Recent advances in the aqueous chemistry of the calcium(II)-gluconate system – Equilibria, structure and composition of the complexes forming in neutral and in alkaline solutions

Of the sugar carboxylates, D-gluconate is clearly the most significant representative: the world’s annual production of this organic compound is estimated to be in the order of 10$^{5}$ tonnes. The reason of its mass production is due to its outstandingly broad range of practical (medical, pharmaceutical, industrial, etc.) applications. D-gluconate is a well-known and exceptionally popular complexing agent; accordingly, it has been the subject of a large number of coordination chemical research investigations. Its complexation properties are specially remarkable in alkaline to hyperalkaline pH conditions, where the deprotonation of one or more of its alcoholic OH groups provides a favourable frame for the formation of very stable chelate complexes with a large variety of metal cations. With the aim to show the state of the art of some relevant issues in the aqueous chemistry of the D-gluconate ion, the current paper focusses on the acidbase properties and calcium(II) complexation of the compound encompassing the entire experimentally available pH-range in water. The accessible literature on the deprotonation of carboxylic and alcoholic OH groups is collected and critically evaluated. The lactonization equilibria of D-gluconic acid are also scrutinized. The available data on the calcium complexes forming in neutral and in (hyper)alkaline solutions (both in terms of composition, formation constants and solution structure) are also discussed. Where feasible, some of these properties are compared with those of D-glucose and its derivatives as well as some less common sugar carboxylates, structurally related to D-gluconate, (i.e., D-heptagluconate, Lgulonate and α-D-isosaccharinate). Special emphasis is laid on the relationship between complex stability and the type of metal-binding groups

The Structure of Hyperalkaline Aqueous Solutions Containing High Concentrations of Gallium - a Solution X-ray Diffraction and Computational Study

Highly concentrated alkaline NaOH/Ga(OH)3 solutions with 1.18 M Ga(III)T 2.32 M and 2.4 M NaOHT 4.9 M (where the subscript T denotes total or analytical concentrations) have been prepared and investigated by solution X-ray diffraction and also by ab initio quantum chemical calculations. The data obtained are consistent with the presence of only one predominant Ga(III)-bearing species in these solutions, that is the tetrahedral hydroxo complex Ga(OH)4–. This finding is in stark contrast to that found for Al(III)-containing solutions of similar concentrations, in which, besides the monomeric complex, an oxo-bridged dimer was also found to form. From the solution X-ray diffraction measurements, the formation of the dimeric (OH)3Ga–O–Ga(OH)32– could not unambiguously be shown, however, from the comparison of experimental IR, Raman and 71Ga NMR spectra with calculated ones, its formation can be safely excluded. Moreover, higher mononuclear stepwise hydroxo complexes, like Ga(OH)63–, that have been claimed to exist by others in the literature, was not possible to experimentally detect in these solutions with any of the spectroscopic techniques used

Recent advances in the aqueous chemistry of the calcium(II)-gluconate system – Equilibria, structure and composition of the complexes forming in neutral and in alkaline solutions

Of the sugar carboxylates, D-gluconate is clearly the most significant representative: the world’s annual production of this organic compound is estimated to be in the order of 10$^{5}$ tonnes. The reason of its mass production is due to its outstandingly broad range of practical (medical, pharmaceutical, industrial, etc.) applications. D-gluconate is a well-known and exceptionally popular complexing agent; accordingly, it has been the subject of a large number of coordination chemical research investigations. Its complexation properties are specially remarkable in alkaline to hyperalkaline pH conditions, where the deprotonation of one or more of its alcoholic OH groups provides a favourable frame for the formation of very stable chelate complexes with a large variety of metal cations. With the aim to show the state of the art of some relevant issues in the aqueous chemistry of the D-gluconate ion, the current paper focusses on the acidbase properties and calcium(II) complexation of the compound encompassing the entire experimentally available pH-range in water. The accessible literature on the deprotonation of carboxylic and alcoholic OH groups is collected and critically evaluated. The lactonization equilibria of D-gluconic acid are also scrutinized. The available data on the calcium complexes forming in neutral and in (hyper)alkaline solutions (both in terms of composition, formation constants and solution structure) are also discussed. Where feasible, some of these properties are compared with those of D-glucose and its derivatives as well as some less common sugar carboxylates, structurally related to D-gluconate, (i.e., D-heptagluconate, Lgulonate and α-D-isosaccharinate). Special emphasis is laid on the relationship between complex stability and the type of metal-binding groups

Synthesis and In Vitro Evaluation of Oxindole Derivatives as Potential Radioligands for 5-HT7 Receptor Imaging with PET

[Image: see text] The most recently discovered serotonin (5-HT) receptor subtype, 5-HT(7), is considered to be associated with several CNS disorders. Noninvasive in vivo positron emission tomography (PET) studies of cerebral 5-HT(7) receptors could provide a significant advance in the understanding of the neurobiology and eventual dysfunctions of the 5-HT(7) receptor. To date, no appropriate 5-HT(7) receptor PET ligand has been developed. Here, we modified known 5-HT(7) selective phenylpiperazinyl-butyloxindole derivatives so that they may be labeled either with carbon-11 or fluorine-18. A set of potential 5-HT(7) ligands for PET molecular imaging was successfully synthesized. Two compounds (10 and 14) were tested against a range of targets. Both compounds display a promising in vitro profile with respect to PET imaging of the 5-HT(7) receptor in thalamic regions