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51.
Kavosh Majlesi Clemente Bretti Rosalia Maria Cigala Concetta De Stefano Kimia Majlesi Silvio Sammartano 《Journal of solution chemistry》2018,47(3):528-543
A potentiometric method has been used for the determination of the protonation constants of N-(2-hydroxyethyl)iminodiacetic acid (HEIDA or L) at various temperatures 283.15?≤?T/K?≤?383.15 and different ionic strengths of NaCl(aq), 0.12?≤?I/mol·kg?1?≤?4.84. Ionic strength dependence parameters were calculated using a Debye–Hückel type equation, Specific Ion Interaction Theory and Pitzer equations. Protonation constants at infinite dilution calculated by the SIT model are \( \log_{10} \left( {{}^{T}K_{1}^{\text{H}} } \right) = 8.998 \pm 0.008 \) (amino group), \( \log_{10} \left( {{}^{T}K_{2}^{\text{H}} } \right) = 2.515 \pm 0.009 \) and \( \log_{10} \left( {{}^{T}K_{3}^{\text{H}} } \right) = 1.06 \pm 0.002 \) (carboxylic groups). The formation constants of HEIDA complexes with sodium, calcium and magnesium were determined. In the first case, the formation of a weak complex species, NaL, was found and the stability constant value at infinite dilution is log10KNaL?=?0.78?±?0.23. For Ca2+ and Mg2+, the CaL, CaHL, CaL2 and MgL species were found, respectively. The calculated stability constants for the calcium complexes at T?=?298.15 K and I?=?0.150 mol·dm?3 are: log10βCaL?=?4.92?±?0.01, log10βCaHL?=?11.11?±?0.02 and \( \log_{10} \beta_{\text{Ca{L}}_{2}} \)?=?7.84?±?0.03, while for the magnesium complex (at I?=?0.176 mol·dm?3): log10βMgL?=?2.928?±?0.006. Protonation thermodynamic functions have also been calculated and interpreted. 相似文献
52.
Diphenylcyclopropenone(1) reacts with a variety of thiopseudoureas to eventually afford dihydrouracils 相似文献
53.
Francesco Crea Concetta De Stefano Giuseppe Manfredi Silvio Sammartano 《Journal of Molecular Liquids》2010,151(2-3):138-144
The interactions of two high molecular weight polycarboxylic ligands [polyacrylic-co-maleic, MW = 70 kDa, and poly(methyl vinyl ether-co-maleic acid), MW = 15 kDa] with some polyamines [1,4-diaminobutane (or putrescine), histamine and poly(allyl)amine, MW = 15 kDa] were studied, at t = 25 °C and at low ionic strength (I = 0.015 mol L? 1) by potentiometric measurements. For all investigated systems, the formation of (am)(L)Hi species was found (am = amine, L = polycarboxylic ligand, i = 1…4); the stability of polyammonium–polycarboxylate complexes is fairly high and the formation percentage of most species reaches ~ 90% in the experimental conditions (mmolar concentration of reactants). The dependence on temperature and ionic strength of the stability of polyamine–polycarboxylate species was studied using some semiempirical equations and enthalpy data for the protonation of both components. The sequestering ability of polyelectrolytes towards amines was modeled by a sigmoid Boltzman type equation and was defined by calculating the parameter pL50 (the total ligand concentration, as ? log CL, able to bind 50% of cation); this parameter gives an objective representation of this ability. The dependence of pL50 on pH, ionic strength and temperature was studied too. 相似文献
54.
Berto S Crea F Daniele PG De Stefano C Prenesti E Sammartano S 《Annali di chimica》2006,96(7-8):399-420
In this paper we report the results of an investigation performed by potentiometric (H+-glass electrode) and visible spectrophotometric measurements on the interaction of UO2(2+) ion towards some carboxylic ligands (acetate, malonate, succinate, azelate). The measurements were carried out at T= 25 degrees C in different ionic media (KNO3 and NaCl) at different ionic strengths (0.1 < or = I/mol L(-1) < or = 1.0, NaCl; I/mol L(-1) = 0.1, KNO3). The dependence on ionic strength of formation constants was taken into account by using both a simple Debye-Hückel type equation and the SIT (Specific ion Interaction Theory) approach. Different speciation models (depending on concentration of reagents, ionic strength, pH-range) both for different carboxylates and different ionic media have been obtained. Linear combinations between formation constants, stoichiometric coefficients and length of alkyl chain of dicarboxylates have been observed and predicted formation constants at I= 0 mol L(-1) are reported for the interaction of UO2(2+) with HOOC-(CH2)n-COOH with 1 < or = n < or = 7. Finally, a visible absorption spectrum for each complex reaching a significant percentage of formation in solution (KNO3 medium) has been calculated to characterise the compounds found by pH-metric refinement. 相似文献
55.
