Thermoresponsive functional polymers based on 2,6-diaminopyridine motif with tunable UCST behaviour in water/alcohol mixtures

Asadujjaman, Asad; Ahmadi, Vahid; Yalcin, Meral; Brummelhuis, Niels ten; Bertin, Annabelle

doi:10.1039/c7py00539c

Cited by 26 publications

(25 citation statements)

References 65 publications

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“…While the polymers swell significantly, the mostly swollen polymer structure still remains below Θ—conformation. Even when we take PMMA as a test case, there are systems, such as corn starch 35 and poly( N -(6-acetamidopyridin-2-yl)acrylamide) 36 , which also show collapse–swelling–collapse behavior. Interestingly, the solvent–cosolvent mixtures in these cases are also aqueous alcohol mixtures.…”

Section: Discussionmentioning

confidence: 99%

Depleted depletion drives polymer swelling in poor solvent mixtures

et al. 2017

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Establishing a link between macromolecular conformation and microscopic interaction is a key to understand properties of polymer solutions and for designing technologically relevant “smart” polymers. Here, polymer solvation in solvent mixtures strike as paradoxical phenomena. For example, when adding polymers to a solvent, such that all particle interactions are repulsive, polymer chains can collapse due to increased monomer–solvent repulsion. This depletion induced monomer–monomer attraction is well known from colloidal stability. A typical example is poly(methyl methacrylate) (PMMA) in water or small alcohols. While polymer collapse in a single poor solvent is well understood, the observed polymer swelling in mixtures of two repulsive solvents is surprising. By combining simulations and theoretical concepts known from polymer physics and colloidal science, we unveil the microscopic, generic origin of this collapse–swelling–collapse behavior. We show that this phenomenon naturally emerges at constant pressure when an appropriate balance of entropically driven depletion interactions is achieved.

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Section: Discussionmentioning

confidence: 99%

Depleted depletion drives polymer swelling in poor solvent mixtures

et al. 2017

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“…For x c = 0.5, the above equation will lead to a ∼11% variation in χ sc values with respect to the standard values calculated when ρ total is kept constant [51]. Therefore, in this system the [33] Water MeOH, EtOH, or iPrOH Poly(N-(6-acetamidopyridin-2-yl)acrylamide) [34] Water MeOH, EtOH, or iPrOH PMMA [49] 2 Predominantly observed in aqueous alcohol solution χ sc parameter relevant to the FH analysis keeps consistent values throughout the range of compositions.…”

Section: Co-solvency Revisitedmentioning

confidence: 94%

Collapse in two good solvents, swelling in two poor solvents: defying the laws of polymer solubility?

Mukherji

Marques

Kremer

2017

J. Phys.: Condens. Matter

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In this work we discuss two mirror but distinct phenomena of polymer paradoxical properties in mixed solvents: co-non-solvency and co-solvency. When a polymer collapses in a mixture of two miscible good solvents the phenomenon is known as co-non-solvency, while co-solvency is a phenomenon that is associated with the swelling of a polymer in poor solvent mixtures. A typical example of co-non-solvency is provided by poly(N-isopropylacrylamide) in aqueous alcohol, while poly(methyl methacrylate) in aqueous alcohol shows co-solvency. We discuss these two phenomena to compare their microscopic origins and show that both can be understood within generic universal concepts. A broad range of polymers is therefore expected to exhibit these phenomena where specific chemical details play a lesser role than the appropriate combination of interactions between the trio of molecular components.

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“…The supramolecular 2,6‐diaminopyridine motif with alternating H‐bond donors (D) and H‐bond acceptors (A) is commonly used as side chain in polymers for controlling the tacticity of polymers, binding metal ions or for molecularly imprinted polymer sensors . In our previous work, we reported a 2,6‐diaminopyridine‐based homopolymers, poly( N ‐(6‐acetamidopyridin‐2‐yl)acrylamide) (PNAcAPAM), exhibits UCST‐type phase transition behavior in water/alcohol mixtures. However, in pure water or alcohol, the PNAcAPAM was insoluble and no phase transition behavior was observed.…”

Section: Introductionmentioning

confidence: 99%

2,6‐Diaminopyridine and Acrylamide‐Based Copolymers with Upper Critical Solution Temperature‐type Behavior in Aqueous Solution

Asadujjaman

Ahmadi

Franc

et al. 2019

J. Polym. Sci. Part A: Polym. Chem.

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A novel copolymer based on supramolecular motif 2,6-diaminopyridine and water-soluble acrylamide, poly[N-(6-acetamidopyridin-2-yl) acrylamide-co-acrylamide], was synthesized via reversible addition-fragmentation chain transfer (RAFT) polymerization with various monomer compositions. The thermoresponsive behavior of the copolymers was studied by turbidimetry and dynamic light scattering (DLS). The obtained copolymers showed an upper critical solution temperature (UCST)-type phase transition behavior in water and electrolyte solution. The phase transition temperature was found to increase with decreasing amount of acrylamide in the copolymer and increasing concentration of the solution. Furthermore, the phase transition temperature varied in aqueous solutions of electrolytes according to the nature and concentration of the electrolyte in accordance with the Hoffmeister series. A dramatic solvent isotope effect on the transition temperature was observed in this study, as the transition temperature was almost 10-12 C higher in D 2 O than in H 2 O at the same concentration and acrylamide composition. The size of the aggregates below the transition temperature was larger in D 2 O compared to that in H 2 O that can be explained by deuterium isotope effect. The thermoresponsive behavior of the copolymers was also investigated in different cell medium and found to be exhibited UCST-type phase transition behavior in different cell medium. Such behavior of the copolymers can be useful in many applications including biomedical, microfluidics, optical materials, and in drug delivery.

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Thermoresponsive functional polymers based on 2,6-diaminopyridine motif with tunable UCST behaviour in water/alcohol mixtures

Abstract: Two thermoresponsive polyacrylamides based on the 2,6-diaminopyridine motif were synthesized and their UCST-type reversible thermoresponsive behaviour was studied in water/alcohol mixtures.

Cited by 26 publications

References 65 publications

Depleted depletion drives polymer swelling in poor solvent mixtures

Depleted depletion drives polymer swelling in poor solvent mixtures

Collapse in two good solvents, swelling in two poor solvents: defying the laws of polymer solubility?

2,6‐Diaminopyridine and Acrylamide‐Based Copolymers with Upper Critical Solution Temperature‐type Behavior in Aqueous Solution

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