Fibrillar gel self-assembly via cononsolvency of amphiphilic polymer

Buglakov, Aleksandr I.; Vasilevskaya, V. V.

doi:10.1016/j.jcis.2022.01.095

Cited by 9 publications

(6 citation statements)

References 50 publications

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“…Description of this procedure can be found in our previous papers. 44,45 With homogeneous distribution of macromolecules, in all subcells, the local polymer content p (%) is p = c• 100%. When macromolecules aggregate, the part of subcells loses the macromolecules and even becomes completely free of polymer (p = 0), while in the others, the numerical polymer density increases.…”

Section: ■ Model and Simulation Detailsmentioning

confidence: 99%

“…Characteristic distribution of amphiphilic macromolecules in the solution was measured through the calculation of local polymer content p expressed as % of the total number of monomer units in the system in cubic subcells with edge L s . Description of this procedure can be found in our previous papers. , With homogeneous distribution of macromolecules, in all subcells, the local polymer content p (%) is p = c· 100%. When macromolecules aggregate, the part of subcells loses the macromolecules and even becomes completely free of polymer ( p = 0), while in the others, the numerical polymer density increases.…”

Section: Model and Simulation Detailsmentioning

confidence: 99%

“…Another promising, yet still poorly studied, candidate for the nanofiber formation is graft copolymers with amphiphilicity at the level of a repeating unit. − Recently, our group showed via generic mesoscale simulation the universal ability of such macromolecules to easily self-assemble into fibrillar networks in the selective solvent or solvent mixtures. , Further, amphiphilic homopolymer and comb-like macromolecules due to the effective surface activity of monomer units and their connectivity with each other can be affected by specific interactions, unique for these types of macromolecules . This is the so-called orientation-induced attraction, which allows us to reduce the entropy losses of side pendants and leads to the formation of clusters from few core–shell aggregates.…”

Section: Introductionmentioning

confidence: 99%

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Self-Assembled Graft Copolymer Nanofibers with an Adjustable Internal and External Structure

Buglakov,

Vasilevskaya

2023

Macromolecules

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The nanofibers with designed internal and external morphology are of great interest for tissue engineering, regenerative medicine, and novel materials design. In this letter, we report on a possible mechanism for creating and tuning nanofibers from amphiphilic graft copolymers. The aggregation process in these polymers is governed not only by surface to bulk energy tradeoff but also by orientational entropy of pendants, which leads to the emergence of specific interactions in such systems known as orientation-induced attraction. Due to the orientation-induced attraction, the semiflexible amphiphilic graft copolymers can assemble into various fibrillar structures and undergo a non-obvious series of transitions upon changing solvent quality for pendants. The fibrils formed in a poor solvent, when the quality of the solvent is improved, first self-assemble into fibers and only then dissolve. Fibers are bundles of fibrils interconnected by jumpers from pendants. Their internal structure can be tuned by solvent quality and graft copolymer structure. Using a mesoscopic simulation approach, we revealed the conditions for these self-assembly processes to be realized and resolved inner and external morphology of each stage depending on the selective solvent quality and grafting density of pendants.

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Section: ■ Model and Simulation Detailsmentioning

confidence: 99%

Section: Model and Simulation Detailsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Self-Assembled Graft Copolymer Nanofibers with an Adjustable Internal and External Structure

Buglakov,

Vasilevskaya

2023

Macromolecules

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“…However, experimental evidence suggests that the choice of different cosolvents influences nanoparticle sizes [ 27 , 28 ] as well as structures [ 29 , 30 ], the cosolvent/selective solvent ratio impacts chain conformation [ 31 , 32 ], and the distribution of the cosolvent in the polymer domain is distinguished from that in the bulk solution [ 33 ]; moreover, the cosolvent dispersed in the core and the corona also may be much different [ 29 , 30 , 32 ]. All of the phenomena indicate the important role of the cosolvent in the self-assembly process and should be considered individually [ 21 , 34 , 35 ].…”

Section: Introductionmentioning

confidence: 99%

Effect of Cosolvent on the Vesicle Formation Pathways under Solvent Exchange Process: A Dissipative Particle Dynamics Simulation

et al. 2023

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The effective control over the vesicle formation pathways is vital for tuning its function. Recently, a liquid–liquid phase-separated intermediate (LLPS) is observed before a vesicular structure during the solvent exchange self-assembly of block copolymers. Though the understanding of polymer structures and chemical compositions on the competition between LLPS and micellization has made some progress, little is known about the role of cosolvent on it. In this study, the influence of cosolvent on the vesicle formation pathways is investigated by using dissipative particle dynamics. The results show that the range of water fraction within which the LLPS is favored will be highly dependent on the affinity difference of cosolvent to water and to polymer repeat units. The change of the cosolvent–water interaction and the water fraction impact the distribution of cosolvent in the polymer domain, the miscibility between the components in the system as well as the chain conformations, which finally induce different self-assembly behaviors. Our findings would be helpful for understanding the LLPS and controlling the morphologies of diblock polymers in solutions for further applications.

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“…12 Using coarse-grained simulations, such polymers were tailored into specific morphologies through manipulation of solvent ratios and miscibility. 13 In immiscible solvent mixtures, high energy interfaces can clearly play a large role in the assembly of amphiphilic polymers.…”

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confidence: 99%

Dynamic Transformation of Bio-Inspired Single-Chain Nanoparticles at Interfaces

Hilburg

Jin

Alexander‐Katz

2023

Preprint

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Interfacial behavior of macromolecules dictates their intermolecular interactions, which can impact processing and application of polymers for pharmaceutical and synthetic use. Using molecular dynamics simulations, we observe the evolution of a random heteropolymer in the presence of liquid-liquid interfaces. The system of interest forms single-chain nanoparticles through hydrophobic collapse in water, lacking permanent crosslinks and making their morphology mutable in new environments. The complex amphiphilic polymers are shown capable of stabilizing high energy water-hexane interfaces, often unfolding to maximize surface coverage. Despite drastic changes to polymer conformation, monomer presence in the water phase is generally maintained and most changes are due to increased hydrophobic solvent exposure towards the oil phase. These results are then compared to behavior at the water-graphene, where the macromolecules adsorb but do not remodel. The polymer behavior is shown to depend significantly upon both its own amphiphilic character and the deformability of the interface.

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Fibrillar gel self-assembly via cononsolvency of amphiphilic polymer

Cited by 9 publications

References 50 publications

Self-Assembled Graft Copolymer Nanofibers with an Adjustable Internal and External Structure

Self-Assembled Graft Copolymer Nanofibers with an Adjustable Internal and External Structure

Effect of Cosolvent on the Vesicle Formation Pathways under Solvent Exchange Process: A Dissipative Particle Dynamics Simulation

Dynamic Transformation of Bio-Inspired Single-Chain Nanoparticles at Interfaces

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