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Block Copolymers: Self-Assembly and Applications, 2nd Edition

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

Deadline for manuscript submissions: 30 September 2025 | Viewed by 1594

Special Issue Editor


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Guest Editor
Laboratory of Industrial Chemistry, Department of Chemistry, National and Kapodistrian University of Athens, 15771 Zografou, Greece
Interests: polymer synthesis; polymer characterization; self-assembly of copolymers in selective solvents
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Special Issue Information

Dear Colleagues,

One of the most intriguing features of block copolymers is their ability to self-assemble either in bulk or in selective solvents. In bulk, the immiscibility of the constituent blocks leads to microphase separation, with the formation of long-range ordered structures such as cubic arrays, cylinders, bicontinuous phases, and lamellae with sizes comparable to the chain dimensions. In a selective solvent, i.e., a thermodynamically good solvent, for the one block and a precipitant for the other, block copolymers associate and form micellar aggregates. From a morphological point of view, block copolymer micelles consist of a more or less swollen core of insoluble blocks surrounded by a corona formed by soluble blocks. Due to their stability, variety of sizes, and core–shell structure, micelles can be used in diverse practical applications, such as colloidal stabilization, latex technology, compatibilization in polymer blends, controlled drug delivery, water purification, viscosity, and surface modification, etc.

Many studies, both experimental and theoretical, have been devoted to the study of micellar and associated structural parameters (critical micelle concentration, CMC, aggregation number, overall micellar size, core and shell dimensions) as well as the kinetics and thermodynamics of micellization. A combination of several experimental techniques is required to explore these parameters, including static and dynamic light scattering, neutron scattering, small-angle X-ray scattering, membrane osmometry, MO, dilute solution viscometry, electron microscopy, nuclear magnetic resonance spectroscopy, NMR, sedimentation velocity and fluorescence techniques, size exclusion chromatography, SEC, etc. Micellization is a dynamic procedure and thus can be influenced by many factors, e.g., chemical nature, composition and molecular weight of the blocks, solvent quality, pH, concentration, temperature, etc.

An enormous number of studies has been conducted using di- and triblock copolymers. However, recent advances in synthetic polymer chemistry have enabled the preparation of various well-defined complex macromolecular topologies, stimulating efforts to link polymer architecture and supramolecular assembly of copolymers in selective solvents. From these reports, macromolecular architecture has emerged as a very important parameter for the manipulation of micellar properties, providing a new tool for the tuning of micellization behavior and for designing materials with specific applications. As a result, tapered copolymers, star-block, linear-dendritic, cyclic, miktoarm stars, graft, H-, super H-,  π-shaped and more complex brush-like copolymers have been studied in selective solvents, confirming the tremendous impact of macromolecular architecture on micellization properties.

This Special Issue will focus on the recent developments in the self-assembly behavior of amphiphilic copolymers and their applications. Special interest will be given to the effect of macromolecular architecture on micellization behavior.

Prof. Dr. Marinos Pitsikalis
Guest Editor

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Keywords

  • synthesis of micellar structures
  • advanced characterization techniques of micellar structures
  • thermodynamics of micellization
  • kinetics of micellization
  • applications of polymeric micellar systems
  • effect of macromolecular architecture on self-assembly behavior
  • theoretical approaches to micellization behavior

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Published Papers (2 papers)

