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Density Scaling Based Detection of Thermodynamic Regions of Complex Intermolecular Interactions Characterizing Supramolecular Structures.

ABSTRACT: In this paper, applying the density scaling idea to an associated liquid 4-methyl-2-pentanol used as an example, we identify different pressure-volume-temperature ranges within which molecular dynamics is dominated by either complex H-bonded networks most probably leading to supramolecular structures or non-specific intermolecular interactions like van der Waals forces. In this way, we show that the density scaling law for molecular dynamics near the glass transition provides a sensitive tool to detect thermodynamic regions characterized by intermolecular interactions of different type and complexity for a given material in the wide pressure-volume-temperature domain even if its typical form with constant scaling exponent is not obeyed. Moreover, we quantify the observed decoupling between dielectric and mechanical relaxations of the material in the density scaling regime. The suggested methods of analyses and their interpretations open new prospects for formulating models based on proper effective intermolecular potentials describing physicochemical phenomena near the glass transition.

SUBMITTER: Pawlus S

PROVIDER: S-EPMC7283260 | biostudies-literature | 2020 Jun

REPOSITORIES: biostudies-literature

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Density Scaling Based Detection of Thermodynamic Regions of Complex Intermolecular Interactions Characterizing Supramolecular Structures.

Pawlus Sebastian S Grzybowski Andrzej A Kołodziej Sławomir S Wikarek Michał M Dzida Marzena M Góralski Paweł P Bair Scott S Paluch Marian M

Scientific reports 20200609 1

In this paper, applying the density scaling idea to an associated liquid 4-methyl-2-pentanol used as an example, we identify different pressure-volume-temperature ranges within which molecular dynamics is dominated by either complex H-bonded networks most probably leading to supramolecular structures or non-specific intermolecular interactions like van der Waals forces. In this way, we show that the density scaling law for molecular dynamics near the glass transition provides a sensitive tool to ...[more]

PMID: 32518282

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Project description:Polymer networks crosslinked via non-covalent interactions afford interesting materials for a wide range of applications due to their self-healing capability, recyclability, and tunable material properties. However, when strong non-covalent binding motifs in combination with high crosslink density are used, processing of the materials becomes troublesome because of high viscosities and the formation of insoluble gels. Here, we present an approach to control the processability of grafted polymers containing strong non-covalent interactions by balancing the interplay of intra- and intermolecular hydrogen bonding. A library of copolymers with different degrees of polymerization and content of protected ureido-pyrimidinone-urea (UPy-urea) grafts was prepared. Photo-deprotection in a good solvent like tetrahydrofuran (THF) at low concentrations (≤1 mg mL-1) created intramolecularly assembled nanoparticles. Remarkably, the intrinsic viscosity of these nanoparticle solutions was an order of magnitude lower compared to solutions of the intermolecularly assembled analogues, highlighting the crucial role of intra- versus intermolecular interactions. Due to the strong hydrogen bonds between UPy dimers, the intramolecularly assembled structures were kinetically trapped. As a result, the polymer nanoparticles were readily processed into a bulk material, without causing major changes in the morphology as verified by atomic force microscopy. Subsequent intermolecular crosslinking of the nanoparticle film, by heating to temperatures where the hydrogen-bond exchange becomes fast, resulted in a crosslinked network. The reversibility of the hereby obtained polymer networks was shown by retrieving the intramolecularly assembled nanoparticles via redissolution and sonication of the intermolecularly crosslinked film in THF with a small amount of acid. Our results highlight that the stability and processability of highly supramolecularly crosslinked polymers can be controlled both in solution and in bulk by using the interplay of intra- and intermolecular non-covalent interactions in grafted polymers.

Dataset Information

Density Scaling Based Detection of Thermodynamic Regions of Complex Intermolecular Interactions Characterizing Supramolecular Structures.

Publications

Density Scaling Based Detection of Thermodynamic Regions of Complex Intermolecular Interactions Characterizing Supramolecular Structures.

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