Poly(ethylene succinate) (PES) is one of the most promising biodegradable and biocompatible polyesters and is widely used in different biomedical applications. However, little information is available on its solubility and precipitation properties, despite that these solution behavior properties affect its applicability. In order to systematically study these effects, biodegradable and biocompatible poly(ethylene succinate) (PES) was synthesized using ethylene glycol and succinic acid monomers with an equimolar ratio. Despite the optimized reaction temperature (T = 185 °C) of the direct condensation polymerization, relatively low molecular mass values were achieved without using a catalyst, and the M_n was adjustable with the reaction time (40–100 min) in the range of ~850 and ~1300 Da. The obtained crude products were purified by precipitation from THF (“good” solvent) with excess of methanol (“bad” solvent). The solvents for PES oligomers purification were chosen according to the calculated values of solubility parameters by different approaches (Fedors, Hoy and Hoftyzer-van Krevelen). The theta-solvent composition of the PES solution was 0.3 v/v% water and 0.7 v/v% DMSO in this binary mixture. These measurements were also allowed to determine important parameters such as the coefficients A (=0.67) and B (=3.69 × 10⁴) from the Schulz equation, or the K_η (=8.22 × 10⁻²) and α (=0.52) constants from the Kuhn–Mark–Houwink equation. Hopefully, the prepared PES with different molecular weights is a promising candidate for biomedical applications and the reported data and constants are useful for other researchers who work with this promising polyester.

The aim of the performed studies was to thoroughly examine the internal structure of self-assembled nanocarriers (i.e., polymeric micelles—PMs) by means of a hydrophobic phthalocyanine probe in order to identify the crucial features that are required to enhance the photoactive probe stability and reactivity. PMs of hydrophilic poly(ethylene glycol) and hydrophobic poly(ε-caprolactone) (PCL) or poly(d,l-lactide) (PDLLA) were fabricated and loaded with tetra tert-butyl zinc(II) phthalocyanine (ZnPc-t-but₄), a multifunctional spectroscopic probe with a profound ability to generate singlet oxygen upon irradiation. The presence of subdomains, comprising “rigid” and “flexible” regions, in the studied block copolymers’ micelles as well as their interactions with the probe molecules, were assessed by various high-resolution NMR measurements [e.g., through-space magnetic interactions by the 1D NOE effect, pulsed field gradient spin-echo, and spin–lattice relaxation time (T₁) techniques]. The studies of the impact of the core-type microenvironment on the ZnPc-t-but₄ photochemical performance also included photobleaching and reactive oxygen species measurements. ZnPc-t-but₄ molecules were found to exhibit spatial proximity effects with both (PCL and PDLLA) hydrophobic polymer chains and interact with both subdomains, which are characterized by different rigidities. It was deduced that the interfaces between particular subdomains constitute an optimal host space for probe molecules, especially in the context of photochemical stability, photoactivity (i.e., for significant enhancement of singlet oxygen generation rates), and aggregation prevention. The present contribution proves that the combination of an appropriate probe, high-resolution NMR techniques, and UV–vis spectroscopy enables one to gain complex information about the subtle structure of PMs essential for their application as nanocarriers for photoactive compounds, for example, in photodynamic therapy, nanotheranostics, combination therapy, or photocatalysis, where the micelles constitute the optimal microenvironment for the desired photoreactions.

One of the most important properties of hydrophobically functionalized polyelectrolytes (HF-PEs) and their assemblies is their ability to encapsulate hydrophobic/amphiphilic agents and provide release on demand of the entrapped payload. The aim of the present work was to synthesize and study self-organization behavior in aqueous solution of hydrophobically functionalized poly(acrylic acid) (PAA) comprising the ester-type pH labile moiety with various degrees of hydrophobization and side-chain lengths in the absence and presence of appropriate mono- and polyvalent electrolytes (i.e., NaCl or CaCl₂). The synthesis and purification of hydrophobically functionalized PAA were performed under mild conditions in order to avoid chemical degradation of the polymers. The modified polyelectrolytes self-assembly in aqueous systems was monitored using diffusion-ordered nuclear magnetic resonance (DOSY NMR). The performed studies, supported by the all-atoms molecular dynamics simulations, revealed a strong dependence of polyelectrolyte self-assembled state on concentration—specific concentration regions with the coexistence of both smaller and larger aggregates were observed (values of hydrodynamic diameter D_H around one nanometer and between two to six nanometers, respectively). Our investigations enabled us to gain crucial information about the self-assembly of the hydrophobically functionalized poly(acrylic acid) and opened the possibility of understanding and predicting its performance under various conditions.

