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Reactive Polymer Multilayers Fabricated by Covalent Layer-by-Layer Assembly: 14-Conjugate Addition-Based Approaches to the Design of Functional Biointerfaces

机译:反应性聚合物多层捏造通过共价层逐层大会:14-共轭加成的办法处理功能生物界面的设计

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摘要

We report on conjugate addition-based approaches to the covalent layer-by-layer assembly of thin films and the post-fabrication functionalization of biointerfaces. Our approach is based on a recently reported approach to the ‘reactive’ assembly of covalently-crosslinked polymer multilayers driven by the 1,4-conjugate addition of amine functionality in poly(ethyleneimine) (PEI) to the acrylate groups in a small-molecule pentacrylate species (5-Ac). This process results in films containing degradable β-amino ester crosslinks and residual acrylate and amine functionality that can be used as reactive handles for the subsequent immobilization of new functionality. Layer-by-layer growth of films fabricated on silicon substrates occurred in a supra-linear manner to yield films ~750 nm thick after the deposition of 80 PEI/5-Ac layers. Characterization by AFM suggested a mechanism of growth that involves the reactive deposition of nanometer-scale aggregates of PEI and 5-Ac during assembly. IR spectroscopy studies revealed covalent assembly to occur by 1,4-conjugate addition without formation of amide functionality. Additional experiments demonstrated that acrylate-containing films could be post-functionalized via conjugate addition reactions with small-molecule amines that influence important bio-interfacial properties, including water contact angles and the ability of film-coated surfaces to prevent or promote the attachment of cells in vitro. For example, whereas conjugation of the hydrophobic molecule decylamine resulted in films that supported cell adhesion and growth, films treated with the carbohydrate-based motif D-glucamine resisted cell attachment and growth almost completely for up to 7 days in serum-containing media. We demonstrate that this conjugate addition-based approach also provides a means of immobilizing functionality through labile ester linkages that can be used to promote the long-term, surface-mediated release of conjugated species and promote gradual changes in interfacial properties upon incubation in physiological media (e.g., over a period of at least one month). These covalently-crosslinked films are relatively stable in biological media for prolonged periods, but they begin to physically disintegrate after ~30 days, suggesting opportunities to use this covalent layer-by-layer approach to design functional biointerfaces that ultimately erode or degrade to facilitate elimination.
机译:我们报告了基于共轭的逐层组装的薄膜的逐层组装和生物融合的后制造官能化的方法。我们的方法基于最近报道的共价交联聚合物多层的“反应性”组装的方法,其由聚(亚乙基亚胺)(PEI)中的1,4-缀合物加入胺官能团(PEI)中的胺官能团中的小分子中的丙烯酸酯基团。戊二酸酯物种(5-AC)。该方法导致含有可降解的β-氨基酯交联和残留丙烯酸酯和胺官能团的薄膜,其可用作随后的新功能的活性手柄。在硅基衬底上制造的薄膜的层逐层生长以沉积80PEI / 5-AC层后产生〜750nm厚的薄膜。 AFM表征提出了一种增长机制,其涉及在组装期间PEI和5-AC的纳米级聚集体的反应性沉积。 IR光谱学研究显示,通过1,4-缀合物的加法显示共价组件,而不会形成酰胺官能度。另外的实验证明,含丙烯酸酯的薄膜可以通过与小分子胺的缀合物添加反应后官能化,该小分子胺影响重要的生物界面性质,包括水接触角度和薄膜涂层表面预防或促进细胞附着的能力体外。例如,虽然疏水分子甲胺的缀合导致薄膜负载粘附和生长,用基于碳水化合物的基胺D-葡聚糖的膜处理的薄膜在含血清培养基中几乎完全抵抗电池附着和生长最多7天。我们证明这种基于共轭添加的方法还通过不稳定的酯键提供了可用于促进共轭物质的长期,表面介导的缀合物释放的不稳定酯连杆的方法,并促进在生理介质中孵育时界面性质的逐渐变化(例如,在至少一个月的时间内)。这些共价交联的薄膜在生物介质中相对稳定,长时间,但它们在〜30天后开始物理崩解,建议使用这种共价层逐层方法设计最终侵蚀或降解的功能性生物界面以便于消除。

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  • 期刊名称 other
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  • 年(卷),期 -1(13),5
  • 年度 -1
  • 页码 1523–1532
  • 总页数 23
  • 原文格式 PDF
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