Formation of quasi-free and bubble positronium states in water and aqueous solutions

It is shown that in aqueous solutions a positronium atom is first formed in the quasi-free state, and, after 50-100 ps, becomes localized in a nanobubble. Analysis of the annihilation spectra of NaNO3 aqueous solutions shows that the hydrated electron is not involved in the positronium (Ps) formation

Activity of water in aqueous systems; A frequently neglected property

In this critical review, the significance of the term ‘activity’ is examined in the context of the properties of aqueous solutions. The dependence of the activity of water(ℓ) at ambient pressure and 298.15 K on solute molality is examined for aqueous solutions containing neutral solutes, mixtures of neutral solutes and salts. Addition of a solute to water(ℓ) always lowers its thermodynamic activity. For some solutes the stabilisation of water(ℓ) is less than and for others more than in the case where the thermodynamic properties of the aqueous solution are ideal. In one approach this pattern is accounted for in terms of hydrate formation. Alternatively the pattern is analysed in terms of the dependence of practical osmotic coefficients on the composition of the aqueous solution and then in terms of solute–solute interactions. For salt solutions the dependence of the activity of water on salt molalities is compared with that predicted by the Debye–Hückel limiting law. The analysis is extended to consideration of the activities of water in binary aqueous mixtures. The dependence on mole fraction composition of the activity of water in binary aqueous mixtures is examined. Different experimental methods for determining the activity of water in aqueous solutions are critically reviewed. The role of water activity is noted in a biochemical context, with reference to the quality, stability and safety of food and finally with regard to health science.

A New Strategy to Stabilize Oxytocin in Aqueous Solutions: I. The Effects of Divalent Metal Ions and Citrate Buffer

In the current study, the effect of metal ions in combination with buffers (citrate, acetate, pH 4.5) on the stability of aqueous solutions of oxytocin was investigated. and divalent metal ions (Ca2+, Mg2+, and Zn2+) were tested all as chloride salts. The effect of combinations of buffers and metal ions on the stability of aqueous oxytocin solutions was determined by RP-HPLC and HP-SEC after 4 weeks of storage at either 4°C or 55°C. Addition of sodium or potassium ions to acetate- or citrate-buffered solutions did not increase stability, nor did the addition of divalent metal ions to acetate buffer. However, the stability of aqueous oxytocin in aqueous formulations was improved in the presence of 5 and 10 mM citrate buffer in combination with at least 2 mM CaCl2, MgCl2, or ZnCl2 and depended on the divalent metal ion concentration. Isothermal titration calorimetric measurements were predictive for the stabilization effects observed during the stability study. Formulations in citrate buffer that had an improved stability displayed a strong interaction between oxytocin and Ca2+, Mg2+, or Zn2+, while formulations in acetate buffer did not. In conclusion, our study shows that divalent metal ions in combination with citrate buffer strongly improved the stability of oxytocin in aqueous solutions

Dielectric relaxation of DNA aqueous solutions

We report on a detailed characterization of complex dielectric response of Na-DNA aqueous solutions by means of low-frequency dielectric spectroscopy (40 Hz - 110 MHz). Results reveal two broad relaxation modes of strength 20<\Delta\epsilon_LF<100 and 5<\Delta\epsilon_HF<20, centered at 0.5 kHz<\nu_LF<70 kHz and 0.1 MHz<\nu_HF<15 MHz. The characteristic length scale of the LF process, 50<L_LF<750nm, scales with DNA concentration as c_DNA^{-0.29\pm0.04} and is independent of the ionic strength in the low added salt regime. Conversely, the measured length scale of the LF process does not vary with DNA concentration but depends on the ionic strength of the added salt as I_s^{-1} in the high added salt regime. On the other hand, the characteristic length scale of the HF process, 3<L_HF<50 nm, varyes with DNA concentration as c_DNA^{-0.5} for intermediate and large DNA concentrations. At low DNA concentrations and in the low added salt limit the characteristic length scale of the HF process scales as c_DNA^{-0.33}. We put these results in perspective regarding the integrity of the double stranded form of DNA at low salt conditions as well as regarding the role of different types of counterions in different regimes of dielectric dispersion. We argue that the free DNA counterions are primarily active in the HF relaxation, while the condensed counterions play a role only in the LF relaxation. We also suggest theoretical interpretations for all these length scales in the whole regime of DNA and salt concentrations and discuss their ramifications and limitations.Comment: 15 pages, 9 figure

