Self-Assembly of Block Copolymers: Preparation of Nanostructured Materials for Industrial and Biomedical Applications

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

Deadline for manuscript submissions: closed (30 June 2021) | Viewed by 10256

Special Issue Editor


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Guest Editor
Department of Chemistry, University College London, London WC1H 0AJ, UK
Interests: Controlled polymerization techniques; block copolymer self-assembly; polymerization-induced self-assembly (PISA); stimuli-responsive nanostructures; polymeric nanoreactors; polypeptides; targeted drug delivery.

Special Issue Information

Dear Colleagues,

We would like to invite you to contribute a full article, short communication, or review article to the Special Issue entitled “Self-Assembly of Block Copolymers: Preparation of Nanostructured Materials for Industrial and Biomedical Applications”. Over the past few decades, the advancement of controlled/living polymerization techniques has facilitated the synthesis of well-defined block copolymers with precisely controlled composition, topology, and functionality. Importantly, the preparation of copolymers comprising discrete blocks that differ significantly in their solvophilicity leads to microphase separation between the incompatible domains either in bulk or in solution in the system’s effort to minimize unfavorable polymer–polymer and polymer–solvent interactions. This behavior, also known as block copolymer self-assembly, in turn, results in the formation of nanostructured materials with unique properties.

In bulk, copolymers containing immiscible blocks can self-assemble into a wide variety of ordered morphologies, including spheres, cylinders, gyroids, lamellae, etc., driven by both enthalpic and entropic factors. In a similar manner, amphiphilic block copolymers self-assemble in solution into nano-sized formulations with distinct solvophilic and solvophobic domains, such as core-shell spherical and worm-like micelles, bilayer lamellae, polymersomes, and other more complex morphologies, owing to strong attraction forces and aggregation between the associating blocks.

The most widely utilized methodologies for the development of self-assembled polymeric nano-objects in solution involve either conventional self-assembly approaches, such as solvent-switch and thin-film rehydration, or alternative techniques, such as dispersion/emulsion polymerization, crystallization-driven self-assembly (CDSA), and polymerization-induced self-assembly (PISA). Ultimately, owing to the unique properties of self-assembled block copolymer nanostructures, such materials have been successfully utilized in a wide range of industrial and biomedical applications, including oil modification, nanolithography, drug delivery, diagnostic imaging and sensing, catalysis, and cell mimicry.

The aim of this Special Issue is to highlight recent advances in the field of block copolymer self-assembly for the development of nanomaterials of industrial or biomedical interest. Special emphasis will be given to novel self-assembly methodologies, such as CDSA and PISA, for the formation of well-defined polymeric nano-objects of controllable morphology, as well as the preparation of stimuli-responsive and biocompatible nanostructures.

Dr. Spyridon Varlas
Guest Editor

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Keywords

  • block copolymers
  • self-assembly
  • polymer nanoparticles
  • amphiphiles
  • crystallization-driven self-assembly (CDSA)
  • polymerization-induced self-assembly (PISA)
  • nanomaterials
  • soft matter
  • applications

Published Papers (3 papers)

