal Chemical Biology, Key Laboratory of Functional Polymer Materials, Ministry of Education, Collaborative Innovation Center of Chemical Science and Engineering(Tianjin), Institute of Polymer Chemistry, Nankai University, Tianjin, 300071, China
Linqi Shi, State Key Laboratory of Medicinal Chemical Biology, Key Laboratory of Functional Polymer Materials, Ministry of Education, Collaborative Innovation Center of Chemical Science and Engineering(Tianjin), Institute of Polymer Chemistry, Nankai University, Tianjin, 300071, China

Keywords

ionic block copolymer, bioactive self-assembly, metalloporphyrin, reversible dioxygen-binding, proton sponge effect

Abstract

A complex micelle as a hemoglobin functional model with the biaoactive function of reversible oxygen transfer has been constructed through the hierarchical assembly of the diblock copolymer poly(ethylene glycol)-blockpoly(4-vinylpyridine-co-N-heptyl-4-vinylpyridine) (PEG-b-P(4VP-co-4VPHep)), tetrakis(4-sulfonatophenyl)porphinato iron(II) (Fe(II)TPPS) and β-cyclodextrin (β-CD). The μ-oxo dimer of Fe(II)TPPS was successfully inhibited because the Fe(II)TPPS was included into the cavities of β-CDs through host-guest interaction. Fe(II)TPPS coordinated with pyridine groups functions as the active site to reversibly bind dioxygen. In adition, the host-guest inclusion (β-CD/Fe(II)TPPS) was encapsulated in the hydrophobic core of the complex micelle and tightly fixed by P4VP chains. The hydrophilic PEG blocks stretched in aqueous solution to constitute the shells which stabilize the structure of the complex micelle as well as endow the complex micelle with sufficient blood circulation time. Dioxygen can be bound to the Fe(II)TPPS located in the confined space and excellent reversibility of the binding–release process of dioxygen can be achieved. The quaternary amine N-heptyl-4-vinylpyridine can coerce abundant S2O42– ions into the core of the complex micelle to facilitate the self-reduction process. Dioxygen adducts (Fe(II)TPPS(O2)) were effectively protected by the double hydrophobic barriers constructed by the cavity of the cyclodextrin and the core of the complex micelle which enhances the ability to resist nucleophilic molecules. Therefore, the rationally designed amphiphilic structure can work as a promising artificial O2 carrier. Potentially, the complex micelle can be expected to improve the treatment of diseases linked with hypoxia.

Graphical Abstract

Publisher

Tsinghua University Press

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