Supramolecular interaction of two tryptophans with p-sulfonated calix[4,6,8]arene

The complex characteristics of p-sulfonated calix[n]arene (SCnA) and two tryptophans N-[(tert-butoxy) carbonyl]-tryptophan (trp-A) and N-carbobenzoxy-tryptophane (trp-B) were examined through various techniques. Spectrofluorimetry was performed at different temperatures to determine the stability constants and evaluate the thermodynamic parameters of the two complexes. The effect of pH on complex formation was estimated. According to the fluorescence data, the assumption about the steric hindrance of the tert-butyl group of trp-A and the phenyl group of trp-B was put forward. (1)H NMR was also performed to determine the binding interaction mechanism. Results showed that the indole benzene rings of the two tryptophans partly penetrated into the cavity of p-sulfonated calix[n]arene. The shift in Ha, Hb and Hc, Hd positions became more significant as the number of phenolic units of the calixarene ring increased. Molecular modeling of the complexes elucidated the assumption about the steric hindrance of the tert-butyl group of trp-A and the phenyl group of trp-B. These observations of molecular modeling computation are consistent with previous fluorescence data and (1)H NMR results.