Deferiprone: new environmental perspectives. Insights into its sequestering ability vs. different metal cations.

Deferiprone, generally, is considered an important chelating agent for Fe3+ overload. From a literature data analysis, a lack of information on the interaction of this molecule toward a series of metal cations emerged, inducing to fill out the topic. The complexing ability of deferiprone toward Ca2+, Mg2+, Cd2+ and Pb2+ was studied by potentiometry and 1H NMR spectroscopy, in KCl aqueous solutions at different ionic strength values (0.1 ≤ I/mol dm-3 ≤ 1.0) and T = 298.15 K. The same speciation model featured by the ML, ML2, ML3 and ML(OH) (M = metal and L = deferiprone or DFP) species was obtained for Cd2+ and Pb2+; the formation constants calculated at infinite dilution are: logTß = 7.23±0.02, 12.47±0.03, 16.70±0.04, and -2.53±0.04, respectively for Cd2+ and 9.91±0.01, 15.99±0.02, 19.93±0.05 and 0.99±0.02 for Pb2+. Only two species, namely ML and ML2, were determined for Ca2+ and Mg2+, whose formation constants at infinite dilution are respectively: 3.72±0.01 and 6.50±0.02, for the first one, 5.31±0.01 and 9.58±0.01, for the second. The ligand sequestering ability and affinity toward M2+ were evaluated by determining the pL0.5 and pM parameters at different pHs and ionic strengths. The results suggest that deferiprone has the best complexing and sequestering ability toward Pb2+, followed by Cd2+, Mg2+ and Ca2+, respectively. 1H NMR studies confirmed the DFP affinity for Cd2+ and Pb2+, and in combination with DFT calculations showed that metal cations are bound to the hydroxo-oxo moiety of the pyridinone ring. The data reported in this study provide information on the possible employment of a small molecule like deferiprone, as a chelating and sequestering agent for Pb2+ accumulation or overload from environmental and biological matrices.

The Effect of Metal Cations on the Aqueous Behavior of Dopamine. Thermodynamic Investigation of the Binary and Ternary Interactions with Cd2+, Cu2+ and UO22+ in NaCl at Different Ionic Strengths and Temperatures.

The interactions of dopamine [2-(3,4-Dihydroxyphenyl)ethylamine, (Dop-)] with cadmium(II), copper(II) and uranyl(VI) were studied in NaCl(aq) at different ionic strengths (0 ≤ I/mol dm-3 ≤ 1.0) and temperatures (288.15 ≤ T/K ≤ 318.15). From the elaboration of the experimental data, it was found that the speciation models are featured by species of different stoichiometry and stability. In particular for cadmium, the formation of only MLH, ML and ML2 (M = Cd2+; L = dopamine) species was obtained. For uranyl(VI) (UO22+), the speciation scheme is influenced by the use of UO2(acetate)2 salt as a chemical; in this case, the formation of ML2, MLOH and the ternary MLAc (Ac = acetate) species in a wide pH range was observed. The most complex speciation model was obtained for the interaction of Cu2+ with dopamine; in this case we observed the formation of the following species: ML2, M2L, M2L2, M2L2(OH)2, M2LOH and ML2OH. These speciation models were determined at each ionic strength and temperature investigated. As a further contribution to this kind of investigation, the ternary interactions of dopamine with UO22+/Cd2+ and UO22+/Cu2+ were investigated at I = 0.15 mol dm-3 and T = 298.15K. These systems have different speciation models, with the MM'L and M2M'L2OH [M = UO22+; M' = Cd2+ or Cu2+, L = dopamine] common species; the species of the mixed Cd2+ containing system have a higher stability with respect the Cu2+ containing one. The dependence on the ionic strength of complex formation constants was modelled by using both an extended Debye-Hückel equation that included the Van't Hoff term for the calculation of the formation enthalpy change values and the Specific Ion Interaction Theory (SIT). The results highlighted that, in general, the entropy is the driving force of the process. The quantification of the effective sequestering ability of dopamine towards the studied cations was evaluated by using a Boltzmann-type equation and the calculation of pL0.5 parameter. The sequestering ability was quantified at different ionic strengths, temperatures and pHs, and this resulted, in general, that the pL0.5 trend was always: UO22+ > Cu2+ > Cd2+.

