Phase behavior of polyion-surfactant ion complex salts: effects of surfactant chain length and polyion length

The aqueous phase behavior of a series of complex salts, containing cationic surfactants with polymeric counterions, has been investigated by visual inspection and small-angle X-ray scattering (SAXS). The salts were alkyltrimethylammonium polyacrylates, CxTAPAy, based on all combinations of five surfactant chain lengths (C6, C8, C10, C12, and C16) and two lengths of the polyacrylate chain (30 and 6 000 repeating units). At low water contents, all complex salts except C6TAPA6000 formed hexagonal and/or cubic Pm3n phases, with the hexagonal phase being favored by lower water contents. The aggregate dimensions in the liquid crystalline phases changed with the surfactant chain length. The determined micellar aggregation numbers of the cubic phases indicated that the micelles were only slightly aspherical. At high water contents, the C6TAPAy salts were miscible with water, whereas the other complex salts featured wide miscibility gaps with a concentrated phase in equilibrium with a (sometimes very) dilute aqueous solution. Thus, the attraction between oppositely charged surfactant aggregates and polyions decreases with decreasing surfactant chain length, and with decreasing polyion length, resulting in an increased miscibility with water. The complex salt with the longest surfactant chains and polyions gave the widest miscibility gap, with a concentrated hexagonal phase in equilibrium with almost pure water. A decrease in the attraction led to cubic-micellar and micellar-micellar coexistence in the miscibility gap and to an increasing concentration of the complex salt in the dilute phase. For each polyion length, the mixtures for the various surfactant chain lengths were found to conform to a global phase diagram, where the surfactant chain length played the role of an interaction parameter.     

The aqueous phase behavior of polyion-surfactant ion complex salts mixed with nonionic surfactants

The aim of this work was to study intermolecular interactions in systems containing charged polyion (polyacrylate, PA(-)), charged surfactant (C(16)TA(+)) and nonionic surfactant (C(12)E(5) or C(12)E(8)). To achieve this we have created four different phase diagrams using two different so-called complex salts, C(16)TAPA(25) and C(16)TAPA(6000), both consisting of positively charged surfactant (C(16)TA(+)) with polyacrylate (PA(-)) as counterions (no simple salt). The difference between the salts is the length of the polyion (25 or 6000 monomers). Both are insoluble in water. The results revealed that decreasing polyion length and increasing the PEO chain length of the nonionic surfactant were important factors for increasing the solubility of the complex salt. We also found that the curvature effects are quite small at low water content when gradually exchanging C(12)E(8) for either one of the complex salts while there is a gradual change in curvature for the systems containing C(12)E(5). Another interesting observation was the possibility for relatively large amounts of complex salt to be incorporated into a V(1) (Ia3d, bicontinuous) phase in the C(12)E(8)-containing systems. This gives rise to several questions regarding arrangements and dynamics of the polyion in this phase. In the dilute regime several different liquid crystalline phases can coexist with a dilute liquid phase containing the nonionic surfactant.     

Complex polyion-surfactant ion salts in equilibrium with water: changing aggregate shape and size by adding oil

The phase behavior of ternary mixtures containing an alkyltrimethylammonium polyacrylate complex salt, water, and a nonpolar "oil" (n-decanol, p-xylene or cyclohexane) is investigated. The complex salts were prepared with short or long polyacrylates (30 or 6000 repeating units) and with hexadecyltrimethylammonium or dodecyltrimethylammonium surfactant ions. Phase diagrams and structures were determined by visual inspection and small-angle X-ray scattering analyses. Systems containing decanol display a predominance of lamellar phases, while hexagonal phases prevail in systems containing p-xylene or cyclohexane. The difference is interpreted as a result of the different locations of the oils within the surfactant aggregates. Decanol is incorporated at the aggregate interface, leading to a decrease in its curvature, which favors the appearance of lamellar structures. p-Xylene and cyclohexane, on the other hand, are mostly incorporated in the interior of the cylindrical aggregate, as reflected by its swelling as the oil content increases. The comparison of these results with those reported for similar systems with monovalent (bromide) counterions indicates a much more limited swelling of the lamellar phases with polymeric counterions by water. This limited swelling behavior is predominantly ascribed to bridging due to the polyions.     

