Synthesis of new p-tert -butylcalix[4]arene-based polyammonium triazolyl amphiphiles and their binding with nucleoside phosphates

The synthesis of new calix[4]arenes adopting a stereoisomeric form bearing two or four azide fragments on the upper rim and water-soluble triazolyl amphiphilic receptors with two or four polyammonium headgroups via copper-catalyzed azide-alkyne cycloaddition reaction has been performed for the first time. It was found that the synthesized macrocycles form stable aggregates with hydrodynamic diameters between 150-200 nm and electrokinetic potentials about +40 to +60 mV in water solutions. Critical aggregation concentration (CAC) values were measured using a micelle method with pyrene and eosin Y as dye probes. The CAC values of tetraalkyl-substituted macrocycles , (5 µM for both) are significantly lower than those for dialkyl-substituted macrocycles , (790 and 160 µM, respectively). Premicellar aggregates of macrocycles , and , with the dye eosin Y were used for nucleotides sensing through a dye replacement procedure. It is unusual that disubstituted macrocycles , bind more effectively a less charged adenosine 5'-diphosphate (ADP) than adenosine 5'-triphosphate (ATP). A simple colorimetric method based on polydiacetylene vesicles decorated with was elaborated for the naked-eye detection of ADP with a detection limit of 0.5 mM.