Rosalia Maria Cigala

Sequestering Ability of Phytate toward Biologically and Environmentally Relevant Trivalent Metal Cations

Quantitative parameters for the interactions between phytate (Phy) and Al(3+), Fe(3+), and Cr(3+) were determined potentiometrically in NaNO(3) aqueous solutions at I = 0.10 mol L(-1) and T = 298.15 K. Different complex species were found in a wide pH range. The various species are partially protonated, depending on the pH in which they are formed, and are indicated with the general formula MH(q)Phy (with 0 ≤ q ≤ 6). In all cases, the stability of the FeH(q)Phy species is several log K units higher than that of the analogous AlH(q)Phy and CrH(q)Phy species. For example, for the MH(2)Phy species, the stability trend is log K(2) = 15.81, 20.61, and 16.70 for Al(3+), Fe(3+), and Cr(3+), respectively. The sequestering ability of phytate toward the considered metal cations was evaluated by calculating the pL(0.5) values (i.e., the total ligand concentration necessary to bind 50% of the cation present in trace in solution) at different pH values. In general, phytate results in a quite good sequestering agent toward all three cations in the whole investigated pH range, but the order of pL(0.5) depends on it. For example, at pH 5.0 it is pL(0.5) = 5.33, 5.44, and 5.75 for Fe(3+), Cr(3+), and Al(3+), respectively (Fe(3+) < Cr(3+) < Al(3+)); at pH 7.4 it is pL(0.5) = 9.94, 9.23, and 8.71 (Al(3+) < Cr(3+) < Fe(3+)), whereas at pH 9.0 it is pL(0.5) = 10.42, 10.87, and 8.34 (Al(3+) < Fe(3+) < Cr(3+)). All of the pL(0.5) values, and therefore the sequestering ability, regularly increase with increasing pH, and the dependence of pL(0.5) on pH was modeled using some empirical equations.

Speciation of Al3+ in fairly concentrated solutions (20–200 mmol L−1) at I=1 mol L−1 (NaNO3), in the acidic pH range, at different temperatures

Abstract The hydrolysis of Al3+ was studied in aqueous 1 mol L−1 NaNO3 solution at different concentrations (20–200 mmol L−1) and temperatures (283.15–343.15 K) by potentiometry (ISE-H+, glass electrode). Many different speciation models were considered in the calculations and it was found that the best model is represented by the following species: Al(OH)2+, Al(OH)45+, Al13(OH)327+. Hydrolysis constants and enthalpy changes at different temperatures are reported.

Solubility and modeling acid-base properties of adrenaline in NaCl aqueous solutions at different ionic strengths and temperatures.

Solubility and acid-base properties of adrenaline were studied in NaCl aqueous solutions at different ionic strengths (0<I/mol L(-1)<3.0) and temperatures (T=298.15 and 310.15K), by means of different techniques: potentiometry, UV-spectrophotometry and spectrofluorimetry. The intrinsic solubility of the ligand was calculated from simple mass balance equations, by using the free hydrogen concentration and the protonation constants of the ligand determined in the same experimental conditions of the solubility measurements. The salting-In or Out parameters and the activity coefficient of the neutral species were calculated by means of the Setschenow equation. The dependence of the protonation constants on the ionic strength was modeled by means of the Debye-Hückel type equation and of the SIT (Specific ion Interaction Theory) approach. The specific interaction parameters of the ion pairs were also reported. For the protonation constants, the following thermodynamic values at infinite dilution were obtained: T=298.15 K, logK1(H0)=10.674±0.018 and logK2(H0)=8.954±0.022; T=310.15K, logK1(H0)=10.355±0.018 and logK2(H0)=8.749±0.030.

On the complexation of metal cations with “pure” diethylenetriamine-N,N,N′,N′′,N′′-pentakis(methylenephosphonic) acid

The complex formation between a series of biologically, environmentally, and technologically relevant cations (namely Sn2+, Zn2+, Cu2+, Fe2+, Fe3+ and Al3+) and diethylenetriamine-N,N,N′,N′′,N′′-pentakis(methylenephosphonic) acid (DTPMPA) has been investigated in NaCl aqueous solutions at I = 0.1 and 0.3 mol dm−3 and T = 298.15 K. The ligand used has been obtained in sufficient purity by a new efficient synthetic procedure for the determination of accurate and reliable data on its acid–base properties and metal complex formation. The stability constants determined in this work under different experimental conditions have been then used to assess the speciation of many systems containing the above-cited cations, and to quantify the sequestering ability of DTPMPA toward them, by means of the calculation of several pL0.5 values under various conditions simulating those of many real systems where this chelant is employed as a cationic sequestrant. Finally, some 1H- and 31P-NMR studies have also been performed to gain a further insight into the binding mode of DTPMPA toward metal cations.

