Monitoring the Microscopic Molecular Mechanisms of Proton Transfer in Acid-base Reactions in Aqueous Solutions

2015 ◽  
Vol 55 (11-12) ◽  
pp. 1240-1251 ◽  
Author(s):  
Dina Pines ◽  
Erik T. J. Nibbering ◽  
Ehud Pines
2012 ◽  
Vol 66 (4) ◽  
pp. 182-186 ◽  
Author(s):  
Mateusz L. Donten ◽  
Joost VandeVondele ◽  
Peter Hamm

Author(s):  
Hyun-Wook Lee ◽  
Jill W. Verlander ◽  
Gary E Shull ◽  
Autumn N. Harris ◽  
I. David Weiner

The molecular mechanisms regulating ammonia metabolism are fundamental to acid-base homeostasis. Deleting the A splice variant of the Na⁺-bicarbonate cotransporter, electrogenic, isoform 1 (NBCe1-A) partially blocks the effect of acidosis to increase urinary ammonia excretion, and this appears to involve the dysregulated expression of ammoniagenic enzymes in the proximal tubule (PT) in the cortex, but not in the outer medulla (OM). A second NBCe1 splice variant, NBCe1-B, is present throughout the PT, including the OM, where NBCe1-A is not present. The current studies determined the effects of combined renal deletion of NBCe1-A and NBCe1-B on systemic and proximal tubule ammonia metabolism. We generated NBCe1-A/B deletion using Cre-loxP techniques and used Cre-negative mice as controls. Since renal NBCe1-A and NBCe1-B expression is limited to the proximal tubule, Cre-positive mice had proximal tubule NBCe1-A/B deletion (PT-NBCe1-A/B KO). While on basal diet, PT-NBCe1-A/B KO mice had severe metabolic acidosis, yet urinary ammonia excretion was not changed significantly. PT-NBCe1-A/B KO decreased expression of phosphate-dependent glutaminase (PDG) and phospho­enol­pyruvate carboxy­kinase (PEPCK) and increased expression of glutamine synthetase (GS), an ammonia recycling enzyme, in PT in both the cortex and OM. Exogenous acid-loading increased ammonia excretion in control mice, but PT-NBCe1-A/B KO prevented any increase. PT-NBCe1-A/B KO significantly blunted acid loading-induced changes in PDG, PEPCK, and GS expression in the proximal tubule in both the cortex and OM. We conclude that NBCe1-B, at least in the presence of NBCe1-A deletion, contributes to proximal tubule ammonia metabolism in the OM and thereby to systemic acid-base regulation.


Polyhedron ◽  
2019 ◽  
Vol 158 ◽  
pp. 117-124 ◽  
Author(s):  
Ákos Buckó ◽  
Bence Kutus ◽  
Gábor Peintler ◽  
István Pálinkó ◽  
Pál Sipos

Author(s):  
Oleg A. Petrov ◽  
Aleksandr S. Semeykin ◽  
Mariya V. Shilovskaya ◽  
Tatiana V. Lyubimova

The reaction of acid-base interaction of octa(4-tert-butylphenyl)tetrapyrazinophosphyrazine with pyridine, 2-methylpyridine, morhpoline, pipyridine, n-butylamine, tert-butylamine, diethylamine, triethylamine and dimethylsulfoxide in benzene was investigated. It is shown that the researched porphyrazine forms kinetically stable proton transfer complexes with pyridine, 2-methylpyridine, morpholine and dimethylsulfoxide. In benzene-base system an acid-base equilibrium between the molecular form of octa(4-tert-butylphenyl)tetrapyrazinoporphyrazine and its proton transfer complex was established. The interaction of substituted tetrapyrazinoporphyrazine with morpholine in benzene was revealed to be a kinetically controllable process which occurs with low reaction rate and high values of activation energy. Such values are not inherent to most of relatively simple liquid-phase acid-base systems. The kinetic equation of the process was found, and, based on the spectral changes accompanying the reaction, a cheme of two-stage process of proton transfer of NH-groups of octa(4-tert-butylphenyl)tetrapyrazinoporphyrazine to morpholine in benzene was proposed. A possible structure of proton transfer complex of octa(4-tert-butylphenyl)tetrapyrazinoporphyrazine with organic bases is shown. In these complexes the inner hydrogen atoms of the cycle, bonded with base molecules, lie under and above the plane of the molecule, and the proton transfer from acid to base is limited either by the H-complex or the ion-ion associates constituting an H-bonded ion pair. Depending on the proton accepting tendency of the base, the acid-base equilibrium can shift towards or away from the more or less polarized structure. It was revealed that in benzene - n-butylamine (tri-butylamine, diethylamine, triethylamine, pipyridine) system the acid-base interaction involving octa(4- tert-butylphenyl)tetrapyrazinoporphyrazine occurs incredibly fast, with rates not measurable by standard spectrophotography methods. The forming proton transfer complexes are highly labile due to concurrent proton reaction occurring, leading to the formation of dianion form of octa(4- tert-butylphenyl)tetrapyrazinoporphyrazine. This form undergoes spontaneous dissolution into low-molecular colorless products due to the lack of compensation of excess charge in the macrocycle.


2009 ◽  
Vol 74 (11-12) ◽  
pp. 1777-1789 ◽  
Author(s):  
Petr Zuman

There are two possibilities how to follow equilibria of organic compounds established in aqueous solutions using polarography: for very fast reactions, information can be obtained from shifts of half-wave potentials. For slowly established equilibria, the changes in the limiting current are followed. In both cases variation of the half-wave potentials or limiting currents with concentration of a reactant, present in excess, is followed. The types of reactions, which had been followed in this way, are as follows: hydration–dehydration equilibria, additions of hydroxide ion to carbonyl and nitroso compounds, the role of slowly established acid–base equilibria involving C-acids; further also reactions involving the addition of ammonia, primary amines, hydroxylamine, and hydrazine to carbonyl compounds.


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