Equilibrium constants of UO 2 2+ , Cu2+ with dicarboxylic acids in dioxane-water mixtures

1977 ◽  
Vol 86 (5) ◽  
pp. 497-501
Author(s):  
D N Shelke ◽  
D V Jahagirdar
2012 ◽  
Vol 10 (4) ◽  
pp. 1253-1261 ◽  
Author(s):  
Mohamed Shehate ◽  
Mohamed Shoukry ◽  
Mona Ragab

AbstractThe Pd(DMPA)Cl2 complex, where DMPA = N,N-dimethylaminoproylamine, was synthesized and characterized. The stoichiometry and stability constants of the complexes formed between various dicarboxylic acids and [Pd(DMPA)(H2O)2]2+ were investigated. The effect of solvent dielectric constant, chloride ion concentration of the medium and temperature on the stability constant of the cyclobutanedicaroxylic acid (CBDCA) complex was investigated. The equilibrium constants for the displacement of coordinated CBDCA by inosine, taken as an example of DNA constituents, were calculated. The results are expected to contribute to the chemistry of antitumour agents.


2020 ◽  
Vol 20 (21) ◽  
pp. 13131-13143
Author(s):  
Noora Hyttinen ◽  
Reyhaneh Heshmatnezhad ◽  
Jonas Elm ◽  
Theo Kurtén ◽  
Nønne L. Prisle

Abstract. We have used the COSMOtherm program to estimate activity coefficients and solubilities of mono- and α,ω-dicarboxylic acids and water in binary acid–water systems. The deviation from ideality was found to be larger in the systems containing larger acids than in the systems containing smaller acids. COnductor-like Screening MOdel for Real Solvents (COSMO-RS) underestimates experimental monocarboxylic acid activity coefficients by less than a factor of 2, but experimental water activity coefficients are underestimated more especially at high acid mole fractions. We found a better agreement between COSMOtherm-estimated and experimental activity coefficients of monocarboxylic acids when the water clustering with a carboxylic acid and itself was taken into account using the dimerization, aggregation, and reaction extension (COSMO-RS-DARE) of COSMOtherm. COSMO-RS-DARE is not fully predictive, but fit parameters found here for water–water and acid–water clustering interactions can be used to estimate thermodynamic properties of monocarboxylic acids in other aqueous solvents, such as salt solutions. For the dicarboxylic acids, COSMO-RS is sufficient for predicting aqueous solubility and activity coefficients, and no fitting to experimental values is needed. This is highly beneficial for applications to atmospheric systems, as these data are typically not available for a wide range of mixing states realized in the atmosphere, due to a lack of either feasibility of the experiments or sample availability. Based on effective equilibrium constants of different clustering reactions in the binary solutions, acid dimer formation is more dominant in systems containing larger dicarboxylic acids (C5–C8), while for monocarboxylic acids (C1–C6) and smaller dicarboxylic acids (C2–C4), hydrate formation is more favorable, especially in dilute solutions.


2009 ◽  
Vol 2009 ◽  
pp. 1-10 ◽  
Author(s):  
Eman Mohamed Shoukry

The[Pd(DEEN)Cl2]and[Pt(DEEN)Cl2]complexes were synthesized and characterized whereDEEN=N,N-diethylethylenediamine. The stoichiometry and stability of the complexes formed between various biologically relevant ligands (amino acids, peptides, DNA constituents and dicarboxylic acids) and[Pd(DEEN)(H2O)2]2+were investigated at37∘Cand 0.16 M ionic strength. The stability constant of the complexes formed in solution were determined and the binding centres of the ligands were assigned. The concentration distribution diagrams of the complexes were evaluated The equilibrium constants for the displacement of representative coordinated ligands such as inosine, glycine or methionine by cysteine were calculated and the concentration distribution diagrams of the various species were evaluated. The kinetics of base hydrolysis of free and coordinated S-methylcysteine methyl ester was investigated. The mechanism of hydrolysis was discussed.


2020 ◽  
Author(s):  
Noora Hyttinen ◽  
Reyhaneh Heshmatnezhad ◽  
Jonas Elm ◽  
Theo Kurtén ◽  
Nønne L. Prisle

Abstract. We have used the COSMOtherm program to estimate activity coefficients and solubilities of mono- and α, ω-dicarboxylic acids, and water in binary acid-water systems. The deviation from ideality was found to be larger in the systems containing larger acids than in the systems containing smaller acids. We found a better agreement between estimated and experimental activity coefficients of monocarboxylic acids when the water clustering with a carboxylic acid and itself was taken into account using the dimerization, aggregation and reaction extension (COSMO-RS-DARE) of COSMOtherm. Based on effective equilibrium constants of different clustering reactions in the binary solutions, acid dimer formation is more dominant in systems containing larger dicarboxylic acids (C5–C8), while for monocarboxylic acids (C1–C6) and smaller dicarboxylic acids (C2–C4), hydrate formation is more favorable, especially in dilute solutions.


