Alkylated polyethyleneimine-cationic surfactant-calix[4]resorcinarene-chloroform catalytic system

Abstract

The polymer-colloid complexes that form in solutions of polymers and nonmacromolecular amphiphilic compounds as a result of noncovalent interactions can function as nanoreactors produc ing metal nanoparticles [1] and catalysts for the hydrolysis of phosphorus acid esters [2, 3] and 2 (4 alkoxyphenyl) 1,3 dioxolanes [4]. The amphiphilic component can be a conventional surfactant (anionic, cationic, or nonionic) [5], a pyrimidi nophane [6,7], or a calixarene [8,9]. In the latter case, in addition to the sorption and solubilization binding of the reactants by the polymer-colloid aggregates, there can be inclusion type interactions [5] that enhance the reactant concentrating effect and are thus favorable for the catalytic action of the system.Here, we report the catalytic activity of supramo lecular systems based on alkylated polyethyleneimine, cationic surfactants with different structures, and calix[4]resorcinarenes (CRs) with 2 hydroxyethoxy and phosphorus containing substituents on the upper rim and alkyl substituents on the lower rim of the mac romolecule in chloroform.The polymer component was branched polyethylene imine modified with alkyl (n tetradecyl) substituents (APEI). The molar mass of its unit was 229. The degree of substitution (ratio of the number of substi tuted polyethyleneimine fragments to the number of unsubstitued fragments) was 0.6. The surfactants had a cyclic or bicyclic head. The former group of surfac tants consisted of hexadecylpyridinium bromide (HPB) and N octadecyl N (2 hydroxyethyl)piperi dinium bromide (OHPB), and the latter consisted of alkylated derivatives of 1,4 diazabicyclo[2.2.2]octane (AD 12, AD 16, and AD 18):Abstract-The kinetics of phosphorylation of alkylated polyethyleneimine in chloroform in the presence of cationic surfactants with a cyclic or bicyclic head group and alkylated calix[4]resorcinarenes has been inves tigated by UV spectrophotometry. The catalytic activity of individual and mixed solutions of the amphiphilic admixtures depends on the structure of the constituents of the composition, on their concentrations in the solution, and on their relative amounts. In the presence of a calixarene, a decrease in the surfactant and poly mer concentrations enhances the catalytic effect of the system.

Cationic Surfactants: Self-Assembly, Structure-Activity Correlation and Their Biological Applications

“…Despite the key role of hydrophobicity of surfactants in their micellization and functional activity, this aspect is poorly studied for alkylated DABCO excepting isolated publications. Our work focused on the aggregation activity of mono-( 3 ) and di-( 4 ) and tetracationic ( 5 ) derivatives of DABCO (Figure 2) in water, chloroform, and biological fluids [138,141,142], their catalytic and biological activity [142,143], adsorption on the air/water interface [141,144] in both single solution and in the presence of calixarenes [145,146,147], organophosphorus substrates [148,149,150], and polymers [151]. As can be seen from the structural formulas (Figure 2), these surfactant series allow the comparison of the behavior of gemini surfactants bearing two charged fragments and two long-chain alkyl groups with dicationic surfactants bearing one long-chain alkyl fragment.…”

Self-Aggregation and Solubilizing Properties of the Supramolecular System Based on Azobenzenesulfonate Calix[4]arene and CTAB

“…The use of calixarenes and surfactants [13,14,[16][17][18][19][20][21][22] in the creation of superamphiphiles is of particular interest. It is known that macrocycles, thanks to the presence of a molecular cavity and the preorganization of functional groups, are able to participate in guest-host interactions.…”

“…On the other hand, interest in macrocycles is due to the specific geometry of their molecules, which is important in the design of drug delivery systems and the development of antiviral drugs. [18][19][20] In the process of formation of mixed surfactant-calixarene compositions one can observe: (1) the increase in the solubility of macrocyclic compounds; [23] (2) the activation of binding processes of hydrophobic and hydrophilic substrates by monitoring the morphology of mixed aggregates; [13][14][15] (3) the decrease in the critical aggregation concentration. [13] The non-toxicity of calixarenes and surfactants makes them attractive for constructing receptors and carriers in solving biotechnological problems.…”