Department of Chemical Engineering and ‡Department of Engineering Physics, McMaster University , 1280 Main Street West, Hamilton, Ontario Canada , L8S 4L7.
ACS Appl Mater Interfaces. 2017 Feb 15;9(6):5622-5628. doi: 10.1021/acsami.6b15319. Epub 2017 Feb 6.
Layer-by-layer (LbL) assemblies of polyvinylamine with grafted TEMPO moieties (PVAm-T) with sodium polystyrenesulfonate (PSS) were prepared on gold-sulfonate surfaces, and the redox properties were measured by cyclic voltammetry. LbL compositions were probed by quartz crystal microbalance (wet) and ellipsometric (dry) film measurements. Approximately 30% of the TEMPO moieties in the LbL assemblies were redox-active when the total TEMPO coverage was varied up to 6 μmol/m, by either varying the TEMPO content in PVAm-T or by varying the number of LbL bilayers. Three non-redox-active PVAm/PSS blocking bilayers were required to prevent the electrode from oxidizing PVAm-T in the exterior LbL layer. This suggests significant intermixing between the layers in the LbL film. In addition to contributing to the small but growing body of work on redox polymers based on grafted TEMPO, this work serves as a reference point for understanding the redox properties of colloidal PVAm-T-laccase complexes in future work.
将接枝有 TEMPO 部分的聚乙烯亚胺（PVAm-T）与聚苯乙烯磺酸钠（PSS）进行层层（LbL）组装在金硫酸盐表面上，并通过循环伏安法测量其氧化还原性质。通过石英晶体微天平（湿）和椭圆光度法（干）薄膜测量来探测 LbL 组成。当总 TEMPO 覆盖率高达 6 μmol/m 时，通过改变 PVAm-T 中的 TEMPO 含量或改变 LbL 双层的数量，LbL 组装体中约有 30%的 TEMPO 部分具有氧化还原活性。需要三个非氧化还原活性的 PVAm/PSS 阻断双层来防止电极在外层 LbL 层中氧化 PVAm-T。这表明 LbL 薄膜中的层之间存在明显的混合。除了为基于接枝 TEMPO 的氧化还原聚合物的少量但不断增长的研究工作做出贡献外，这项工作还为未来理解胶体 PVAm-T-漆酶复合物的氧化还原性质提供了参考点。