Bifunctional 3-Hydroxy-4-Pyridinones as Potential Selective Iron(III) Chelators: Solution Studies and Comparison with Other Metals of Biological and Environmental Relevance.

The binding ability of five bifunctional 3-hydroxy-4-pyridinones towards Cu2+ and Fe3+ was studied by means of potentiometric and UV-Vis spectrophotometric measurements carried out at I = 0.15 mol L-1 in NaCl(aq),T = 298.15 K and 310.15 K. The data treatments allowed us to determine speciation schemes featured by metal-ligand species with different stoichiometry and stability, owing to the various functional groups present in the 3-hydroxy-4-pyridinones structures, which could potentially participate in the metal complexation, and in the Cu2+ and Fe3+ behaviour in aqueous solution. Furthermore, the sequestering ability and metal chelating affinity of the ligands were investigated by the determination of pL0.5 and pM parameters at different pH conditions. Finally, a comparison between the Cu2+ and Fe3+/3-hydroxy-4-pyridinones data herein presented with those already reported in the literature on the interaction of Zn2+ and Al3+ with the same ligands showed that, from the thermodynamic point of view, the 3-hydroxy-4-pyridinones are particularly selective towards Fe3+ and could therefore be considered promising iron-chelating agents, also avoiding the possibility of competition, and eventually the depletion, of essential metal cations of biological and environmental relevance, such as Cu2+ and Zn2+.

Biopolymeric Nanocomposites for CO2 Capture.

Carbon dioxide (CO2) impacts the greenhouse effect significantly and results in global warming, prompting urgent attention to climate change concerns. In response, CO2 capture has emerged as a crucial process to capture carbon produced in industrial and power processes before its release into the atmosphere. The main aim of CO2 capture is to mitigate the emissions of greenhouse gas and reduce the anthropogenic impact on climate change. Biopolymer nanocomposites offer a promising avenue for CO2 capture due to their renewable nature. These composites consist of biopolymers derived from biological sources and nanofillers like nanoparticles and nanotubes, enhancing the properties of the composite. Various biopolymers like chitosan, cellulose, carrageenan, and others, possessing unique functional groups, can interact with CO2 molecules. Nanofillers are incorporated to improve mechanical, thermal, and sorption properties, with materials such as graphene, carbon nanotubes, and metallic nanoparticles enhancing surface area and porosity. The CO2 capture mechanism within biopolymer nanocomposites involves physical absorption, chemisorption, and physisorption, driven by functional groups like amino and hydroxyl groups in the biopolymer matrix. The integration of nanofillers further boosts CO2 adsorption capacity by increasing surface area and porosity. Numerous advanced materials, including biopolymeric derivatives like cellulose, alginate, and chitosan, are developed for CO2 capture technology, offering accessibility and cost-effectiveness. This semi-systematic literature review focuses on recent studies involving biopolymer-based materials for CO2 capture, providing an overview of composite materials enriched with nanomaterials, specifically based on cellulose, alginate, chitosan, and carrageenan; the choice of these biopolymers is dictated by the lack of a literature perspective focused on a currently relevant topic such as these biorenewable resources in the framework of carbon capture. The production and efficacy of biopolymer-based adsorbents and membranes are examined, shedding light on potential trends in global CO2 capture technology enhancement.

Identification of Dual Inhibitors Targeting Main Protease (Mpro) and Cathepsin L as Potential Anti-SARS-CoV-2 Agents.