Electrophoretic measurement of water charge density and ion hydration

Water exchange between bulk water and water-ion complexes will be at equilibrium when the charge density of the complex surface equals the charge density of bulk water, producing a constant radius water-ion complex. This complex will migrate in an electric field at a velocity proportional to the complex radius. CE velocity is the sum of the complex charge-dependent velocity and the buffer electro-osmotic flow. Simultaneous use of both a base (1.07 mM imidazole) and an acid (1.5 mM MOPS) buffer negates EOF at pH 7.4. Electric fields below 300 V/cm (potassium, calcium) and 400 V/cm (magnesium) yield migration velocities with no dehydration of the water-ion complexes. The number of waters per complex increase with the ion charge density: K⁺ 1.90, Ca⁺⁺ 5.90, Mg⁺⁺ 6.59 waters/ion. The charge densities of the complexes are similar: K⁺ 1.24, Ca⁺⁺ 1.43, Mg⁺⁺ 1.21 e/nm², for an average bulk water charge density of 1.29 ± 0.11 (SD) e/nm². The addition of 0.1% Triton increases the number of waters for Mg⁺⁺ to 25.33 and lowers the charge density to 0.497 e/nm². High electric field dehydration shows that calcium will be fully dehydrated at 638.3 V/cm and magnesium fully dehydrated at 925.5 V/cm, which occur at 6.15 and 5.78 nm from the membrane. Dehydrated magnesium will then bind to calcium channels leading to decreased smooth muscle activation.     

Ionic equilibria in alkaline aqueous solutions of metal complex salts

A thermodynamic analysis of the formation conditions of metal hydroxides was performed. The areas of stable formation of metal hydroxide precipitates in the coordinates pH-metal concentration, including also solutions containing various kinds of complexing agents, were evaluated. With the precipitation of cadmium hydroxide as example, X-ray phase analysis confirmed the formation of metal hydroxide in the chemical composition areas where its formation is predicted by a thermodynamic analysis.     

Phase behavior of DNA solutions in the presence of salts

The thermodynamic behavior of DNA solutions in the presence of salts is studied using a new phenomenological model of Helmholtz free energy of the system. The activity coefficient of the DNA–salt solution system is calculated and its asymptotic behavior suggests the formation of gel precipitate. Phase instability analysis of the derived free energy predicts multivalent salt concentration at which DNA precipitates. However the model is incapable to predict the redissolution of DNA at higher salt concentration.     

Phase diagrams and water activities of aqueous ammonium salts of malonic acid

Malonic acid has been observed in the free troposphere and as a component of tropospheric aerosol, among other dicarboxylic acids. These aerosols can uptake ammonia, which partially or completely neutralizes the acids. Therefore, the impact of ammoniated dicarboxylic acids on the phases that can exist in aerosols at atmospheric temperatures needs investigation. To that end, the low temperature, solid/liquid phase diagrams of ammonium hydrogen malonate/water, ammonium malonate/water, and triammonium hydrogen malonate/water have been investigated with differential scanning calorimetry and infrared spectroscopy of thin films. Results show that the order of increasing solubility is triammonium hydrogen malonate, ammonium hydrogen malonate, malonic acid, and ammonium malonate. We have also determined a hydrate may form in the ammonium malonate system and decompose below 240 K. We report water activities at the ice melting points for each system up to the respective eutectic concentrations, and find for a given mole fraction of water, increasing ammonium content leads to decreasing water activity coefficients.     

Influences of solution property and charge density on the self-assembly behavior of water-insoluble polyelectrolyte sulfonated poly(sulphone) sodium salts

Two sulfonated poly(sulphone) sodium salts (SPSF) with different molecular weights and ionic exchange capacities in a N,N-dimethyl formamide/water (DMF-H2O) mixed solvent with various DMF contents were selected as a model system for investigating the influences of solvent composition, solution properties, and charge density of polyelectrolytes on the layer-by-layer (LbL) self-assembly of water-insoluble polyelectrolytes. Poly(dimethyldiallylammonium chloride) (PDDA) in aqueous solution was used as the counterpart. The PDDA/SPSF multilayer films grew nearly linearly with the layer numbers regardless of the volume fraction of DMF, phiDMF, in the SPSF solutions. The total absorption amount of the PDDA/SPSF multilayer films was strongly dependent on the charge density of the SPSF molecules and the phiDMF value of the SPSF solutions. Minimum values of absorption amount were observed at phiDMF = 0.6 to approximately 0.7. The surface hydrophobicity and roughness of the multilayer films can be tuned by varying phiDMF. These observations were rationalized in terms of the chain dimension and the ionization degree of the SPSF molecules as a function of phiDMF, which was characterized by the intrinsic viscosity ([eta]SPSF) and conductivity (LSPSF) of the SPSF solutions. The results indicate that the molecular structures of the DMF-H2O mixed solvent strongly affect the solution properties of SPSF, which in turn determine the growth behavior and physical properties of the PDDA/SPSF multilayer films.     

Polyelectrolyte behavior and conformation of poly-L-methionine S-methylsulfonium salts in aqueous solution

The influence of the species of counterion on the polyelectrolyte behavior and the conformation of poly-L -methionine S-methylsulfonium salts in aqueous solution was studied by viscometric, electrochemical, and optical measurements. The degree of binding of small counterions to charged polyions increases in the sequence: chloride ? bromide < iodide < thiocyanate. The conformations of chloride and bromide salts are independent of polymer concentration. On the contrary, iodide and thiocyanate salts indicate a conformational transition, probably from a random-coil conformation to an intermolecularly stabilized β-form, with the increase of polymer concentration. The results suggest the existence of a strong specific interaction between counterion and macroion in iodide and thiocyanate salt solutions at high polymer concentration.     

