Alberto Pettignano

SALMO and S3M: A saliva model and a single saliva salt model for equilibrium studies

A model of synthetic saliva (SALMO, SALiva MOdel) is proposed for its use as standard medium in in vitro equilibrium and speciation studies of real saliva. The concentrations come out from the literature analysis of the composition of both real saliva and synthetic saliva. The chief interactions of main inorganic components of saliva, as well as urea and amino acids, are taken into account on the basis of a complex formation model, which also considers the dependence of the stability constants of these species on ionic strength and temperature. These last features allow the modelling of the speciation of saliva in different physiological conditions deriving from processes like dilution, pH, and temperature changes. To simplify equilibrium calculations, a plain approach is also proposed, in order to take into account all the interactions among the major components of saliva, by considering the inorganic components of saliva as a single 1 : 1 salt (MX), whose concentration is c MX = (1/2)∑c i (c i = analytical concentration of all the ions) and z ion charge calculated as z=±(I/c MX)1/2 = ±1.163. The use of the Single Saliva Salt Model (S3M) considerably reduces the complexity of the systems to be investigated. In fact, only four species deriving from internal ionic medium interactions must be considered.

Sequestering ability of some chelating agents towards methylmercury(II)

AbstractA study on the interactions between CH3Hg+ and some S, N and O donor ligands (2-mercaptopropanoic acid (thiolactic acid (H2TLA)), 3-mercaptopropanoic acid (H2MPA), 2-mercaptosuccinic acid (thiomalic acid (H3TMA)), d,l-penicillamine (H2PSH), l-cysteine (H2CYS), glutathione (H3GSH), N,N′-bis(3-aminopropyl)-1-4-diaminobutane (spermine (SPER)), 1,2,3,4,5,6-benzenehexacarboxylic acid (mellitic acid (H6MLT)) and ethylenediaminetetraacetic acid (H4EDTA)) is reported. The speciation models in aqueous solution and the possible structures of the complexes formed are discussed on the basis of potentiometric, calorimetric, UV spectrophotometric and electrospray mass spectrometric results. For the CH3Hg+–S donor ligand systems, the formation of ML1–z and MLH2–z complex species is observed, together with a diprotonated MLH23–z species for CYS2−, PSH2− and GSH3− and the mixed hydrolytic one ML(OH)−z for TLA2− and MPA2−. The dependence of the stability on ionic strength and on temperature is also analysed. In the other CH3Hg+-L systems (L = MLT6−, SPER and EDTA4−), ML1–z, MLH2–z and MLH23–z complex species are formed, together with the MLH34–z species for SPER, the mixed hydrolytic ML(OH)–z one for SPER and EDTA, and the M2L2–z for EDTA only. On the basis of the speciation models proposed, the sequestering ability of the ligands towards methylmercury(II) cation is evaluated. All S donor ligands show a good sequestering power (at 10−11 mol L−1 level, in the pH range 4 to 8) following the trend MPA2− < PSH2− < GSH3− < TLA2− < CYS2− < TMA3−, while significantly lower is the sequestering ability of MLT, SPER and EDTA (at 10−3–10−5 mol L−1 level, in the pH range 4 to 8). FigureSum of fractions of CH3Hg+-Lz– species (L = S, O and N donor ligands vs. pL

Pb(II) adsorption by a novel activated carbon alginate composite material. A kinetic and equilibrium study

The adsorption capacity of an activated carbon - calcium alginate composite material (ACAA-Ca) has been tested with the aim of developing a new and more efficient adsorbent material to remove Pb(II) ion from aqueous solution. The study was carried out at pH=5, in NaCl medium and in the ionic strength range 0.1-0.75molL-1. Differential Pulse Anodic Stripping Voltammetry (DP-ASV) technique was used to check the amount of Pb(II) ion removed during kinetic and equilibrium experiments. Different kinetic (pseudo first order, pseudo second order and Vermuelen) and equilibrium (Langmuir and Freundlich) models were used to fit experimental data, and were statistically compared. Calcium alginate (AA-Ca) improves the adsorption capacity (qm) of active carbon (AC) in the ACAA-Ca adsorbent material (e.g., qm=15.7 and 10.5mgg-1 at I=0.25molL-1, for ACAA-Ca and AC, respectively). SEM-EDX and thermogravimetric (TGA) measurements were carried out in order to characterize the composite material. The results of the speciation study on the Pb(II) solution and of the characterization of the ACAA-Ca and of the pristine AA-Ca and AC were evaluated in order to explain the specific contribution of AC and AA-Ca to the adsorption of the metal ion.

Palladium(II) sequestration by phytate in aqueous solution – speciation analysis and ionic medium effects