In this structure-activity relationship (SAR) study, we report the development of dual inhibitors with antiviral properties targeting the SARS-CoV-2 main protease (Mpro) and human cathepsin L (hCatL). The novel molecules differ in the aliphatic amino acids at the P2 site and the fluorine position on the phenyl ring at the P3 site. The identified dual inhibitors showed Ki values within 1.61 and 10.72 µM against SARS-CoV-2 Mpro; meanwhile, Ki values ranging from 0.004 to 0.701 µM toward hCatL were observed. A great interdependency between the nature of the side chain at the P2 site and the position of the fluorine atom was found. Three dual-targeting inhibitors exhibited antiviral activity in the low micromolar range with CC50 values >100 µM. Docking simulations were executed to gain a deeper understanding of the SAR profile. The findings herein collected should be taken into consideration for the future development of dual SARS-CoV-2 Mpro/hCatL inhibitors.

Binary and ternary complexes of epinephrine with alginate and biologically and environmentally relevant metal cations.

The speciation of epinephrine (Eph -) in the presence of alginate (Alg 2-) and two biological and environmental relevant metal cations (Cu2+, UO2 2+) was investigated at T = 298.15K, I = 0.15-1.00 mol dm-3 in NaCl(aq). The formation of binary and ternary complexes was evaluated and, since epinephrine can behave as a zwitterion, the Eph -/Alg 2- interaction was studied by means of DOSY NMR. The dependence of the equilibrium constants on ionic strength was studied using an extended Debye-Hückel type equation and the SIT approach. The effect of temperature was investigated by means of isoperibolic titration calorimetry: the entropic contribution was the driving force for the Cu2+/Eph - complexes formation. The sequestering ability of Eph - and Alg 2- on Cu2+, evaluated by the pL0.5 calculation, increased with pH and ionic strength. The determination of pM parameter showed that Eph - had a higher Cu2+ affinity with respect to Alg 2-. The formation of Eph -/Alg 2- species was also investigated by UV-Vis spectrophotometry and 1H NMR measurements. The ternary Cu2+/Eph -/Alg 2- and Cu2+/UO2 2+/Eph - interactions were also studied. The "extra-stability" calculated for the mixed ternary species confirmed that their formation was thermodynamically favorable.

Modeling the acid-base properties of glutathione in different ionic media, with particular reference to natural waters and biological fluids.

The acid-base properties of γ-L-glutamyl-L-cysteinyl-glycine (glutathione, GSH) were determined by potentiometry (ISE-H(+), glass electrode) in pure NaI((aq)) and in NaCl((aq))/MgCl(2(aq)), and NaCl((aq))/CaCl(2(aq)) mixtures, at T = 298.15 K and different ionic strengths (up to I(c) ~ 5.0 mol L(-1)). In addition, the activity coefficients of glutathione were also determined by the distribution method at the same temperature in various ionic media (LiCl((aq)), NaCl((aq)), KCl((aq)), CsCl((aq)), MgCl(2(aq)), CaCl(2(aq)), NaI((aq))). The results obtained were also used to calculate the Specific ion Interaction Theory (SIT) and Pitzer coefficients for the dependence on medium and ionic strength of glutathione species, as well as the formation constants of weak Mg(j)H( i )(GSH)((i+2j-3)) and Ca(j)H(i)(GSH)((i+2j-3)) complexes. Direct calorimetric titrations were also carried out in pure NaCl((aq)) and in NaCl((aq))/CaCl(2(aq)) mixtures at different ionic strengths (0.25 ≤ I (c )/mol L(-1) ≤ 5.0) in order to determine the enthalpy changes for the protonation and complex formation equilibria in these media at T = 298.15 K. Results obtained are useful for the definition of glutathione speciation in any aqueous media containing the main cations of natural waters and biological fluids, such as Na(+), K(+), Mg(2+), and Ca(2+). Finally, this kind of systematic studies, where a series of ionic media (e.g., all alkali metal chlorides) is taken into account in the determination of various thermodynamic parameters, is useful for the definition of some trends in the thermodynamic behavior of glutathione in aqueous solution.

Environmental behaviour of a pesticide metabolite, the AMPA. Sequestration of Ca2+, Mg2+, Cu2+, Zn2+ and Al3.

