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Open Chemistry
|
2010
|
vol. 8
|
issue 3
674-686
EN
The ability of new chelate ligands, benzoxazol-5-yl-alanine derivatives substituted in position 2 by heteroaromatic substituent, to form complexes with selected metal ions in acetonitrile are studied by means of absorption and steady-state and time-resolved fluorescence spectroscopy. Among the ligands studied, only azaaromatic derivatives form stable complexes with transition metal ions in the ground state. Their absorption bands are bathochromically shifted enabling to use those ligands as ratiometric sensors. The fluorescence of each ligand is quenched by metal ions, however, in the presence of Cd(II) and Zn(II) ions a new red shifted emission band is observed. [...]
EN
The influence of peptide sequence and Leu chirality in linear and cyclic peptides containing 3-[2-(9-anthryl)benzoxazol-5-yl]alanine on interaction with β-cyclodextrin were studied using fluorescence and NMR spectroscopy. The analysis of enthalpy-entropy compensation effect (α=1.05±0.02 and TΔS00=15.1±0.5 kJ mol−1) indicates that the entropic contribution connected with the solvent reorganization is the major factor governing the peptides-β-cyclodextrin complexation. Moreover, spatial orientation of guest-host molecule depends more than association constant on Leu residue configuration. However, the cyclization of the peptide chain substantially decrease the association constant with β-CD. An analysis of 2D NMR spectra reveals that inclusion complex is formed by penetration of cyclodextrin cavity from wider and narrow rims by anthryl group in the case of Box(Ant)-SPKL or anthryl and Leu residues for Box(Ant)-SPK(D)L analogue. [...]
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