Fabrication of multifunctional surfaces with complexity approaching that found in nature requires the application of a modular approach to surface engineering. We describe a versatile post-polymerization modification strategy to synthesize multifunctional polymer brush surfaces via combination of surface-initiated photopolymerization (SIP) and orthogonal thiol-click reactions. Specifically, we demonstrate two routes to multifunctional brush surfaces: in the first approach, alkyne-functionalized homopolymer brushes are modified with multiple thiolsvia a statistical, radical-mediated thiol-yne co-click reaction; and in the second approach, statistical copolymer brushes carrying two distinctly-addressable reactive moieties are sequentially modified via orthogonal base-catalyzed thiol-X (where X represents an isocyanate, epoxy, or α-bromoester) and radical-mediated thiol-yne reactions. In both cases, we show that surface properties, in the form of wettability, can be easily tuned over a wide range by judicious choice of brush composition and thiol functionality.
要制造出复杂程度接近自然界的多功能表面,需要采用模块化的表面工程方法。我们介绍了一种多功能聚合后改性策略,通过结合表面引发的光聚合(SIP)和正交巯基点击反应合成多功能聚合物刷表面。具体来说,我们展示了两种获得多功能刷表面的途径:在第一种方法中,通过统计、自由基介导的巯基-炔基共点击反应,用多个巯基对炔基官能化均聚物刷进行改性;在第二种方法中,通过正交碱催化的巯基-X(其中 X 代表
异氰酸酯、环氧
树脂或 α-
溴酯)和自由基介导的巯基-炔基反应,依次改性携带两个不同地址活性分子的统计共聚物刷。在这两种情况下,我们都表明,通过明智地选择刷成分和
硫醇官能度,可以很容易地在很大范围内调整润湿性形式的表面特性。