Mixing effects on the protonation of some polycarboxylates in NaClaq + KClaq at different ionic strengths

Protonation constants of succinic, 1,2,3-propanetricarboxylic and 1,2,3,4-butanetetracarboxylic anions were determined in NaCl(aq)+KCl(aq) mixtures, at three ionic strengths, I=1.2, 3 and 4.5molL(-1). Experimental evidences showed that the function log K(H)=f(y) (y=[Na(+)]/([Na(+)]+[K(+)])) is not linear, indicating mixing effects on the protonation constants. The Guggenheim zeroth approximation holds that the above function can be written as:where K(Na)(H)andK(K)(H) represent protonation constants in pure salt solutions and Delta is a parameter that accounts for the mixing effect. Fitting of protonation constants to the above function gives excellent results. The Delta values can be treated in terms of mixing free energy. The behaviour of protonation constants in mixed salt solution can be interpreted by considering the formation of simple and mixed weak complexes; the protonation constants in mixed NaKCl electrolytes can be fitted to the equation: log(10)K(Na-K)(H)=log(10)K(K)(H)-log(10)(1+A(1)C(Na)+A(2)C(Na)C(K)), where A(1) is a measure of the interaction of Na(+) with the carboxylic anion and A(2) is proportional to the triple interaction Na(+)-K(+)-L(z-). Moreover, by using suitable calculation methods, it is possible to calculate the formation constants of simple and mixed ion pairs. As an example, for 1,2,3,4-butanetracarboxylic anion (L(4-)), we calculated K(Na(+)+H(i)L((4-i)-)=NaH(i)L((3-i)-))=0.67, 0.33 and 0.13; K(K(+)+NaH(i)L((3-i)-)=KNaH(i)L((2-i)-))=1.41, 1.29 and 0.9 for i=0, 1 and 2, respectively, indicating a significant tendency to form mixed alkali metal ion pairs.

Potentiometric, UV and 1H NMR study on the interaction of penicillin derivatives with Zn(II) in aqueous solution

The interaction of Zn(II) with ampicillin [(2S,5R,6R)-6-([(2R)-2-amino-2-phenylacetyl]amino)-3,3-dimethyl-7-oxo-4-thia-1-azabicyclo[3.2.0]heptane-2- carboxylic acid] and amoxicillin [(2S,5R,6R)-6-{[(2R)-2-amino-2-(4-hydroxyphenyl)-acetyl]amino}-3,3-dimethyl-7-oxo-4-thia-1-azabicyclo[3.2.0]heptane-24-carboxylic acid] in NaCl aqueous solution at different ionic strengths and at t=25°C was investigated by potentiometric, UV and 1H NMR techniques. Fairly similar speciation models were obtained for the two systems. At I=0.15molL-1, two different sets of measurements, at low and high concentrations, were carried out. For the Zn2+-amoxicillin system, the Zn2L2(OH)2 species was obtained in the set of measurements at high concentration. The spectrophotometric and 1H NMR results thus obtained are fully consistent with the speciation models found from potentiometric investigations, confirming the formation as well as the relative stability of the complex species. The dependence of the stability constants on the ionic strength was modeled by means of the Debye-Hückel and SIT (Specific ion Interaction Theory) approaches, and the parameter that accounts for the variation of the stability constants with the ionic strength and the specific ion interaction parameters were determined for all the ionic species. The sequestering ability of the ligands towards Zn2+ was evaluated by determining the pL0.5 parameter at different ionic strengths. It resulted that the sequestering ability of ampicillin is higher of ~0.5 order of magnitude with respect to amoxicillin.

Bifunctional 3-hydroxy-4-pyridinones as effective aluminium chelators: synthesis, solution equilibrium studies and in vivo evaluation

This paper reports the results on the study of a set of synthesized bifunctional 3-hydroxy-4-pyridinones chelators as potential aluminium sequestering agents. They were N-functionalized with alkyl-amino, -carboxylic and -(amino-carboxylic) groups, envisaging the improvement of the Al3+ sequestering capacity, in comparison with the marketed chelating drug deferiprone. The main focus of this work was given to the assessment of their binding ability towards Al3+, which was studied by potentiometric and UV-Vis spectrophotometric measurements carried out at T = 298.15 K. The speciation models were characterized by AlpLqHr(3p+r-qz) species with different stoichiometry. Depending on ligand side-chain structures and on their thermodynamic properties, different trends of stability was found. Furthermore, the sequestering ability of the ligands towards Al3+ was investigated by the calculation of pL0.5 values at different experimental conditions. These results clearly indicate that the presence of amino-carboxylic groups in the ligands increases the sequestering ability towards Al3+. The in silico evaluation of pharmacokinetic descriptors indicated no violation to the Lipinskis rule and drug-likeness properties. Furthermore, the in vivo bioassays on a model of metal-overload mice showed for three investigated ligands a higher metal-sequestering capacity than for the chelating drug deferiprone, thus suggesting their potential interest as Al-chelating drug candidates.

Exploring various ligand classes for the efficient sequestration of stannous cations in the environment

Metal pollution, coming from both natural and anthropogenic sources, has become one of the most serious environmental problems. Various strategies have been tested with the aim of removing heavy metals from environment. In this contribution, containing a robust experimental work together with a critical literature analysis, the sequestering ability of a variety of ligands towards Sn2+ cation will be evaluated in the conditions of several natural fluids, i.e. sea water, fresh water, human blood plasma, urine and saliva. 13 structural and 11 thermodynamic descriptors will be selected for a total of thirty-eight molecules belonging to different classes (carboxylic acids, amines, amino acids, phosphonates, polyelectrolytes etc. …). For the filling of those missing data relative to the 11 thermodynamic descriptors, different strategies will be adopted, including simple correlations and Nipals algorithm. The evaluation of the sequestering ability of the ligands is assessed in terms of estimation of pL0.5 (total concentration of ligand required to bind the 50% of metal in solution), an empirical parameter that takes into account all the side reactions in solutions and does not depend on the speciation scheme. Partial least square calculations were performed to model the pL0.5 and to determine its correlation with the abovementioned descriptors. The possibility to design and build up new tailor-made molecules capable of effectively sequester Sn2+ in various conditions is crucial for practical applications in biosphere, hydrosphere and lithosphere.