Wang Guang, Garvey Christopher J, Zhang Juan, O'Dell Luke A, Krause-Heuer Anwen M, Forsyth Maria, Darwish Tamim A, Miloš Steinhart, Kong Lingxue
Deakin University, Geelong, Institute for Frontier Materials, Locked Bag 20000, VIC 3220, Australia. Institute of Macromolecular Chemistry, Czech Academy of Sciences, Heyrovského nám.2, 162062, Prague 6, Czech Republic.
J Phys Condens Matter. 2020 Feb 13;32(7):075101. doi: 10.1088/1361-648X/ab49a8. Epub 2019 Oct 1.
Producing nanopores from hexagonal lyotropic liquid crystals (LLCs) templates requires not only retaining phase morphology of the templates but also precisely controlling structural dimensions of unit cells. In this study, SAXS and H NMR are used to investigate dimensional evolutions of ternary systems consisting of polymerizable species, (ethylene glycol) diacrylate (PEGDA) and/or 2-hydroxyethyl methacrylate (HEMA), in a LLCs template of hexagonally packed cylinders formed from dodecyl trimethylammonium bromide (DTAB) and water. With the addition of those polymerizable species, the system rearranges into a new hexagonal system with a smaller aggregation number, smaller pores and a thicker pore wall thickness. The hexagonal system will coexist with an aqueous-rich phase containing isotropically distributed DTAB if sufficient PEGDA is applied but the single hexagonal system could be restored by partially replacing the PEGDA with HEMA. The mobility of DTAB molecules within the aggregates varies depending on monomer compositions. The changes in structural dimensions of the unit cells and phase behaviors after adding polymerizable monomers allow dimensional control of mesochannels and potentially enable the control of selectivity and robustness of polymerized nanomaterials via molecular design.
从六方溶致液晶(LLCs)模板制备纳米孔不仅需要保留模板的相形态,还需要精确控制晶胞的结构尺寸。在本研究中,小角X射线散射(SAXS)和氢核磁共振(H NMR)被用于研究由可聚合物质、(乙二醇)二丙烯酸酯(PEGDA)和/或甲基丙烯酸2-羟乙酯(HEMA)组成的三元体系在由十二烷基三甲基溴化铵(DTAB)和水形成的六方堆积圆柱状LLCs模板中的尺寸演变。随着这些可聚合物质的加入,体系重排成一个新的六方体系,其聚集数更小、孔更小且孔壁厚度更厚。如果加入足够的PEGDA,六方体系将与含有各向同性分布的DTAB的富水相共存,但通过用HEMA部分替代PEGDA可以恢复单一的六方体系。聚集体内DTAB分子的迁移率因单体组成而异。加入可聚合单体后晶胞结构尺寸和相行为的变化允许对介孔通道进行尺寸控制,并有可能通过分子设计实现对聚合纳米材料的选择性和稳定性的控制。