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

Biomolecules ◽  
2021 ◽  
Vol 11 (9) ◽  
pp. 1312
Author(s):  
Antonio Gigliuto ◽  
Rosalia Maria Cigala ◽  
Anna Irto ◽  
Maria Rosa Felice ◽  
Alberto Pettignano ◽  
...  
Keyword(s):  
Divalent Cations ◽  
Formation Constants ◽  
Binuclear Complexes ◽  
Interaction Theory ◽  
Thermodynamic Investigation ◽  
Experimental Conditions ◽  
Complex Formation Constants ◽  
Specific Ion Interaction Theory ◽  
Speciation Model ◽  
Starting Solutions

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.

scholarly journals Understanding the Solution Behavior of Epinephrine in the Presence of Toxic Cations: A Thermodynamic Investigation in Different Experimental Conditions

Molecules ◽  
2020 ◽  
Vol 25 (3) ◽  
pp. 511 ◽  
Author(s):  
Francesco Crea ◽  
Concetta De Stefano ◽  
Anna Irto ◽  
Gabriele Lando ◽  
Stefano Materazzi ◽  
...  
Keyword(s):  
Ionic Strength ◽  
Complex Formation ◽  
Formation Constants ◽  
Titration Calorimetry ◽  
Interaction Theory ◽  
Thermodynamic Investigation ◽  
Experimental Conditions ◽  
Complex Formation Constants ◽  
Specific Ion Interaction Theory ◽  
Enthalpy Changes

The interactions of epinephrine ((R)-(−)-3,4-dihydroxy-α-(methylaminomethyl)benzyl alcohol; Eph−) with different toxic cations (methylmercury(II): CH3Hg+; dimethyltin(IV): (CH3)2Sn2+; dioxouranium(VI): UO22+) were studied in NaClaq at different ionic strengths and at T = 298.15 K (T = 310.15 K for (CH3)2Sn2+). The enthalpy changes for the protonation of epinephrine and its complex formation with UO22+ were also determined using isoperibolic titration calorimetry: ΔHHL = −39 ± 1 kJ mol−1, ΔHH2L = −67 ± 1 kJ mol−1 (overall reaction), ΔHML = −26 ± 4 kJ mol−1, and ΔHM2L2(OH)2 = 39 ± 2 kJ mol−1. The results were that UO22+ complexation by Eph− was an entropy-driven process. The dependence on the ionic strength of protonation and the complex formation constants was modeled using the extended Debye–Hückel, specific ion interaction theory (SIT), and Pitzer approaches. The sequestering ability of adrenaline toward the investigated cations was evaluated using the calculation of pL0.5 parameters. The sequestering ability trend resulted in the following: UO22+ >> (CH3)2Sn2+ > CH3Hg+. For example, at I = 0.15 mol dm−3 and pH = 7.4 (pH = 9.5 for CH3Hg+), pL0.5 = 7.68, 5.64, and 2.40 for UO22+, (CH3)2Sn2+, and CH3Hg+, respectively. Here, the pH is with respect to ionic strength in terms of sequestration.

scholarly journals 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

Molecules ◽  
2021 ◽  
Vol 26 (24) ◽  
pp. 7679
Author(s):  
Antonio Gigliuto ◽  
Rosalia Maria Cigala ◽  
Anna Irto ◽  
Maria Rosa Felice ◽  
Alberto Pettignano ◽  
...  
Keyword(s):  
Ionic Strength ◽  
Formation Enthalpy ◽  
Type Equation ◽  
Formation Constants ◽  
Common Species ◽  
Interaction Theory ◽  
Complex Formation Constants ◽  
Ternary Interactions ◽  
Wide Ph Range ◽  
Ph Range

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+.

