Competing Interactions and Levels of Ordering in Self-Organizing Polymeric Materials

Muthukumar, Murugappan; Ober, Christopher K.; Thomas, Edwin L.

doi:10.1126/science.277.5330.1225

Cited by 725 publications

(643 citation statements)

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“…If the Alexander-De Gennes approximation is used to calculate the periodicity, it is found that 2 and f the volume fraction A blocks (composition) of the diblock copolymer. 48 The assumption of a uniform distribution of homopolymer is in line with the Alexander-De Gennes approximation.…”

Section: Resultsmentioning

confidence: 99%

“…[1][2][3][4][5][6][7][8][9][10][11][12][13][14] Morphology and domain sizes can easily be controlled by adjusting the pertinent parameters such as composition, molar mass, etc. Simple examples, that are related to the subject of the present paper, include the production of nanoporous membranes and nano-objects, which can readily be acquired by selectively removing one of the blocks of suitably self-assembled block copolymer systems.…”

Section: Introductionmentioning

confidence: 99%

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Incorporation of PPE in Lamellar Self-Assembled PS-b-P4VP(PDP) Supramolecules and PS-b-P4VP Diblock Copolymers

et al. 2006

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Self-assembled blends of PS-b-P4VP(PDP) supramolecules, obtained by hydrogen bonding of pentadecylphenol (PDP) side chains to poly(4-vinylpyridine), and poly(2,6-dimethyl-1,4-diphenyl oxide) (PPE) were investigated by thermal analysis and small-angle X-ray scattering (SAXS) and compared with blends of PS-b-P4VP and PPE. Differential scanning calorimetry (DSC) measurements showed a single composition dependent T g of the PPE/PS layers for both systems, demonstrating that PPE is distributed throughout the PS layers. Furthermore, DSC showed that for the PPE/PS-b-P4VP(PDP) blends the presence of PDP is not restricted to the P4VP layers. Its partial presence in the PS-containing domains was confirmed by nuclear magnetic resonance (NMR) spectroscopy on PS-P4VP core-corona nanorods prepared from hexagonally self-assembled PS-b-P4VP-(PDP) supramolecules. The results of the SAXS study on the dependence of the lamellar period of PPE/PS-b-P4VP blends on the amount of PPE were in excellent agreement with a theoretical model based on the Alexander-De Gennes approximation assuming a uniform distribution of PPE throughout the PS layers. For PPE/PS-b-P4VP(PDP) blends the dependence of the long period on the amount of PPE turned out to be somewhat stronger, which may be related to the supramolecular comb-shaped nature of the P4VP(PDP) blocks.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Incorporation of PPE in Lamellar Self-Assembled PS-b-P4VP(PDP) Supramolecules and PS-b-P4VP Diblock Copolymers

et al. 2006

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“…The manipulation of the chemistry and processing of liquid crystals or block copolymers to tailor their properties in some prescribed manner is a desirable goal. The driving forces for mesophase formation and microphase separation may also be similarly manipulated due to the tandem interaction of liquid crystallinity with microphase separation [3]. Interest in these materials is growing quickly, as their liquid crystallinity, coupled to their ability to self-assemble, makes them attractive for application to sensing and display devices based on their electro-optic, mechano-optic, and thermo-optic properties.…”

Section: Introductionmentioning

confidence: 99%

Understanding and controlling the morphology of styrene–isoprene side-group liquid crystalline diblock copolymers

Osuji

Chen

Mao

et al. 2000

Polymer

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In side-chain liquid crystalline diblock copolymers, driving forces for ordering of the material may be provided by the chemical incompatibility between the blocks and by the liquid crystalline nature of one of the blocks. We study the microstructure and its development from initially isotropic solutions in side-group liquid crystalline copolymers based on styrene-isoprene diblocks. Hierarchical structure from the 5 Å to the 500 Å length scale is observed, the product of coherent block copolymer microphase separation and liquid crystalline mesophase formation. The presence of cylindrical microdomains of either the poly(isoprene-LC) or poly(styrene) block markedly increased the thermal stability of the LC. Confinement of the LC to cylindrical microdomains strongly inhibited defect formation within the mesophase after suitable orientation and thermal treatment, readily manifested by the significantly improved optical clarity of these samples versus LC matrix or LC lamellar samples. We consider the relative stabilities of parallel-transverse, perpendicular-parallel, parallel-parallel and transverse-perpendicular arrangements of the microdomain and mesophase structures in interpreting the development of structure in these materials under oscillatory shear. ᭧

