Surface modification of polymers with self-assembled molecular structures: Multitechnique surface characterization

Surface modification of polymers with self-assembled molecular structures: Multitechnique surface characterization
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DOI:
10.1021/bm000292w
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发表时间:
2000-03-01
期刊:
影响因子:
6.2
通讯作者:
Ratner, BD
Ratner, BD
中科院分区:
化学2区
文献类型:
--
作者:
Kwok, CS;Mourad, PD;Ratner, BD

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开发了一种简单的一步法,通过氨基甲酸乙酯键在聚合物表面生成有序的结晶亚甲基链。在双酸二丁基锡催化下,异氰酸十二酯与表面羟基官能团反应,在交联聚甲基丙烯酸2-羟乙基(pHEMA)底物上形成全反式晶体结构。未观察到阿尔法酸盐侧分支反应。x射线光电子能谱和飞行时间二次离子质谱分析表明,在60°c温度下,30 min后表面反应达到饱和。无偏振傅里叶变换红外衰减全反射表明,在30 min后,拉伸频率nu CH2,对称和nu CH2,对称。减小并接近2920和2850 cm(-1),表明结晶相。两个羟基之间的距离大约是4埃。根据两相和Harrick薄膜近似,偏振ATR测量的二向色比估计出倾斜角度为33.5°+/- 2.4°。本文报道的研究结果具有重要意义,因为使用类似于自组装单层(sam)结构的可能性超出了大多数文献中使用的刚性金和硅表面。因此,sam,有序脂质细胞壁结构的仿生学,可以应用于现实世界的生物医学聚合物,以改变生物相互作用。类sam结构的末端基团可以用生物分子或抗体进一步功能化,以开发基于表面的诊断、生物传感器或生物材料。
A simple, one-step procedure for generating ordered, crystalline methylene chains on polymeric surfaces via urethane linkages was developed. The reaction of dodecyl isocyanate with surface hydroxyl functional groups, catalyzed by dibutyltin dilaurate, formed a predominantly all-trans, crystalline structure on a crosslinked poly(2-hydroxyethyl methacrylate) (pHEMA) substrate. Allophanate side-branching reactions were not observed. Both X-ray photoelectron spectrocopy and time-of-flight secondary ion mass spectrometry show that the surface reaction reached saturation after 30 min at 60 degreesC. Unpolarized Fourier transform infrared-attenuated total reflection showed that, after 30 min, the stretching frequencies, nu CH2,asym and nu CH2,sym. decreased and approached 2920 and 2850 cm(-1), indicative of a crystalline phase. The distance between two hydroxyl groups is roughly 4 Angstrom. A tilt angle of 33.5 degrees +/- 2.4 degrees was estimated by dichroic ratios measured in polarized ATR according to the two-phase and Harrick thin film approximations. The findings reported here are significant in that the possibilities for using structures similar to self-assembled monolayers (SAMs) are expanded beyond the rigid gold and silicon surfaces used through most of the literature. Thus, SAMs, biomimetics for ordered lipid cell wall structures, can be applied to real-world biomedical polymers to modify biological interactions. The terminal groups of the SAM-like structure can be further functionalized with biomolecules or antibodies to develop surface-based diagnostics, biosensors, or biomaterials.