Poly(Acrylic Acid-b-Styrene) Amphiphilic Multiblock Copolymers as Building Blocks for the Assembly of Discrete Nanoparticles.
Poly(Acrylic Acid-b-Styrene) Amphiphilic Multiblock Copolymers as Building Blocks for the Assembly of Discrete Nanoparticles.
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DOI：
10.1021/ma102869y
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发表时间：
2011-03-04
期刊：
影响因子：
5.5
通讯作者：
Kiick KL
中科院分区：
文献类型：
--
作者：
Greene AC;Zhu J;Pochan DJ;Jia X;Kiick KL
为了扩大现有聚合物胶束系统的实用性，我们开发了含有聚丙烯酸和聚苯乙烯交替嵌段的两亲性多嵌段共聚物。通过原子转移自由基聚合（ATRP）合成了含有α-炔和ω-叠氮化物的杂遥爪聚（丙烯酸叔丁酯-b-苯乙烯）二嵌段共聚物，可以控制分子量，同时保持窄的多分散指数。该多嵌段共聚物是通过叠氮-炔末端官能化二嵌段共聚物的铜催化叠氮-炔环加成反应构建的，然后通过 1H NMR、FT-IR 和 SEC 进行表征。聚(丙烯酸叔丁酯-b-苯乙烯)多嵌段共聚物的叔丁基部分很容易被除去，形成聚(丙烯酸-b-苯乙烯)多嵌段共聚物((PAA-PS)9)，其含有多达9个二嵌段重复序列。两亲性多嵌段 (PAA-PS)9 (Mn = 73.3 kg/mol) 通过溶解到四氢呋喃中并用去离子水广泛透析 4 天来自组装。 (PAA-PS)9 的临界胶束浓度 (CMC) 使用芘作为荧光探针通过荧光光谱法测定，结果发现临界胶束浓度非常低，为 2 × 10-4 mg/mL。还通过动态光散射 (DLS) 和透射电子显微镜 (TEM) 分析了 (PAA-PS)9 多嵌段。发现颗粒的流体动力学直径为11 nm。通过TEM观察到离散的球形颗粒，平均粒径为14nm。球形颗粒的聚（丙烯酸）外围应允许生物分子将来结合。
In order to expand the utility of current polymeric micellar systems, we have developed amphiphilic multiblock copolymers containing alternating blocks of poly(acrylic acid) and poly(styrene). Heterotelechelic poly(tert-butyl acrylate-b-styrene) diblock copolymers containing an α-alkyne and an ω-azide were synthesized by atom transfer radical polymerization (ATRP), allowing control over the molecular weight while maintaining narrow polydispersity indices. The multiblock copolymers were constructed by copper-catalyzed azide-alkyne cycloaddition of azide-alkyne end functional diblock copolymers which were then characterized by 1H NMR, FT-IR and SEC. The tert-butyl moieties of the poly(tert-butyl acrylate-b-styrene) multiblock copolymers were easily removed to form the poly(acrylic acid-b-styrene) multiblock copolymer ((PAA-PS)9), which contained up to 9 diblock repeats. The amphiphilic multiblock (PAA-PS)9 (Mn = 73.3 kg/mol) was self-assembled by dissolution into tetrahydrofuran and extensive dialysis against deionized water for 4 days. The critical micelle concentration (CMC) for (PAA-PS)9 was determined by fluorescence spectroscopy using pyrene as a fluorescent probe and was found to be very low at 2 × 10-4 mg/mL. The (PAA-PS)9 multiblock was also analyzed by dynamic light scattering (DLS) and transmission electron microscopy (TEM). The hydrodynamic diameter of the particles was found to be 11 nm. Discrete spherical particles were observed by TEM with an average particle diameter of 14 nm. The poly(acrylic acid) periphery of the spherical particles should allow for future conjugation of biomolecules.
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