Tracing chirality from molecular organization to triply-periodic network assemblies: Threading biaxial twist through block copolymer gyroids
Chirality transfer from the level of molecular structure up to mesoscopic lengthscales of supramolecular morphologies is a broad and persistent theme in self-assembled soft materials, from biological to synthetic matter. Here, we analyze the mechanism of chirality transfer in a prototypical self-ass...
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| Format: | Article |
| Language: | English |
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Elsevier
2023-06-01
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| Series: | Giant |
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| Online Access: | http://www.sciencedirect.com/science/article/pii/S2666542523000267 |
| _version_ | 1797801736758362112 |
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| author | Ishan Prasad Abhiram Reddy Gregory M. Grason |
| author_facet | Ishan Prasad Abhiram Reddy Gregory M. Grason |
| author_sort | Ishan Prasad |
| collection | DOAJ |
| description | Chirality transfer from the level of molecular structure up to mesoscopic lengthscales of supramolecular morphologies is a broad and persistent theme in self-assembled soft materials, from biological to synthetic matter. Here, we analyze the mechanism of chirality transfer in a prototypical self-assembly system, block copolymers (BCPs), in particular, its impact on one of the most complex and functionally vital phases: the cubic, triply-periodic, gyroid network. Motivated by recent experimental studies, we consider a self-consistent field model of ABC* triblock copolymers possessing an end-block of chiral chain chemistry and examine the interplay between chirality at the scale of networks in alternating double network phases and the patterns of segmental order within tubular network domains. We show that while segments in gyroids exhibit twist in both polar and nematic segmental order parameters, the magnitude of net nematic twist is generically much larger than polar twist, and more surprising, reverses handedness relative to the sense of polar order as well as the sense of dihedral twist of the network. Careful analysis of the intra-domain nematic order reveals that this unique chirality transfer mechanism relies on the strongly biaxial nature of segmental order in BCP networks and relates the biaxial twist to complex patterns of frame rotation of the principal directors in the intra-domain texture. Finally, we show that this mechanism of twist reversal leads to chirality selection of alternating gyroid networks in ABC* triblocks, in the limit of very weak chirality. |
| first_indexed | 2024-03-13T04:55:01Z |
| format | Article |
| id | doaj.art-ddb6a5beb414484c84ad3c1a3161ddef |
| institution | Directory Open Access Journal |
| issn | 2666-5425 |
| language | English |
| last_indexed | 2024-03-13T04:55:01Z |
| publishDate | 2023-06-01 |
| publisher | Elsevier |
| record_format | Article |
| series | Giant |
| spelling | doaj.art-ddb6a5beb414484c84ad3c1a3161ddef2023-06-18T05:03:29ZengElsevierGiant2666-54252023-06-0114100164Tracing chirality from molecular organization to triply-periodic network assemblies: Threading biaxial twist through block copolymer gyroidsIshan Prasad0Abhiram Reddy1Gregory M. Grason2Department of Chemical Engineering, University of Massachusetts, Amherst, MA 01003, USADepartment of Polymer Science and Engineering, University of Massachusetts, Amherst, MA 01003, USACorresponding author.; Department of Polymer Science and Engineering, University of Massachusetts, Amherst, MA 01003, USAChirality transfer from the level of molecular structure up to mesoscopic lengthscales of supramolecular morphologies is a broad and persistent theme in self-assembled soft materials, from biological to synthetic matter. Here, we analyze the mechanism of chirality transfer in a prototypical self-assembly system, block copolymers (BCPs), in particular, its impact on one of the most complex and functionally vital phases: the cubic, triply-periodic, gyroid network. Motivated by recent experimental studies, we consider a self-consistent field model of ABC* triblock copolymers possessing an end-block of chiral chain chemistry and examine the interplay between chirality at the scale of networks in alternating double network phases and the patterns of segmental order within tubular network domains. We show that while segments in gyroids exhibit twist in both polar and nematic segmental order parameters, the magnitude of net nematic twist is generically much larger than polar twist, and more surprising, reverses handedness relative to the sense of polar order as well as the sense of dihedral twist of the network. Careful analysis of the intra-domain nematic order reveals that this unique chirality transfer mechanism relies on the strongly biaxial nature of segmental order in BCP networks and relates the biaxial twist to complex patterns of frame rotation of the principal directors in the intra-domain texture. Finally, we show that this mechanism of twist reversal leads to chirality selection of alternating gyroid networks in ABC* triblocks, in the limit of very weak chirality.http://www.sciencedirect.com/science/article/pii/S2666542523000267Supramolecular assemblyChirality transferBlock copolymersTriply-periodicBicontinuous networksBiaxial order |
| spellingShingle | Ishan Prasad Abhiram Reddy Gregory M. Grason Tracing chirality from molecular organization to triply-periodic network assemblies: Threading biaxial twist through block copolymer gyroids Giant Supramolecular assembly Chirality transfer Block copolymers Triply-periodic Bicontinuous networks Biaxial order |
| title | Tracing chirality from molecular organization to triply-periodic network assemblies: Threading biaxial twist through block copolymer gyroids |
| title_full | Tracing chirality from molecular organization to triply-periodic network assemblies: Threading biaxial twist through block copolymer gyroids |
| title_fullStr | Tracing chirality from molecular organization to triply-periodic network assemblies: Threading biaxial twist through block copolymer gyroids |
| title_full_unstemmed | Tracing chirality from molecular organization to triply-periodic network assemblies: Threading biaxial twist through block copolymer gyroids |
| title_short | Tracing chirality from molecular organization to triply-periodic network assemblies: Threading biaxial twist through block copolymer gyroids |
| title_sort | tracing chirality from molecular organization to triply periodic network assemblies threading biaxial twist through block copolymer gyroids |
| topic | Supramolecular assembly Chirality transfer Block copolymers Triply-periodic Bicontinuous networks Biaxial order |
| url | http://www.sciencedirect.com/science/article/pii/S2666542523000267 |
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