Zwitterionic poly(amino acid methacrylate) brushes.

Zwitterionic poly(amino acid methacrylate) brushes.
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DOI:
10.1021/ja503400r
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发表时间:
2014-07-02
影响因子:
15
通讯作者:
Armes, Steven P.
Armes, Steven P.
中科院分区:
化学1区
文献类型:
--
作者:
Alswieleh, Abdullah M.;Cheng, Nan;Canton, Irene;Ustbas, Burcin;Xue, Xuan;Ladmiral, Vincent;Xia, Sijing;Ducker, Robert E.;El Zubir, Osama;Cartron, Michael L.;Hunter, C. Neil;Leggett, Graham J.;Armes, Steven P.

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一种新的半胱氨酸基甲基丙烯酸单体(CysMA)方便地合成通过选择性thia-Michael加成的市售的甲基丙烯酸酯-丙烯酸酯前体在水溶液中,而不求助于保护基化学。采用原子转移自由基聚合法在硅片表面制备了聚半胱氨酸甲基丙烯酸酯(PCysMA)刷。刷厚度ca.在20 °C下在270分钟内达到27 nm。每个CysMA残基包含伯胺和羧酸。表面zeta电位和原子力显微镜(AFM)的pH响应PCysMA刷的研究证实,它们是高度扩展低于pH 2或高于pH 9.5,因为它们具有阳离子或阴离子的字符,分别。在中等pH下,PCysMA刷是两性离子的。在生理pH下,它们表现出优异的抗生物污染性和可忽略的细胞毒性。PCysMA刷进行光降解:AFM形貌成像表明从刷层的显着质量损失,而XPS研究证实,暴露于UV辐射产生的表面醛的网站,可以随后与胺衍生。使用光掩模的UV曝光产生尖锐的、轮廓分明的微图案化的PCysMA刷,其用能够与绿色荧光蛋白(GFP)缀合的醛基官能化。使用干涉光刻法获得纳米图案化的PCysMA刷,并且共聚焦显微镜再次证实GFP的选择性缀合。最后,PCysMA在碱性溶液中经历复杂的碱催化降解,导致几个小分子的消除。然而,当PCysMA刷浸入生理pH的水溶液中时,观察到良好的长期化学稳定性。
A new cysteine-based methacrylic monomer (CysMA) was conveniently synthesized via selective thia-Michael addition of a commercially available methacrylate-acrylate precursor in aqueous solution without recourse to protecting group chemistry. Poly(cysteine methacrylate) (PCysMA) brushes were grown from the surface of silicon wafers by atom-transfer radical polymerization. Brush thicknesses of ca. 27 nm were achieved within 270 min at 20 °C. Each CysMA residue comprises a primary amine and a carboxylic acid. Surface zeta potential and atomic force microscopy (AFM) studies of the pH-responsive PCysMA brushes confirm that they are highly extended either below pH 2 or above pH 9.5, since they possess either cationic or anionic character, respectively. At intermediate pH, PCysMA brushes are zwitterionic. At physiological pH, they exhibit excellent resistance to biofouling and negligible cytotoxicity. PCysMA brushes undergo photodegradation: AFM topographical imaging indicates significant mass loss from the brush layer, while XPS studies confirm that exposure to UV radiation produces surface aldehyde sites that can be subsequently derivatized with amines. UV exposure using a photomask yielded sharp, well-defined micropatterned PCysMA brushes functionalized with aldehyde groups that enable conjugation to green fluorescent protein (GFP). Nanopatterned PCysMA brushes were obtained using interference lithography, and confocal microscopy again confirmed the selective conjugation of GFP. Finally, PCysMA undergoes complex base-catalyzed degradation in alkaline solution, leading to the elimination of several small molecules. However, good long-term chemical stability was observed when PCysMA brushes were immersed in aqueous solution at physiological pH.
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期刊: Langmuir : the ACS journal of surfaces and colloids
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