3D Interconnected Ionic Nano-Channels Formed in Polymer Films: Self-Organization and Polymerization of Thermotropic Bicontinuous Cubic Liquid Crystals

Ichikawa, Takahiro; Yoshio, Masafumi; Hamasaki, Atsushi; Kagimoto, Junko; Ohno, Hiroyuki; Kato, Takashi

doi:10.1021/ja106707z

Cited by 183 publications

(190 citation statements)

References 90 publications

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“…Recently, cross-linked bicontinuous cubic Li þ -conducting materials based on thermotropic (that is, solvent-free) LC monomers have been developed by researchers in Japan as a complementary approach to the use of polymerizable Q-phase LLC assemblies. 46 SUMMARY Robust, nanoporous polymer materials with 3D-interconnected, molecular-size pores can be formed via the direct cross-linking of Q phases formed by reactive LLCs or via the templated polymerization of conventional monomers included in Q phases. These materials have exceptional potential for use in a number of transport applications.…”

Section: Design and Development Of Directly Cross-linked Q-phase Llc mentioning

confidence: 99%

Nanoporous polymer materials based on self-organized, bicontinuous cubic lyotropic liquid crystal assemblies and their applications

Wiesenauer

Gin

2012

Polym J

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The bicontinuous cubic (Q) lyotropic liquid crystal (LLC) phases formed by the phase-separation and self-organization of amphiphilic molecules in water are intriguing structures for a number of transport-related applications because they possess ordered, uniform, 3D-interconnected water channels on the size of single molecules. Polymeric materials formed from either the templated polymerization or cross-linking of conventional monomers around Q phases, or the direct polymerization or cross-linking of Q phases formed by reactive amphiphiles retain the desired LLC nanostructure but are more robust for true application development. The structures of Q LLC phases were only elucidated in the late 1980s, and the first successful preparation of polymers based on Q phases was reported soon after. However, the development and demonstration of these nanoporous polymers for material applications were not realized until the first decade of the twenty-first century. This focus review provides an overview of work in the area of Q LLC phase-based polymer materials, with a focus on the work of our research group and that of our collaborators on polymer networks prepared by the direct polymerization of reactive Q phases and their development as functional materials for several engineering applications. Keywords: bicontinuous cubic; liquid crystal; lyotropic; nanoporous; polymer INTRODUCTION Lyotropic liquid crystals (LLCs) are amphiphilic molecules typically composed of a hydrophilic headgroup section and a hydrophobic tail section that have the ability to phase-separate and self-organize into nanostructured assemblies in the presence of water. The resulting fluid, ordered LLC phases have varying degrees of average order, different levels of hydrophilic and hydrophobic domain interconnectivity, and uniform periodic features in the circa 1-10 nm size range (For general reviews on LLC phases and their classifications, see: refs 1-3). LLC phases have recently attracted a great deal of attention because of their benefits as a versatile platform for the design of functional, nanoporous polymer materials. For example, by employing reactive LLCs (that is, monomers), the desired phase can be locked-in directly via chemical cross-linking to afford robust, nanoporous polymer networks (For reviews on the synthesis and applications of nanostructured polymers made from polymerizable LLCs, see: refs 4-6). LLC networks made by this approach have been used for applications such as templated nanocomposite synthesis, drug delivery, molecular transport/separation and heterogeneous catalysis. 7,8 Alternatively, non-polymerizable LLC phases have been used as nanostructured templates for the polymerization of conventional monomers dissolved in either the hydrophilic or hydrophobic domains. Subsequent

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Section: Design and Development Of Directly Cross-linked Q-phase Llc mentioning

confidence: 99%

Nanoporous polymer materials based on self-organized, bicontinuous cubic lyotropic liquid crystal assemblies and their applications

