scholarly journals Formation of mono- and binuclear neodymium(iii)–gluconate complexes in aqueous solutions in the pH range of 2–8

2017 ◽  
Vol 46 (18) ◽  
pp. 6049-6058 ◽  
Author(s):  
Bence Kutus ◽  
Norbert Varga ◽  
Gábor Peintler ◽  
Alexandru Lupan ◽  
Amr A. A. Attia ◽  
...  

The structure and stability constants of four mononuclear and two, so far unknown and highly stable binuclear complexes have been determined.

Molecules ◽  
2019 ◽  
Vol 24 (11) ◽  
pp. 2098 ◽  
Author(s):  
Matteo Savastano ◽  
Carla Bazzicalupi ◽  
Giovanni Ferraro ◽  
Emiliano Fratini ◽  
Paola Gratteri ◽  
...  

The Zr4+ complexes with desferrioxamine (H3DFO) and its derivatives are the only 89Zr-based imaging agents for proton emission tomography (PET) that have been used so far in clinical trials. Nevertheless, a complete speciation of the Zr4+/H3DFO system in solution has never been performed and the stability constants of the relevant complexes are still unknown. Here we report, for the first time, the speciation of this system in water, performed by potentiometric titrations, and the determination of the stability constants of all complexes formed in the pH range 2.5–11.5. Surprisingly, although desferrioxamine gives rise to very stable 1:1 complexes with Zr4+ (logK = 36.14 for Zr4+ + DFO3− = [ZrDFO]+), 2:2 and 2:3 ones are also formed in solution. Depending on the conditions, these binuclear complexes can be main species in solution. These results were corroborated by small-angle X-ray scattering (SAXS) and MALDI mass spectrometry analyses of complex solutions. Information on complex structures was obtained by means of density functional theory (DFT) calculations.


2014 ◽  
Vol 13 (1) ◽  
Author(s):  
Dariusz Wyrzykowski ◽  
Joanna Pranczk ◽  
Dagmara Jacewicz ◽  
Aleksandra Tesmar ◽  
Bogusław Pilarski ◽  
...  

AbstractA potentiometric titration method (PT) and a stopped-flow kinetic technique monitored by a UV−Vis spectroscopy have been used to characterize the stability of series of Co(II)- and Ni(II)-thiodiacetato complexes, M(TDA), in the presence of 1,10-phenanthroline (phen) or 2,2’-bipyridine (bipy) in aqueous solutions. The stability constants of the binary (1:1), ternary (1:1:1) as well as the resulting hydroxo complexes were evaluated and compared to the corresponding oxydiacetate complexes. Based on the species distribution as a function of pH the relative predominance of the species in the system over a pH range was discussed. Furthermore, the kinetic measurements of the substitution reactions of the aqua ligands to phen or bipy in the coordination sphere of the binary complexes M(TDA) were performed in the 288–303 K temperature range, at a constant concentration of phen or bipy and at seven different concentrations of the binary complexes (0.2–0.5 mM). The kinetic stability of the M(TDA) complexes was discussed in relation to the experimental conditions and the kind of the auxiliary ligands (phen/bipy). Moreover, the influence of the type of primary ligand (thiodiacetate/oxydiacetate) on the substitution rate of the auxiliary ligands was also compared.


1978 ◽  
Vol 33 (3) ◽  
pp. 293-299 ◽  
Author(s):  
Joachim Stauff ◽  
Wolfgang Jaeschke

Abstract The reactions of diluted aqueous solutions of SO2 resp. HSO3-ions with MnO4-or Ce4+ ions in the pH range 1-4 produce chemiluminescence in the spectral region of 450-600 nm. Measurements of the time course of the light emission and their simulation on an analog computer led to a reaction scheme in which a recombination product of primarily formed HSO3 radicals -of a lifetime of about 1 second -appears as precursor of electronically excited SO2 molecules. The participation of singlet oxygen can be excluded because at least the reaction with Ce4+ ions proceeds also in the absence of oxygen.


Soft Matter ◽  
2021 ◽  
Author(s):  
Bing Jiang ◽  
Yu Liu ◽  
Linlin Zhao ◽  
Li Zhao ◽  
Ce Wang ◽  
...  

Here we present a pH-responsive self-assembly based on a β-cyclodextrin (β-CD) derivative bearing a dansyl terminus (βCD-C6-Dns). Vesicular structures were formed over the entire studied pH range (8.5-0.7); however, the...


