Path-Dependent Preparation of Complex Micelle Packings of a Hydrated Diblock Oligomer

Jayaraman, Ashish; Zhang, Diana Y.; Dewing, Beth L.; Mahanthappa, Mahesh K.

doi:10.1021/acscentsci.8b00903

Cited by 45 publications

(39 citation statements)

References 62 publications

(181 reference statements)

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“…Jung and Park observed A15 in a blend of ionic liquids with charge-tethered diblock copolymers (25) leading to improved ion transport relative to other common phases (26). Mahanthappa and coworkers also recently observed A15 in a hydrated AB diblock oligomer (27). Chanpuriya et al studied a more complex ABA′C tetrablock terpolymer sequence that Significance Block copolymers are prevalent throughout industry and academe due to their self-assembly into well-ordered nanostructures, but only a handful of morphologies are known with the simplest materials built from two chemically distinct blocks.…”

mentioning

confidence: 96%

Stability of the A15 phase in diblock copolymer melts

Bates

Lequieu

Barbon

et al. 2019

Proc. Natl. Acad. Sci. U.S.A.

151

231

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The self-assembly of block polymers into well-ordered nanostructures underpins their utility across fundamental and applied polymer science, yet only a handful of equilibrium morphologies are known with the simplest AB-type materials. Here, we report the discovery of the A15 sphere phase in single-component diblock copolymer melts comprising poly(dodecyl acrylate)−block−poly(lactide). A systematic exploration of phase space revealed that A15 forms across a substantial range of minority lactide block volume fractions (fL = 0.25 − 0.33) situated between the σ-sphere phase and hexagonally close-packed cylinders. Self-consistent field theory rationalizes the thermodynamic stability of A15 as a consequence of extreme conformational asymmetry. The experimentally observed A15−disorder phase transition is not captured using mean-field approximations but instead arises due to composition fluctuations as evidenced by fully fluctuating field-theoretic simulations. This combination of experiments and field-theoretic simulations provides rational design rules that can be used to generate unique, polymer-based mesophases through self-assembly.

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mentioning

confidence: 96%

Stability of the A15 phase in diblock copolymer melts

Bates

Lequieu

Barbon

et al. 2019

Proc. Natl. Acad. Sci. U.S.A.

151

231

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“…Minimal hydration of molecular amphiphiles induces their mesoscale self-assembly into 3D periodic, micellar lyotropic liquid crystals (LLCs). Scale-invariant hard-sphere packing models anticipate the observed occurrence of high-symmetry body-centered cubic (BCC), face-centered cubic (FCC), and hexagonally closestpacked (HCP) micelle phases (18,19). However, privileged amphiphiles form complex lyotropic FK A15 (20,21) and σ phases (22,23).…”

mentioning

confidence: 99%

Dodecagonal quasicrystals of oil-swollen ionic surfactant micelles

Jayaraman

Baez-Cotto

Mann

et al. 2021

Proc. Natl. Acad. Sci. U.S.A.

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A delicate balance of noncovalent interactions directs the hierarchical self-assembly of molecular amphiphiles into spherical micelles that pack into three-dimensional periodic arrays, which mimic intermetallic crystals. Herein, we report the discovery that adding water to a mixture of an ionic surfactant and n-decane induces aperiodic ordering of oil-swollen spherical micelles into previously unrecognized, aqueous lyotropic dodecagonal quasicrystals (DDQCs), which exhibit local 12-fold rotational symmetry and no long-range translational order. The emergence of these DDQCs at the nexus of dynamically arrested micellar glasses and a periodic Frank–Kasper (FK) σ phase approximant sensitively depends on the mixing order of molecular constituents in the assembly process and on sample thermal history. Addition of n-decane to mixtures of surfactant and water instead leads only to periodic FK A15 and σ approximants with no evidence for aperiodic order, while extended ambient temperature annealing of the DDQC also reveals its transformation into a σ phase. Thus, these lyotropic DDQCs are long-lived metastable morphologies, which nucleate and grow from a stochastic distribution of micelle sizes formed by abrupt segregation of varied amounts of oil into surfactant micelles on hydration. These findings indicate that molecular building block complexity is not a prerequisite for the formation of aperiodic supramolecular order, while also establishing the generic nature of quasicrystalline states across metal alloys and self-assembled micellar materials.

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“…10,11 Often, the dodecagonal quasicrystal (DDQC) phase with 12-fold orientational symmetry and only one-dimensional (1D) translational symmetry are closely associated with F-K phases, due to similarities in local tetrahedral packing rules. [12][13][14] Complex F-K phases and the DDQC phase have not only been observed in broad soft matter systems, including diblock copolymers, [15][16][17][18][19][20][21][22][23] dendrimers, 13,[24][25][26][27][28][29][30][31] polymer colloids, 32 small molecular surfactants, [33][34][35] giant molecules, [36][37][38][39][40] and very recently, sugar-polyolefin conjugates, 41,42 but also mesoporous silica, 43,44 binary nanocrystal superlattices, 45,46 and DNA functionalized nanoparticles. 47,48 Several types of F-K phases only have considerably small differences between their overall free energies.…”

Section: Introductionmentioning

confidence: 99%

Constituent Isomerism-Induced Quasicrystal and Frank–Kasper σ Superlattices Based on Nanosized Shape Amphiphiles

Huang

Shan

et al. 2021

CCS Chem

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Naturally, subtle variations in the chemical structures of constituent molecules may significantly affect their multiscale spatial arrangements, properties, and functions. Deceptively simple spherical assemblies supply an ideal platform to investigate how subtle chemical differences affect hierarchically assembled structures. Here, the authors report two sets of nanosized shape amphiphiles, which were constructed by a triphenylene core and six polyhedral oligomeric silsesquioxane cages peripherally grafted through linkers. The slight differences in these samples are merely several methylene units in their linkers, including several pairs of constituent isomers. These nanosized shape amphiphiles self-assemble into a variety of unconventional spherical packing structures, which include the Frank-Kasper σ phase and dodecagonal quasicrystal. Several types of unconventional phase transitions were systematically investigated. The authors alternated the conventional columnar phases of discotic molecules to unconventional spherical packing phases. These unconventional structures may shed light into discovering discotic mesogens-based materials with new properties and functions.

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Path-Dependent Preparation of Complex Micelle Packings of a Hydrated Diblock Oligomer

Cited by 45 publications

References 62 publications

Stability of the A15 phase in diblock copolymer melts

Stability of the A15 phase in diblock copolymer melts

Dodecagonal quasicrystals of oil-swollen ionic surfactant micelles

Constituent Isomerism-Induced Quasicrystal and Frank–Kasper σ Superlattices Based on Nanosized Shape Amphiphiles

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