Glassy worm-like micelles in solvent and shear mediated shape transitions

Chakraborty, Kaushik; Vijayan, Kandaswamy; Brown, André E. X.; Discher, Dennis E.; Loverde, Sharon M.

doi:10.1039/c8sm00080h

Cited by 6 publications

(8 citation statements)

References 61 publications

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“…Initially, the SPAM method (maps spelled in reverse) was applied to calculate the relative free energy difference between water molecules at the protein surface from the distribution of interaction energies between the water molecules and the environment . Later, we also used this method to calculate the relative free energy of an encapsulated hydrophobic solvent in diblock copolymer micelles . According to this method, the free energy of an ion can be represented as G SPAM = − RT ln Q SPAM ; Q SPAM is the partition function defined as Q SPAM = ∑ ES [ P ( E I ) exp(− E I / RT )], where P ( E I ) is the probability of a ion having interaction energy E I with its surroundings.…”

Section: Discussionmentioning

confidence: 99%

“…The number of EO (ethylene oxide) monomers, N EO , plus the number of hydrophobic monomers, N h , gives N total = N EO + N h , and one can calculate f EO = N EO m EO /( N EO m EO + N h m h ), where the m i ’s are the monomer masses that establish the total molecular weight of the polymer M tot . Previously, we have shown that this PEO–PS model with different copolymer lengths can also describe the characteristic partitioning of model hydrophobic solvents in the micellar phase . The CG parameters for PEO were originally developed by Shinoda et al The CG parameters for PS are developed by our laboratory using the Shinoda–DeVane–Klein (SDK) CG methodology.…”

Section: Simulation Detailsmentioning

confidence: 99%

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Domain Formation in Charged Polymer Vesicles

et al. 2021

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Microphase separation can occur on a polymersome membrane surface. The phase behavior depends on the mixture of charged and uncharged diblock copolymers and the salt concentration in solution. Using coarse-grained molecular dynamics simulations, we evaluate the elastic properties of mixed charged and uncharged diblock copolymer membranes as a function of charged polymer concentration for the case of divalent counterions in solution. We find that both the area elastic modulus and bending modulus increase with increasing charged copolymer concentration. We find that the membrane thickness decreases and the membrane overlap increases with increasing charged copolymer concentration. We next perform large-scale simulations of a nearly 30 nm polymersome and characterize the growth of domains over a 0.5 μs simulation time. We characterize the size, shape, and surface topology of the domains as they grow. These results add insight into the underlying mechanisms guiding the growth of domains in both synthetic and living cells.

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Section: Discussionmentioning

confidence: 99%

Section: Simulation Detailsmentioning

confidence: 99%

Domain Formation in Charged Polymer Vesicles

et al. 2021

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“…It also enables a versatile way for constructing highly effective vehicles for the cellular delivery of biomolecular cargo. synthetic polymers [7] have been used to create supramolecular assemblies with different morphologies and functions by utilizing non-covalent interactions and stimuli such as pH, [8] electrolyte concentration, [9,10] solvent switching, [11][12][13] chemical, and enzymatic reactions, [8,[14][15][16] shear forces, [17] seeding, [18,19] light, [20] and temperature. [13,21,22] Especially the latter stimulus has been applied extensively both in natural and synthetic systems.…”

Section: Introductionmentioning

confidence: 99%

“…Self‐assembly is an intriguing phenomenon found in nature that chemists are increasingly able to employ in order to create supramolecular smart materials. Information‐rich natural building blocks based on DNA, [ 1,2 ] peptides/proteins, [ 3–6 ] and synthetic polymers [ 7 ] have been used to create supramolecular assemblies with different morphologies and functions by utilizing non‐covalent interactions and stimuli such as pH, [ 8 ] electrolyte concentration, [ 9,10 ] solvent switching, [ 11–13 ] chemical, and enzymatic reactions, [ 8,14–16 ] shear forces, [ 17 ] seeding, [ 18,19 ] light, [ 20 ] and temperature. [ 13,21,22 ] Especially the latter stimulus has been applied extensively both in natural and synthetic systems.…”

