Tuning the critical solution temperature of polymers by copolymerization

Schulz, B.; Chudoba, Richard; Heyda, Jan; Dzubiella, Joachim

doi:10.1063/1.4934017

Cited by 9 publications

(18 citation statements)

References 44 publications

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“…(13), increasing the fractions of hydrophobic (represented by ni) or hydrophilic (represented by mi) units (see Figure 3(a)), linearly changes T ℓ of a copolymer chain. Because of this linear behavior, which was also observed in a generic molecular simulation study (80), these copolymer sequences provide a rather flexible molecular toolbox for desired applications. Moreover, these systems also show severe Here the hydrophobic methylene units (represented by n 1 and n 2 ) and hydrophilic ethylene oxide units (represented by m 1 and m 2 ) are tuned to obtain different amphiphilic sequences.…”

Section: Effect Of Copolymer Sequencementioning

confidence: 66%

Smart Responsive Polymers: Fundamentals and Design Principles

Mukherji

Marques

Kremer

2020

Annu. Rev. Condens. Matter Phys.

101

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In this review, we summarize recent theoretical and computational developments in the field of smart responsive materials, together with complementary experimental data. A material is referred to as smart responsive when a slight change in external stimulus can drastically alter its structure, function, or stability. Because of this smart responsiveness, these systems are used for the design of advanced functional materials. The most characteristic properties of smart polymers are discussed, especially polymer properties in solvent mixtures. We show how multiscale simulation approaches can shed light on the intriguing experimental observations. Special emphasis is given to two symmetric phenomena: co-non-solvency and co-solvency. The first phenomenon is associated with the collapse of polymers in two miscible good solvents, whereas the latter is associated with the swelling of polymers in poor solvent mixtures. Furthermore, we discuss when the standard Flory–Huggins-type mean-field polymer theory can (or cannot) be applied to understand these complex solution properties. We also sketch a few examples to highlight possible future directions, that is, how smart polymer properties can be used for the design principles of advanced functional materials.

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Section: Effect Of Copolymer Sequencementioning

confidence: 66%

Smart Responsive Polymers: Fundamentals and Design Principles

Mukherji

Marques

Kremer

2020

Annu. Rev. Condens. Matter Phys.

101

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“…For example, T ℓ ≈ 300 − 305 K for X = Valine [80], while T ℓ ≈ 305 − 310 K for X = Glycine (i.e., more hydrophilic residue) [44,80]. This is identical to the typical LCST based copolymers, where T ℓ can be tuned by changing hydrophobic or hydrophilic units along the backbone [19,40,41,63]. Therefore, for this study we investigate two sequences, namely −(VPGVG)− and −(VPGGG)−, for T < T ℓ .…”

Section: Conformation Of Elastin-like Polypeptides In Aqueous Ethanolmentioning

confidence: 78%

Why Do Elastin-Like Polypeptides Possibly Have Different Solvation Behaviors in Water–Ethanol and Water–Urea Mixtures?

et al. 2020

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The solvent quality determines the collapsed or the expanded state of a polymer. For example, a polymer dissolved in a poor solvent collapses, whereas in a good solvent it opens up. While this standard understanding is generally valid, there are examples when a polymer collapses even in a mixture of two good solvents. This phenomenon, commonly known as co-non-solvency, is usually associated with a wide range of synthetic (smart) polymers. Moreover, recent experiments have shown that some biopolymers, such as elastin-like polypeptides (ELPs) that exhibit lower critical solution behavior T ℓ in pure water, show co-non-solvency behavior in aqueous-ethanol mixtures. In this study, we investigate the phase behavior of elastin-like polypeptides (ELPs) in aqueous binary mixtures using molecular dynamics simulations of all-atom and complementary explicit solvent generic models. The model is parameterized by mapping the solvation free energy obtained from the all-atom simulations onto the generic interaction parameters. For this purpose, we derive segment based (monomer level) generic parameters for four different peptides, namely proline (P), valine (V), glycine (G) and alanine (A), the first three constitute the basic building blocks of ELPs.Here we compare the conformational behavior of two ELP sequences, namely −(VPGGG)− and −(VPGVG)−, in aqueous-ethanol and -urea mixtures. Consistent with recent experiments, we find that ELPs show co-non-solvency in aqueous-ethanol mixtures. Ethanol molecules have preferential binding with all ELP residues, with an interaction contrast of 6 − 8kBT , and thus driving the coilto-globule transition. On the contrary, ELP conformations show weak variation in aqueous-urea mixtures. Our simulations suggest that the glycine residues dictate the overall behavior of ELPs in aqueous-urea, where urea molecules have a rather weak preferential binding with glycine, i.e., less than kBT . This weak interaction dilutes the overall effect of other neighboring residues and thus ELPs exhibit different conformational behavior in aqueous-urea in comparison to aqueousethanol mixtures. While the validation of the latter findings will require more detailed experimental investigation, the results presented here may provide a new twist to the present understanding of cosolvent interactions with peptides and proteins. * Electronic address: corteshu@mpip-mainz.mpg.de † Electronic address: debashish.mukherji@ubc.ca

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“…[25] This effect of hydrophobic comonomers on the polymer transition temperature is well captured also in a simulation or theory context. [26] Besides its thermosensitivity, the response of PNIPAM to pressure is often overlooked: [27] precipitated (> LCST) PNIPAM can be re-solvated by increasing pressure. [28] Theoretically, this effect can be explained by the pressure-induced decrease of the volume of the solventinaccessible cavities, which are formed by hydrophobic interactions.…”

Section: Main Textmentioning

confidence: 99%

Stimulated Transitions of Directed Nonequilibrium Self‐Assemblies

et al. 2017

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Near-equilibrium stimulus-responsive polymers have been used extensively to introduce morphological variations in dependence of adaptable conditions. Far-less-well studied are triggered transformations at constant conditions. These require the involvement of metastable states, which are either able to approach the equilibrium state after deviation from metastability or can be frozen on returning from nonequilibrium to equilibrium. Such functional nonequilibrium macromolecular systems hold great promise for on-demand transformations, which result in substantial changes in their material properties, as seen for triggered gelations. Herein, a diblock copolymer system consisting of a hydrophilic block and a block that is responsive to both pressure and temperature, is introduced. This species demonstrates various micellar transformations upon leaving equilibrium/nonequilibrium states, which are triggered by a temperature deflection or a temporary application of hydrostatic pressure.

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Tuning the critical solution temperature of polymers by copolymerization

Cited by 9 publications

References 44 publications

Smart Responsive Polymers: Fundamentals and Design Principles

Smart Responsive Polymers: Fundamentals and Design Principles

Why Do Elastin-Like Polypeptides Possibly Have Different Solvation Behaviors in Water–Ethanol and Water–Urea Mixtures?

Stimulated Transitions of Directed Nonequilibrium Self‐Assemblies

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