The chelating and sequestering ability of a glyphosate metabolite, the aminomethylphosphonic acid (AMPA) towards bi- and trivalent metal cations, such as Ca2+, Mg2+, Zn2+, Cu2+ and Al3+, were investigated in aqueous solutions of NaCl, in an ionic strength range of 0.1 ≤ I/mol dm-3 ≤ 1.0 and at constant temperature of T = 298.15 ± 0.15 K. The investigations on the acid-base properties and complexing ability were performed, by means of potentiometry, in conditions of different cM:cAMPA molar ratios and pH values. The formation of insoluble species was experimentally observed in the Mn+/AMPA2- systems, and the solid phases were characterized by means of X-Ray Diffractometry (XRD), Scanning Electron Microscopy (SEM) and InfraRed Attenuated Total Reflection spectroscopy (IR-ATR). The dependence on ionic strength of the stability constants of the Mn+/AMPA2- complexes species, determined at different ionic strengths, was modelled by the Debye-Hückel type equation. The sequestering ability of AMPA toward the investigated metal cations was evaluated by pL0.5 parameter.

Indole-3-acetic acid correlates with monocyte-to-high-density lipoprotein (HDL) ratio (MHR) in chronic kidney disease patients.

PURPOSE: Indole-3-acetic acid is a protein-bound indolic uremic toxin deriving from tryptophan metabolism. Increased levels are associated with higher thrombotic risk and both cardiovascular and all-cause mortality. An emerging biomarker of cardiovascular disease is the monocyte-to-high-density lipoprotein ratio (MHR). The main purpose of this study was to investigate the association of indole-3-acetic acid with MHR and other markers of cardiovascular risk in patients with chronic kidney disease (CKD). METHODS: We enrolled 61 non-dialysis CKD patients and 6 dialysis patients. Indole-3-acetic acid levels were measured with ELISA technique. RESULTS: In the whole cohort of 67 patients, indole-3-acetic acid was directly related to Ca × P (ρ = 0.256; P = 0.0365) and MHR (ρ = 0.321; P = 0.0082). In the 40 patients with previous cardiovascular events, indole-3-acetic acid correlated with uric acid (r = 0.3952; P = 0.0116) and MHR (ρ = 0.380; P = 0.0157). MHR was related with fibrinogen (ρ = 0.426; P = 0.0010), arterial hypertension (ρ = 0.274; P = 0.0251), C-reactive protein (ρ = 0.332; P = 0.0061), gender (ρ = - 0.375; P = 0.0017; 0 = male, 1 = female), and CKD stage (ρ = 0.260; P = 0.0337). A multiple regression analysis suggested that indole-3-acetic acid might be an independent predictor of MHR. CONCLUSION: This study shows a significant association between indole-3-acetic acid and MHR. Prospective studies are required to evaluate if decreasing indole-3-acetic acid concentrations may reduce MHR levels and cardiovascular events and improve clinical outcomes.

The Solution Behavior of Dopamine in the Presence of Mono and Divalent Cations: A Thermodynamic Investigation in Different Experimental Conditions.

The interactions of dopamine [2-(3,4-Dihydroxyphenyl)ethylamine, (Dop-)] with methylmercury(II) (CH3Hg+), magnesium(II), calcium(II), and tin(II) were studied in NaCl(aq) at different ionic strengths and temperatures. Different speciation models were obtained, mainly characterized by mononuclear species. Only for Sn2+ we observed the formation of binuclear complexes (M2L2 and M2LOH (charge omitted for simplicity); M = Sn2+, L = Dop-). For CH3Hg+, the speciation model reported the ternary MLCl (M = CH3Hg+) complex. The dependence on the ionic strength of complex formation constants was modeled by using both an extended Debye-Hückel equation that included the Van't Hoff term for the calculation of enthalpy change values of the formation and the Specific Ion Interaction Theory (SIT). The results highlighted that, in general, the entropy is the driving force of the process. The sequestering ability of dopamine towards the investigated cations was evaluated using the calculation of pL0.5 parameter. The sequestering ability trend resulted to be: Sn2+ > CH3Hg+ > Ca2+ > Mg2+. For example, at I = 0.15 mol dm-3, T = 298.15 K and pH = 7.4, pL0.5 = 3.46, 2.63, 1.15, and 2.27 for Sn2+, CH3Hg+, Ca2+ and Mg2+ (pH = 9.5 for Mg2+), respectively. For the Ca2+/Dop- system, the precipitates collected at the end of the potentiometric titrations were analyzed by thermogravimetry (TGA). The thermogravimetric calculations highlighted the formation of solid with stoichiometry dependent on the different metal:ligand ratios and concentrations of the starting solutions.

