The Influence of Triton X-100 on Protolytic Properties of Aminomethylated Calix[4]resorcinarene and Its Interaction with Copper(II)

The influence of Triton X-100 (concentration 5 mM) on acid-base properties of aminomethylated calix[4]resorcinarene (H₈L) containing alkyl (R¹ = C₁₁H₂₃) and dimethylaminomethyl (R² = CH₂N(CH₃)₂) substituents and interaction of H₈L with copper(II) is studied by potentiometry and mathematical simulation of equilibria in solutions. It is found that the presence of a nonionic surfactant favors the aggregation of H₈L (the degree of aggregation is higher than four), whereas, in 80% isopropanol at the same pH ≈ 10.2, a neutral species of the compound is only dimerized. The addition of Triton X-100 affects both the composition and stability of formed copper(II) complexes. The fraction of the highly charged tetranuclear [Cu₄(H₄L)]⁴⁺ complex sharply decreases. The formation of a large amount of [Cu(H₇L)]⁺ complex appears to be preferable compared to [Cu(H₈L)₂]²⁺ complex containing two ligands in the coordination sphere (pH ≈ 5.7). An enhancement of the acidic properties of protonated species of the compound and a decrease in the apparent constants of H₈L-copper(II) complex formation in Triton X-100 solutions compared to those in water-alcohol solutions are attributed to the formation of mixed micelles.__________Translated from Kolloidnyi Zhurnal, Vol. 67, No. 4, 2005, pp. 527–533.Original Russian Text Copyright © 2005 by Sal’nikov, Boos, Ryzhkina, Lukashenko, Tiforova.     

Self-association of α-tocopherol: a computer simulation

Self-association of α-tocopherol molecules in the gas phase was simulated using quantum chemical calculations in the B3LYP/6-31G(d,p)/6-31G(d) approximation. The influence of electric field on the energy characteristics of oligomerization of α-tocopherol was also considered.     

The Reactivity of Associates of Aminomethylated Calix [4] Resorcinolarenes towards P-Nitrophenyl Esters of Phosphorus Acids

Abstract

The kinetics of reactions of aminoinethylated calixarenes (AMC) of different structure (substituents at nitrogen atom as well as on the “lower” rim of cavity are varied) with esters of phosphorus acids has been studied under pseudofirst order conditions in water-DMF and water-alcohol (i-PrOH) solutions by spectrophotometry. The dependences of the observed rate constants of the reactions on the concentrations of AMC reach a plateaus at the investigated values of pH 8 - 1 1. This indicates binding of the substrates by the aggregates of AMC and allows to calculate the parameters of the reactions: CCA, k_a, K_b. It was shown by NMR ³¹P method, that AMC are the catalysts of hydrolysis of esters of phosphorus acids in water-DMF solutions. The higher reactivity of AMC as compared with the one of calix[4]resorcinolarenes and o-aminomethylphenols was found. It was revealed AMC preceeds in both media, however the reactivity of the aggregates is considerably less in the water - alcohol solutions than those in the water - DMF solutions.     

The relationship between self-organization and membrane effects of aqueous dispersion systems of the thyroliberin oligopeptide

The relationship between rearrangement of the dispersed phase inducing considerable changes in the pH and nonmonotonic concentration dependences of membrane effects in aqueous systems of the endogenous regulatory peptide, thyroliberin (thyrotropin-releasing hormone), in 10^–3–10^–16 mol/L concentration range was demonstrated for the first time. The membrane structure modification in the 10^–13–10^–16 mol/L range was found to be due to accumulation of nanoassociates, while the oppositely directed pronounced structural changes in the 10^–6–10^–12 mol/L range may be associated with the coexistence and rearrangement of dispersed phases of various nature (domains and associates) whose action on membrane lipid components is regulated in this concentration range by the correlated changes in the dispersed phase parameters and pH.