Complex micelles with the bioactive function of reversible oxygen transfer
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- 作者：Liangliang Shen ; Lizhi Zhao ; Rui Qu ; Fan Huang ; Hongjun Gao ; Yingli An…
- 关键词：ionic block copolymer ; bioactive self ; assembly ; metalloporphyrin ; reversible dioxygen ; binding ; proton sponge effect
- 刊名：Nano Research
- 出版年：2015
- 出版时间：February 2015
- 年：2015
- 卷：8
- 期：2
- 页码：491-501
- 全文大小：2,794 KB
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- 刊物主题：Chinese Library of Science
Chemistry
Nanotechnology- 出版者：Tsinghua University Press, co-published with Springer-Verlag GmbH
- ISSN：1998-0000
文摘
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 S2O4 2?/sup> 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.