Solubility and acid-base properties and activity coefficients of chitosan in different ionic media and at different ionic strengths, at T=25°C
Studies on the acid-base properties and solubility of a polyammonium polyelectrolyte (chitosan) with different molecular weights (MW 310 and 50 kDa), were performed at T=25 °C, in the pH range 2.5–7. The protonation of chitosan was investigated by potentiometry ([H+]-glass electrode) in NaCl, NaNO3 and mixed NaNO3+Na2SO4 ionic media, at different ionic strengths. Protonation constants were calculated as a function of dissociation degree α by means of two different models, namely, a simple linear model and the modified Henderson–Hasselbalch equation. Experimental data were also fitted using a model independent of α (Diprotic-like model), according to which the acid-base properties can be sim…
Modeling the acid-base properties of molybdate(VI) in different ionic media, ionic strengths and temperatures, by EDH, SIT and Pitzer equations
This paper reports the results of a study on the determination of the protonation constants of MoO42 −, in NaClaq, NaNO3aq, KClaq, at different ionic strengths (0 < I/mol dm− 3 ≤ 5.0 in NaClaq, 0 < I/mol dm− 3 ≤ 3.0 in NaNO3aq and KClaq) and temperatures (278.15 ≤ T/K ≤ 318.15 in NaClaq, only 298.15 K in NaNO3aq and KClaq), by potentiometric (ISE-H+ glass electrode) and spectrophotometric (UV/Vis) titrations. After a critical analysis of results and literature findings, the proposed speciation model takes into account the formation of two monomeric and four heptameric species, namely: MoO4H−, MoO4H2, (MoO4)7H86 −, (MoO4)7H95 −, (MoO4)7H104 − and (MoO4)7H113 −. Due to the complexity of…
Supramolecular Assemblies Based on Complexes of Nonionic Amphiphilic Cyclodextrins and a meso-Tetra(4- sulfonatophenyl)porphine Tributyltin(IV) Derivative: Potential Nanotherapeutics against Melanoma
Amphiphilic cyclodextrin (ACyD) provides water-soluble and adaptable nanovectors by modulating the balance between the hydrophobic and hydrophilic chains at both CyD sides. This work aimed to design nanoassemblies based on nonionic and hydrophilic ACyD (SC6OH) for the delivery of a poor-water-soluble organotin(IV)-porphyrin derivative [(Bu3Sn)4TPPS] to melanoma cancer cells. To characterize the porphyrin derivatives under simulated physiological conditions, a speciation was performed using complementary techniques. In aqueous solution (≤ 20 μM), (Bu3Sn)4TPPS primarily exists as a monomer (2 in Figure 1), as suggested by the low static anisotropy (ρ ≈ 0.02) with a negligible formation of por…
Understanding the Solution Behavior of Epinephrine in the Presence of Toxic Cations: A Thermodynamic Investigation in Different Experimental Conditions
The interactions of epinephrine ((R)-(&minus
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)
Speciation Studies of Bifunctional 3-Hydroxy-4-Pyridinone Ligands in the Presence of Zn2+ at Different Ionic Strengths and Temperatures
The acid&ndash
Speciazione di Sn(II) in presenza di leganti O-donatori di interesse biologico
Lo stagno è il ventiquattresimo elemento più abbondante nella crosta terrestre ed ha il più elevato numero di isotopi stabili (dieci). Generalmente questo elemento non viene annoverato tra gli inquinanti più importanti, in quanto lo stagno inorganico non risulta particolarmente tossico. Tuttavia, molti dei suoi sali lo sono. Infatti, la corrosione di contenitori in stagno da parte di cibi e bevande acide ha causato in passato numerosi intossicazioni ad opera di composti solubili di questo metallo. Inoltre, la bioalchilazione dello stagno inorganico porta alla formazione di composti ancor più nocivi per l’ambiente. Per tali ragioni, per esempio, la Food Standards Agency del Regno Unito ha im…
Acid−Base Properties of Synthetic and Natural Polyelectrolytes: Experimental Results and Models for the Dependence on Different Aqueous Media
Protonation constants of several natural and synthetic humates and fulvates were determined by ISE-H+ potentiometry in different ionic media (alkali metal halides and tetraethylammonium iodide) at different ionic strengths and T ) 298.15 K. Experimental data obtained in previous studies of different synthetic (polyacrylates, polymethacrylates, polyacrylate-co-maleate) and naturally occurring (alginate, humic substances) polycarboxylates were also taken into account in the general analysis of acid-base properties of polyelectrolytes. Protonation constants were expressed as a function of the dissociation degree (R) using three models, namely, a simple linear model, the Ho¨gfeldt three-paramet…
Special issue “chemical speciation of organic and inorganic components of environmental and biological interest in natural fluids: Behaviour, interaction and sequestration”
Several different definitions were in the past proposed to describe the term chemical speciation, and some of them were accepted from the scientific community [...]