1974 ◽  
Vol 143 (3) ◽  
pp. 541-553 ◽  
Author(s):  
Terrance G. Owen ◽  
Peter W. Hochachka

1. Mitochondrial and supernatant aspartate transaminases (EC 2.6.1.1) and supernatant alanine transaminase (EC 2.6.1.2) were purified 89-, 204- and 240-fold respectively, from dolphin muscle. Starch-gel electrophoresis of crude and purified preparations revealed that all three enzymes exist as single forms. 2. Km values of α-oxoglutarate, alanine, pyruvate and glutamate for the alanine transaminase were 0.45, 8.2, 0.87 and 15mm respectively. For the aspartate transaminases, the Km values of α-oxoglutarate, aspartate, oxalacetate and glutamate were 0.76, 0.50, 0.10 and 9.4mm respectively, for the mitochondrial form and 0.13, 2.4, 0.06 and 3.2mm respectively, for the supernatant form. 3. In all cases, as the assay pH value was decreased from pH7.3, the Km values of the α-oxo acids decreased whereas those of the amino acids increased. 4. The apparent equilibrium constants for the aspartate transaminases were independent of pH. These values were 9.2 and 6.8 for the mitochondrial and supernatant forms respectively, where [Formula: see text] 5. Studies of the inhibition of the aspartate transaminases by dicarboxylic acids indicated that these enzymes may be controlled by pools of metabolic intermediates. 6. Three key roles are suggested for the transaminases in the energy metabolism of the diving animal. First, it is believed that a combined action of the transaminases could enhance energy production during hypoxia by providing (a) fumarate from aspartate for the ATP-producing reversal of succinate dehydrogenase, and (b) α-oxoglutarate from glutamate for the GTP-producing succinyl thiokinase reaction. Secondly, diving mammals probably accumulate more NADH than other mammals during hypoxia. The aspartate transaminases seem particularly well suited for restoring and maintaining redox balance via the malate–aspartate cycle after aerobic metabolism is resumed. Finally, since the preferred fuel for aerobic work is fat, the combined reactions of the transaminases could be instrumental in providing increased supplies of oxaloacetate for sparking the tricarboxylic acid cycle.


2019 ◽  
Author(s):  
Mohammad Mosharraf Hossain ◽  
Joshua Atkinson ◽  
Scott Hartley

Dissipative (nonequilibrium) assembly powered by chemical fuels has great potential for the creation of new adaptive chemical systems. However, while molecular assembly at equilibrium is routinely used to prepare complex architectures from polyfunctional monomers, species formed out of equilibrium have, to this point, been structurally very simple. In most examples the fuel simply effects the formation of a single transient covalent bond. Here, we show that chemical fuels can assemble bifunctional components into macrocycles containing multiple transient bonds. Specifically, dicarboxylic acids give aqueous dianhydride macrocycles on treatment with a carbodiimide. The macrocycle is assembled efficiently as a consequence of both fuel-dependent and -independent mechanisms: it undergoes slower decomposition, building up as the fuel recycles the components, and is a favored product of the dynamic exchange of the anhydride bonds. These results create new possibilities for generating structurally sophisticated out-of-equilibrium species.


2019 ◽  
Author(s):  
Mohammad Mosharraf Hossain ◽  
Joshua Atkinson ◽  
Scott Hartley

Dissipative (nonequilibrium) assembly powered by chemical fuels has great potential for the creation of new adaptive chemical systems. However, while molecular assembly at equilibrium is routinely used to prepare complex architectures from polyfunctional monomers, species formed out of equilibrium have, to this point, been structurally very simple. In most examples the fuel simply effects the formation of a single transient covalent bond. Here, we show that chemical fuels can assemble bifunctional components into macrocycles containing multiple transient bonds. Specifically, dicarboxylic acids give aqueous dianhydride macrocycles on treatment with a carbodiimide. The macrocycle is assembled efficiently as a consequence of both fuel-dependent and -independent mechanisms: it undergoes slower decomposition, building up as the fuel recycles the components, and is a favored product of the dynamic exchange of the anhydride bonds. These results create new possibilities for generating structurally sophisticated out-of-equilibrium species.


Author(s):  
N. N. Loy ◽  
S. N. Gulina

The effect of presowing seed treatment on various concentrations of dicarboxylic (organic) acids on the sowing characteristics of spring barley has been studied. Seeds were treated with organic acids obtained by exposing cuttings to the radiation with a dose of 100 kGy and consequent hydrolysis, in concentrations: 1•10-7 %; 1•10-9; 1•10-11; 1•10-13 and 1•10-15 % on a laboratory rotary machine RVO-64 for one day before laying for germination. Distilled water was used for the control case. The rate of application of the working solution calculated as 10 liters / ton of seeds. Seeds were germinated in filter paper rolls in accordance with GOST 12038-84 requirements. The temperature was maintained at +24 ° C in the thermostat where the glasses with rolls were placed. For determination of germinative power and laboratory germination the sprouted seeds were evaluated after three and seven days, respectively. In laboratory experiments it was established that the treatment of barley seeds of varieties Zazersky 85, Nur and Vladimir with organic acids (OK) in different concentrations had both a stimulating and a negative effect. On the Zazersky 85 variety, in variants with acid concentrations of 1•10-9 and 1•10-11, an increase in germination energy (EP) by 2-4% and a significant decrease (by 3-4%) of laboratory germination (LV) of barley seeds were noted. On the Nur variety, the increase in EP was observed at 4% (concentration 1•10-11), LV and seed growth force (CPC) by 2-7% at a concentration of 1•10-7 and in the dose range 1•10-11 - 1•10-14 compared to the control values. On the grade of Vladimir, an increase in EP, LV, and CPC was found to increase by 1-6% at concentrations OK 1•10-7 and 1•10-13. It was shown that the treatment of seeds with acids led to an increase in the length of the germ in all studied varieties (by 3-9%) and dry biomass of 7-day-old seedlings - by 3-6%. Consequently, the treatment of seeds with a mixture of dicarboxylic acids has a stimulating effect on the sowing quality of spring barley.


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