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Polymers
Special Issues
Polymer Brushes: Synthesis, Properties and Structure
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Polymer Brushes: Synthesis, Properties and Structure

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

Deadline for manuscript submissions: closed (25 December 2022) | Viewed by 12422

Special Issue Editor

Dr. Karol Wolski

E-Mail Website
Guest Editor
Faculty of Chemistry, Jagiellonian University, Gronostajowa 2, 30-387 Krakow, Poland
Interests: synthesis of conjugated polymer brushes for electrical applications; development of new synthetic strategies toward polymer brushes with advanced architectures; nanomechanical and electrical characterization of thin organic films by atomic force microscopy; structure–property relationships of polymeric materials; kinetics studies of surface-initiated polymerizations; development of new metal free and photoinduced ATRP methods for controlled synthesis of polymer brushes; energy/electron transfer processes in confined environments

Special Issue Information

Dear Colleagues,

Polymer brushes are assemblies of stretched and densely packed polymer chains with one end grafted to a particular substrate, which could be a single polymer chain (molecular brushes), nano/microparticles, porous materials or planar surfaces. Covalent attachment of the macromolecules ensures advantageous properties (higher mechanical stability, lower coefficient of friction, decreased entanglement of polymer chains) compared to physically adsorbed films. Furthermore, as a consequence of the perpendicular arrangement of surface-grafted polymers with respect to the substrate, they often exhibit anisotropic properties crucial for many applications, such as chemo- and bio-sensors, organic solar cells, nanoelectronics, platforms for controlled cell growth or stimuli-responsive systems.

Polymer brushes are commonly synthesized by two main approaches called “grafting from” and “grafting to”. The former allows formation of the layers with high grafting density and hence anisotropic characteristics. Therefore, there is a huge demand on the development and understanding of new techniques compatible with the “grafting from” approach, allowing synthesis of advanced hybrid materials, preferably in air conditions, using simplified reaction systems.

The growing interest of decorating various organic and inorganic substrates with functional polymer brushes has motivated us to create this Special Issue, which is aimed at collecting research papers on the following topics:

  • Development of new synthetic strategies toward functional polymer brushes;
  • Grafting of polymers from various substrates: single polymer chains, organic and inorganic materials, nano/microparticles, nanoporous materials and planar surfaces;
  • Synthesis of polymer brushes with advanced architectures;
  • Structure–property relationship of surface-grafted polymers;
  • Development of stimuli-responsive hybrid polymeric materials;
  • Physicochemical characterization of polymer brushes;
  • Kinetics studies of surface-initiated polymerizations;
  • Applications of polymer brushes.

We encourage you to publish full papers, reviews as well as communications.

Dr. Karol Wolski
Guest Editor

Manuscript Submission Information

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All submissions that pass pre-check are peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Polymers is an international peer-reviewed open access semimonthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2700 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

  • polymer brushes
  • surface-initiated polymerization
  • surface-grafted polymers
  • stimuli-responsive polymers
  • grafting from
  • structure–property relationship
  • reversible deactivation radical polymerization
  • kinetics of surface-initiated polymerizations
  • nanomechanical and electrical characterization
  • applications of polymer brushes

Published Papers (4 papers)

