Assessing the formation of weak sodium complexes with negatively charged ligands.

The stability of sodium complexes with poly-carboxylic and polyamino-carboxylic acids is investigated with ion-selective electrode-Na(+) potentiometry, working at strictly constant ionic strength. It is observed that the formation constants of the Na(+) complexes with monoligand stoichiometry (ML) increase with the number of charges on the ligand. For example, in poly-carboxylic acids this dependency is linear and is well captured by an experimental equation. A different behaviour is observed for the poly-amino carboxylic acids, which show higher complexation capabilities reaching a plateau of the binding energy past a specific ligand size. The experimental results are discussed qualitatively using ab initio calculations based on DFT B3LYP, and the principal electronic characteristics of the ligands under investigation are identified. As a result of the flexibility imparted by the long chains of polyamino-carboxylic ligands, both experimental and theoretical models demonstrate that nitrogen atoms in proximity of Na(+) ions can participate in the metal coordination, thus providing further stabilization for the complexes. Moreover, by increasing the ligand size the stabilization gained in terms of ΔG reached a plateau for EDTA, in agreement with experimental observations.

Ionic strength dependence of formation constants-I Protonation constants of organic and inorganic acids.

The protonation constants of formic, acetic, benzoic, oxalic, phthalic, maleic, malonic, succinic, dl-malic, dl-tartaric, aminoacetic, citric, nitrilotriacetic, ethylenediaminetetra-acetic, sulphuric and orthophosphoric acids have been determined from pH measurements, in tetraethylammonium iodide solution, at various ionic strengths in the range 0.01-1.0M (for phosphoric and sulphuric acids 0.01-0.5M). For each acid the dependence of the protonation constants on ionic strength was determined and an equation, valid for all the acids studied, to describe this was derived. The use of tetraethyl-ammonium salts as background to avoid ion-pair formation is discussed.

Mixed complexes of Ni(2+) or Zn(2+) and citric acid with 2,2'-bipyridyl in aqueous solution.

The stability constants of ternary Ni(2+) or Zn(2+) complexes with 2,2'-bipyridyl and citric acid have been determined by means of pH-titrations at 25.0 +/- 0.2 degrees and an ionic strength of 0.1M (KNO(3)). The stability constants of ternary complexes have been compared with those of similar ternary species.

Ionic strength dependence of formation constants-V Protonation constants of some nitrogen-containing ligands at different temperatures and ionic strengths.

The protonation constants of 2,2'-bipyridyl, 1,10-phenanthroline, 1,3-diaminopropane, l-histidine and histamine have been determined potentiometrically, in the temperature range 10-40 degrees and at ionic strengths ranging from 0.04 to 1 (potassium chloride). The dependence of the protonation constants on ionic strength is described by a simple general equation. The enthalpy changes for the protonation of the ligands have been calculated from the temperature dependence of the protonation constants.

Ionic strength dependence of formation constants-XVIII. The hydrolysis of iron(III) in aqueous KNO(3) solutions.

The hydrolysis of iron(III) was studied potentiometrically at different ionic strengths in KNO(3) aqueous solutions, at 25 degrees C, to determine the dependence of hydrolysis constants on ionic strength (nitrate media), to check the existence of nitrate-ferric ion interactions, and to confirm the formation of high polymeric species. Under the experimental conditions 0.03 I (KNO(3)) 1M, 0.3 C 12 mM, the species Fe(OH)(2+), Fe(2)(OH)(4+)(2), Fe(OH)(+)(2) and Fe(12)(OH)(2+)(34) were found, and the hydrolysis constants log beta(11) = 2.20, log beta(12) = -2.91, log beta(22) = -5.7, log beta(12,34) = -48.9 (I = 0M) were calculated. The ionic strength dependence of hydrolysis constants is quite close to that found for several protonation and metal complex formation constants reported elsewhere.

Copper(II) complexes of N-(phosphonomethyl)glycine in aqueous solution: a thermodynamic and spectrophotometric study.

Copper(II) complexes with the herbicide N-(phosphonomethyl)glycine (glyphosate) have been investigated in aqueous solution by means of pH-metric measurements at different temperatures, 5

Ionic-strength dependence of formation constants-XII A model for the effect of background on the protonation constants of amines and amino-acids.

From analysis of literature data on the protonation of N-donor and N,O-donor ligands at 25 degrees , a simple model has been derived for the dependence of amine and amino-acid protonation constants on the background electrolytes, which takes into account the formation of weak complexes between the protonated forms of the amines (or amino-acids) and the background anions and between the amino-acid carboxylate group and alkali-metal cations.

