Polymer collapse in miscible good solvents is a generic phenomenon driven by preferential adsorption

Mukherji, Debashish; Marques, Carlos M.; Kremer, Kurt

doi:10.1038/ncomms5882

Cited by 227 publications

(420 citation statements)

References 27 publications

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“…While the current paper focuses on demonstrating that consolvency and cononsolvency can be explained by standard classic FH theory, statements 9,10 in the literature suggest the inapplicability FH theory to describe cononsolvency phenomena. We stress, however, that the cited inadequacy of FH theory applies only to infinitely dilute polymer solutions, where conformational transitions between swollen and expanded polymer coils can occur and will be discussed in a future paper.…”

Section: Discussionmentioning

confidence: 99%

“…As an example from materials science, the dissolution of a polymer in a mixture of two quite miscible solvents with which the polymer is individually miscible can lead to polymer phase separation (cononsolvency), [4][5][6][7][8][9][10][11] while dissolving a polymer in two individually poor solvents can yield highly stable polymer solutions (cosolvency). 12,13 Many of these types of mixed solvent systems have found applications in the health care, cosmetics, and pharmaceutical industries.…”

Section: Introductionmentioning

confidence: 99%

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Communication: Cosolvency and cononsolvency explained in terms of a Flory-Huggins type theory

Dudowicz

Freed

Douglas

2015

The Journal of Chemical Physics

116

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Standard Flory-Huggins (FH) theory is utilized to describe the enigmatic cosolvency and cononsolvency phenomena for systems of polymers dissolved in mixed solvents. In particular, phase boundaries (specifically upper critical solution temperature spinodals) are calculated for solutions of homopolymers B in pure solvents and in binary mixtures of small molecule liquids A and C. The miscibility (or immiscibility) patterns for the ternary systems are classified in terms of the FH binary interaction parameters { χ α β } and the ratio r = φ A /φ C of the concentrations φ A and φ C of the two solvents. The trends in miscibility are compared to those observed for blends of random copolymers (A x C 1−x ) with homopolymers (B) and to those deduced for A/B/C solutions of polymers B in liquid mixtures of small molecules A and C that associate into polymeric clustersAlthough the classic FH theory is able to explain cosolvency and cononsolvency phenomena, the theory does not include a consideration of the mutual association of the solvent molecules and the competitive association between the solvent molecules and the polymer. These interactions can be incorporated in refinements of the FH theory, and the present paper provides a foundation for such extensions for modeling the rich thermodynamics of polymers in mixed solvents. C 2015 AIP Publishing LLC.[http://dx

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Section: Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Communication: Cosolvency and cononsolvency explained in terms of a Flory-Huggins type theory

Dudowicz

Freed

Douglas

2015

The Journal of Chemical Physics

116

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“…Such a polymer model is widely used (see for example Ref. [49][50][51][52][53] just to mention some recent works). The interaction between neighbor monomers is given by an harmonic potential…”

Section: Simulation Detailsmentioning

confidence: 99%

Non-monotonous polymer translocation time across corrugated channels: Comparison between Fick-Jacobs approximation and numerical simulations

Bianco

Malgaretti

2016

The Journal of Chemical Physics

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We study the translocation of polymers across varying-section channels. Using systematic approximations, we derive a simplified model that reduces the problem of polymer translocation through varying-section channels to that of a point-like particle under the action of an effective potential. Such a model allows us to identify the relevant parameters controlling the polymers dynamics and, in particular, their translocation time. By comparing our analytical results with numerical simulations we show that, under suitable conditions, our model provides reliable predictions of the dynamics of both Gaussian and self-avoiding polymers, in two-and three-dimensional confinement. Moreover, both theoretical predictions, as well Brownian dynamic results, show a non-monotonous dependence of polymer translocation velocity as a function of polymer size, a feature that can be exploited for polymer separation.

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“…In recent years, a number of simulation studies focused on solutepolymer interactions that affect the conformation [18], solubility [19] as well as critical solution temperature of a PNIPAM polymer [20]. A particular attention was given to understanding of cononsolvency effects [21][22][23], which appear with increasing solute concentrations [24,25].…”

Section: Introductionmentioning

confidence: 99%

Selective solute adsorption and partitioning around single PNIPAM chains

Kanduč

Chudoba

Pałczynski

et al. 2017

Phys. Chem. Chem. Phys.

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Thermoresponsive polymer architectures have become integral building blocks of 'smart' functional materials in modern applications. For a large range of developments, e.g., for drug delivery or nanocatalytic carrier systems, the selective adsorption and partitioning of molecules (ligands or reactants) inside the polymeric matrix are key processes that have to be controlled and tuned for the desired material function. In order to gain insights into the nanoscale structure and binding details in such systems, we here employ molecular dynamics simulations of the popular poly(Nisopropylacrylamide) (PNIPAM) polymer in explicit water in the presence of various representative solute types with focus on aromatic model reactants. We model a PNIPAM polymer chain and explore the influence of its elongation, stereochemistry, and temperature on the solute binding affinities. While we find that the excess adsorption generally raises with the size of the solute, the temperaturedependent affinity to the chains is highly solute specific and has a considerable dependence on the polymer elongation (i.e., polymer swelling state). We elucidate the molecular mechanisms of the selective binding in detail and eventually present how the results can be extrapolated to macroscopic partitioning of the solutes in swollen polymer architectures, such as hydrogels.

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Polymer collapse in miscible good solvents is a generic phenomenon driven by preferential adsorption

Cited by 227 publications

References 27 publications

Communication: Cosolvency and cononsolvency explained in terms of a Flory-Huggins type theory

Communication: Cosolvency and cononsolvency explained in terms of a Flory-Huggins type theory

Non-monotonous polymer translocation time across corrugated channels: Comparison between Fick-Jacobs approximation and numerical simulations

Selective solute adsorption and partitioning around single PNIPAM chains

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