Preferential adsorption of the additive is not a prerequisite for cononsolvency in water-rich mixtures

Wang, Jian; Wang, Nian; Liu, Biaolan; Bai, Jia; Gong, Pei; Ru, Geying; Feng, Jiwen

doi:10.1039/c7cp04384h

Cited by 25 publications

(41 citation statements)

References 63 publications

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“…It should be highlighted that earlier works also showed that the preferential cosolventmonomer drives co-non-solvency (107,108). A more recent work, however, also emphasized that the preferential cosolvent-monomer binding is not a prerequisite for co-non-solvency (109) As it turned out the preferential binding of one of the solvents to the polymer is driving the conformational transition of a polymer in mixed good solvents. This is in particularly important because if both solvents like polymer equally then only weak traces of the nonideal mixing of the solvents are left, which are not sufficient to drive segregation.…”

Section: Multiscale Simulations Complex Mixtures and Polymer In Mixed Solventsmentioning

confidence: 98%

“…For example, the collapse of a PNIPAm in aqueous urea mixtures was shown to be driven by bridging-like hydrogen bonding of urea with two NIPAm monomers (15,35). Furthermore, there are also other works showing that bridging interactions are responsible for a polymer collapse in a mixtures of two cosolvents (36,37), while another work highlighted that the preferential binding may not be prerequisite for co-non-solvency (109).…”

Section: Competitive Displacement Of Solvent By Cosolventmentioning

confidence: 99%

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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: Multiscale Simulations Complex Mixtures and Polymer In Mixed Solventsmentioning

confidence: 98%

Section: Competitive Displacement Of Solvent By Cosolventmentioning

confidence: 99%

Smart Responsive Polymers: Fundamentals and Design Principles

Mukherji

Marques

Kremer

2020

Annu. Rev. Condens. Matter Phys.

101

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“…Recent studies have also shown that preferential attraction of the cosolvent is not a prerequisite for cononsolvency. 35,36 Further, cononsolvency is absent in the case of PDEA, water and methanol mixtures even when the preferential attraction of PDEA with methanol is higher in comparison to PNiPAM. 37 Thus, it can be seen that the questions regarding the applicability of a mean-field theory are not yet resolved.…”

Section: A Backgroundmentioning

confidence: 99%

Kosmotropic effect leads to LCST decrease in thermoresponsive polymer solutions

Bharadwaj

Kumar

Komura

et al. 2018

The Journal of Chemical Physics

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We study the phenomena of decrease in lower critical solution temperature (LCST) with addition of kosmotropic (order-making) cosolvents in thermoresponsive polymer solutions. A combination of explicit solvent coarse-grained simulations and mean-field theory has been employed. The polymer-solvent LCST behavior in the theoretical models has been incorporated through the Kolomeisky-Widom solvophobic potential. Our results illustrate how the decrease in the LCST can be achieved by the reduction in the bulk solvent energy with the addition of cosolvent. It is shown that this effect of cosolvent is weaker with an increase in polymer hydrophilicity which can explain the absence of a LCST decrease in poly(N,N-diethylacrylamide), water, and methanol systems. The coarse-grained nature of the models indicates that a mean energetic representation of the system is sufficient to understand the phenomena of LCST decrease.

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“…However, recent investigations demonstrated that the preferential affinity of the cosolvent toward PNIPAM is not a general requirement for co-nonsolvency [41,42]. Furthermore, Pica and Graziano [43] bring into question that the preferential binding of cosolvent molecules to PNIPAM is the cause of co-nonsolvency in water-methanol.…”

Section: Introductionmentioning

confidence: 99%

Molecular description of the coil-to-globule transition of Poly(N-isopropylacrylamide) in water/ethanol mixture at low alcohol concentration

Tavagnacco

Zaccarelli

Chiessi

2020

Journal of Molecular Liquids

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Poly(N-isopropylacrylamide), PNIPAM, is a widely studied polymer, which serves as a key constituent of nanostructured soft materials with responsive properties. Upon increasing temperature the PNIPAM polymer chain undergoes a reversible coil-to-globule transition at T ∼305K, which is reflected by a volume phase transition in cross-linked architectures, such as microgels, valuable for many practical applications. The addition of a cosolvent is a simple method to tune the transition temperature according to the specific purpose. In this study, we use atomistic molecular dynamics simulations to explore the solution behavior of a PNIPAM chain in a mixture of water and ethanol, acting as cosolvent, at low alcohol concentration. Our simulations reproduce the occurrence of the coil-to-globule transition of the polymer chain at 289 K, a temperature lower than that measured in water, in full agreement with experimental findings. By monitoring the temperature evolution of structural and dynamical properties of the PNIPAM-water-ethanol ternary system, we detect a localization of ethanol molecules at the polymer interface, mainly due to interactions between isopropyl and ethyl groups. We observe that the transition occurs without a release of adsorbed ethanol molecules, but with a loss of water molecules from the surrounding of PNIPAM hydrophobic moieties that favours the aggregation of ethanol molecules close to the polymer. Our results support the idea that both the decreased chemical potential of water in the bulk of the mixture and the competition between water and ethanol molecules in the interactions with the polymer play a driving role in the transition.

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Preferential adsorption of the additive is not a prerequisite for cononsolvency in water-rich mixtures

Cited by 25 publications

References 63 publications

Smart Responsive Polymers: Fundamentals and Design Principles

Smart Responsive Polymers: Fundamentals and Design Principles

Kosmotropic effect leads to LCST decrease in thermoresponsive polymer solutions

Molecular description of the coil-to-globule transition of Poly(N-isopropylacrylamide) in water/ethanol mixture at low alcohol concentration

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