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Herein two sensitive techniques, i.e., NMR self-diffusion measurements and dielcometry are involved to test the association of cationic surfactant 4-aza-1-tetradecyl-1-azoniabicyclo[2.2.2]octane bromide (BC-14) and polyethyleneimine hydrophobized with tetradecyl moieties (PEI-14) in their chloroform solutions. The data obtained make it possible to nominate these methods as highly powerful instruments for the identification of a very uncooperative aggregation. Mixed BC-14/PEI-14 association is probably observed only at a relatively high polymer concentration, which is indicated by a decrease in the diffusivity of surfactant molecules. Aggregation is strongly promoted by the addition of water, with a high [water]/[BC-14] molar ratio of 60 attained. Even a very slight association has a serious impact on the reactivity, the pre-concentration effect and the shift of acid–base equilibrium of solutes. A 4-fold acceleration of the reactivity of an organophosphorus pollutant occurs in the BC-14 reverse micelles due to the concentration of reagents and changes in their microenvironment, which strongly supports the very idea of association. The high binding constants derived from the analysis of kinetic data provide evidence on high degree of concentration of compounds, while changes in the microenvironment affect their ionization. These impacts may be of key importance in analytical procedures and the chemical reactivity of compounds in nonpolar media.

Phosphorylation of alkylated polyethyleneimine in chloroform in the presence of alkylated calyx[4]-resorcinolarenes with 2-hydroxyethoxy- and phosphorus-containing substituents and cetyl(3-hydroxypropyl)-dimethylammonium bromide was studied by means of the UV spectrophotometry. It was found that the character and the degree of the effect of calyxarene and its mixture with the surfactant depend on the hydrophobicity of macroring and the ratio of concentrations of components in the solution. The increase in the content of calyxarene and decrease in the concentration of polymer leads to the transformation of the catalytic action into the inhibiting one.

By means of the dielcometric titration and the dynamic light scattering, the association in the systems based on the alkylated polyethylenimines, hydroxyalkyl cationic surfactants, and calix[4]arenes in chloroform was studied. By means of the UV spectrophotometry the catalytic effect of the aggregates formed on the phosphorylation of polyethylenimines was established. Catalytic effect of the system depends on the structure of surfactants and calixarenes, and also on the relative content of the solution components.

The phosphorylation of alkylated poly(ethyleneimine) with 4-nitrophenyl bis(chloromethyl)phosphinate in chloroform in the presence of cetyltrimethylammonium bromide (CTAB), calix[4]resorcinarene (CR), or their mixture was studied by UV spectrophotometry. The catalytic effect of CTAB and CR on the process of polymer phosphorylation was shown to depend on the concentration of the surfactant and poly(ethyleneimine) in solution. The catalytic effect of the system is ascribed to the formation of poly(ethyleneimine)-CTAB, poly(ethyleneimine)-CR, and poly(ethyleneimine)-CTAB-CR mixed aggregates. Their existence was confirmed by the methods of light scattering and UV spectroscopy.

Aggregation of amphiphilic calix[4]resorcinarenes (CRA) modified by carboxymethyl (1), 2-hydroxyethyl (2), methylamino acetal (3), and aminomethyl (4) fragments and their interaction with some synthetic (5, 6) and natural (7, 8) surfactants in the low-polarity solvent (chloroform) were studied by permittivity measurements and FT-IR spectroscopy. Compounds 1–4 and surfactants form aggregates at critical micelle concentrations (CMC) of 2.0·10−5–7.5·10−5 and 1.7·10−5–2.0·10−3 mol L−1, respectively. The CMC values of CRA—surfactant mixed aggregates depend on the surfactant structure and the structure and concentration of CRA. Analysis of the IR spectra of solutions of a series of amphiphilic CRA (2–4, 9, 10) and their mixtures with the cationic surfactant N-cetyl-N,N-dimethyl-N-(2-hydroxyethyl)ammonium bromide (5) showed that an increase in the concentration of the solutions in individual and mixed systems is accompanied by a decrease in the molar integral intensities and intensities in the maxima of the absorption bands of the O—H and C—H bonds down to the CMC point, after which these values change slightly. The discovered effect, which is differently pronounced for all systems studied, indicates that both the polar “head” groups and nonpolar fragments of CRA and surfactant are involved in the formation of supramolecules of the reverse micelle type in all cases.

Micelle formation in a cetyltrimethylammonium bromide-poly(ethylene glycol)-600 monolaurate-chloroform system in the absence and presence of hydroxybenzylated polyethylenimines (PEI) was studied by dielcometric titration, NMR self-diffusion, light scattering, and kinetic methods. A catalytic effect of mixed micelles on the reaction of 4-nitrophenylbis(chloromethyl)phosphinate with PEI was shown. The catalytic effect depends on the degree of substitution of PEI and composition of a surfactant mixture.

Micellization in the cetyltrimethylammonium bromide (CTAB)-polyoxyethylene 600 monolaurate (PL)-chloroform system is studied with dielcometric titration, NMR self-diffusion (2D DOSY), 13C NMR spectroscopy, and light scattering methods. The formation of mixed aggregates of surfactants is established. It is shown that CTAB and PL polar moieties interact in the inverse micelle core in the vicinity of PL carbonyl group.

Reactions of a macrocycle containing three pyrimidine fragments and N,N′-bis(2-methylthio-6-methylpyrimidin-4-yl)-hexamethylenediamine with p-nitrophenyl bis(chloromethyl)phosphinate in the micellar solutions of cetyltrimethylammonium bromide, polyethyleneglycol-600 laurate and their mixture in chloroform was investigated spectrophotometrically. Catalytic activity of micelles depends on their structure, concentration of surfactants, molar fraction of the latter in solution, and structure of the nucleophilic reagent.

The aggregation in polyethylenimine-chloroform and cetyltrimethylammonium bromide-polyethylenimine-chloroform systems is studied by dielcometric titration. Inverse micelles of cetyltrimethylammonium bromide catalyze the phosphorylation of hydroxybenzylated polyethylenimines in chloroform. The dependence of parameters of the micelle-catalyzed reaction on the structure and concentration of polyethylenimine and on the reaction temperature is studied. The inverse micelles affect the complexation of polyethylenimines with 4-nitrophenol.

The presence of the aminomethyl fragment in the calix[4]resorcinolarene molecule favors its phosphorylation in chloroform. Reverse micelles of (2-hydroxyethyl)dimethylpentadecylammonium bromide catalyze this reaction, the catalytic effect being dependent on the length of the hydrocarbon chain of a calixarene and detergent concentration.

Micelle formation by n-alkyl(2-hydroxyethyl)dimethylammonium bromides in chloroform was studied by dielcometric titration and kinetic method. Increase in the length of the hydrocarbon chain leads to reduced critical micelle concentration. The region of structural reorganization of micelles was determined. n-Alkyl(2-hydroxyethyl)dimethylammonium bromides catalyze phosphorylation of tetrakis(dimethylamino- methyl)calixresorcin[4]arene. The catalytic activity of micelles depends on the hydrophobic properties and concentration of the surface-active substance, as well as on structural features of its aggregates.

Reactions of calixarenes with methylaminoacetaldehyde dimethyl acetal and formalin gave Mannich bases with the calixarene platform. It was found by dielcometric titration that calix[4]resorcinols with acetal groups in the aminomethyl fragment form head-to-head supra-molecular aggregates in chloroform at low concentrations.