Chemical speciation of environmentally significant metals with inorganic ligands. Part 5: The Zn2+ + OH–, Cl–, CO32–, SO42–, and PO43– systems (IUPAC Technical Report)

2013 ◽  
Vol 85 (12) ◽  
pp. 2249-2311 ◽  
Author(s):  
Kipton J. Powell ◽  
Paul L. Brown ◽  
Robert H. Byrne ◽  
Tamás Gajda ◽  
Glenn Hefter ◽  
...  
Keyword(s):  
Chemical Speciation ◽  
Formation Constants ◽  
Water Systems ◽  
Organic Ligands ◽  
Interaction Theory ◽  
Interaction Coefficients ◽  
Weakly Alkaline ◽  
Specific Ion Interaction Theory ◽  
Technical Report ◽  
Inorganic Ligands

The numerical modeling of ZnII speciation amongst the environmental inorganic ligands Cl–, OH–, CO32–, SO42–, and PO43– requires reliable values for the relevant stability (formation) constants. This paper compiles and provides a critical review of these constants and related thermodynamic data. It recommends values of log10βp,q,r° valid at Im = 0 mol·kg–1 and 25 °C (298.15 K), and reports the empirical reaction ion interaction coefficients, ∆ε, required to calculate log10βp,q,r values at higher ionic strengths using the Brønsted–Guggenheim–Scatchard specific ion interaction theory (SIT). Values for the corresponding reaction enthalpies, ∆rH, are reported where available. There is scope for additional high-quality measurements for the Zn2+ + H+ + CO32– system and for the Zn2+ + OH– and Zn2+ + SO42– systems at I > 0. In acidic and weakly alkaline fresh water systems (pH < 8), in the absence of organic ligands (e.g., humic substances), ZnII speciation is dominated by Zn2+(aq). In this respect, ZnII contrasts with CuII and PbII (the subjects of earlier reviews in this series) for which carbonato- and hydroxido- complex formation become important at pH > 7. The speciation of ZnII is dominated by ZnCO3(aq) only at pH > 8.4. In seawater systems, the speciation at pH = 8.2 is dominated by Zn2+(aq) with ZnCl+, Zn(Cl)2(aq), ZnCO3(aq), and ZnSO4(aq) as minor species. This behaviour contrasts with that for CuII and PbII for which at the pH of seawater in equilibrium with the atmosphere at 25 °C (log10 {[H+]/c°} ≈ 8.2) the MCO3(aq) complex dominates over the MCln(2–n)+ species. The lower stability of the different complexes of ZnII compared with those of CuII, PbII, and CdII is also illustrated by the percentage of uncomplexed M2+ in seawater, which is ca. 55, 3, 2, and 3.3 % of [MII]T, respectively.

scholarly journals Thermodynamic Study of Oxidovanadium(IV) with Kojic Acid Derivatives: A Multi-Technique Approach

2021 ◽  
Vol 14 (10) ◽  
pp. 1037
Author(s):  
Rosita Cappai ◽  
Guido Crisponi ◽  
Daniele Sanna ◽  
Valeria Ugone ◽  
Andrea Melchior ◽  
...  
Keyword(s):  
Complex Formation ◽  
Kojic Acid ◽  
Formation Constants ◽  
Biological Action ◽  
Binuclear Complexes ◽  
Complex Formation Equilibria ◽  
Complex Formation Constants ◽  
Coordination Model ◽  
Starting Point ◽  
Pharmacologically Active

The good chelating properties of hydroxypyrone (HPO) derivatives towards oxidovanadium(IV) cation, VIVO2+, constitute the precondition for the development of new insulin-mimetic and anticancer compounds. In the present work, we examined the VIVO2+ complex formation equilibria of two kojic acid (KA) derivatives, L4 and L9, structurally constituted by two kojic acid units linked in position 6 through methylene diamine and diethyl-ethylenediamine, respectively. These chemical systems have been characterized in solution by the combined use of various complementary techniques, as UV-vis spectrophotometry, potentiometry, NMR and EPR spectroscopy, ESI-MS spectrometry, and DFT calculations. The thermodynamic approach allowed proposing a chemical coordination model and the calculation of the complex formation constants. Both ligands L4 and L9 form 1:1 binuclear complexes at acidic and physiological pHs, with various protonation degrees in which two KA units coordinate each VIVO2+ ion. The joined use of different techniques allowed reaching a coherent vision of the complexation models of the two ligands toward oxidovanadium(IV) ion in aqueous solution. The high stability of the formed species and the binuclear structure may favor their biological action, and represent a good starting point toward the design of new pharmacologically active vanadium species.

