Gabriele Lando

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.

Experimental study and modelling of inorganic Cd2+ speciation in natural waters

Environmental context Cadmium(II) is considered as one of the most dangerous pollutants in natural waters. We performed a complete study on the interactions of cadmium(II) with inorganic components of natural waters, by using new experiments and some literature data. The body of results can be considered an improvement in modelling the inorganic speciation of cadmium(II) in natural waters. Abstract An analysis of literature data together with new potentiometric and voltammetric studies on the interaction between Cd2+ and the common environmental inorganic ligands, such as OH–, Cl–, F–, CO32– and SO42–, was reported at t = 25°C. New formation constant values for CdCl+, CdCl20, CdCl(OH)0, CdSO40, CdCO30 and CdF+ species at different ionic strengths (0.1 ≤ I ≤ 1 mol L–1) were determined. The cumulative seawater ligand capacity was evaluated by using a model in which synthetic seawater is expressed as a single salt BA, where the major cations (Na+, K+, Ca2+ and Mg2+) are represented by a single cation Bz+ and the anions (Cl– and SO42–) by a single anion Az– (|z| = 1.117). The formation of CdA0.883+ and CdA(OH)0.117– species was proposed and formation constants are reported at different salinities (5 ≤ S ≤ 45). The ionic strength dependence of the stability constants was studied by means of Pitzer and SIT (Specific ion Interaction Theory) equations.

Alkali Metal Ion Complexes with Phosphates, Nucleotides, Amino Acids, and Related Ligands of Biological Relevance. Their Properties in Solution

Alkali metal ions play very important roles in all biological systems, some of them are essential for life. Their concentration depends on several physiological factors and is very variable. For example, sodium concentrations in human fluids vary from quite low (e.g., 8.2 mmol dm(-3) in mature maternal milk) to high values (0.14 mol dm(-3) in blood plasma). While many data on the concentration of Na(+) and K(+) in various fluids are available, the information on other alkali metal cations is scarce. Since many vital functions depend on the network of interactions occurring in various biofluids, this chapter reviews their complex formation with phosphates, nucleotides, amino acids, and related ligands of biological relevance. Literature data on this topic are quite rare if compared to other cations. Generally, the stability of alkali metal ion complexes of organic and inorganic ligands is rather low (usually log K < 2) and depends on the charge of the ligand, owing to the ionic nature of the interactions. At the same time, the size of the cation is an important factor that influences the stability: very often, but not always (e.g., for sulfate), it follows the trend Li(+) > Na(+) > K(+) > Rb(+) > Cs(+). For example, for citrate it is: log K ML = 0.88, 0.80, 0.48, 0.38, and 0.13 at 25 °C and infinite dilution. Some considerations are made on the main aspects related to the difficulties in the determination of weak complexes. The importance of the alkali metal ion complexes was also studied in the light of modelling natural fluids and in the use of these cations as probes for different processes. Some empirical relationships are proposed for the dependence of the stability constants of Na(+) complexes on the ligand charge, as well as for correlations among log K values of NaL, KL or LiL species (L = generic ligand).

[1.1.1]Cryptand: A Molecular Automatic Titrator

Molecules are sometimes synthesized,characterized, and set aside, and it is only afterwards thattheirpotentialforusefulapplicationsisrevealed.Moreover,adevicethatwasinitiallyusedforaparticularpurposecanlaterbe used as a different device. This is the case for [1.1.1]crypt-and (4,10,15-trioxa-1,7-diazabicyclo[5.5.5]heptadecane),which behaves as a proton sponge that can capture hydrogenions from solution equilibria in a selective, slow, andirreversible way.

A novel thermodynamic approach for the complexation study of toxic metal cations by a landfill leachate

Landfill leachates can contaminate nearby aquifers. The hazards deriving from this contamination also depend on the chemical speciation of various contaminants. A novel approach is proposed here to face this problem from a chemical thermodynamics point of view. The complexing ability of the soluble fraction of a landfill leachate (collected from Bellolampo, Palermo, Italy) towards Pb2+, Cd2+ and Cu2+ has been investigated at T = 298.15 K in NaClaq at I = 0.1 mol dm−3. The soluble fraction of the landfill leachate was first characterized by different analytical techniques. Then, its acid–base properties were studied by ISE-H+ potentiometric titrations and modelled by the so-called diprotic-like model. Differential Pulse Anodic Stripping Voltammetry (DP-ASV) titrations of metal ion aqueous solutions with a diluted landfill leachate were carried out, successively, in order to determine the stability constants of the leachate-metal complexes. The stability of the Pb2+/OH− and Pb2+/Cl− complexes was also studied by the same technique. Finally, the sequestering ability of the leachate towards the investigated metal cations has been quantified by the calculations of various pL0.5 values under different pH conditions. The results proved that the landfill leachate is a good sequestering agent toward those cations, reducing the fraction of the free cations in solution, and that it can be a selective sequestrant at different pH.

Hydrophobic interactions in the formation of a complex between a polycationic water-soluble oxacalix[4]arene and a neutral aromatic guest

Abstract Polycationic oxacalix[4]arene 1·4HCl was found to be able to recognise, in water, the neutral π-rich aromatic guest 2,7-dihydroxynaphthalene, despite earlier studies indicating that the binding cleft of the oxacalixarene is π rich in nature. 1H NMR titrations at different pH values demonstrate that the tricationic receptor 1·3H+ displays the highest affinity towards DHN. According to a combination of NMR data and semiempirical (PM6) calculations, hydrophobic interactions play a prominent role in the formation of the complex. Graphical abstract

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.