Modelling the dependence on medium and ionic strength of molybdate acidbase properties, and its interactions with phytate
The importance of molybdenum from a biological, environmental and technological point of view is very well known since many decades [15]. In particular, it is mainly present in aqueous solutions as molybdate (MoO42), which is the biologically active form, entering in the cells by active transport systems. Though molybdate is the major species in neutral to basic pH conditions, at lower pH it undergoes protonation and, chiefly, polymerization, even at millimolar concentration levels [2]. Consequently, the modelling of its speciation and acidbase properties is not very simple, as demonstrated by the nonhomogeneity of available literature data. In this light, our group has started a systematic…
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 …
Interactions of Dioxouranium(VI) with Amines in Aqueous Solution
The interaction of the dioxouranium(VI) ion with five low molecular weight polyamines (ethylenediamine, putrescine, cadaverine, spermidine, and spermine) and with poly(allyl)amine (15 kDa) was studied potentiometrically (ISE-H + glass electrode) at T ) 298.15 K. Investigations were carried out in NaNO3 ionic medium, at I ) 0.1 mol · L -1 (and 0.5 mol · L -1 for poly(allyl)amine only), in the pH range 3.5 to 5.5, before the formation of uranyl insoluble species. The results gave evidence for the formation of two species, namely, UO2L 2+ and UO2L(OH) + for the diamine systems (ethylenediamine, putrescine, cadaverine), UO2L 2+ and UO2LH 3+ for spermidine, and UO2LH 3+ and UO2LH2 4+ for spermin…
Binding of acrylic and sulphonic polyanions by open-chain polyammonium cations
Abstract The interactions between some acrylic and sulphonic polyanions and some protonated amines (diamines NH 2 -(CH 2 ) x -NH 2 , x =2,…,10; linear tri-, tetra-, penta- and hexa-amines) were studied potentiometrically in aqueous solution, at 25°C. For both types of polyanions AL 2 H i (L − , monomer of polyanion, A, amine) species are formed, with i =1,…, n ( n =number of amino groups in the amine). The stability of these species is strictly dependent on the polyammonium cation charge, and fairly independent of the type of amine (in diamine species maximum stability is observed for x =4, 5). Acrylic and sulphonic polyanion complexes are considerably stronger than analogous species formed…
Modelling of natural synthetic polyelectrolyte interactions in natural waters by using SIT, Pitzer and Ion Pairing approaches
Abstract In this paper SIT and Pitzer models are used for the first time to describe the interactions of natural and synthetic polyelectrolytes in natural waters. Measurements were made potentiometrically at 25 °C in single electrolyte media, such as Et 4 NI and NaCl (for fulvic acid 0.1 − 1 S single salt ” BA, with cation B and anion A representing all the major cations (Na + , K + , Mg 2+ , Ca 2+ ) and anions (Cl − , SO 4 2− ) in natural sea water, respectively. The ion pair formation model was also applied to fulvate and alginate in artificial sea water by examining the interaction of polyanions with the single sea water cation. Results were compared with those obtained from previous sp…
Biochar from byproduct to high value added material – A new adsorbent for toxic metal ions removal from aqueous solutions
Abstract An activated biochar coming from pyrolysis of dead Posidonia oceanica residues has been tested as adsorbent material for Cd2+, Pb2+ and Cu2+ ions. The biomass, the activated and the non activated biochars were previously characterized by using several instrumental techniques. The pH of metal ion solution in kinetic and thermodynamic adsorption experiments was fixed at 5 whilst, the dependence on ionic medium, ionic strength and temperature have been evaluated carrying out batch experiments at different experimental conditions. Differential Pulse Anodic Stripping Voltammetry and Inductively Coupled Plasma Optical Emission Spectroscopy have been used to measure the metal ion concentr…
Hydrolysis of dioxouranium(VI): a calorimetric study in NaClaq and NaClO4aq, at 25°C
Abstract We report the results of a calorimetric study on the hydrolysis of UO 2 2+ in different ionic media (NaClO 4 aq , NaCl aq ) at 25 °C. Experiments in NaCl were performed at different ionic strength, at I ≤1 mol l −1 . The species considered in both ionic media were UO 2 (OH) + , (UO 2 ) 2 (OH) 2 2+ and (UO 2 ) 3 (OH) 5 + , and in addition (UO 2 ) 3 (OH) 4 2+ and (UO 2 ) 3 (OH) 7 − in NaCl aq . The dependence on ionic strength of enthalpy changes in NaCl aq was expressed by the simple linear equation Δ H pq =Δ H ° pq + aI 1/2 ( a , empirical parameter). Comparison with literature findings is given and some recommended values are reported.
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 inin vitroequilibrium 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, a…
Protonation of Carbonate in Aqueous Tetraalkylammonium Salts at 25°C.
