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Advances in Surfactant Systems: Thermodynamics, Molecular Interactions, and Applications

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

Deadline for manuscript submissions: 20 March 2026 | Viewed by 312

Special Issue Editor


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Guest Editor
Department of Pharmacy, Faculty of Medicine, University of Novi Sad, Hajduk Veljka 3, 21000 Novi Sad, Serbia
Interests: drug nanocarriers and targeted delivery systems; surfactants; mixed micelles; thermodynamic stability; micellar solubility; bile salts
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Special Issue Information

Dear Colleagues,

Surfactants are particles that possess both hydrophobic and hydrophilic molecular segments. They come in various architectural forms, including surfactants with rigid hydrophobic or hydrophilic chains, flexible hydrophobic chains, and gemini, bolaform, and polymeric surfactants. Designing and chemically synthesizing a surfactant with a specific architecture and properties is challenging. Similarly, developing a mathematical model that can predict surfactant properties, such as a critical micellar concentration, aggregation number, and micelle geometric shape, presents its own set of difficulties.

There is ongoing research into the relationship between the thermodynamic functions of micelle formation and the state functions of surfactants at the interface. Additionally, the mechanism of self-association at the microscopic level is an active study area. The scientific community has discussed applying phase separation theory to micelle formation in conjunction with the association model based on the law of mass action.

Beyond chemical synthesis, desired surface activity properties can also be achieved through binary and ternary mixtures of surfactants. However, debates continue regarding the physicochemical models used to describe the state of mixed micelles. The theory of regular solutions is the most commonly used model. However, it has faced significant criticism regarding its applicability based on surfactant structure and the ionic strength of aqueous solutions. Consequently, there is a pressing need to develop new theories and state functions for mixed surfactant systems or for theories that are utilized for carryout out validations using the regular solution approach.

Topics of interest for this Special Issue encompass the following:

  1. Theories of micelle formation.
  2. Thermodynamics of binary and ternary mixed micelles: models used to describe them.
  3. Experimental techniques in characterizing surfactant interactions in their mixed micelles and their correlation with thermodynamic parameters.
  4. Interactions of surfactants with biologically (pharmacologically) active molecules in the pre-micellar and micellar states (Benessi–Hildebrand and Kawamura methods).
  5. Behavior of surfactants and their mixtures on boundary surfaces.
  6. Surfactant systems in pharmaceutical formulations and their influence on the kinetics and bioavailability of drugs.
  7. Synthesis of new surfactants and their use in the characterization and testing of detergent properties.
  8. Membranotoxicity (destruction of biological membranes) of surfactants.

Prof. Dr. Mihalj Poša
Guest Editor

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Keywords

  • micelles
  • mixed micelles
  • thermodynamic functions of micellization
  • micellar solubilization
  • enthalpy–entropy compensation
  • boundary surface
  • Langmuir isotherm
  • theoretical models

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Published Papers (1 paper)

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Research

21 pages, 3707 KB  
Article
Theoretical View: Thermodynamics of the Saturation Dissolution of a Molecular (Solid) Dispersion of a Hydrophobic Molecule and Polymeric Surfactant in an Aqueous Solution
by Mihalj Poša
Int. J. Mol. Sci. 2025, 26(23), 11756; https://doi.org/10.3390/ijms262311756 - 4 Dec 2025
Abstract
Hot-melt extrusion produces a solid dispersion (SD) containing a poorly water-soluble drug (k) and matrix polymer surfactant (PS), thereby enhancing k’s solubility. When dissolving the SD, the PS is first dissolved, forming micelles. The amorphous form of the solid phase [...] Read more.
Hot-melt extrusion produces a solid dispersion (SD) containing a poorly water-soluble drug (k) and matrix polymer surfactant (PS), thereby enhancing k’s solubility. When dissolving the SD, the PS is first dissolved, forming micelles. The amorphous form of the solid phase k remains and is further dissolved by micellar solubilization. The goal here is to rigorously derive, on the basis of thermodynamics, a new expression for the change in the standard Gibbs free energy (GΣ 0). This change serves as a measure for increasing the degree of spontaneity in the dissolution of amorphous k from an SD with a polymeric surfactant relative to the dissolution of the crystalline-form k in an aqueous solution without surfactants (reference state). In the micelle-pseudophase model, it was found that GΣ 0 depends on the natural logarithm of the ratio of mole fraction k in the aqueous phase to mole fraction k in the micellar pseudophase. In a simpler model, GΣ 0 can be expressed as ln of the solubility ratio of the crystalline and SD forms, assuming that the activity coefficient depends on the process of incorporating k into the micellar particles and that the total amount of surfactants is many times smaller than the water amount, which is acceptable for polymeric surfactants with low values of the critical micellar concentration. Full article
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