Synthesis, 1H, 13C, 15N, and 113Cd NMR, ESI-TOF MS, Semiempirical MO (PM3), ab initio/HF and Cation/Anion Binding Studies of N-deoxycholyl-l-tryptophan

The synthesis, structural characterization, and cation/anion binding properties ofa new bile acid-amino acid conjugate, N-deoxycholyl-l-tryptophan, aredescribed. The structures of the ligand and its cadmium adduct at different pHconditions and various cadmium perchlorate concentrations were determined bymodern multinuclear magnetic resonance spectroscopic as well as ESI-TOF MStechniques. Also semiempirical PM3 and ab initio/HF molecular modellingstudies were performed. Based on 1H,1H NOESY measurementsN-deoxycholyl-l-tryptophan in alkaline conditions was found to appearin a bent conformation which was clearly different from the conformations in neutraland acidic solutions. According to molecular modelling in its minimum energy structurethe tryptophan backbone of the ligand was folded close to the deoxycholic acid skeletonand the structure was stabilized by an intramolecular hydrogen bond. The multinuclearmagnetic resonance experiments indicated that Cd2+-cation was bound with theligand in neutral and alkaline conditions while in acidic conditions protons block thebinding site. ESI-TOF MS revealed clearly a competition between sodium and cadmiumions, the ligand having a stronger affinity for sodium. Cadmium binding occurred onlywhen excess of cadmium was used. Further, ESI-TOF MS spectra showed that variouschlorine oxyanions originated from perchlorate anion formed together with cationsdifferent adducts with the ligand.