1968 ◽  
Vol 21 (3) ◽  
pp. 641 ◽  
Author(s):  
RS Saxena ◽  
KC Gupta ◽  
ML Mittal

Potentiometric and conductometric studies of the nickel-thiomalic acid system, in aqueous medium of 0. lM KNO3, reveal the formation of two complexes; one light violet 1 : 1 predominating at pH 6.5-7.5 and another deep violet 1 : 2 in the pH range 8.5-10.0. The stability constants of the complexes formed have been determined by applying Calvin and Melchior's extension of Bjerrum's method at three different temperatures and were further refined by using alternative methods. The logK values (final) for 1 : 1 and 1 : 2 complexes at 20, 25, and 30� have been found to be 7.86, 7.87, 7.96, and 6.24, 6.31, 6.39 respectively. The values of the overall changes in ΔG, ΔH, and ΔS accompanying the reaction have also been evaluated at 25� and found to be -19.31 kcal/mole, -8.77 kcal/mole, and +35.36 cal/deg respectively.


1992 ◽  
Author(s):  
Αναστασία Κοτρωναρου

The ultrasonic irradiation of para-nitrophenol, S(-II), and parathion is studied in aqueous solutions at 20 kHz and ~ 75 W-cnT2. Para-nitrophenol was degraded primarily by denitration and secondarily by ΌΗ radical attack to yield N 02, NO3, benzoquinone, hydroquinone, 4-nitrocatechol, formate and oxalate. These reaction products and the kinetic observations are consistent with a model involving high-temperature reactions of p-nitrophenol in the interfa.cia.1 region of cavitation bubbles. The average effective temperature of the interfacial region surrounding the cavitation bubbles was estimated to be T ~ 800 K. Ultrasonic irradiation of S(-II) is studied in aqueous solutions over the pH range 7 - 12. The reaction of HS“ with OH is the principal pathway for theoxidation of S(-II) at pH > 10; the oxidation products are SO2“, SO2", and S20 Upon prolonged sonication, SO2" is the only observed product. At pH < 8.5, thermal decomposition of H2S within or near collapsing cavitation bubbles becomes the important pathway and elemental sulfur is found as an additional product of the sonolysis of S(-II). The sonolytic oxidation of H2S at pH > 10 was successfully modeled with an aqueous-phase free-radical chemistry mechanism and assumingcontinuous and uniform ΌΗ input into solution from the imploding cavitation bubbles. Parathion degradation occurred primarily by enhanced hydrolysis and secondarily by direct ΌΗ radical attack.The effect of various physical and chemical parameters on sonolytic yields is examined. The observed effects are in qualitative agreement with the sonolysis mechanisms proposed for the chemicals of interest and the existing hydrodynamic theories of acoustic cavitation. The formation of iodine upon ultrasonic irradiation of potassium iodide solutions and the sonolysis of S(-II) are used as probes to compare the sonochemical efficiency of different experimental set-ups. This work elucidates the mechanisms of the ultrasonic decomposition of typical organic and inorganic pollutants. It is shown that ultrasound has the potential to become a viable alternative for the destruction of chemical contaminants in water and wastewater. The current limitation of sonolysis is its low energy utilization efficiency, but there is room for improvement by optimizing reactor design and physical/chemical operation conditions. This work offers some recommendations and insight in that respect.


1971 ◽  
Vol 49 (3) ◽  
pp. 375-383 ◽  
Author(s):  
A. D. Kirk ◽  
K. C. Moss ◽  
J. G. Valentin

The photolysis reactions of the complex ions [Cr(en)2ox]+ and [Cren(ox)2]− have been studied in the pH range 1 → 3 and at temperatures from 0 to 25 °C. It has been found that both ions photoaquate to a monodentate protonated ethylenediamine complex which then undergoes further aquation thermally with loss of the ethylenediamine ligand. Quantum yields for these aquations were measured for irradiation into the ligand field bands, the values obtained being 0.18 and 0.02, respectively. The results are discussed in terms of known empirical correlations for Cr(III) complexes. Assuming these reactions may occur from the 4T2g state as precursor, arguments are presented that the correlation between quantum yield and ΔE may depend on mixing of the 4T2g and 2Eg states, and its effect on the intersystem crossing rate constant.


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