Synthesis and self-assembly of well-defined poly(amino acid) end-capped poly(ethylene glycol) and poly(2-methyl-2-oxazoline).
Synthesis and self-assembly of well-defined poly(amino acid) end-capped poly(ethylene glycol) and poly(2-methyl-2-oxazoline).
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DOI：
10.1021/bm201048x
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发表时间：
2011-10-10
影响因子：
6.2
通讯作者：
Scholz C
中科院分区：
文献类型：
--
作者：
Obeid R;Scholz C
聚乙二醇（PEG）和聚（2-甲基-2-恶唑啉）（PMOx）是具有隐身溶血活性的水溶性生物相容性聚合物。以聚氨基酸末端衍生物PEG和PMOx为大引发剂，在尿素存在下，室温下分别制备了γ-苄基保护的l -谷氨酸n -羧基氢化物和s -苄基氧羰基保护的l -半胱氨酸n -羧基氢化物的开环聚合反应。PAA分子量保持在Mn = 2,200 ~ 3,000 g mol - 1之间，PMOx通过阳离子开环聚合得到分子量为Mn = 5,000 ~ 10,000 g mol - 1， PEG为Mn = 5,000 g mol - 1的商品产物。在这里，我们研究了两亲性嵌段共聚物在水中的自组装，以及嵌段共聚物的化学结构对自组装纳米结构溶液性能的影响。peg -嵌段聚（氨基酸）、PEG-b-PAA和pmox -嵌段聚（氨基酸）、PMOx-b-PAA嵌段共聚物分子量分布窄且呈单峰分布（PDI < 1.3）。用动态光散射和荧光光谱技术研究了它们在水中的自组装。在水溶液中，嵌段共聚物结合成颗粒，其流体动力学半径（RH）的大小从RH 70到130 nm不等，这取决于嵌段共聚物的结构和聚合物的分子量。含有聚（s -苄基羰基- l-半胱氨酸）的共聚物相对于它们的聚（γ-苄基- l-谷氨酸）类似物获得了更大的相对湿度和临界缔合浓度值。FTIR研究表明，聚（γ-苄基- l-谷氨酸）嵌段呈螺旋结构，而聚（s -苄基羰基- l-半胱氨酸）嵌段以β -薄片形式存在。
Poly(ethylene glycol) (PEG) and poly(2-methyl-2-oxazoline) (PMOx) are water-soluble, biocompatible polymers with stealth hemolytic activities. Poly(amino acid) (PAA) end-capped PEG and PMOx were prepared using amino-terminated derivatives of PEG and PMOx as macroinitiators for the ring-opening polymerization of γ-benzyl protected L-glutamate N-carboxyanhydride and S-benzyloxycarbonyl protected L-cysteine N-carboxyanhydride, respectively, in the presence of urea, at room temperature. The molecular weight of the PAA moiety was kept between Mn = 2,200 and 3,000 g mol−1, PMOx was polymerized by cationic ring-opening polymerization resulting in molecular weights of Mn = 5,000 and 10,000 g mol−1, PEG was a commercial product with Mn = 5,000 g mol−1. Here, we investigate the self-assembly of the resulting amphiphilic block copolymers in water and the effect of the chemical structure of the block copolymers on the solution properties of self-assembled nanostructures. The PEG-block-poly(amino acid), PEG-b-PAA, and PMOx-block-poly(amino acid), PMOx-b-PAA, block copolymers have a narrow and monomodal molecular weight distribution (PDI < 1.3). Their self-assembly in water was studied by dynamic light scattering and fluorescence spectroscopy. In aqueous solution, the block copolymers associate into particles with hydrodynamic radii (RH) ranging in size from RH 70 to 130 nm, depending on the block copolymer architecture and the polymer molecular weight. Larger RH and critical association concentration values were obtained for copolymers containing poly(S-benzyloxycarbonyl-L-cysteine) compared to their poly(γ-benzyl-L-glutamate) analog. FTIR investigations revealed that the poly(γ-benzyl-L-glutamate) block adopts a helical conformation, while the poly(S-benzyloxycarbonyl-L-cysteine) block exists as β–sheet.
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影响因子：
15
作者：
KALYANASUNDARAM, K;THOMAS, JK
通讯作者：
THOMAS, JK
影响因子：
64.8
作者：
Deming, TJ
通讯作者：
Deming, TJ
影响因子：
15
作者：
LUNDBERG, RD;DOTY, P
通讯作者：
DOTY, P
影响因子：
4.6
作者：
Vayaboury, W;Giani, O;Schué, F
通讯作者：
Schué, F
影响因子：
41.2
作者：
Bellomo, EG;Wyrsta, MD;Deming, TJ
通讯作者：
Deming, TJ