Sequestering ability of some chelating agents towards methylmercury(II).
A study on the interactions between CH3Hg+ and some S, N and O donor ligands (2-mercaptopropanoic acid (thiolactic acid (H2 TLA)), 3-mercaptopropanoic acid (H2 MPA), 2-mercaptosuccinic acid (thiomalic acid (H3 TMA)), d,l-penicillamine (H2 PSH), l-cysteine (H2 CYS), glutathione (H3 GSH), N,N′-bis(3-aminopropyl)-1-4-diaminobutane (spermine (SPER)), 1,2,3,4,5,6-benzenehexacarboxylic acid (mellitic acid (H6 MLT)) and ethylenediaminetetraacetic acid (H4 EDTA)) 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 t…
Chemical speciation of nucleotide 5′-monophosphates in the presence of biogenic amines
The interaction of adenosine-, uridine-, inosine- and guanosine-5’-monophosphates with protonated ethylenediamine, putrescine, cadaverine, spermidine and spermine, was studied potentiometrically, a...
Thermodynamic and spectroscopic study of the binding of dimethyltin(IV) by citrate at 25°C
Thermodynamic (potentiometric and calorimetric) and spectroscopic ( 1 H NMR, 119 Sn Mossbauer) studies were performed in aqueous solution in order to characterize the interaction of dimethyltin(IV) cation with citrate ligand. Six species {(CH 3 ) 2 Sn(cit) - ; [(CH 3 ) 2 Sn] 2 (cit) 2 2- ; (CH 3 ) 2 Sn(cit)H 0 ; (CH 3 ) 2 Sn(cit)OH 2- ; [(CH 3 ) 2 Sn] 2 (cit)OH 0 ; [(CH 3 ) 2 Sn] 2 (cit)(OH) 2 - } were found. All the species formed in this system are quite stable and formation percentages are fairly high. For example, at pH = 7.5 and C (CH3)2Sn = C cit = 10 mmol l -1 , E% for [(CH 3 ) 2 Sn] 2 (cit)(OH) 2 - and (CH 3 ) 2 Sn(cit)OH 2- species reaches 65%. Overall thermodynamic parameters obta…
Aqueous solution chemistry of alkyltin(IV) compounds for speciation studies in biological fluids and natural waters
Abstract Organotin(IV) cations behave as Lewis acids of different strength depending on the charge, according to the following acidity scale: RSn3+ > R2Sn2+ > R3Sn+. For this reason they can react with Lewis bases containing –O, –N, –S donor groups to form complex species of different stability. Complex formation of organotin(IV) moieties with a great number of inorganic and organic ligands in aqueous solution is reviewed here in the light of their environmental and biological impact. To this end, complex species formation was considered in different ionic media and at different ionic strengths, with reference to the composition of natural waters and biological fluids. In particular, the in…
Speciation of organotin compounds in NaCl aqueous solution: interaction of mono-, di- and tri-organotin(IV) cations with nucleotide 5′ monophosphates
Formation constants for complex species of mono-, di- and tri-alkyltin(IV) cations with some nucleotide 5'-monophosphates (AMP, UMP, IMP and GMP) are reported, at T=25°C and at I = 0.16 mol 1 -1 (NaCI). The investigation was performed in the light of speciation of organometallic compounds in natural fluids in the presence of nucleotides whose biological importance is well recognized. The simple and mixed hydrolytic complex species formed in all the systems investigated in the pH range 3-9 are (L = nucleotide; M = organotin cation R x Sn (4-x)+ , with x = 1 to 3): ML + , ML(OH)° and ML(OH) 2 - for the system CH 3 Sn 3+ -L (L = AMP, IMP, UMP); ML 0 and ML(OH)-for the system (C 2 H 5 ) 2 Sn 2+…
Interaction of methyltin(IV) compounds with carboxylate ligands. Part 1: formation and stability of methyltin(IV)–carboxylate complexes and their relevance in speciation studies of natural waters.
Quantitative data on the stability of mono-, di- and trimethyltin(IV)-carboxylate complexes (acetate, malonate, succinate, malate, oxydiacetate, diethylenetrioxydiacetate, tricarballylate, citrate, butanetetracarboxylate and mellitate) are reported at t=25°C and I → 0 mol l - 1 . Several mononuclear, mixed proton, mixed hydroxo and polynuclear species are formed in these systems. As expected, the stability trend is mono- > di- > trimethyltin(IV) and mono < di < tri < tetra < hexa for the organotin moieties and carboxylate ligands investigated, respectively. Moreover, ligands containing, in addition to carboxylic,-O-and-OH groups show a significantly higher stability with respect to analogou…
Interaction of methyltin(IV) compounds with carboxylate ligands. Part 2: Formation thermodynamic parameters, predictive relationships and sequestering ability.
Thermodynamic data of mono-, di- and tri-methyltin(IV)-carboxylate complexes (acetate, malonate, succinate, oxydiacetate, diethylenetrioxydiacetate, malate, citrate, 1,2,3-tricarballylate, 1,2,3,4-butanetetracarboxylate, 1,2,3,4,5,6-benzenehexacarboxylate) in aqueous solution are reported at t = 25 °C and I = 0 mol l−1. Thermodynamic parameters obtained were analysed to formulate empirical predictive relationships as a function of different parameters, such as the number of carboxylate groups of the ligand and the charge of the alkyltin(IV) cation. Sequestration diagrams of citrate and 1,2,3-tricarballylate towards alkyltin(IV) cations at different pH values are also reported and discussed.…
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…