The design of multifunctional microcarriers has attracted significant attention because they combine various functions within a single system. In this study, we developed a set of multilayered hydrogel microcarriers, which were first loaded with chemotherapeutic curcumin (CUR), then, using the layer-by-layer (LbL) technique, coated through a polyelectrolyte shell consisting of chitosan (CHIT) or poly(allylamine hydrochloride) (PAH). As an outer layer with antimicrobial function, newly synthesised alkylene quaternary ammonium salt functionalised polyelectrolytes (A-QAS-PEs) were applied. For this purpose, poly(acrylic acid) (PAA) was decorated with different hydrophobic side chains (n-hexane and n-dodecane side entities) and different degrees of substitution (m) of quaternary ammonium groups (abbreviated as PAA-C(O)O-(CH₂)_n-N⁺(CH₃)₃(m); n = 6, 12; m = 8–14%). The grafting approach of PAA with the alkylene quaternary ammonium salt moiety was performed under mild reaction conditions using Steglich esterification followed by quaternisation. The structure of antimicrobial decorated PAA was confirmed by ¹H NMR and FTIR, and the mean diameter of all multifunctional microparticles was characterised by SEM. The viscoelastic properties of the functional layers were studied using quartz crystal microbalance with a dissipation (QCM-D). The release of CUR from the microcarriers was described using a hybrid model, i.e., a combination of first-order kinetics and the Korsmeyer-Peppas model. The antimicrobial activity of functionalised PAA and multilayered CUR-loaded hydrogel microcarriers with quaternary ammonium function was assessed against Staphylococcus aureus and Serratia marcescens by the agar diffusion assay method. Only a limited inhibition zone of PAA was observed, but in the case of both antimicrobial decorated PAA and the corresponding multilayered nanocarriers, the inhibitory activity increase was achieved against both strains of bacteria.

Contemporary research concerning surfactant science and technology comprises a variety of requirements relating to the design of surfactant structures with widely varying architectures to achieve physicochemical properties and dedicated functionality. Such approaches are necessary to make them applicable to modern technologies, such as nanostructure engineering, surface structurization or fine chemicals, e.g., magnetic surfactants, biocidal agents, capping and stabilizing reagents or reactive agents at interfaces. Even slight modifications of a surfactant’s molecular structure with respect to the conventional single-head–single-tail design allow for various custom-designed products. Among them, multicharge structures are the most intriguing. Their preparation requires specific synthetic routes that enable both main amphiphilic compound synthesis using appropriate step-by-step reaction strategies or coupling approaches as well as further derivatization toward specific features such as magnetic properties. Some of the most challenging aspects of multicharge cationic surfactants relate to their use at different interfaces for stable nanostructures formation, applying capping effects or complexation with polyelectrolytes. Multiheaded cationic surfactants exhibit strong antimicrobial and antiviral activity, allowing them to be implemented in various biomedical fields, especially biofilm prevention and eradication. Therefore, recent advances in synthetic strategies for multiheaded cationic surfactants, their self-aggregation and performance are scrutinized in this up-to-date review, emphasizing their applications in different fields such as building blocks in nanostructure engineering and their use as fine chemicals.

Encapsulation of hydrophilic and amphiphilic drugs in appropriate colloidal carrier systems for sustained release is an emerging problem. In general, hydrophobic bioactive substances tend to accumulate in water-immiscible polymeric domains, and the release process is controlled by their low aqueous solubility and limited diffusion from the nanocarrier matrix. Conversely, hydrophilic/amphiphilic drugs are typically water-soluble and insoluble in numerous polymers. Therefore, a core-shell approach─nanocarriers comprising an internal core and external shell microenvironments of different properties─can be exploited for hydrophilic/amphiphilic drugs. To produce colloidally stable poly(lactic-co-glycolic) (PLGA) nanoparticles for mitomycin C (MMC) delivery and controlled release, a unique class of amphiphilic polymers─hydrophobically functionalized polyelectrolytes─were utilized as shell-forming materials, comprising both stabilization via electrostatic repulsive forces and anchoring to the core via hydrophobic interactions. Undoubtedly, the use of these polymeric building blocks for the core-shell approach contributes to the enhancement of the payload chemical stability and sustained release profiles. The studied nanoparticles were prepared via nanoprecipitation of the PLGA polymer and were dissolved in acetone as a good solvent and in an aqueous solution containing hydrophobically functionalized poly(4-styrenesulfonic-co-maleic acid) and poly(acrylic acid) of differing hydrophilic-lipophilic balance values. The type of the hydrophobically functionalized polyelectrolyte (HF-PE) was crucial for the chemical stability of the payload─derivatives of poly(acrylic acid) were found to cause very rapid degradation (hydrolysis) of MMC, in contrast to poly(4-styrenesulfonic-co-maleic acid). The present contribution allowed us to gain crucial information about novel colloidal nanocarrier systems for MMC delivery, especially in the fields of optimal HF-PE concentrations, appropriate core and shell building materials, and the colloidal and chemical stability of the system.