pyrophosphate and cyclen

Pyrene labelled Zn(2+)-cyclen 1 and bis-Zn(2+)-bis-cyclen 2 complexes were synthesized. The reversible coordination at physiological pH of Zn(2+)-cyclens to phosphate anions and to imide moieties, as present in thymine and uracil nucleotides, is well known. In the presence of analytes bearing a phosphate and an imide or two phosphate groups the formation of a ternary complex consisting of two pyrene-labelled metal complexes and the analyte molecule, is observed. The close proximity of the pyrene labels in the complex induces pyrene excimer emission, which is observable by the unarmed eye. By this, the presence of UMP, UDP, UTP and TTP in buffered aqueous solution is signalled, while other nucleotides are not able to induce excimer emission. In the same way, Zn(2+)-cyclen-pyrene acts as luminescent chemosensor for PP(i) and fructose-1,6-bisphosphate in aqueous buffer.

Topics: Coordination Complexes; Cyclams; Diphosphates; Heterocyclic Compounds; Pyrenes; Spectrometry, Fluorescence; Thymine Nucleotides; Uridine Triphosphate; Zinc

The host-guest interaction between orthophosphate, pyrophosphate and triphosphate anions and three cyclen-based macrotricyclic ligands was investigated by potentiometric measurements and NMR spectroscopy. The ligands differ from one another by the nature of their spacers, which are 1,3-dimethylbenzene (TMC), 2,6-dimethylpyridine (TPyC) or a combination of the two (TMPyC). In aqueous solution, each ligand gave protonated species that further formed ternary complexes after binding with anions; these complexes were analyzed as a result of hydrogen bond formation and coulombic attraction between the organic host and the inorganic guest. The equilibrium constants found for all the detected species are reported and the selectivity, illustrated with species distribution diagrams, is discussed. The results unambiguously showed that the ligand possessing a single supplementary anchoring site (the pyridinyl spacer) exhibited the greatest affinity for the phosphate species in a large p[H] range.

Topics: Chelating Agents; Cyclams; Diphosphates; Heterocyclic Compounds; Hydrogen-Ion Concentration; Ligands; Magnetic Resonance Spectroscopy; Models, Chemical; Models, Molecular; Phosphates; Polycyclic Compounds; Potentiometry; Protons; Pyridines; Xylenes

The host-guest interaction between orthophosphate, pyrophosphate and triphosphate anions and three cyclen based macrotricyclic ligands possessing ortho- (TOC), meta- (TMC) and para-xylenyl (TPC) linkers was investigated by potentiometric measurements. The ternary species present in solution and their stability constants have been determined. The different behaviours are explained in terms of hydrogen bond formation and coulombic attraction between the organic host and the inorganic guest. The selectivity, illustrated with species distribution diagrams, is discussed. The results unambiguously showed the importance of the distance between the two cyclen cores and emphasized the increasing of the triphosphate species selectivity together with the cavity size of the ligand. A comparison of the present results with those obtained with their mono-bridged homologues is also discussed.

Topics: Anions; Chelating Agents; Cyclams; Diphosphates; Heterocyclic Compounds; Ligands; Magnetic Resonance Spectroscopy; Models, Chemical; Models, Molecular; Organophosphates; Phosphates; Polycyclic Compounds; Potentiometry; Protons; Structure-Activity Relationship