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Research

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15 pages, 3188 KiB  
Article
Synthetic Route to Conjugated Donor–Acceptor Polymer Brushes via Alternating Copolymerization of Bifunctional Monomers
by Anna Grobelny, Karolina Lorenc, Łucja Skowron and Szczepan Zapotoczny
Polymers 2022, 14(13), 2735; https://doi.org/10.3390/polym14132735 - 04 Jul 2022
Cited by 1 | Viewed by 1995
Abstract
Alternating donor–acceptor conjugated polymers, widely investigated due to their applications in organic photovoltaics, are obtained mainly by cross-coupling reactions. Such a synthetic route exhibits limited efficiency and requires using, for example, toxic palladium catalysts. Furthermore, the coating process demands solubility of the macromolecules, [...] Read more.
Alternating donor–acceptor conjugated polymers, widely investigated due to their applications in organic photovoltaics, are obtained mainly by cross-coupling reactions. Such a synthetic route exhibits limited efficiency and requires using, for example, toxic palladium catalysts. Furthermore, the coating process demands solubility of the macromolecules, provided by the introduction of alkyl side chains, which have an impact on the properties of the final material. Here, we present the synthetic route to ladder-like donor–acceptor polymer brushes using alternating copolymerization of modified styrene and maleic anhydride monomers, ensuring proper arrangement of the pendant donor and acceptor groups along the polymer chains grafted from a surface. As a proof of concept, macromolecules with pendant thiophene and benzothiadiazole groups were grafted by means of RAFT and metal-free ATRP polymerizations. Densely packed brushes with a thickness up to 200 nm were obtained in a single polymerization process, without the necessity of using metal-based catalysts or bulky substituents of the monomers. Oxidative polymerization using FeCl3 was then applied to form the conjugated chains in a double-stranded (ladder-like) architecture. Full article
(This article belongs to the Special Issue Polymer Brushes: Synthesis, Properties and Structure)
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16 pages, 8145 KiB  
Article
Preparation of Homopolymer, Block Copolymer, and Patterned Brushes Bearing Thiophene and Acetylene Groups Using Microliter Volumes of Reaction Mixtures
by Joanna Smenda, Karol Wolski, Kamila Chajec and Szczepan Zapotoczny
Polymers 2021, 13(24), 4458; https://doi.org/10.3390/polym13244458 - 19 Dec 2021
Cited by 4 | Viewed by 2993
Abstract
The synthesis of surface-grafted polymers with variable functionality requires the careful selection of polymerization methods that also enable spatially controlled grafting, which is crucial for the fabrication of, e.g., nano (micro) sensor or nanoelectronic devices. The development of versatile, simple, economical, and eco-friendly [...] Read more.
The synthesis of surface-grafted polymers with variable functionality requires the careful selection of polymerization methods that also enable spatially controlled grafting, which is crucial for the fabrication of, e.g., nano (micro) sensor or nanoelectronic devices. The development of versatile, simple, economical, and eco-friendly synthetic strategies is important for scaling up the production of such polymer brushes. We have recently shown that poly (3-methylthienyl methacrylate) (PMTM) and poly (3-trimethylsilyl-2-propynyl methacrylate) (PTPM) brushes with pendant thiophene and acetylene groups, respectively, could be used for the production of ladder-like conjugated brushes that are potentially useful in the mentioned applications. However, the previously developed syntheses of such brushes required the use of high volumes of reagents, elevated temperature, or high energy UV-B light. Therefore, we present here visible light-promoted metal-free surface-initiated ATRP (metal-free SI-ATRP) that allows the economical synthesis of PMTM and PTPM brushes utilizing only microliter volumes of reaction mixtures. The versatility of this approach was shown by the formation of homopolymers but also the block copolymer conjugated brushes (PMTM and PTPM blocks in both sequences) and patterned films using TEM grids serving as photomasks. A simple reaction setup with only a monomer, solvent, commercially available organic photocatalyst, and initiator decorated substrate makes the synthesis of these complex polymer structures achievable for non-experts and ready for scaling up. Full article
(This article belongs to the Special Issue Polymer Brushes: Synthesis, Properties and Structure)
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11 pages, 2327 KiB  
Article
In Situ Surface-Initiated Atom-Transfer Radical Polymerization Utilizing the Nonvolatile Nature of Ionic Liquids: A First Attempt
by Ryo Satoh, Saika Honma, Hiroyuki Arafune, Ryo Shomura, Toshio Kamijo, Takashi Morinaga and Takaya Sato
Polymers 2021, 13(1), 61; https://doi.org/10.3390/polym13010061 - 25 Dec 2020
Cited by 4 | Viewed by 2748
Abstract
In this paper, in situ surface-initiated atom-transfer radical polymerization (SI-ATRP) based on both an open and a coated system, without using volatile reagents, was developed to overcome the limited usage of ATRP due to the necessity of sealing. Nonvolatile ionic liquid (IL)-type components [...] Read more.
In this paper, in situ surface-initiated atom-transfer radical polymerization (SI-ATRP) based on both an open and a coated system, without using volatile reagents, was developed to overcome the limited usage of ATRP due to the necessity of sealing. Nonvolatile ionic liquid (IL)-type components were used, specifically N,N-diethyl-N-(2-methacryloylethyl)-N-methylammonium bis(trifluoromethylsulfonyl)imide as the polymerizable monomer and N,N-diethylmethyl(2-methoxyethyl)ammonium bis(trifluoromethylsulfonyl)imide as the polymerization solvent. In the experiment, the reversible-deactivation radical polymerization characteristics are properly ensured in nonvolatile ATRP solution coated on silicon wafer as thin liquid film, to form concentrated polymer brushes (CPBs). The average molecular weight and molecular-weight distribution of the polymer produced in the liquid film and formed on silicon wafer were measured by gel permeation chromatography, which confirms that the polymerization reaction occurred as designed. Furthermore, it is clarified that the surface of the polymer brush synthesized in situ swollen by IL also exhibited low friction characteristics, comparable to that synthesized in a typical immersion process. This paper is the first to establish the effectiveness of in situ preparation for CPBs by using the coating technique. Full article
(This article belongs to the Special Issue Polymer Brushes: Synthesis, Properties and Structure)
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Review

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33 pages, 5442 KiB  
Review
Temperature-Responsive Polymer Brush Coatings for Advanced Biomedical Applications
by Svyatoslav Nastyshyn, Yuriy Stetsyshyn, Joanna Raczkowska, Yuriy Nastishin, Yuriy Melnyk, Yuriy Panchenko and Andrzej Budkowski
Polymers 2022, 14(19), 4245; https://doi.org/10.3390/polym14194245 - 10 Oct 2022
Cited by 34 | Viewed by 3551
Abstract
Modern biomedical technologies predict the application of materials and devices that not only can comply effectively with specific requirements, but also enable remote control of their functions. One of the most prospective materials for these advanced biomedical applications are materials based on temperature-responsive [...] Read more.
Modern biomedical technologies predict the application of materials and devices that not only can comply effectively with specific requirements, but also enable remote control of their functions. One of the most prospective materials for these advanced biomedical applications are materials based on temperature-responsive polymer brush coatings (TRPBCs). In this review, methods for the fabrication and characterization of TRPBCs are summarized, and possibilities for their application, as well as the advantages and disadvantages of the TRPBCs, are presented in detail. Special attention is paid to the mechanisms of thermo-responsibility of the TRPBCs. Applications of TRPBCs for temperature-switchable bacteria killing, temperature-controlled protein adsorption, cell culture, and temperature-controlled adhesion/detachment of cells and tissues are considered. The specific criteria required for the desired biomedical applications of TRPBCs are presented and discussed. Full article
(This article belongs to the Special Issue Polymer Brushes: Synthesis, Properties and Structure)
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