Glucose-Responsive Hybrid Nanoassennblies in Aqueous Solutions: Ordered Phenylboronic Acid within Intermixed Poly(4-hydroxystyrene)-block-poly(ethylene oxide) Block Copolymer
Glucose-Responsive Hybrid Nanoassennblies in Aqueous Solutions: Ordered Phenylboronic Acid within Intermixed Poly(4-hydroxystyrene)-block-poly(ethylene oxide) Block Copolymer
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DOI：
10.1021/acs.biomac.5b01325
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发表时间：
2015-12-01
影响因子：
6.2
通讯作者：
Stepanek, Miroslav
中科院分区：
文献类型：
--
作者：
Matuszewska, Alicja;Uchman, Mariusz;Stepanek, Miroslav
研究了双亲水性嵌段共聚物聚（4-羟基苯乙烯）-嵌段聚（环氧乙烷）（PHOS-PEO）与三种疏水性不同的两亲性苯基硼酸（PBA）、4-十二烷氧基苯基硼酸（C12）、4-辛氧基苯基硼酸（C8）和4-异丁氧基苯基硼酸（i-Bu）在碱性水溶液和混合物中的共组装行为。通过自旋回波 H-1 NMR 光谱、动态和电泳光散射以及 SAXS 分析 NaOHaq/THF。研究表明，只有 C12 与 PHOS PEO 共组装才能提供具有混合的 PHOS 和 PEO 块的球形纳米颗粒，其中含有密集的 C12 胶束。 NMR 测量表明，PHOS-PEO 和 C12 的空间接近导致 PHOS 嵌段的 OH 和 -B(OH)(2) 的羟基之间形成酯键。由于 PBA 部分的存在，通过添加与 PBA 竞争性结合的过量葡萄糖，可以触发通过与 PBA 共价结合而负载在共组装的 PHOS-PEO/PBA 纳米颗粒中的具有 1,2-或 1,3-二羟基基团的化合物的释放。后一个特征已通过使用茜素红作为模型化合物的荧光测量得到证实。通过光散射检测，纳米颗粒被证明表现出对葡萄糖的响应而膨胀。
Coassembly behavior of the double hydrophilic block copolymer poly(4-hydroxystyrene)-block-poly(ethylene oxide) (PHOS-PEO) with three amphiphilic phenylboronic acids (PBA) differing in hydrophobicity, 4-dodecyloxyphenylboronic acid (C12), 4-octyloxyphenylboronic acid (C8), and 4-isobutoxyphenylboronic acid (i-Bu) was studied in alkaline aqueous solutions and in mixtures of NaOHaq/THF by spin echo H-1 NMR spectroscopy, dynamic and electrophoretic light scattering, and SAXS. The study reveals that only the coassembly of C12 with PHOS PEO provides spherical nanoparticles with intermixed PHOS and PEO blocks, containing densely packed C12 micelles. NMR measurements have shown that spatial proximity of PHOS-PEO and C12 leads to the formation of ester bonds between OH of PHOS block and hydroxyl groups of -B(OH)(2). Due to the presence of PBA moieties, the release of compounds with 1,2- or 1,3-dihydroxy groups loaded in the coassembled PHOS-PEO/PBA nanoparticles by covalent binding to PBA can be triggered by addition of a surplus of glucose that bind to PBA competitively. The latter feature has been confirmed by fluorescence measurements using Alizarin Red as a model compound. Nanoparticles were proved to exhibit swelling in response to glucose as detected by light scattering.