Amphiphilic comb macromolecules with different distribution statistics of side-chain grafting sites: Mathematical modeling

Starostina, A. A.; Klochkov, A. A.; Vasilevskaya, V. V.; Khokhlov, Alexei R.

doi:10.1134/s0965545x08090101

Cited by 13 publications

(2 citation statements)

References 22 publications

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“…The transition from an elongated to a smaller globular SCPN upon changing solvent from isopropanol to water at high temperature is likely caused by solvophobic interactions. This observation is in line with simulations and experimental studies on amphiphilic polymers. − Interestingly, cooling down the system in waterdecreasing the solvent quality but also increasing BTA self-assemblyresults in larger more elongated SCPNs. This expansion reveals that the polymer is forced to adapt its conformation to the BTA structure that it comprises in its interior.…”

Section: Resultssupporting

confidence: 87%

Sticky Supramolecular Grafts Stretch Single Polymer Chains

et al. 2013

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The folding of single polymeric chains into single chain polymeric nanoparticles (SCPNs) is a unique strategy to prepare ordered structures at the nanoscopic level. Structure forming elements are attached to a polymer chain designed to fold it into a well-defined object, the SCPN. The self-assembly of these units has been investigated in great detail. However, little is known about the impact of the resulting secondary structure on the conformation of the polymer chain. Here we employ a combination of scattering methods and spectroscopy to study how pendant chiral benzene-1,3,5-tricarboxamides (BTAs) fold oligo(ethylene glycol) methyl ether methacrylate-based polymers into SCPNs. Circular dichroism spectroscopy shows that the extent of BTA self-assembly on the polymer chain in water can be fine-tuned by means of temperature and cosolvent addition (isopropanol). Small-angle neutron scattering experiments demonstrate that single polymer chains have an asymmetric shape with a constant cross section, R cs, and variable length, L, with L > R cs. The polymer chain extends and shortens in response to variations in temperature and solvent composition, which also influence the self-assembly of the BTA units. The SCPNs stretch upon association and shrink upon disassociation of the grafted supramolecular moieties.

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Section: Resultssupporting

confidence: 87%

Sticky Supramolecular Grafts Stretch Single Polymer Chains

et al. 2013

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“…The discontinuous coil‐to‐globule transitions are also characteristic for some amphiphilic polymers42–47 involving both soluble (H) and insoluble (P) groups in their chains (either in distinct units in the case of amphiphilic copolymers or as parts of the same unit in amphiphilic homopolymers). Amphiphilic polymers with annealed HP structure (i.e., when each monomer unit can reversibly switch between H and P states) can undergo a first‐order coil‐to‐globule transition even in the case of completely flexible chains42: the density of the HP globule at the transition point remains finite in the limit of very long chains N → ∞ (the density is defined by the energy contrast between P and H states in the dilute regime).…”

Section: Discussionmentioning

confidence: 99%

Polyelectrolyte Complexes Consisting of Macromolecules With Varied Stiffness: Computer Simulation

Lazutin

Semenov

Vasilevskaya

2012

Macro Theory & Simulations

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Monte Carlo simulations are employed in order to analyze the structure of polyelectrolyte complexes consisting of two identical but oppositely charged macroions with varying chain stiffness. It is shown that two complex structures can arise depending on the stiffness of the constituent chains. Stiff chains are organized into a ''ladder'' structure in which chains are located parallel to each other and monomeric units are arranged into ionic pairs according to their position in the chain. Flexible chains form a globular ''scrambled-egg'' structure with a disordered position of monomer units. The conformational transition between the two structures proceeds as a phase transition.

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Synthesis and Solution Properties of Loose Polymer Brushes Having Polyimide Backbone and Methylmethacrylate Side Chains

Krasova

Belyaeva

Тарабукина

et al. 2012

Macromolecular Symposia

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Summary: Graft‐copolymers with polyimide backbone and PMMA side chains are synthesized by ATRP of methylmethacrylate on the polyimide macroinitiator. The obtained copolymers, macroinitiator, and cleaved side chains are investigated by 1H NMR, SEC, static and dynamic light scattering, sedimentation, and viscosimetry in solutions. The synthesized copolymer is relatively loose polymer brushes: the average distance between grafted PMMA chains is ∼11 nm (4 repeat units of the backbone). The hydrodynamic and conformational characteristics of graft‐copolymers change on passage from ethylacetate to chloroform due to difference in the thermodynamic quality of the solvents with respect to the copolymer components. The backbone is characterized more extended conformation than individual polyimide macromolecule.

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Amphiphilic comb macromolecules with different distribution statistics of side-chain grafting sites: Mathematical modeling

Cited by 13 publications

References 22 publications

Sticky Supramolecular Grafts Stretch Single Polymer Chains

Sticky Supramolecular Grafts Stretch Single Polymer Chains

Polyelectrolyte Complexes Consisting of Macromolecules With Varied Stiffness: Computer Simulation

Synthesis and Solution Properties of Loose Polymer Brushes Having Polyimide Backbone and Methylmethacrylate Side Chains

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