Dyes adsorption from aqueous solutions by Chitosan

In this study the ability of chitosan to remove acid, basic, reactive and direct dyestuffs by adsorption was studied. The effect of several factors influencing dye adsorption such as dye concentration, grain size, pH and temperature were investigated. Desorption of dyes at different pH was also examined. It was shown that the adsorption capacities of chitosan were comparatively high for acid and direct dyes and that the adsorption was controlled by the acidity of the solution. The kinetics of adsorption were found to be of pseudo second order. Batch isotherm studies showed that adsorption of dyes from aqueous solution by chitosan was described by the Langmuir equation

A route to explain water anomalies from results on an aqueous solution of salt

In this paper we investigate the possibility to detect the hypothesized liquid-liquid critical point of water in supercooled aqueous solutions of salts. Molecular dynamics computer simulations are conducted on bulk TIP4P water and on an aqueous solution of sodium chloride in TIP4P water, with concentration c = 0.67 mol/kg. The liquid-liquid critical point is found both in the bulk and in the solution. Its position in the thermodynamic plane shifts to higher temperature and lower pressure for the solution. Comparison with available experimental data allowed us to produce the phase diagrams of both bulk water and the aqueous solution as measurable in experiments. Given the position of the liquid-liquid critical point in the solution as obtained from our simulations, the experimental determination of the hypothesized liquid-liquid critical point of water in aqueous solutions of salts appears possible.Comment: 5 pages, 6 figures. Accepted for publication on the Journal of Chemical Physics (2010)

Adhesion attenuation and enhancement in aqueous solutions

When two surfaces confine water layers between them at the nanoscale, the behaviour of these confined water molecules can deviate significantly from the behaviour of bulk water, and it could reflect on the adhesion of such surfaces. This study assesses the role of confined water layers on the adhesion of hydrophilic surfaces and how sensitive this adhesion is to the presence of contaminants. Our methodology used atomic force microscopy adhesion measurements, whereby an alumina-sputtered sphere-tipped cantilever was interacted versus a flat alumina single crystal. Testing was performed under immersed conditions using (i) water, (ii) water/dimethylformamide mixtures, (iii) water/ethanol mixtures, and (iv) water/formamide mixtures. These solutions were intended to assess the influence of dielectric constant, molecule size, and the number of hydrogen bonding opportunities available to molecules upon confinement between surfaces. It was found that dilute concentrations of ethanol and formamide decreased the adhesion. In contrast, the adhesion increased in the presence of dilute concentrations of dimethylformamide. The adhesion was attenuated by in excess of two orders of magnitude for high concentrations of the organic solutes

A study on the reaction between CO2 and alkanolamines in aqueous solutions

Literature data on the rates of reaction between CO2 and alkanolamines (MEA, DEA, DIPA, TEA and MDEA) in aqueous solution are discussed. These data induced us to carry out absorption experiments of CO2 into aqueous DEA, DIPA, TEA and MDEA solutions from which the respective rate constants\ud \ud The results for DEA and DIPA were analysed by means of a zwitterion-mechanism which was derived from the mechanism originally proposed by Danckwerts [1\ud \ud The reaction rate of CO2 with aqueous TEA and MDEA solutions shows a significant base catalysis effect which is also reported by Donaldson and Ngu

Supramolecular Complexation of \u3cem\u3eN\u3c/em\u3e-Alkyl- and \u3cem\u3eN\u3c/em\u3e,\u3cem\u3eN\u3c/em\u3e′-Dialkylpiperazines with Cucurbit[6]uril in Aqueous Solution and in the Solid State

Water seeds: Complex stoichiometry/composition and degree of oligomerization (oligomeric supramolecular complex formation) of cucurbit[6]uril (CB[6]) with N-alkyl- and N,N′-dialkylpiperazine were investigated in aqueous solutions by means of isothermal titration calorimetry (ITC), ESI-MS, NMR and light scattering measurements. Complex stoichiometry/composition and degree of oligomerization (oligomeric supramolecular complex formation) of cucurbit[6]uril (CB[6]) with N-alkyl- and N,N′-dialkylpiperazine were investigated in aqueous solutions by means of isothermal titration calorimetry (ITC), ESI-MS, NMR and light scattering measurements. It was found that the complex stability and the degree of oligomerization increase with elongating the alkyl chain attached to the piperazine core. X-ray crystallographic studies revealed a clear correlation between the structure of CB[6]–alkylpiperazine crystals obtained from aqueous solutions and the molecular weight/properties of host–guest oligomers existed in the solution as supramolecular “seeds” of crystal formation