Environmental context.In the last 20 years, the demand for palladium and other platinum-group elements has intensified, causing a significant increase in their concentration in the environment, with particular accumulation in urban areas. Knowledge about Pd2+ speciation in aqueous media is fundamental for the understanding of its biological and environmental activity in contaminated areas. Phytic acid appears to be a good sequestering agent towards Pd2+ under various conditions, indicating its potential use in the remediation of contaminated sites. Abstract. Palladium(II) speciation in the presence of phytate (Phy12–) was studied by H+ ion selective electrode (ISE) potentiometry at 25°C in NaNO3(aq) and in NaCl(aq) at ionic strength I = 0.1 mol L–1, in order to evaluate the effect of the ionic medium on the sequestering ability of phytate towards palladium(II). Owing to the discrepancies found in the literature on both the nature and the stability of hydrolytic species formed by this cation, Pd2+ hydrolysis was studied under the same experimental conditions as phytate/PdII measurements. As palladium(II) forms stable complex species with the chloride ion, the stability constants of various Pd2+–Cl– species were also calculated, as well as those of weak species formed with nitrate. The stability constants of six palladium(II)–phytate species, namely PdPhyOH11–, PdPhy10–, PdPhyH9–, PdPhyH28–, PdPhyH37– and PdPhyH46–, were determined. The sequestering ability of this ligand towards Pd2+ was evaluated by the calculation of various pL50 values (total ligand concentrations, as antilogarithm, necessary to bind the 50% of the metal ion as a trace present in the solution) under different conditions. Phytate sequestering ability towards palladium(II) was then compared with that towards other divalent cations under various conditions. Finally, the dependence of pL50 on pH was modelled by a simple empirical relationship.

Sequestration of organometallic compounds by synthetic and naturally occurring polycarboxylate ligands. Binding of monomethylmercury(II) by polyacrylic and alginic acids

Abstract The sequestering capacity of synthetic and naturally occurring polycarboxylate ligands towards mono-methylmercury(II) was evaluated by stability quantitative data on the interaction of CH3Hg+ with different molecular weight synthetic polyacrylates (2 and 20kDa average M.wt) and alginate (70–100 kDa) extracted from brown algae Macrocystis pyrifera. The influence of ionic medium was evaluated by measurements on the CH3Hg+-polyacrylate systems in NaNO3 medium at different ionic strengths (0.10, 0.25, 0.50 and 0.75 mol L−1), and a Debye-HiJckel type equation was used for the dependence of complex formation constants on ionic strength. Measurements on the CH3Hg+ - alginate system were carried out at l = 0.10 mol L−1 in NaNO3 medium. By using the stability data, the sequestering capacity of both ligands towards monomethylmercury(II) was determined at different pH values. Results obtained show that the binding ability of polyacrylic ligands (PAA) is stronger than the alginate (AA), following the trend PAA (20 kDa)> PAA (2kDa)>AA.

Speciation of vanadium in urban, industrial and volcanic soils by a modified Tessier method

Vanadium (V) concentrations in industrial, urban and volcanic soils were sequentially extracted using a modified Tessiers method. The voltammetric technique was used to determine V concentrations in solutions obtained from the various extraction steps. At the reference stations, the V concentrations (sum of four individual fractions) in soils ranged from 0.72 to 0.24 g kg(-1) dry weight (d.w.) with a mean value of 0.18 g kg(-1) d.w. V concentrations in soils of the Palermo urban area ranged from 0.34 to 2.1 g kg(-1) d.w., in the Milazzo (industrial) area between 0.26 and 5.4 g kg(-1) d.w. and in the volcanic area near Mt. Etna from 0.91 to 2.9 g kg(-1) d.w. When the V concentrations around Mt. Etna were compared with those obtained at the reference stations, it was confirmed that Mt. Etna is a continuous source of V. In all the samples analyzed, the majority of V (from 94 to 100%) was detected in the fourth fraction.

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.

Palladium nanoparticles immobilized on halloysite nanotubes covered by a multilayer network for catalytic applications

The synthesis of pure fine chemicals for industrial purposes is one of the most attractive challenges of chemical research. The use of catalytic pathways mediated by palladium nanoparticles (PdNPs) for C–C bond formation is a useful way to obtain these kinds of compounds. To achieve this objective, the PdNPs can be efficiently loaded on a functionalized natural nanostructured support such as halloysite nanotubes (HNTs). Hybrid materials based on thiol functionalized halloysite nanotubes and highly cross-linked imidazolium salts were successfully developed and used for the stabilization of PdNPs. The HNT/Pd hybrids were thoroughly characterized from a physico-chemical point of view and tested as a catalyst in the Suzuki and Heck C–C coupling reactions under microwave irradiation to obtain innovative materials for fine chemicals synthesis. Catalytic tests highlighted the fact that the HNT/Pd hybrids show high performance and full recyclability (up to ten cycles) in both reactions. Regarding the Suzuki reaction, under the best experimental conditions, the remarkable values of a turnover number of 194 000 and a turnover frequency of 3 880 000 h−1 were achieved without metal contamination in the final products.

Multi-doped Brookite-Prevalent TiO2 Photocatalyst with Enhanced Activity in the Visible Light

Enabling solar and/or visible light-driven photocatalysis is a crucial step to access innovative applications in environmental science and sustainable energy. Titanium dioxide is the most used photocatalyst because of its low cost and toxicity, however it is also limitedly active under visible light irradiation due to its wide band gap. Among its polymorphs, brookite holds promising optoelectronic properties for visible light photocatalysis, which have to the best of our knowledge been limitedly exploited. Here, a C,S,N-doped brookite-based TiO2 has been prepared via a rapid one-pot sol–gel synthesis. Besides substantially extending the visible light absorption via band gap narrowing, its photocatalytic activity has been enhanced further by optimising valence and conductive band position and by minimising electron–hole recombination. These materials showed a 100% boost in visible light absorption along with nearly 50-times enhanced photocatalytic activity per specific surface area than standard TiO2 Degussa-P25, giving the best performance among the brookite-based photo-catalytically active materials and resulting among the TiO2 top-performers under visible light.Graphical Abstract