Protonation constants of carbonate were determined in tetramethylammonium chloride (Me4NClaq 0.1≤I/mol kg−1 ≤4) and tetraethylammonium iodide (Et4NIaq 0.1≤I/mol kg−1 ≤1) by potentiometric ([H+]-glass electrode) measurements. Dependence of protonation constants on ionic strength was taken into account by modified specific ion interaction theory (SIT) and by Pitzer models. Literature data on the protonation of carbonate in NaClaq (0.1≤I/mol kg−1 ≤6) were also critically analysed. Both protonation constants of carbonate follow the trend Et4NI>Me4NCl > NaCl. An ion pair formation model designed to take into account the different protonation behaviours of carbonate in different supporting electr…
Thermodynamic Parameters for the Protonation of Poly(allylamine) in concentrated LiCl(aq) and NaCl(aq)
The acid-base properties of poly(allylamine) (MW ) 15 kDa) were determined by potentiometry and calorimetry in aqueous solutions at t ) 25 °C. Potentiometric measurements were carried out in a wide range of ionic strengths (0.1 e I/molâL-1 e 5.0) in NaCl(aq) and LiCl(aq), while enthalpy changes for the protonation of poly(allylamine) were determined by calorimetry in the same ionic strength range but only in NaCl(aq). Analysis of the experimental data was carried out using two different models: the first based on a modified Henderson-Hasselbalch two parameter equation and the second on the three parameter equation proposed by Ho¨gfeldt. Protonation constants are given for both models and io…
Chemical speciation of organic matter in natural waters. Interaction of nucleotide 5′ mono-, di- and triphosphates with major components of seawater
AbstractThe interactions of nucleotide 5’ mono-, di- and triphosphates in a multicomponent ionic medium simulating the macro-composition of seawater (Na+, K+, Ca2+, Mg2+, Cl-, SO42-, Synthetic Sea Water, SSW) have been investigated at different ionic strengths and at T= 25°C. A chemical speciation model, according to which all the internal interactions between the components of the ionic medium are taken into account, was applied to determine the effective formation constants of species in the nucleotide-seawater system. The results were compared to protonation parameters calculated from single electrolyte systems. A simpler model (SSW considered as a single salt BA, with Bz+ and Az-), repr…
8-Hydroxyquinoline-2-Carboxylic Acid as Possible Molybdophore: A Multi-Technique Approach to Define Its Chemical Speciation, Coordination and Sequestering Ability in Aqueous Solution.
8-hydroxyquinoline-2-carboxylic acid (8-HQA) has been found in high concentrations (0.5&ndash
Polycarboxylic acids in sea water: acid–base properties, solubilities, activity coefficients, and complex formation constants at different salinities
This paper reports the results of the investigations carried out in synthetic sea water at different salinities for different classes of polycarboxylic acids. The investigations can be summarized as follows: (a) Determination of the protonation constants in such multicomponent solution in a salinity range 15 ≤ S ≤ 45, at t = 25 °C, for the linear dicarboxylic acids HOOC-(CH2) n –COOH (0 ≤ n ≤ 8), and aromatic polycarboxylic acids (o-phthalic and 1,2,4-benzenetricarboxylic acids). For malonic, succinic, 1,2,3-benzenetricarboxylic, and 1,2,3,4-benzenetetracarboxylic acids, investigations were also carried out at t = 10 and 37 °C; (b) Determination of the total and intrinsic solubility (S T an…
Speciation of tin(II) in aqueous solution: thermodynamic and spectroscopic study of simple and mixed hydroxocarboxylate complexes
This contribution reports the results of potentiometric and Mossbauer investigations on the formation, stability, and structure of binary and ternary mono- and binuclear complexes of Sn2+ with three hydroxocarboxylic ligands (namely L = tartrate, malate, and citrate) and chloride at T = 298.15 K in different ionic media and ionic strengths (0.15 and 1.00 mol dm−3 in NaCl(aq) and 1.00 mol dm−3 in NaNO3(aq)). The stability constants of various simple Sn i H j L (2+−) and mixed Sn i H j L k Cl (2+−−) species obtained in the different experimental conditions are reported, and various speciation diagrams of the simple and mixed systems are shown in different conditions. The sequestering ability …
Advances in the investigation of dioxouranium(VI) complexes of interest for natural fluids
Abstract The interactions of dioxouranium(VI) cation with different organic and inorganic ligands of environmental and biological interest were carefully examined with the aim to draw a chemical speciation picture of this ion in natural aquatic ecosystems and in biological fluids. Since UO22+ ion shows a significant tendency to hydrolyze, particular attention was paid in considering the hydrolysis species formation both in the presence and in absence of ligands. The results reported in the literature show that formation of the hydrolytic species assumes a great importance in the complexation models for all the UO22+-ligand systems considered. In particular, the following ligands have been t…