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“…The side-chains can also be rod-like mesogenic, thus incorporating conformation contrast between the constituents to drive towards self-assembling hierarchies. 8 For generalization, we have started to investigate higher level hierarchies by making use of the packing frustration of disks, rods, and coils, in combination with the polypeptide conformational control. 48 Fig .…”

Section: This Journal Is ª the Royal Society Of Chemistry 2009mentioning

confidence: 99%

“…[1][2][3][4][5][6][7] Selfassemblies can be achieved based on competing repulsive and attractive interactions, where the latter ones can be permanent covalent or weaker physical interactions. 8 Hierarchical structure formation takes place if the different constituent mechanisms act simultaneously at different length scales. 9,10 Nature provides a wealth of examples on self-assemblies allowing tailored materials properties, for example, based on proteins, tough and strong inorganic-organic hybrid structures, plant cell wall cellulosic structures, and multilevel inorganic/organic hierarchical fibrillar constructs.…”

Section: Introductionmentioning

confidence: 99%

Solid state nanofibers based on self-assemblies: from cleaving from self-assemblies to multilevel hierarchical constructs

et al. 2009

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Link to publication in University of Groningen/UMCG research database Citation for published version (APA): Ikkala, O., Ras, R. H. A., Houbenov, N., Ruokolainen, J., Paakko, M., Laine, J., ... Lindström, T. (2009). Solid state nanofibers based on self-assemblies: from cleaving from self-assemblies to multilevel hierarchical constructs. Faraday Discussions, 143, 95-107. DOI: 10.1039/b905204f Copyright Other than for strictly personal use, it is not permitted to download or to forward/distribute the text or part of it without the consent of the author(s) and/or copyright holder(s), unless the work is under an open content license (like Creative Commons).Take-down policy If you believe that this document breaches copyright please contact us providing details, and we will remove access to the work immediately and investigate your claim.Downloaded from the University of Groningen/UMCG research database (Pure): http://www.rug.nl/research/portal. For technical reasons the number of authors shown on this cover page is limited to 10 maximum. Self-assemblies and their hierarchies are useful to construct soft materials with structures at different length scales and to tune the materials properties for various functions. Here we address routes for solid nanofibers based on different forms of self-assemblies. On the other hand, we discuss rational ''bottom-up'' routes for multi-level hierarchical self-assembled constructs, with the aim of learning more about design principles for competing interactions and packing frustrations. Here we use the triblock copolypeptide poly(L-lysine)-b-poly(gbenzyl-L-glutamate)-b-poly(L-lysine) complexed with 2 0 -deoxyguanosine 5 0 -monophosphate. Supramolecular disks (G-quartets) stabilized by metal cations are formed and their columnar assembly leads to a packing frustration with the cylindrical packing of helical poly(g-benzyl-L-glutamate), which we suggest is important in controlling the lateral dimensions of the nanofibers. We foresee routes for functionalities by selecting different metal cations within the G-quartets. On the other hand, we discuss nanofibers that are cleaved from bulk self-assemblies in a ''top-down'' manner. After a short introduction based on cleaving nanofibers from diblock copolymeric self-assemblies, we focus on native cellulose nanofibers, as cleaved from plant cell wall fibers, which are expected to have feasible mechanical properties and to be templates for functional nanomaterials. Long nanofibers with 5-20 nm lateral dimensions can be cleaved within an aqueous medium to allow hydrogels and water can be removed to allow highly porous, lightweight, and flexible aerogels. We further describe inorganic/

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Competing Interactions and Levels of Ordering in Self-Organizing Polymeric Materials

Cited by 725 publications

References 35 publications

Incorporation of PPE in Lamellar Self-Assembled PS-b-P4VP(PDP) Supramolecules and PS-b-P4VP Diblock Copolymers

Incorporation of PPE in Lamellar Self-Assembled PS-b-P4VP(PDP) Supramolecules and PS-b-P4VP Diblock Copolymers

Understanding and controlling the morphology of styrene–isoprene side-group liquid crystalline diblock copolymers

Solid state nanofibers based on self-assemblies: from cleaving from self-assemblies to multilevel hierarchical constructs

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