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聚恶唑啉的一锅法聚合及表面涂层:从合成到抗污染性能全面超越聚环氧乙烷。

Poly(2-oxazoline)s One-Pot Polymerization and Surface Coating: From Synthesis to Antifouling Properties Out-Performing Poly(ethylene oxide).

机构信息

Institute of Macromolecular Chemistry , Czech Academy of Sciences , Heyrovskeho nam. 2 , 162 06 Prague 6 , Czech Republic.

出版信息

Biomacromolecules. 2019 Sep 9;20(9):3453-3463. doi: 10.1021/acs.biomac.9b00751. Epub 2019 Aug 5.

Abstract

Poly(2-alkyl-2-oxazoline)s (PAOx) represent a class of emerging polymers that can substitute or even outperform poly(ethylene oxide) (PEO) standard in various applications. Despite the great advances in PAOx research, there is still a gap in the direct experimental comparison of antifouling properties between PAOx and the golden standard PEO when exposed to blood. Motivated by this, we developed a straightforward protocol for the one-pot PAOx polymerization and surface coating by a "grafting to-" approach. First, we synthesized a library of hydrophilic poly(2-methyl-2-oxazoline)s (PMeOx) and poly(2-ethyl-2-oxazoline)s (PEtOx) with molar mass ranging from 1.5 to 10 kg/mol (DP = 16-115). The PAOx living chains were directly terminated by amine and hydroxyl groups of polydopamine (PDA) anchor layer providing the highest so far reported grafting densities ranging from 0.2 to 2.1 chains/nm. In parallel, PEO chains providing the same degree of polymerization (molar mass from 1.2 to 5 kg/mol, DP = 28-116) bearing thiol groups were grafted to PDA. The thickness, surface-related parameters, covalent structure, and antifouling properties of the resulting polymer brushes were determined via various surface sensitive techniques. The comparison of the synthesized PAOx and PEO brushes led us to the conclusion that at the same surface-related parameters, PMeOx brushes show significantly better antifouling character when challenged against human blood plasma.

摘要

聚(2-烷基-2-恶唑啉)(PAOx)代表了一类新兴的聚合物,在各种应用中可以替代甚至优于聚(氧化乙烯)(PEO)标准。尽管在 PAOx 研究方面取得了巨大进展,但在将其与作为金标准的 PEO 直接暴露于血液的情况下进行抗污性能的实验对比方面仍存在差距。受此启发,我们开发了一种通过“接枝到”方法进行一锅法 PAOx 聚合和表面涂层的简单方案。首先,我们合成了一系列亲水性聚(2-甲基-2-恶唑啉)(PMeOx)和聚(2-乙基-2-恶唑啉)(PEtOx),其分子量从 1.5 到 10 千克/摩尔(DP=16-115)不等。PAOx 活性链直接被聚多巴胺(PDA)锚定层中的氨基和羟基终止,提供了迄今为止报道的最高接枝密度,范围从 0.2 到 2.1 链/纳米。同时,具有巯基的提供相同聚合度(分子量从 1.2 到 5 千克/摩尔,DP=28-116)的 PEO 链被接枝到 PDA 上。通过各种表面敏感技术来确定所得聚合物刷的厚度、表面相关参数、共价结构和抗污性能。对合成的 PAOx 和 PEO 刷的比较使我们得出结论,在相同的表面相关参数下,PMeOx 刷在与人血浆接触时表现出明显更好的抗污特性。

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