Section: Introductionmentioning

confidence: 99%

Pathway‐Dependent Co‐Assembly of Elastin‐Like Polypeptides

Pille

Aloi

et al. 2021

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In natural systems, temperature‐induced assembly of biomolecules can lead to the formation of distinct assembly states, created out of the same set of starting compounds, based on the heating trajectory followed. Until now it has been difficult to achieve similar behavior in synthetic polymer mixtures. Here, a novel pathway‐dependent assembly based on stimulus‐responsive polymers is shown. When a mixture of mono‐ and diblock copolymers, based on elastin‐like polypeptides, is heated with a critical heating rate co‐assembled particles are created that are monodisperse, stable, and have tunable hydrodynamic radii between 20 and 120 nm. Below this critical heating rate, the constituents separately form polymer assemblies. This process is kinetically driven and reversible in thermodynamically closed systems. Using the co‐assembly pathway, fluorescent proteins and bioluminescent enzymes are encapsulated with high efficiency. Encapsulated cargo shows unperturbed function even after delivery into cells. The pathway‐dependent co‐assembly of elastin‐like polypeptides is not only of fundamental interest from a materials science perspective, allowing the formation of multiple distinct assemblies from the same starting compounds, which can be interconverted by going back to the molecularly dissolved states. It also enables a versatile way for constructing highly effective vehicles for the cellular delivery of biomolecular cargo.

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“…The relatively large fluctuations in Rg for both systems are due to the dynamic processes of micelle formation in the aqueous media. Relevant papers include [15][16][17][18][19][20][21][22][23][24][25][26][27][28][29][30].…”

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confidence: 99%

Self‐assembly mechanism of PEG‐b‐PCL and PEG‐b‐PBO‐b‐PCL amphiphilic copolymer micelles in aqueous solution from coarse grain modeling

Sadeghi

Moghbeli

Goddard

2021

Journal of Polymer Science

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We followed the self-assembly of high-molecular weight MePEG-b-PCL (poly (methyl ethylene glycol)-block-poly(ε-caprolactone)) diblock and MePEG-b-PBO-b-PCL (poly(methyl ethylene glycol)-block-poly(1,2-butylene oxide)-blockpoly(ε-caprolactone)) into micelles using molecular dynamics simulation with a coarse grain (CG) force field based on quantum mechanics (CGq FF). The triblock polymer included a short poly(1,2-butylene oxide) (PBO) at the hydrophilic-hydrophobic interface of these systems. Keeping the hydrophilic length fixed (MePEG 45), we considered 250 chains in which the hydrophobic length changed from PCL 44 or PBO 6-b-PCL 43 to PCL 62 or PBO 9-b-PCL 61. The polymers were solvated in explicit water for 2 μs of simulations at 310.15 K. We found that the longer diblock system undergoes a morphological transition from an intermediate rod-like micelle to a prolate-sphere, while the micelle formed from the longer triblock system is a stable rod-like micelle. The two shorter diblock and triblock systems show similar self-assembly processes, both resulting in slightly prolate-spheres. The dynamics of the self-assembly is quantified in terms of chain radius of gyration, shape anisotropy, and hydration of the micelle cores. The final micelle structures are analyzed in terms of the local density components. We conclude that the CG model accurately describes the molecular mechanisms of self-assembly and the equilibrium micellar structures of hydrophilic and hydrophobic chains, including the quantity of solvent trapped inside the micellar core.

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Glassy worm-like micelles in solvent and shear mediated shape transitions

Cited by 6 publications

References 61 publications

Domain Formation in Charged Polymer Vesicles

Domain Formation in Charged Polymer Vesicles

Pathway‐Dependent Co‐Assembly of Elastin‐Like Polypeptides

Self‐assembly mechanism of PEG‐b‐PCL and PEG‐b‐PBO‐b‐PCL amphiphilic copolymer micelles in aqueous solution from coarse grain modeling

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