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

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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