Molecular (Bottle) Brushes: From Solution Properties to Nanostructured Materials

A special issue of Polymers (ISSN 2073-4360). This special issue belongs to the section "Polymer Chemistry".

Deadline for manuscript submissions: closed (15 February 2023) | Viewed by 4492

Special Issue Editors


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Guest Editor
Institut des Sciences Analytiques et de Physico-Chimie pour l’Environnement et les Matériaux, UMR 5254 CNRS UPPA, 64000 Pau, France
Interests: molecular brushes; block copolymers; self-assemble; polyelectrolyte; pH-respons; thermo-responsive; emulsion polymerization
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Guest Editor
Institute of Macromolecular Compounds, Russian Academy of Sciences, 199004 St.Petersburg, Russia
Interests: theory of polymers; polymer brushes; polyelectrolytes; block copolymers; macromolecular self-assembly; nanoscale self-organization

Special Issue Information

Dear Colleagues,

Molecular brushes (aka bottlebrushes) represent a particular class of regularly branched macromolecules in which multiple side chains are attached to a long main chain (backbone) with high grafting density. Although all major synthetic strategies towards molecular brushes (“grafting to”, “grafting from”, “grafting through”) were elaborated a few decades ago, and properties of brush-like macromolecules in melts and solutions have been extensively studied, interest in the polymeric materials that compose the molecular brushes has recently increased quite significantly.

Contemporary synthetic approaches enable perfectly controlled variations in the basic architectural parameters of molecular brushes (degrees of polymerization of the main and side chains, grafting density). As a result, the paradigm of encoding the structural and rheological properties of polymeric materials through the control of the macromolecular architecture of bottlebrush components has emerged. Moreover, the mechanical properties of crosslinked elastomers and swelling gels with bottlebrushes as elementary strands can be adjusted to mimic, for example, the elasticity of living tissues.

Block copolymers comprising two or more chemically different (incompatible) bottlebrush blocks demonstrate self-assembly capability in the melt state or in selective solvent, giving rise to nanostructures, mesophases, or swollen mesogels with structural, mechanical, and optical properties controlled by tuning the set of architectural parameters of constituent bottlebrush blocks.

Despite remarkable recent advances in the experimental and theoretical research of solutions, melts, nanostructured materials, and elastomers constituting molecular brushes, our knowledge in this domain is still far from comprehensive. This is clearly indicated by the dramatic increase in the number of relevant publications in the field.

This Special Issue aims to attract research articles focused on synthetic and experimental studies, as well as theory and computer simulations of the solution and bulk properties of bottlebrush (co)polymers with major emphasis on the enlarged spectrum of molecular architectures (including barbwire brushes, dendronized polymers, etc.), and further progress towards understanding systematic relations between the architecture of the bottlebrushes on one hand, and the structural, rheological, and mechanical properties of their solutions, bulk materials, and elastomers on the other. 

Prof. Dr. Oleg V. Borisov
Prof. Dr. Ekaterina B. Zhulina
Guest Editor

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Keywords

  • molecular brushes
  • comblike polymers
  • hierarchically branched macromolecules
  • bottlebrush block copolymers
  • self-assembly
  • mesogels
  • tissue-mimicking materials

Published Papers (2 papers)

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Research

15 pages, 3052 KiB  
Article
Random and Diblock Thermoresponsive Oligo(ethylene glycol)-Based Copolymers Synthesized via Photo-Induced RAFT Polymerization
by Alexey Sivokhin, Dmitry Orekhov, Oleg Kazantsev, Olga Sivokhina, Sergey Orekhov, Denis Kamorin, Ksenia Otopkova, Michael Smirnov and Rostislav Karpov
Polymers 2022, 14(1), 137; https://0-doi-org.brum.beds.ac.uk/10.3390/polym14010137 - 30 Dec 2021
Cited by 8 | Viewed by 2074
Abstract
Amphiphilic random and diblock thermoresponsive oligo(ethylene glycol)-based (co)polymers were synthesized via photoiniferter polymerization under visible light using trithiocarbonate as a chain transfer agent. The effect of solvent, light intensity and wavelength on the rate of the process was investigated. It was shown that [...] Read more.
Amphiphilic random and diblock thermoresponsive oligo(ethylene glycol)-based (co)polymers were synthesized via photoiniferter polymerization under visible light using trithiocarbonate as a chain transfer agent. The effect of solvent, light intensity and wavelength on the rate of the process was investigated. It was shown that blue and green LED light could initiate RAFT polymerization of macromonomers without an exogenous initiator at room temperature, giving bottlebrush polymers with low dispersity at sufficiently high conversions achieved in 1–2 h. The pseudo-living mechanism of polymerization and high chain-end fidelity were confirmed by successful chain extension. Thermoresponsive properties of the copolymers in aqueous solutions were studied via turbidimetry and laser light scattering. Random copolymers of methoxy- and alkoxy oligo(ethylene glycol) methacrylates of a specified length formed unimolecular micelles in water with a hydrophobic core consisting of a polymer backbone and alkyl groups and a hydrophilic oligo(ethylene glycol) shell. In contrast, the diblock copolymer formed huge multimolecular micelles. Full article
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22 pages, 3455 KiB  
Article
Polymer Brush in a Nanopore: Effects of Solvent Strength and Macromolecular Architecture Studied by Self-Consistent Field and Scaling Theory
by Mikhail Y. Laktionov, Ekaterina B. Zhulina, Ralf P. Richter and Oleg V. Borisov
Polymers 2021, 13(22), 3929; https://0-doi-org.brum.beds.ac.uk/10.3390/polym13223929 - 14 Nov 2021
Cited by 4 | Viewed by 1921
Abstract
To study conformational transition occuring upon inferior solvent strength in a brush formed by linear or dendritically branched macromolecules tethered to the inner surface of cylindrical or planar (slit-like) pore, a self-consistent field analytical approach is employed. Variations in the internal brush structure [...] Read more.
To study conformational transition occuring upon inferior solvent strength in a brush formed by linear or dendritically branched macromolecules tethered to the inner surface of cylindrical or planar (slit-like) pore, a self-consistent field analytical approach is employed. Variations in the internal brush structure as a function of variable solvent strength and pore radius, and the onset of formation of a hollow channel in the pore center are analysed. The predictions of analytical theory are supported and complemented by numerical modelling by a self-consistent field Scheutjens–Fleer method. Scaling arguments are used to study microphase segregation under poor solvent conditions leading to formation of a laterally and longitudinally patterned structure in planar and cylindrical pores, respectively, and the effects of confinement on "octopus-like" clusters in the pores of different geometries. Full article
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