Shifting Networks to Achieve Subgroup Symmetry Properties

Hsueh, Han‐Yu; Ling, Yi; Wang, Hsiao Fang; Chien, Lung Yu Chang; Hung, Yu Chueh; Thomas, Edwin L.; Ho, Rong Ming

doi:10.1002/adma.201305618

Cited by 57 publications

(62 citation statements)

References 21 publications

(28 reference statements)

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“…SAXS results of the resulting mS-SiO 2 showed that the symmetry breaking from Pn3m to Fd3m occurred upon heating during calcination. SEM and TEM analyses revealed the random shifting of two non-intersecting skeletal networks by showing various projections of Fd3m in a similar manner to the report by Ho and co-workers 39 (Fig. 6b-f and Supplementary Fig.…”

Section: Articlesupporting

confidence: 85%

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Mesoporous monoliths of inverse bicontinuous cubic phases of block copolymer bilayers

Park

et al. 2015

Nat Commun

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Solution self-assembly of block copolymers into inverse bicontinuous cubic mesophases is a promising new approach for creating porous polymer films and monoliths with highly organized bicontinuous mesoporous networks. Here we report the direct self-assembly of block copolymers with branched hydrophilic blocks into large monoliths consisting of the inverse bicontinuous cubic structures of the block copolymer bilayer. We suggest a facile and scalable method of solution self-assembly by diffusion of water to the block copolymer solution, which results in the unperturbed formation of mesoporous monoliths with largepore (425 nm diameter) networks weaved in crystalline lattices. The surface functional groups of the internal large-pore networks are freely accessible for large guest molecules such as protein complexes of which the molecular weight exceeded 100 kDa. The internal double-diamond (Pn3m) networks of large pores within the mesoporous monoliths could be replicated to self-supporting three-dimensional skeletal structures of crystalline titania and mesoporous silica.

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Section: Articlesupporting

confidence: 85%

“…2f) 38 . Residual solvent molecules localized in the PS-rich domain would plasticize the PS blocks constituting the bilayer, and, therefore, could develop a pressure for the local grains of Pn3m symmetry to be rearranged to a single-diamond phase with some disorder 39 .…”

Section: Articlementioning

confidence: 99%

Mesoporous monoliths of inverse bicontinuous cubic phases of block copolymer bilayers

Park

et al. 2015

Nat Commun

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“…To acquire the epoxy resins with high cross-linking density, the pore-filled PS template was heated at 60 °C for 12 hours followed by 150 °C for 0. identified. Also, it is noted that the shifting network behavior can be recognized [42] ( Figure 5b), reflecting that well-defined nanoporous epoxy with gyroid texture can be obtained. With this approach, it is reasonable to suggest that various nanoporous organics can be successfully fabricated by using the nanoporous PS template fabricated from the self-assembly of PS-PDMS for templated polymerization without delicate synthetic designs.…”

Section: A C C E P T E D Accepted Manuscriptmentioning

confidence: 83%

“…Porous materials are considered as next-generation materials due to their wide application in catalyst carriers [1,2], separators [3][4][5], sensors [2,6,7], photonics [8,9], absorbers [10], and reactors [11]. Yet, many applications in nanotechnology are limited due to the challenge of fabricating well-defined materials at the nanoscale.…”

Section: Introductionmentioning

confidence: 99%

Gyroid-structured nanoporous polymer monolith from PDMS-containing block copolymers for templated synthesis

Lin

Yang

Georgopanos

et al. 2017

Polymer

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“…[1] Thes ingle-diamond (SD) and single-gyroid (SG) structures,f ound in beetles exoskeletons and butterfly wing scales,e xhibit excellent photonic properties. [10] Thecorresponding TiO 2 structure can also be fabricated by the templated sol-gel reaction. [3] Thet hermodynamically favored bicontinuous doubleframework structures consisting of two identical intertwined labyrinths,f or example,d ouble-diamond (DD), doublegyroid (DG) and double-primitive (DP), are widely found, [4] however, they show no CBG as increasing the symmetry would suppress the photonic properties.…”

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confidence: 99%

A Shifted Double‐Diamond Titania Scaffold

Liu

Cao

et al. 2016

Angewandte Chemie

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Photonic crystals are expected to be metamaterials because of their potential to control the propagation of light in the linear and nonlinear regimes.B iological single-network, triply periodic constant mean curvature surface structures are considered excellent candidates owing to their large complete band gap.However,the chemical construction of these relevant structures is rare and developing new structures from thermodynamically stable double-network self-organizing systems is challenging.Herein, we reveal that the shifted double-diamond titania scaffold can achieve ac omplete band gap.T he largest (7.71 %) band gap is theoretically obtained by shifting 0.332 c with the dielectric contrast of titania (6.25). At itania scaffold with similar shifted double-diamond structure was fabricated using ar everse core-shell microphase-templating system with an amphiphilic diblock copolymer and at itania source in am ixture of tetrahydrofuran and water,w hichc ould result in a2 .05-3.78 %gap.Various photonic structures have been exploited for coherent light scattering through periodic changing of refractive indices. [1] Thes ingle-diamond (SD) and single-gyroid (SG) structures,f ound in beetles exoskeletons and butterfly wing scales,e xhibit excellent photonic properties. [2] In particular, SD is known as a" champion" photonic structure because it exhibits the largest complete band gap (CBG) reported so far. [3] Thet hermodynamically favored bicontinuous doubleframework structures consisting of two identical intertwined labyrinths,f or example,d ouble-diamond (DD), doublegyroid (DG) and double-primitive (DP), are widely found, [4] however, they show no CBG as increasing the symmetry would suppress the photonic properties. [3] Thethermodynamically unstable single-network structures have been achieved only through physical holographic lithography, [5] direct laser writing, [6] replication of biological templates, [7] partial occupancy of the initially formed double-network template, [8] and the so-called alternating gyroid method by selective etching one of the original DG subnetworks to yield aSGtemplate. [9] Recently,H oe tal. reported ar andom-shifted DG silica structure that disrupts the inversion symmetry of the networks,leading to the partial photonic band gap related to the subgroup symmetry. [10] Thecorresponding TiO 2 structure can also be fabricated by the templated sol-gel reaction. [11] We reported macroporous silica with azimuthally shifted DD (SDD) frameworks through the self-assembly of an amphiphilic ABC triblock terpolymer in am ixture of tetrahydrofuran and water. [12] However,t he dielectric constant of the silica (3.9) was too low to lead to CBG.In this work, we used titania with high dielectric contrast (6.25) [10] to produce the desirable CBG features of the SDD structure.W ed etermined the band gap of the SDD titania scaffold with different space occupancya nd shift value,a nd compared it to SD and SG structures.T he multi-term nodal equations [13] were used as the structural analogue of these cons...

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Shifting Networks to Achieve Subgroup Symmetry Properties

Cited by 57 publications

References 21 publications

Mesoporous monoliths of inverse bicontinuous cubic phases of block copolymer bilayers

Mesoporous monoliths of inverse bicontinuous cubic phases of block copolymer bilayers

Gyroid-structured nanoporous polymer monolith from PDMS-containing block copolymers for templated synthesis

A Shifted Double‐Diamond Titania Scaffold

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