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Research

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11 pages, 2558 KiB  
Article
Structure/Properties Relationship of Anionically Synthesized Diblock Copolymers “Grafted to” Chemically Modified Graphene
by Dimitrios Katsigiannopoulos, Eftychia Grana, Konstantina Tsitoni, Ioannis Moutsios, Gkreti-Maria Manesi, Evgeniia A. Nikitina, Nikolaos Chalmpes, Dimitrios Moschovas, Dimitrios Gournis, Dimitri A. Ivanov and Apostolos Avgeropoulos
Polymers 2021, 13(14), 2308; https://doi.org/10.3390/polym13142308 - 14 Jul 2021
Cited by 2 | Viewed by 2349
Abstract
A novel approach to obtaining nanocomposite materials using anionic sequential polymerization and post-synthetic esterification reactions with chemically modified graphene sheets (CMGs) is reported. The anionically synthesized diblock copolymer precursors of the PS-b-PI-OH type were grafted to the chemically modified –COOH groups [...] Read more.
A novel approach to obtaining nanocomposite materials using anionic sequential polymerization and post-synthetic esterification reactions with chemically modified graphene sheets (CMGs) is reported. The anionically synthesized diblock copolymer precursors of the PS-b-PI-OH type were grafted to the chemically modified –COOH groups of the CMGs, giving rise to the final composite materials, namely polystyrene-b-poly(isoprene)-g-CMGs, which exhibited enhanced physicochemical properties. The successful synthesis was determined through multiple molecular characterization techniques together with thermogravimetric analysis for the verification of increased thermal stability, and the structure/properties relationship was justified through transmission electron microscopy. Furthermore, the arrangement of CMGs utilizing lamellar and cylindrical morphologies was studied in order to determine the effect of the loaded CMGs in the adopted topologies. Full article
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26 pages, 7963 KiB  
Article
Nano-Assemblies from Amphiphilic PnBA-b-POEGA Copolymers as Drug Nanocarriers
by Angeliki Chroni, Thomas Mavromoustakos and Stergios Pispas
Polymers 2021, 13(7), 1164; https://doi.org/10.3390/polym13071164 - 05 Apr 2021
Cited by 11 | Viewed by 2736
Abstract
The focus of this study is the development of highly stable losartan potassium (LSR) polymeric nanocarriers. Two novel amphiphilic poly(n-butyl acrylate)-block-poly(oligo(ethylene glycol) methyl ether acrylate) (PnBA-b-POEGA) copolymers with different molecular weight (Mw) of PnBA are synthesized via reversible addition fragmentation chain [...] Read more.
The focus of this study is the development of highly stable losartan potassium (LSR) polymeric nanocarriers. Two novel amphiphilic poly(n-butyl acrylate)-block-poly(oligo(ethylene glycol) methyl ether acrylate) (PnBA-b-POEGA) copolymers with different molecular weight (Mw) of PnBA are synthesized via reversible addition fragmentation chain transfer (RAFT) polymerization, followed by the encapsulation of LSR into both PnBA-b-POEGA micelles. Based on dynamic light scattering (DLS), the PnBA30-b-POEGA70 and PnBA27-b-POEGA73 (where the subscripts denote wt.% composition of the components) copolymers formed micelles of 10 nm and 24 nm in water. The LSR-loaded PnBA-b-POEGA nanocarriers presented increased size and greater mass nanostructures compared to empty micelles, implying the successful loading of LSR into the inner hydrophobic domains. A thorough NMR (nuclear magnetic resonance) characterization of the LSR-loaded PnBA-b-POEGA nanocarriers was conducted. Strong intermolecular interactions between the biphenyl ring and the butyl chain of LSR with the methylene signals of PnBA were evidenced by 2D-NOESY experiments. The highest hydrophobicity of the PnBA27-b-POEGA73 micelles contributed to an efficient encapsulation of LSR into the micelles exhibiting a greater value of %EE compared to PnBA30-b-POEGA70 + 50% LSR nanocarriers. Ultrasound release profiles of LSR signified that a great amount of the encapsulated LSR is strongly attached to both PnBA30-b-POEGA70 and PnBA27-b-POEGA73 micelles. Full article
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Review

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18 pages, 2994 KiB  
Review
Protein-, (Poly)peptide-, and Amino Acid-Based Nanostructures Prepared via Polymerization-Induced Self-Assembly
by Spyridon Varlas, Georgia L. Maitland and Matthew J. Derry
Polymers 2021, 13(16), 2603; https://doi.org/10.3390/polym13162603 - 05 Aug 2021
Cited by 12 | Viewed by 4232
Abstract
Proteins and peptides, built from precisely defined amino acid sequences, are an important class of biomolecules that play a vital role in most biological functions. Preparation of nanostructures through functionalization of natural, hydrophilic proteins/peptides with synthetic polymers or upon self-assembly of all-synthetic amphiphilic [...] Read more.
Proteins and peptides, built from precisely defined amino acid sequences, are an important class of biomolecules that play a vital role in most biological functions. Preparation of nanostructures through functionalization of natural, hydrophilic proteins/peptides with synthetic polymers or upon self-assembly of all-synthetic amphiphilic copolypept(o)ides and amino acid-containing polymers enables access to novel protein-mimicking biomaterials with superior physicochemical properties and immense biorelevant scope. In recent years, polymerization-induced self-assembly (PISA) has been established as an efficient and versatile alternative method to existing self-assembly procedures for the reproducible development of block copolymer nano-objects in situ at high concentrations and, thus, provides an ideal platform for engineering protein-inspired nanomaterials. In this review article, the different strategies employed for direct construction of protein-, (poly)peptide-, and amino acid-based nanostructures via PISA are described with particular focus on the characteristics of the developed block copolymer assemblies, as well as their utilization in various pharmaceutical and biomedical applications. Full article
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