RAS inhibition modulates kynurenine levels in a CKD population with and without type 2 diabetes mellitus.

Kynurenine pathway of tryptophan metabolism is involved in the pathophysiology of chronic kidney disease (CKD) and diabetes mellitus, mainly through the inflammation-induced activity of indoleamine 2,3-dioxygenase (IDO), and few studies have investigated its potential link with proteinuria. Renin-angiotensin system inhibitors (RASis) are recommended in these patients to decrease proteinuria, slow CKD progression and reduce cardiovascular risk, but whether these drugs influence kynurenine levels in humans is unknown. We evaluated serum tryptophan and kynurenine in patients suffering from CKD with or without type 2 diabetes mellitus, their correlations with markers of reduced kidney function, and their relationship with RAS-inhibiting therapy. Of 72 adult patients enrolled, 55 were receiving RASis, whereas 17 were not. Tryptophan was assessed by HPLC (high-performance liquid chromatography); kynurenine was measured using an enzyme-linked immunosorbent assay kit; IDO activity (%) was calculated with the formula (kynurenine/tryptophan) × 100. Kynurenine levels were significantly lower in the group under RASis compared to the untreated group (1.56 ± 0.79 vs 2.16 ± 1.51 µmol/l; P = 0.0378). In patients not receiving RASis, kynurenine was inversely related to estimated glomerular filtration rate (eGFR) (r = - 0.4862; P = 0.0478) and directly related to both proteinuria (ρ = 0.493; P = 0.0444) and albuminuria (ρ = 0.542; P = 0.0247). IDO activity was higher in patients with history of cardiovascular disease compared to patients with no such history, and it negatively correlated with eGFR (ρ = - 0.554; P = 0.0210) in the same group. These findings may contribute to explain the well-known beneficial effects of RAS inhibition in CKD population, especially considering that kynurenine is emerging as a potential new biomarker of CKD.

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.

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 Lipinski's 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.

Understanding the bioavailability and sequestration of different metal cations in the presence of a biodegradable chelant MGDA in biological fluids and natural waters.

Thermodynamic information about the metal-ligand interaction between Fe3+, Zn2+, Cu2+ and Sn2+, and a biodegradable ligand as MGDA is reported. The speciation scheme was obtained by means of potentiometric measurements and isothermal titration calorimetry (to determine enthalpy changes) in NaCl medium. The formation of the ML and MLOH species was evidenced for all the metal cations, and for Fe3+ also the ML2 and ML(OH)2 were found. The relative stability, for the ML species, follows the order: Sn2+ > Fe3+ > Cu2+ > Zn2+. Stability constants and enthalpy changes were obtained at different ionic strengths, and data were modeled using the Debye-Hückel and SIT approaches to obtain data in a standard state. At infinite dilution, the enthalpy changes are largely negative for Cu2+ (-34.1 kJ mol-1) and Sn2+ (-16.6 kJ mol-1), slightly negative for Fe3+ (-3.3 kJ mol-1) and positive for Zn2+ (8.7 kJ mol-1). In all cases, the entropic contribution to the stability is predominant. The sequestering ability of MGDA was evaluated determining the pL0.5 values in different conditions. Comparing the data reported in this work and literature ones, some empirical relationships were obtained with predictive purpose. For example, using 11 data in the test set we have: log K (M/MGDA) ± 0.1 = 1.13 + 0.84·log K (M/NTA) Case studies were built up in the conditions of seawater, fresh water and urine to study the possible use of MGDA towards the metal cations here studied. Some considerations were also done in the light of the ocean acidification.

