Kobayashi Tsubasa, Li Ya-Xin, Ono Ayaka, Zeng Xiang-Bing, Ichikawa Takahiro
Department of Biotechnology , Tokyo University of Agriculture and Technology , Naka-cho, Koganei , Tokyo , 184-8588 , Japan . Email:
Department of Materials Science and Engineering , University of Sheffield , Sheffield S1 3JD , UK.
Chem Sci. 2019 Jun 17;10(25):6245-6253. doi: 10.1039/c9sc00131j. eCollection 2019 Jul 7.
A polymerizable amphiphile having two zwitterionic head-groups has been designed. This compound co-organizes with an acid, bis(trifluoromethanesulfonyl)imide (HTfN), into a gyroid bicontinuous cubic liquid-crystalline phase. polymerization of this phase has been successfully achieved by UV irradiation in the presence of a photoinitiator, yielding a self-standing gyroid-nanostructured polymer film. When the polymer film is placed under different relative humidity conditions or in water, it absorbs water owing to the strong hydration ability of the zwitterionic parts. It has been found that the polymer film preserves the gyroid nanostructure after the water absorption. Based on reconstructed electron density maps, it is assumed that the absorbed water molecules form a 3D continuous network along the gyroid minimal surface, which satisfies several key conditions for inducing fast proton conduction. As expected, such hydrated films show high ionic conductivities in the order of 10 S cm when the water content of the film reaches 15.6 wt% at RH = 90%. The high conductivity is attributed to the induction of the Grotthuss mechanism, that is, proton conduction the hydrogen-bonding network of the incorporated water molecules.
一种具有两个两性离子头基的可聚合两亲物已被设计出来。该化合物与一种酸,双(三氟甲磺酰)亚胺(HTfN)共同组装成一种螺旋状双连续立方液晶相。在光引发剂存在下通过紫外线照射成功实现了该相的聚合,得到了一种自立的螺旋状纳米结构聚合物薄膜。当该聚合物薄膜置于不同的相对湿度条件下或水中时,由于两性离子部分的强水合能力,它会吸收水分。已发现该聚合物薄膜在吸水后保留了螺旋状纳米结构。基于重建的电子密度图,推测吸收的水分子沿着螺旋状最小表面形成三维连续网络,这满足了诱导快速质子传导的几个关键条件。正如预期的那样,当薄膜在相对湿度为90%时含水量达到15.6 wt%时,这种水合薄膜显示出高达10 S/cm的高离子电导率。高电导率归因于格罗特斯机制的诱导,即质子通过掺入水分子的氢键网络进行传导。