Valorization of Cork Using Subcritical Water

Granulated cork was submitted to subcritical water extraction/hydrolysis in a semi-continuous reactor at temperatures in the range of 120–200 °C and with a constant pressure of 100 bar. The influence of temperature on the composition of the cork extracts obtained was assessed—namely, their content of carbohydrates and phenolics. The extraction yield increased with the temperature, and this was associated with the decrease in the dielectric constant of water and the increase in its ionic product. Extracts composed of up to 36% phenolics were obtained at temperatures of up to 120 °C, with an antioxidant activity only two times lower than that of pure gallic acid, but in low amounts. Assays at higher temperatures generated extracts richer in carbohydrates and with a phenolics content of ca. 20 wt.% in comparatively far higher amounts. Neither the amount of suberin nor its structure were affected by the subcritical water treatment.

Applied aspects of acid-base interactions and modelling equilibrium concentrations in two-component acid mixtures

Fundamental and applied research into aqueous and non-aqueous solutions of strong and weak electrolytes remains to be highly relevant, which fact is confirmed by a large number of Russian and foreign publications. In almost all such publications, acid-base interactions are considered exclusively with regard to changes in hydrogen ion concentrations. However, the ionic strength of solutions is determined by all ions present in the system, the concentration of which varies during interactions. This is particularly true for potentiometric titration of strong and weak electrolytes not only in aqueous, but also in more complex non-aqueous solutions, which differ significantly in their basic properties (dielectric constant, ionic product, dipole moment, viscosity, etc.). In the study of equilibria, it is more feasible to develop model representations that would greatly simplify and facilitate the computation and evaluation of certain properties of the system under consideration. In this work, acid-base interactions are presented in the form of equations based on mass action laws and those describing equilibrium processes, solvent ionic product, electroneutrality and material balance in electrolyte systems. The proposed equations consider the effect of the concentrations of all charged particles in the system (not only of hydrogen ions – pH) on the ionic strength of the solution, activity coefficients and, as a consequence, the thermodynamic dissociation constant. In addition, these equations allow the dependence between the equilibrium concentrations of all charged particles and the solution acidity determined by the potentiometric method to be expressed in convenient and objective logarithmic coordinates, thus facilitating estimation of the concentration of all particles at any moment of titration.

The HNO− radical anion: A proposed intermediate in diazeniumdiolate synthesis using nitric oxide and alkoxides

The strategy of synthesizing diazeniumdiolates (X–N(O)=NO−) through the coexistence of nitric oxide and alkoxides (RO−) was introduced by Wilhelm Traube 120 years ago. Today, despite the wide use of diazeniumdiolate derivatives to release nitric oxide in the treatment of cancer, the first step of the reaction mechanism for diazeniumdiolate synthesis remains a mystery and is thought to be complex. We have studied the gas-phase reactions of nitric oxide with alkoxides at room temperature. An electron-coupled hydrogen transfer is observed, and the radical anion HNO− is the only ionic product in these reactions. HNO− can further react with nitric oxide to form N2O and HO−.

The Importance of the Ionic Product for Water to Understand the Physiology of the Acid-Base Balance in Humans

Human plasma is an aqueous solution that has to abide by chemical rules such as the principle of electrical neutrality and the constancy of the ionic product for water. These rules define the acid-base balance in the human body. According to the electroneutrality principle, plasma has to be electrically neutral and the sum of its cations equals the sum of its anions. In addition, the ionic product for water has to be constant. Therefore, the plasma concentration of hydrogen ions depends on the plasma ionic composition. Variations in the concentration of plasma ions that alter the relative proportion of anions and cations predictably lead to a change in the plasma concentration of hydrogen ions by driving adaptive adjustments in water ionization that allow plasma electroneutrality while maintaining constant the ionic product for water. The accumulation of plasma anions out of proportion of cations induces an electrical imbalance compensated by a fall of hydroxide ions that brings about a rise in hydrogen ions (acidosis). By contrast, the deficiency of chloride relative to sodium generates plasma alkalosis by increasing hydroxide ions. The adjustment of plasma bicarbonate concentration to these changes is an important compensatory mechanism that protects plasma pH from severe deviations.