Sequestration of Aluminium(III) by different natural and synthetic organic and inorganic ligands in aqueous solution.

The speciation of Al3+ in aqueous solutions containing organic and inorganic ligands important from a biological (citrate (Cit3-), gluconate (Gluc-), lactate (Lac-), silicate (H2SiO42-), carbonate (CO32-), fluoride (F-)) and industrial (Gantrez®; polymethyl-vinyl-ether-co-maleic acids; GTZ S95 and GTZ AN169) point of view is reported. The stability constants of Al3+/Lz- complexes (Lz- = ligand with z- charge) were determined by potentiometry at T = 298.15 K and 0.10 ≤ I/M ≤ 1.00 in NaCl(aq) (in NaNO3(aq) only for Al3+/GTZ S95 and Al3+/Gluc- acid systems). For Al3+/Cit3-, Al3+/Lac- and Al3+/GTZ AN1694- systems, the investigations were also carried out at 283.15 ≤ T/K ≤ 318.15. The dependence of the thermodynamic parameters on ionic strength and temperature was modelled with a Debye-Hückel type equation. Different speciation schemes of Al3+/Lz- systems were obtained, including protonated, simple metal-ligand, polynuclear and hydrolytic mixed species. At I → 0 M and T = 298.15 K the stability trend for the AlL(3-z) species is: 14.28 ± 0.02, 13.99 ± 0.03, 10.16 ± 0.03, 3.16 ± 0.08, 2.84 ± 0.10 for GTZ S95, GTZ AN169, Cit3-, Gluc- and Lac-, respectively. From the investigations at different temperatures, it results that the entropic contribution is the driving force of the reactions. The sequestering ability of the ligands towards Al3+ was investigated determining the pL0.5 parameter at different experimental conditions, finding the following trend: Cit3- ¼ Gluc- > GTZ S954- > GTZ AN1694- > Lac- for the organic ligands, and pL0.5: F- ¼ CO32- > H2SiO42- for the inorganic ones.

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.

Understanding the bioavailability and sequestration of different metal cations in the presence of a biodegradable chelant S,S-EDDS in biological fluids and natural waters.

Ethylenediamine-N,N'-disuccinic acid is a biodegradable alternative to EDTA, therefore its use for the sequestration of Ca(2+), Sn(2+), Cu(2+), Zn(2+) and Fe(3+) is analyzed. New data on its binding ability towards these cations were obtained with potentiometric, voltammetric and calorimetric measurements at different ionic strengths and at T = 298.15 K. Real multi-component fluids, namely fresh water, urine, sea water, saliva and blood plasma were chosen as case studies to evaluate the sequestering ability of EDDS in comparison with EDTA. Speciation diagrams were drawn in selected conditions, considering all interactions among the "natural" components of the fluid and those studied in this work, EDDS and EDTA (cL = 1 mmol dm(-3)) as sequestering agents and the cited metal cations (cM ∼ 10(-5) mol dm(-3)). The comparison of the sequestering ability of EDDS and EDTA is done using pM and pL0.5. In blood plasma the plasma mobilizing index was adopted. It was found that EDDS is a good alternative to EDTA, which tends to bind Ca(2+) and Mg(2+) more than EDDS. In particular, EDTA cannot be used as a sequestrant for Sn(2+) when cCa > cEDTA. EDDS is more efficient than EDTA at pH < 8, particularly in urine, where carbonate is absent. In sea water, the sequestering ability of EDDS towards Fe(3+) is higher than that of EDTA. In blood plasma, the PMI of EDDS towards Cu(2+) is higher than that of EDTA. Thermodynamic information, in terms of ΔH and ΔS, for the protonation and metal complex formation reactions 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

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.