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Research

25 pages, 4391 KiB  
Article
Synthesis, Characterization, and Self-Assembly Behavior of Block Copolymers of N-Vinyl Pyrrolidone with n-Alkyl Methacrylates
by Nikoletta Roka and Marinos Pitsikalis
Polymers 2025, 17(8), 1122; https://doi.org/10.3390/polym17081122 - 21 Apr 2025
Viewed by 141
Abstract
Novel amphiphilic block copolymers of N-vinyl pyrrolidone (NVP) and either n-hexyl methacrylate (HMA, PNVP-b-PHMA) or stearyl methacrylate (SMA, PNVP-b-PSMA) were prepared by RAFT polymerization techniques and the sequential addition of monomers starting from the polymerization of NVP and using [...] Read more.
Novel amphiphilic block copolymers of N-vinyl pyrrolidone (NVP) and either n-hexyl methacrylate (HMA, PNVP-b-PHMA) or stearyl methacrylate (SMA, PNVP-b-PSMA) were prepared by RAFT polymerization techniques and the sequential addition of monomers starting from the polymerization of NVP and using two different Chain Transfer Agents, CTAs. PNVP-b-PHMA are amorphous block copolymers containing constituent blocks with both high and low Tg values, whereas PNVP-b-PSMA are amorphous–semi-crystalline copolymers. Samples with different molecular weights and compositions were obtained. The copolymers were microphase-separated, but partial mixing was also observed. The presence of the amorphous PNVP block reduced the crystallinity of the PSMA blocks in the PNVP-b-PSMA copolymers. The thermal stability of the blocks was influenced by both constituents. The self-assembly behavior in THF, which is a selective solvent for polymethacrylate blocks, and in aqueous solutions, where PNVP was soluble, was examined. Unimolecular or low-aggregation-number micelles were obtained in THF for both types of samples. On the contrary, high-aggregation-number, spherical, and compact micelles were revealed in aqueous solutions. The increase in the steric hindrance of the side ester group of the polymethacrylate chain led to slightly lower degrees of association. The hydrophobic compound curcumin was efficiently encapsulated within the micellar core of the supramolecular structures in aqueous solutions. Micelles with higher aggregation numbers were more efficient in the encapsulation of curcumin. The results of this study were compared with those obtained from other block copolymers based on PNVP. Full article
(This article belongs to the Special Issue Block Copolymers: Self-Assembly and Applications, 2nd Edition)
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19 pages, 5132 KiB  
Article
Double Hydrophilic Hyperbranched Copolymer-Based Lipomer Nanoparticles: Copolymer Synthesis and Co-Assembly Studies
by Angelica Maria Gerardos and Stergios Pispas
Polymers 2024, 16(22), 3129; https://doi.org/10.3390/polym16223129 - 9 Nov 2024
Cited by 1 | Viewed by 1306
Abstract
Double hydrophilic, random, hyperbranched copolymers were synthesized via reversible addition–fragmentation chain transfer (RAFT) polymerization of oligo(ethylene glycol) methyl ether methacrylate (OEGMA) and 2-(dimethylamino)ethyl methacrylate (DMAEMA) utilizing ethylene glycol dimethacrylate (EGDMA) as the branching agent. The resulting copolymers were characterized in terms of their [...] Read more.
Double hydrophilic, random, hyperbranched copolymers were synthesized via reversible addition–fragmentation chain transfer (RAFT) polymerization of oligo(ethylene glycol) methyl ether methacrylate (OEGMA) and 2-(dimethylamino)ethyl methacrylate (DMAEMA) utilizing ethylene glycol dimethacrylate (EGDMA) as the branching agent. The resulting copolymers were characterized in terms of their molecular weight and dispersity using size exclusion chromatography (SEC), and their chemical structure was confirmed using FT-IR and 1H-NMR spectroscopy techniques. The choice of the two hydrophilic blocks and the design of the macromolecular structure allowed the formation of self-assembled nanoparticles, partially due to the pH-responsive character of the DMAEMA segments and their interaction with -COOH end groups remaining from the chain transfer agent. The copolymers showed pH-responsive properties, mainly due to the protonation–deprotonation equilibria of the DMAEMA segments. Subsequently, a nanoscopic polymer–lipid (lipomer) mixed system was formulated by complexing the synthesized copolymers with cosmetic amphiphilic emulsifiers, specifically glyceryl stearate (GS) and glyceryl stearate citrate (GSC). This study aims to show that developing lipid–polymer hybrid nanoparticles can effectively address the limitations of both liposomes and polymeric nanoparticles. The effects of varying the ionic strength and pH on stimuli-sensitive polymeric and mixed polymer–lipid nanostructures were thoroughly investigated. To achieve this, the structural properties of the hybrid nanoparticles were comprehensively characterized using physicochemical techniques providing insights into their size distribution and stability. Full article
(This article belongs to the Special Issue Block Copolymers: Self-Assembly and Applications, 2nd Edition)
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