Formation of CT complexes and electron transfer from excited molecules of anthracene derivatives to methylviologen in aqueous and micellar media

1987 ◽  
Vol 52 (7) ◽  
pp. 1658-1665
Author(s):  
Viktor Řehák ◽  
Jana Boledovičová
Keyword(s):  
Electron Transfer ◽  
Complex Formation ◽  
Fluorescence Quenching ◽  
Rate Constant ◽  
Formation Constants ◽  
Dynamic Quenching ◽  
Micellar Media ◽  
Complex Formation Constants ◽  
Anthracene Derivatives ◽  
Ct Complexes

Disodium 1,5- and 1,8-anthracenedisulphonate (ADS) and 9-acetylanthracene form coloured CT complexes with methylviologen (MV2+) in aqueous and micellar media. The complex formation constants and molar absorptivities were determined by the Benesi-Hildebrandt method. In the fluorescence quenching, its static component plays the major role. The dynamic quenching component is determined by the rate constant of electron transfer from the S1 state of ADS to MV2+.

scholarly journals The formation constants of ionomycin with divalent cations in 80% methanol/water

1991 ◽  
Vol 266 (13) ◽  
pp. 8336-8342
Author(s):  
M.K. Stiles ◽  
M.E. Craig ◽  
S.L. Gunnell ◽  
D.R. Pfeiffer ◽  
R.W. Taylor
Keyword(s):  
Divalent Cations ◽  
Formation Constants

Host–Guest interaction of pesticide bifenox with cyclodextrin molecules. An electrochemical study

2009 ◽  
Vol 74 (11-12) ◽  
pp. 1647-1664 ◽  
Author(s):  
Magdaléna Hromadová ◽  
Romana Sokolová ◽  
Lubomír Pospíšil ◽  
Štěpánka Lachmanová ◽  
Nicolangelo Fanelli ◽  
...  
Keyword(s):  
Complex Formation ◽  
Anion Radical ◽  
Formation Constants ◽  
Aprotic Solvents ◽  
Reduction Wave ◽  
Nitroaromatic Compound ◽  
Complex Formation Constants ◽  
Oh Groups ◽  
Stable Anion ◽  
Main Factor

The reduction of nitroaromatic compound bifenox (methyl 5-(2,4-dichlorophenoxy)-2-nitrobenzoate) was studied in aprotic solvents in the absence or presence of cyclodextrin (CD) molecules of different cavity sizes. βCD and γCD form complexes with bifenox in DMSO with the complex formation constants (5 ± 2) × 102 M–1 [βCD–bifenox] and (3 ± 1) × 102 M–1 [γCD–bifenox], respectively. Bifenox yields a relatively stable anion radical in dimethyl sulfoxide, which is further reduced at more negative potentials by an overall addition of three electrons and four protons to the corresponding phenylhydroxylamine. In the presence of βCD the first reduction wave of bifenox becomes irreversible, it is shifted towards more positive potentials and the uptake of more than one electron is observed (up to four electrons during the exhaustive electrolysis). The first reduction wave of bifenox is not affected by the addition of glucose confirming that a simple availability of protons from the OH groups is not the main factor in further transformation of anion radical in the presence of βCD. The complex formation with βCD facilitates the protonation and additionally protects the molecule from disintegration into 2,4-dichlorophenol. A yield of 2,4-dichlorophenol decreases in the order βCD, γCD and αCD, respectively.

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