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Self- and Forced Assembly of Polymer Systems: Experiment, Theory and Simulation

A special issue of International Journal of Molecular Sciences (ISSN 1422-0067). This special issue belongs to the section "Macromolecules".

Deadline for manuscript submissions: closed (10 May 2024) | Viewed by 2461

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Guest Editor
Institute of Macromolecular Compounds of the Russian Academy of Sciences, 199004 St. Petersburg, Russia
Interests: polymers; polymer brushes; dendrimers; self-organization in polymers; computer simulations
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Special Issue Information

Dear Colleagues,

The assembly of polymers is the phenomena of the organization of polymer chains into two- or three-dimensional structures. Usually, one separates self-assembly/self-ordering and forced assembly. In the first case, such structures arise spontaneously due to the change in the external conditions (temperature, ionic strength, pH) through the molecular "recognition" due to non-covalent interactions (electrostatic, hydrophobic) or the formation of hydrogen bonds. As part of the self-assembly, one can also consider the formation of aggregates in block copolymers or the formation of liquid crystals due to the increase in the polymer concentration in the solution. Self-assembly is also observed in living tissues, where it manifests itself in the formation of structures such as double layers and vesicular (bubbly) structures consisting of one or many lipid bimolecular membranes. Self-assembly is used in the construction of functional ("smart") materials, the structure and properties of which depend on changes in external conditions. The forced assembly occurs under the influence of external factors. An example of this is crystallization under the influence of mechanical impacts. Despite the huge number of works devoted to this subject, both experimental and theoretical, this area still attracts much attention from researchers due to the wide variety of existing and newly discovered structures. The scope and potential of possible applications of this phenomenon in technology and medicine are growing more and more.

Prof. Dr. Anatoly Darinskii
Guest Editor

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Keywords

  • amphiphilic polymers
  • molecular "recognition"
  • micelles
  • globules
  • liposomes
  • polymer complexes aggregaton
  • micropase segregation
  • block copolymers
  • liquid crystals

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Published Papers (2 papers)

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12 pages, 1862 KiB  
Article
Salt-Controlled Vertical Segregation of Mixed Polymer Brushes
by Ivan V. Mikhailov and Anatoly A. Darinskii
Int. J. Mol. Sci. 2024, 25(23), 13175; https://doi.org/10.3390/ijms252313175 - 7 Dec 2024
Cited by 1 | Viewed by 580
Abstract
Using the self-consistent field approach, we studied the salt-controlled vertical segregation of mixed polymer brushes immersed into a selective solvent. We considered brushes containing two types of chains: polyelectrolyte (charged) chains and neutral chains. The hydrophobicity of both types of chains is characterized [...] Read more.
Using the self-consistent field approach, we studied the salt-controlled vertical segregation of mixed polymer brushes immersed into a selective solvent. We considered brushes containing two types of chains: polyelectrolyte (charged) chains and neutral chains. The hydrophobicity of both types of chains is characterized by the Flory–Huggins parameters χC and χN, respectively. It was assumed that the hydrophobicity is varied only for the polyelectrolyte chains (χC), while other polymer chains in the brush remain hydrophilic (χN=0) and neutral. Thus, in our model, the solvent selectivity (χ=χCχN) was varied, which can be controlled in a real experiment, for example, by changing the temperature. At low salt concentrations, the polyelectrolyte chains swell and occupy the surface of the mixed brush. At high salt concentrations, the hydrophobic polyelectrolyte chains collapse and give place to neutral chains on the surface. By changing the selectivity of the solvent and the ionic strength of the solution, the surface properties of such mixed brushes can be controlled. Based on the numerical simulations results, it is shown how the critical selectivity corresponding to the segregation transition in polyelectrolyte/neutral brushes depends on the ionic strength of the solution. It is shown that at the same ionic strength, the critical selectivity increases with an increasing degree of dissociation of charged groups, as well as with an increasing fraction of polyelectrolyte chains in the mixed brush. It has also been shown that at low ionic strengths, the critical selectivity of the solvent decreases with increasing grafting density, while at high ionic strengths, on the contrary, it increases. Within the framework of the mean field theory, a two-parameter model has been constructed that quantitatively describes these dependencies. Full article
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24 pages, 5706 KiB  
Article
Biosourced Multiphase Systems Based on Poly(Lactic Acid) and Polyamide 11 from Blends to Multi-Micro/Nanolayer Polymers Fabricated with Forced-Assembly Multilayer Coextrusion
by Nour Jaouadi, Mohamed Jaziri, Abderrahim Maazouz and Khalid Lamnawar
Int. J. Mol. Sci. 2023, 24(23), 16737; https://doi.org/10.3390/ijms242316737 - 24 Nov 2023
Cited by 1 | Viewed by 1339
Abstract
The objective of the present study was to investigate multiphase systems based on polylactic acid (PLA) and polyamide 11 (PA11) from blends to multilayers. Firstly, PLA/PA11 blends compatibilized with a multifunctionalized epoxide, Joncryl, were obtained through reactive extrusion, and the thermal, morphological, rheological, [...] Read more.
The objective of the present study was to investigate multiphase systems based on polylactic acid (PLA) and polyamide 11 (PA11) from blends to multilayers. Firstly, PLA/PA11 blends compatibilized with a multifunctionalized epoxide, Joncryl, were obtained through reactive extrusion, and the thermal, morphological, rheological, and mechanical behaviors of these materials were investigated. The role of Joncryl as a compatibilizer for the PLA/PA11 system was demonstrated by the significant decrease in particle size and interfacial tension as well as by the tensile properties exhibiting a ductile behavior. Based on these findings, we were able to further clarify the effects of interdiffusion and diffuse interphase formation on the structure, rheology, and mechanics of compatible multilayered systems fabricated with forced-assembly multilayer coextrusion. The results presented herein aim to provide a deeper understanding of the interfacial properties, including the rheological, mechanical, and morphological behaviors, towards the control of the interface and confinement in multilayer polymers resulting from coextrusion, and also to permit their use in advanced applications. Full article
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