Wiesenauer

Gin

2012

Polym J

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“…By virtue of their tethered charges, these networks are selectively conductive, inhibiting the transport of co-ions while facilitating the transport of counter-ions. The broad class of ionomer membranes have important applications in efficient energy conversion devices such as polymer electrolyte membranes for fuel cells [3][4][5][6], dye sensitized solar cells [7], bulk-heterojunction solar cells [8,9], and lithium ion batteries [1,10,11]. Considerable computational and experimental effort has been invested in the design and optimization of membranes with strongly charge-selective transport characteristics.…”

Section: Introductionmentioning

confidence: 99%

Variational Models of Network Formation and Ion Transport: Applications to Perfluorosulfonate Ionomer Membranes

Gavish

Jones

et al. 2012

Polymers

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We present the functionalized Cahn-Hilliard (FCH) energy, a continuum characterization of interfacial energy whose minimizers describe the network morphology of solvated functionalized polymer membranes. With a small set of parameters the FCH characterizes bilayer, pore-like, and micelle network structures. The gradient flows derived from the FCH describe the interactions between these structures, including the merging and pinch-off of endcaps and formation of junctions central to the generation of network morphologies. We couple the FCH gradient flow to a model of ionic transport which incorporates entropic effects to localize counter-ions, yielding a flow which dissipates a total free energy, and an expression for the excess electrochemical potential which combines electrostatic and entropic effects. We present applications to network bifurcation and membrane casting.

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“…The photopolymerization of this mixture readily leads to thermally stable polymer films with a 3D structure exhibiting ionic conductivities in the order of 10 − 3 S cm − 1 . Kato and colleagues 199 also achieved the to the 3D LC networks allowed the development of transparent lithium-ion conductor film (Figure 11). In the same vein, the polymerization of these nanostructured liquid crystals was employed to develop nano-and/or subnano-porous membranes for filtration and separation membranes.…”

Section: Functional Lc Polymers and Networkmentioning

confidence: 98%

“…[197][198][199][200][201][202][203] In this regard, Gin and co-workers reported the wedge-shaped compound 33b bearing acrylate polymerizable groups at the periphery of the three alkyl chains. 198 This molecule forms a lyotropic Cub bi phase (Q II phase) in the presence of lithium perchlorate and propylene carbonate.…”

Section: Functional Lc Polymers and Networkmentioning

confidence: 99%

Functional liquid-crystalline polymers and supramolecular liquid crystals

Kato

Uchida

Ichikawa

et al. 2017

Polym J

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100

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The design and functions of liquid-crystalline (LC) polymers with classifying them into conventional-, supramolecular-, dendriticand network-type LC polymers are described. LC polymers show new functions as new devices in the field of energy and environment by incorporating mesogenic moieties exhibiting photonic, electronic and ionic functions. Supramolecular LC polymers show dynamic and unique properties because the mesogenic moieties are built with non-covalent interactions. Dendritic-type LC polymers exhibit liquid crystallinity by nanosegregation of aromatic and aliphatic moieties. Dendritic fork-like mesogens have also been prepared. A variety of nonmesogeic functional building blocks including fullerene, π-conjugated moieties, catenane, rotaxane and others can be incorporated into LC phases by attaching these dendritic moieties. LC networks are constructed in situ polymerization of polymerizable nematic or nanostructured liquid crystals. The specific characteristics of the LC networks have generated new research trends to develop well-defined polymers that exhibit optical, transport and separation properties. In these materials, through suitable design of LC monomers, the preservation of smectic, columnar and bicontinuous cubic phases has been successfully used for the development of membranes with one-dimensional, two-dimensional and three-dimensional nanostructures.

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3D Interconnected Ionic Nano-Channels Formed in Polymer Films: Self-Organization and Polymerization of Thermotropic Bicontinuous Cubic Liquid Crystals

Cited by 183 publications

References 90 publications

Nanoporous polymer materials based on self-organized, bicontinuous cubic lyotropic liquid crystal assemblies and their applications

Nanoporous polymer materials based on self-organized, bicontinuous cubic lyotropic liquid crystal assemblies and their applications

Variational Models of Network Formation and Ion Transport: Applications to Perfluorosulfonate Ionomer Membranes

Functional liquid-crystalline polymers and supramolecular liquid crystals

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