Specially designed hydrophobically functionalized polyelectrolytes (HF-PEs) provide an important area of study, their unique properties being similar to those of biological systems, among them the strong tendency toward self-organization in aqueous solution caused by a combination of electrostatic and hydrophobic forces. A significant issue in this context is the comprehensive physicochemical characterization of adsorption and aggregation properties of these amphiphilic polyelectrolytes. The main aim of the present research has been to synthesize and study aggregation properties in an aqueous solution of the hydrophobically functionalized poly(4-styrenosulfonic-co-maleic acid) (PSS/MA) with a differing degree of hydrophobization, side-chain lengths and pH-labile moiety type (i.e., ester (PSS/MA-g-C_nOH) or secondary amide (PSS/MA-g-C_nNH₂) groupings). Comprehensive analysis of self-assembly properties, including utilization of high-resolution NMR techniques (diffusion-ordered and nuclear Overhauser effect spectroscopies, T₁ and T₂ relaxometry) and dynamic light scattering, revealed a strong dependence on concentration and type of labile linking group (ester or amide). It has been noticed that more rigid amide bonds hinder the formation of highly organized structures in aqueous systems compared to polyelectrolytes with ester moieties. Our results were supported by molecular modeling. The performed studies enabled us to obtain crucial information about the hydrophobized PEs structure and its influence on aggregation properties that are crucial for their application in pH-sensitive nanosized thin films and nanocarriers.

专门设计的疏水功能化聚电解质（HF-PEs）提供了一个重要的研究领域，其独特的性质与生物系统相似，其中静电和疏水力共同作用导致水溶液中自组织的强烈趋势。在这种情况下，一个重要的问题是这些两亲性聚电解质的吸附和聚集特性的全面物理化学表征。本研究的主要目的是要合成和研究聚集性质的疏水官能化的聚（4- styrenosulfonic-的水溶液共-马来酸）（PSS / MA）与疏水化，侧链长度的不同程度和pH不稳定的部分类型（即酯（PSS / MA-gC_n OH）或仲酰胺（PSS / MA-gC _n NH ₂）分组）。对自组装特性的全面分析，包括使用高分辨率NMR技术（扩散有序和核Overhauser效应光谱学，T ₁和T ₂弛豫法）和动态光散射，显示了对不稳定连接基团（酯或酰胺）的浓度和类型的强烈依赖。已经注意到，与具有酯部分的聚电解质相比，更刚性的酰胺键阻碍了水性体系中高度组织化结构的形成。我们的结果得到了分子模型的支持。进行的研究使我们能够获得有关疏水化PE结构及其对聚集特性的影响的关键信息，这对于将它们应用于pH敏感的纳米级薄膜和纳米载体至关重要。