Osmotic Properties of Aqueous Ionene Solutions

Arh, K.; Pohar, C.; Vlachy, Vojko

doi:10.1021/jp025858k

Cited by 50 publications

(96 citation statements)

References 42 publications

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“…These measurements indicate strong deviations from theoretical predictions based on the continuumsolvent models [3,4,14] of a polyelectrolyte solution. For example, the measured activity and osmotic coefficients are much lower than theoretically predicted [32,35], and the deviations are stronger for more hydrophobic 6,6 and 6,9 ionenes. The osmotic coefficients of ionene solutions with Br -ions as counterions were slightly (but significantly beyond the range of experimental uncertainty) lower than the corresponding chloride solutions.…”

Section: Osmotic Coefficientmentioning

confidence: 70%

“…In addition, they are excellent materials for studying the effects of polyion charge density and hydrophobicity on physicochemical properties. Ionene solutions have been characterized experimentally in several papers: Minakata and coworkers [32][33][34] measured the conductance and activity coefficients of 3,3; 4,5; 6,6; and 6,9 ionene solutions, while heats of dilution and osmotic coefficients were determined by Pohar and coworkers [13,35]. These measurements indicate strong deviations from theoretical predictions based on the continuumsolvent models [3,4,14] of a polyelectrolyte solution.…”

Section: Osmotic Coefficientmentioning

confidence: 99%

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Polyelectrolyte hydration: Theory and experiment

Vlachy

2008

Pure and Applied Chemistry

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A short review of recent theoretical and experimental advances in studies of polyelectrolyte solutions is presented. The focus is on ion-specific effects as revealed in measurements of osmotic pressure and enthalpy of dilution. We review the experimental results for two different polyelectrolyte systems: (i) salts of polyanetholesulfonic acid, and (ii) aliphatic ionenes (polycations) in aqueous solution with various counterions. A theoretical approach based on the extension of Wertheim's integral equation theory [J. Stat. Phys. 35, 19 (1984)] is used to analyze the experimental data. Preliminary results, based on the all-atom simulation of model 3,3 ionene oligomers, are discussed in the light of polyelectrolyte hydration.

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Section: Osmotic Coefficientmentioning

confidence: 70%

Section: Osmotic Coefficientmentioning

confidence: 99%

Polyelectrolyte hydration: Theory and experiment

Vlachy

2008

Pure and Applied Chemistry

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“…Recently, it was shown by chromatography that the molecular mass of 3,3-and 6,6-ionene bromides was 37 and 30 kDa, respectively [46]. The polyelectrolytic character of x, y-ionene solutions was previously confirmed by osmotic coefficient data [22], by small angle neutron scattering (SANS) experiments [47], as well as by viscosity [48,49] and conductivity measurements [25,29,44].…”

Section: Experimental Partmentioning

confidence: 98%

“…The interplay between the hydrophobicity of ionenes and specific ion effects was presented in a series of papers published by our [22][23][24][25][26][27][28][29] and other groups [30][31][32]. It was shown that aqueous ionene solutions exhibit strong specific ion effects, where replacing one counterion species by another may yield qualitatively different behaviour of the solution.…”

Section: Introductionmentioning

confidence: 99%

Thermodynamic analysis of the interaction of partially hydrophobic cationic polyelectrolytes with sodium halide salts in water

et al. 2014

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Isothermal titration calorimetry was used to determine the temperature and concentration dependence of the enthalpy of mixing of 3,3-and 6,6-ionene fluorides, bromides, and iodides with low molecular weight salts (NaF, NaCl, NaBr, and NaI) in water. The magnitudes of the enthalpies, measured in the temperature range from 273 to 318 K, depended on the number of methylene groups on the ionene polyion (hydrophobicity), and on the anion of the added salt (ion-specificity). All enthalpies of mixing of 3,3-and 6,6-ionene fluorides with low molecular weight salts (NaCl, NaBr, and NaI) were negative, which is in contrast to the predictions of standard theories of polyelectrolyte solutions. This fact was interpreted in the light of the ion-water short-range interactions that are not accounted for in those theories. In contrast, the enthalpies of mixing of 3,3-and 6,6-ionene bromides and iodides with NaF were positive, being in accord with theory. Using the calorimetric data, we performed a model thermodynamic analysis of the polyelectrolyte-salt mixing process to obtain changes in the apparent standard Gibbs free energy, enthalpy, entropy, and heat capacity relative to the pure ionene fluorides in water. The results prove that halide ions replace fluoride counterions with a strength increasing in the order chloride < bromide < iodide. The process is enthalpy governed, accompanied by a positive change in the heat capacity.

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“…Besides the classical Poisson-Boltzmann ͑PB͒ theory, 1,5,6 formal statistical mechanical approaches such as the hypernetted chain/mean spherical approximation ͑HNC/MSA͒, 13,14 the PB/MSA, 15 and the modified PB ͑MPB͒ theory [16][17][18][19] have been utilized in conjunction with the cylindrical cell model. The theoretical efforts have been supplemented by numerical computer simulations, viz., with parameters corresponding to DNA, [20][21][22][23][24][25][26][27][28][29][30] PSS, 31,32 ionenes, 33 and polyamines, 19 the focus being principally on polyionsimple ion correlation and the thermodynamics of the solution. The simulations suggest that the PB equation is generally semiquantitative in describing equilibrium properties for monovalent systems but is less certain for higher and/or multivalent systems.…”

Section: Introductionmentioning

confidence: 99%

Ionic correlations in the inhomogeneous atmosphere surrounding cylindrical polyions: Catalytic effects of polyions

Piñero

Bhuiyan

Reščič

et al. 2008

The Journal of Chemical Physics

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The structural properties of linear polyelectrolyte solutions in the presence of a salt as evidenced through ionic correlations in the inhomogeneous atmosphere around a polyion and their consequence such as the catalytic potential are studied by using Monte Carlo simulation techniques. The simulations are performed on the cylindrical cell model where a uniformly charged hard cylinder mimics the linear polyion, which is caged in its own cylindrical cell containing counterions and salt. The cell (volume) average of the interionic correlations is presented as a function of the polyion and salt concentrations and ion radius. These results are utilized to study the catalytic effects of polyions as manifested through the changes in the collision frequency between ions in the double layer surrounding the polyion relative to that in the pure electrolyte solution. The reported results suggest a strong influence of the added salt/polyelectrolyte concentration ratio on the structural properties of the solution and hence on ion-ion collision frequency. The machine simulations are supplemented by nonlinear Poisson-Boltzmann results. Fair agreement between two different theoretical methods of calculating the collision frequency is obtained.

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Osmotic Properties of Aqueous Ionene Solutions

Cited by 50 publications

References 42 publications

Polyelectrolyte hydration: Theory and experiment

Polyelectrolyte hydration: Theory and experiment

Thermodynamic analysis of the interaction of partially hydrophobic cationic polyelectrolytes with sodium halide salts in water

Ionic correlations in the inhomogeneous atmosphere surrounding cylindrical polyions: Catalytic effects of polyions

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