Speciation and structure of copper(II) complexes with histidine-containing peptides in aqueous medium: a combined potentiometric and spectroscopic study.

The complex formation between copper(II) and some histidine-containing peptides has been investigated by means of potentiometric and spectroscopic measurements. Due to the interesting co-ordination mode towards copper(II), peptides with histidyl residue located in second position from the N-terminal amino group have been chosen. The stability constants evaluation has been performed by both pH-metric and ESR (room temperature) measurements; in this context a suitable computer program for the calculation of both stability constant values and the ESR spectrum for each complex has been written. Visible spectrophotometric and circular dichroism spectra, together with the isotropic ESR parameters, were used in order to propose a structure for each complex having a significant percentage of formation in solution.

[LithoRisk: A software for calculating and visualising nephrolithiasis risk profiles]. / LithoRisk: software per il calcolo e la visualizzazione dei profili di rischio di calcolosi renale.

BACKGROUND: The pathogenesis of nephrolithiasis, based on the anomalies of the urinary environment, demands metabolic and physicochemical assessment for the medical management of patients. Standard metabolic protocols include the measurement of pertinent urine chemistry values and the calculation of the extent of saturation in stone-forming salts. However, patients are often given fragmentary and hard-to-consult reports and so this weakens the strength of the therapeutic recommendations. This paper introduces LithoRisk, a dedicated software which graphically represents risk profiles of stone formation, including the extent of saturation. METHODS: LithoRisk uses the results of 24-h urine chemistry values widely available in hospital laboratories, i.e., sodium, potassium, calcium, magnesium, ammonia, phosphate, sulphate, citrate, oxalate, chloride, pH and urine volume. Uric acid and cystine are optional. The relative supersaturation (beta), estimated according to our own ab initio calculation, is given in a scale whereby beta=1 is saturation, beta < 1 under - and beta > 1 oversaturation. LithoRisk is available as a CD-ROM and can be loaded on Windows 95/98/Millenium/XP. Colour or laser printers are suitable for printed records. RESULTS: LithoRisk is easily loaded on any PC by following video instructions. Once the loading of the program is completed a grey icon LithoRisk appears on the Desktop. The program can be opened by clicking twice on the icon. The patients data page first appears on the screen and is followed by the evaluation page for the input of variables. This generates the graph representing the diagnostic lithorisk profile, which is drawn as a line connecting different values, according to a specific scale and related to an arbitrary normal point. Normal values are shown as green lines, whereas abnormal ones are red. The beta values for calcium oxalate and phosphate, uric acid and cystine are instantaneously calculated and reported on the graph. CONCLUSIONS: LithoRisk produces a complete, unique and easy to understand report that includes all relevant parameters, it therefore expresses the overall risk of stone formation. It requires the results of chemistry tests done on the same 24-h urine collection, and carried out using suitable preservatives. If the tests for unusual parameters, i.e. sulphate and ammonia, are unavailable, one can use default values with minimal alterations on beta calculation. In spite of being arbitrary, the normal thresholds values are based on widely accepted literature data. The risk profile recognises the most relevant abnormalities and enables the establishment of individual targets aimed at reducing the propensity towards stone formation.

Characterization of ligand sites on natural sediment particles.

Organic and inorganic ligand sites on sediment particles were alkalimetrically titrated using a glass electrode as indicating device. Data obtained for suspensions containing known masses of sediment were used to calculate the concentration of surface ligand sites and their stability constants for complex formation with proton and copper(II) ion. The relationship between the concentration of ligand sites and the concentrations of metals (Cd, Cr, Cu, Fe, Mn, Pb, and Zn) and of C, N, and S was used to try to discriminate between the contributions of organic and inorganic components to the total ligand capacity of the sediment. The reliability of the chemical model deduced from potentiometric data was checked by comparing calculated values for aqueous copper(II) as a function of pH with values experimentally determined via atomic absorption spectrometry. The procedure proposed might contribute to the modeling of sediment-contaminant interaction, providing information on the nature of the ligands involved.

Interaction of l-malic acid with alkaline metals and open chain polyammonium cations in aqueous solution.

