Tunable dynamic hydrophobic attachment of guest molecules in amphiphilic core–shell polymers

Tunable dynamic hydrophobic attachment of guest molecules in amphiphilic core–shell polymers
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两亲性核壳聚合物中客体分子的可调节动态疏水附着

DOI:
10.1039/c6py01335j
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发表时间:
2016
期刊:
影响因子:
4.6
通讯作者:
Dariush Hinderberger
Dariush Hinderberger
中科院分区:
化学2区
文献类型:
--
作者:
Jörg Reichenwallner;Anja Thomas;Lutz Nuhn;Tobias Johann;Annette Meister;Holger Frey;Dariush Hinderberger

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在这项研究中,两亲性核壳聚合物的合成和动态性能的报告,通过监测它们与小的两亲性分子的相互作用。刷状结构是利用由连接到亚烷基甲基丙烯酸酯的线性聚甘油链组成的大分子单体的受控自由基加成-断裂链转移(RAFT)聚合形成的,其中疏水性核被亲水性壳包围。采用连续波电子顺磁共振(CW EPR)技术研究了两亲性顺磁自旋探针16-DSA(16-doxyl stearic acid)与疏水核中不同链长的亚烷基聚合物和亲水壳中不同链长的聚甘油聚合物的相互作用。自旋探针表现出动态的疏水性连接的聚合物,并揭示了一个间接的,基于动力学的聚合物效应,如温度响应,聚集和配体结合特性的看法。增加聚合物中的疏水亚烷基链长度显著改变了核心区域的物理性质。可以通过聚合度和亚烷基间隔基长度来调节大量可控的官能聚合物性质。聚合物的部分聚集进一步改变了结合特性。应用动态光散射(DLS),透射电子显微镜(TEM)和分子动力学(MD)模拟,与EPR光谱发现的复杂的动力学行为进一步补充和验证。
In this study, synthesis and dynamic properties of amphiphilic core–shell polymers are reported as monitored through their interaction with small amphiphilic molecules. Brush-like structures are formed with a hydrophobic core surrounded by a hydrophilic shell utilizing controlled radical addition–fragmentation chain transfer (RAFT) polymerization of macromonomers consisting of linear polyglycerol chains attached to alkylene methacrylate. Continuous wave electron paramagnetic resonance (CW EPR) spectroscopy is employed to study how the amphiphilic, paramagnetic spin probe 16-DSA (16-doxyl stearic acid) interacts with polymers of different alkylene chain lengths in their hydrophobic cores and different polyglycerol chain lengths in their hydrophilic shells. The spin probe exhibits dynamic hydrophobic attachment to the polymers and reveals an indirect, dynamics-based view of polymer effects such as temperature response, aggregation and ligand binding properties. Increasing the hydrophobic alkylene chain length in the polymers alters the physical properties of the core region significantly. A large set of controllable functional polymer properties can be adjusted by the degree of polymerization and alkylene spacer length. Partial aggregation of the polymers further modifies the binding properties. Applying dynamic light scattering (DLS), transmission electron microscopy (TEM) and molecular dynamic (MD) simulations, the complex dynamic behavior found with EPR spectroscopy was further complemented and verified.
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