Department of Chemical and Biomolecular Engineering, National University of Singapore, Kent Ridge, Singapore 809978.
Langmuir. 2010 Oct 5;26(19):15376-82. doi: 10.1021/la102775y.
A gold substrate with surface-grafted ferrocene functional polymer brushes, or Au-g-PFTMA surface [PFTMA = poly(5-ferrocene-triazolyl methacrylate)], was prepared by a combination of surface-initiated atom transfer radical polymerization (SI-ATRP) and "click chemistry" in one pot, in the presence of 2-azidoethyl methacrylate (AzEMA), ethynyl ferrocene, CuBr catalyst, CuBr(2) deactivator, and pentamethyldiethylenetriamine ligand. Thus, SI-ATRP of AzEMA from the Au substrate (the "grafting from" process) and click chemistry of the ethynyl ferrocene to the azide functional group of AzEMA (the "grafting to" process) proceeded simultaneously to produce the functional PFTMA brushes on the Au surface. Kinetic studies suggest that the reaction involving simultaneous SI-ATRP and click chemistry is still consistent with a controlled/"living" process. The composition and physical properties of the modified gold surface were analyzed by X-ray photoelectron spectroscopy, water contact angle measurement, and cyclic voltammetry. The redox-responsive properties of the ferrocene-functionalized polymer brushes on the Au-g-PFTMA surface were demonstrated in the reversible loading-unloading step of the β-cyclodextrin polymer via host-guest interaction.
金基底表面接枝了二茂铁功能聚合物刷，或 Au-g-PFTMA 表面 [PFTMA = 聚（5-二茂铁基三氮唑基甲基丙烯酸酯）]，通过表面引发原子转移自由基聚合（SI-ATRP）和“点击化学”的一锅法在 2-叠氮乙基甲基丙烯酸酯 (AzEMA)、乙炔基二茂铁、CuBr 催化剂、CuBr(2) 失活剂和五甲基二乙烯三胺配体的存在下制备。因此，从 Au 基底上的 AzEMA 的 SI-ATRP（“从基底上接枝”过程）和乙炔基二茂铁与 AzEMA 的叠氮官能团的点击化学（“向基底上接枝”过程）同时进行，在 Au 表面上生成功能性 PFTMA 刷。动力学研究表明，涉及同时进行的 SI-ATRP 和点击化学的反应仍然符合控制/“活”过程。通过 X 射线光电子能谱、水接触角测量和循环伏安法分析了改性金表面的组成和物理性质。通过主客体相互作用，在 β-环糊精聚合物的可逆加载-卸载步骤中，证明了 Au-g-PFTMA 表面上的二茂铁功能聚合物刷的氧化还原响应特性。