This work reports a potentiometric, calorimetric and spectropolarimetric ultraviolet circular dichroism (UV/CD) study of the interaction of l-malic acid with alkaline metals or (poly)ammonium (methylamine, ethylenediamine, diethylenetriamine, triethylenetetramine, spermine, tetraethylenepentamine and pentaethylenehexamine) cations. Stability data (logK, DeltaG(0)) were obtained potentiometrically for the l-malic acid with (poly)ammonium cations systems; calorimetric measurements (25 degrees C) made it possible to obtain DeltaH(0) and TDeltaS(0) values for the complexes formed in the systems under examination. logK values calculated (for the reaction: H(i)A(i+)+H(j)L((j-z))=ALH(r)((i+j-z)), with r=i+j) range between 0.8 and 4.6, i.e., the interactions are from weak to fairly strong while maximum stability for each system is given by the species with the highest z(anion)xz(cation) (z=charge) value. Enthalpy changes associated with reactions H(n)A(n+)+L(2-)=ALH(n)((n-2)) and H(n)A(n+)+HL(-)=ALH(n+1)((n-1)) are always positive and increase progressively with n. The same is valid for T DeltaS(0) values, which indicate that these species are entropically stabilized, as expected for electrostatic interactions. It was verified that the UV/CD signal depends on both ionic medium and ionic strength value; for comparison, we used the l-malic acid signal recorded in tetramethylammonium chloride as baseline background salt (as in potentiometry). UV/CD spectra were recorded for solutions containing both cationic and anionic species. When the cation was a protonated polyamine, CD spectra calculations were performed for most stable ion pairs: the results show remarkable differences in Deltaepsilon (dm(3) mol(-1) cm(-1)) values at 205 nm (which is the l-malate UV/CD lambda(max)) between the chiral ligand and its complex with a polyamine.

Urine saturation with calcium salts in normal subjects and idiopathic calcium stone-formers estimated by an improved computer model system.

The state of saturation of urine with calcium salts has been estimated by means of a computer model system whose accuracy has been improved by the use of stability constants of 31 complexes which were re-determined at 37 degrees C and at the actual ionic strength of urine. The experimental determination of the concentration solubility products of calcium oxalate monohydrate (CaOx) and of calcium hydrogen phosphate dihydrate (bsh) allows an expression of the saturation degree as free concentration product ratio beta CaOx and beta bsh. Morning urine samples from 50 healthy controls and 50 idiopathic calcium stone-formers and 24 h urines from 40 normal subjects and 192 stone-formers, taking normal diet were investigated by this technique. From our results urine supersaturation with calcium oxalate salts seems to play an important role in calcium stone disease. Hypercalciuria and hyperoxaluria seem to be the main pathological features in this regard. The data concerning beta bsh values have not confirmed previous reports in which this parameter was found to be increased in stone-formers.

Critical evaluation of various forms of therapy for idiopathic calcium stone disease.

The results are presented of the dietary management, alone or in association with thiazides and/or allopurinol, evaluated in 143 idiopathic calcium stone formers after a mean follow-up of 18 months. Diet alone proved to be effective in the prevention of stone relapses. The addition of thiazide and/or allopurinol provided mild improvements of urine environment but seemed to give no further clinical benefits irrespective of underlying metabolic abnormalities.

Serum calcium oxalate saturation in patients on maintenance haemodialysis for primary hyperoxaluria or oxalosis-unrelated renal diseases.

1. The serum oxalate concentration rises in chronic renal failure and it is only partially eliminated by regular dialysis treatment. However, the recent literature is not conclusive on whether progressive oxalate retention and secondary oxalosis should be expected in patients on regular dialysis treatment. 2. To further investigate this, we have estimated the state of saturation with respect to calcium oxalate monohydrate in plasma ultrafiltrates from 28 patients on maintenance haemodialysis and eight healthy control subjects, matched for sex and age. Five patients had type I primary hyperoxaluria and histologically proven oxalosis, whereas 23 had oxalosis-unrelated renal diseases. Dialysis efficiency was quantified as the KdTd/V of urea. Samples were obtained from each patient before, immediately after and 48 h after a dialysis session. Fasting samples were obtained from the control subjects. Oxalate was determined in both plasma ultrafiltrates and the whole dialysate by ion-exchange chromatography, after a non-delayed and [14C]oxalate-recovery-controlled procedure. The state of saturation with calcium oxalate monohydrate was estimated by means of a computer system which solved the interactions among 45 complex species. 3. The fasting plasma oxalate concentration (means +/- SD) in ultrafiltrates from healthy subjects was 3.8 +/- 1.5 (range 1.4-5.8) mumol/l, and the state of saturation with calcium oxalate monohydrate was 0.096 +/- 0.04.(ABSTRACT TRUNCATED AT 250 WORDS)