An efficient and low-cost protocol for the manual synthesis of Peptide Nucleic Acids is reported here. The protocol relies on coupling reactions carried out with 2.5 equiv of PNA monomers activated with HOBT/HBTU, in the presence of pyridine/NMM. The protocol has been tested on four PNA oligomers with a length ranging from 9 to 12 bases and a purine content up to 67%. 相似文献
56.
Concetta De Stefano Ottavia Giuffrè Alberto Pettignano Silvio Sammartano 《Journal of solution chemistry》2003,32(11):967-976
Enthalpies of protonation of polyacrylates and polymethacrylates with different molecular weights in aqueous NaCl solutions, 0 I 2 mol-L–1 were determined by titration calorimetry at 25°C. H values are dependent on both the neutralization degree, , and the molecular weight of polyacids. T S of protonation was obtained using pK values already reported and the present H results. Empirical equations for the dependence on I, , and molecular weight are reported for both H and T S. 相似文献
57.
Bruzzoniti MC Andrensek S Novic M Perrachon D Sarzanini C 《Journal of chromatography. A》2004,1034(1-2):243-247
This work is an upgrade of a previously developed method (J. Chromatogr. A 884 (2000) 251] for epichlorohydrin determination by ion chromatography (IC) and conductivity detection. Here, an ion chromatography-mass spectrometry (IC-MS) coupling has been employed for the separation and the identification of products of epichlorohydrin when reacted with the nucleophilic agent SO3(2-). The high capacity column (IonPac AS11-HC) used for separation provided good resolution. This allowed evaluation of the IC behavior and mass spectrometric identification of epichlorohydrin sulfite derivatives. By using atmospheric pressure interfaces (ESI and APCI) the following species were tentatively identified: 2,3-dihydroxy-1-propanesulfonic, 2,3-epoxy-1-propanesulfonic,1,3-dihydroxy-2-propanesulfonic and 3-oxetanesulfonic acids and 2-hydroxy-1,3-propanedisulfonic acid (or its isomer 3-hydroxy-1,2-propanedisulfonic acid). The study showed that chlorine atoms are displaced from epichlorohydrin during the reaction, while mass spectrometry confirmed that none of the products formed contains chlorine atoms. 相似文献
58.
Zuccarello F Buemi G Gandolfo C Contino A 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2003,59(1):139-151
A conformational study on Barbituric (BA) and Thiobarbituric (TBA) acids was performed at ab initio MP2/6-31G** level on the neutral, protonated, mono- and di-anionic forms. Acid-base equilibria were studied by comparing the electronic transitions evaluated for the most stable conformations and the experimental spectra at different pH values. The electronic transitions were obtained through the ZINDO approach. 相似文献
59.
Pier G. Daniele Alessandro De Robertis Concetta De Stefano Silvio Sammartano 《Journal of solution chemistry》1989,18(1):23-36
Imidazole protonation constants were determined potentiometrically, using a (H+)-glass electrode, in LiCl, NaCl, KCl, CaCl2, MgCl2, tetramethylammonium (Me4N-) iodide and chloride, Et4N-, Pr4N- and Bu4N-iodides. Salt effects were tentatively explained by assuming that complexes [H(Im)X]o (Im = imidazole, X–=Cl– or I–), [M(Im)]2+ (M2+=Mg2+ or Ca2+) and [A(Im)]+ (A+ = tetraalkylammonium cation) were formed in solution. Calcium(II)-selective electrode measurements confirmed our hypothesis about the formation of the Ca2+-imidazole complex. The reliability of the complex formation model is discussed on the basis of its self consistency and in light of previous results. 相似文献
60.
Alessandro de Robertis Concetta de Stefano Rosario Scarcella Carmelo Rigano 《Thermochimica Acta》1984,80(2):197-208
The formation constants for the complexes Mg2+ -, Ca2+ -, Sr2+ - and Ba2+ - succinate (succ2−) have been determined by potentiometric measurements, in aqueous solution, at different temperatures and ionic strengths. The species [M(succ)]0 and [M(succ)H]+ were found for all systems. For the stability constant the ionic strength dependence has been found, and general parameters for the relation log β = f(I) have been obtained. From the temperature dependence of stability constants ΔH values have been deduced. The procedure adopted in calculating all the thermodynamic parameters for the systems under study, where weak complexes are formed, is discussed. The stability of the complexes follows the order Mg < Ca Sr ≈ Ba. 相似文献