Phase behavior of aqueous solutions of copolymers of N,N'-diisopropylfumaramide and N-isopropylacrylamide: effect of the density of side chains

This letter describes the phase behavior of aqueous solutions of an N-isopropylacrylamide (NIPAM) homopolymer and copolymers of N,N'-diisopropylfumaramide (DIPFAM) and NIPAM as studied by transmittance measurements, infrared spectroscopy, and differential scanning calorimetry to reveal the effect of the density of N-isopropylamide side chain upon the phase behavior. The clouding-point and clearing-point temperatures decreased with increasing the mole fraction of DIPFAM (x(D)). It was noteworthy that only an extra side chain per ca. 7 NIPAM units had a remarkable effect on the phase behavior; the interactions between side chains were stronger, the intrapolymer contraction was less favorable, and the cooperativity of phase transition was lower at x(D) = 0.15 presumably because of the steric hindrance of dense side chains.     

Tough polyion complex hydrogel films of natural polysaccharides

The developments of tough hydrogels in recent years have greatly expanded the applications of hydrogels as structural materials. However, most of the tough hydrogels are made of synthetic polymers. To develop biopolymer-based tough hydrogels has both fundamental and practical significances. Here we report a series of polysaccharides-based tough hydrogel films prepared by polyion complexation and solvent evaporation of chondroitin sulfate(CS) and protonated chitosan(CHT) solutions with different weight ratios. The obtained CS/CHT gel films with thickness of 40-80 μm and water content of 66 wt%-81 wt% possess excellent mechanical properties, with tensile breaking stress and breaking strain being 0.4-3 MPa and 160%-320%, respectively. We found that in the mixture solutions there are large amounts of excess CHT in terms of charges; after swelling the films in water, the acetic acid, which is used to protonate the amino groups of CHT, diffuses out of the gel matrix, enhancing the intermolecular interactions between CHT molecules and thus improving the mechanical properties of gel films, besides the ionic bonds between CS and CHT. Antimicrobial tests also showed that the gel films with low weight ratio of CS to CHT, corresponding to the case with excess CHT, have evident antimicrobial effect. These CS/CHT gel films with good mechanical properties and antimicrobial effect should extend the applications of hydrogels in biomedical fields.     

Phase behavior and phase-transfer catalysis of tetrabutylammonium salts. Interface-mediated catalysis

The phase behavior and component composition of the coexisting phases in the tetrabutylammonium bromide (TBABr)/benzene/water/NaBr four-component system were strongly influenced by the temperature, TBABr content, and NaBr concentration. The phase-transfer catalytic activity of TBABr for the reaction of decyl methanesulfonate with sodium bromide was closely related to the phase behavior. Under O (oil-rich phase) + L (TBABr-rich liquid phase) + W (aqueous phase) triphase conditions, the influences of temperature and stirring speed on the phase-transfer catalytic activity were small compared with those under O + W biphase conditions. The addition of other quaternary salts that were able to form w/o aggregates in the O phase enhanced the TBABr catalytic activity even under O + W conditions. The relationship between phase behavior and catalytic activity of tetrabutylammonium chloride or iodide (TBACl or TBAI) was also examined. The results strongly suggested that the catalysis of TBAX was attributable to the interfacial reactions of TBAX with the substrate. The interface includes the water-oil microinterface formed in the microemulsion-like L phase as well as the bulk water-oil interface.     

Lattice potential energy estimation for complex ionic salts from density measurements

This paper is one of a series exploring simple approaches for the estimation of lattice energy of ionic materials, avoiding elaborate computation. The readily accessible, frequently reported, and easily measurable (requiring only small quantities of inorganic material) property of density, rho(m), is related, as a rectilinear function of the form (rho(m)/M(m))(1/3), to the lattice energy U(POT) of ionic materials, where M(m) is the chemical formula mass. Dependence on the cube root is particularly advantageous because this considerably lowers the effects of any experimental errors in the density measurement used. The relationship that is developed arises from the dependence (previously reported in Jenkins, H. D. B.; Roobottom, H. K.; Passmore, J.; Glasser, L. Inorg. Chem. 1999, 38, 3609) of lattice energy on the inverse cube root of the molar volume. These latest equations have the form U(POT)/kJ mol(-1) = gamma(rho(m)/M(m))(1/3) + delta, where for the simpler salts (i.e., U(POT)/kJ mol(-1) < 5000 kJ mol(-1)), gamma and delta are coefficients dependent upon the stoichiometry of the inorganic material, and for materials for which U(POT)/kJ mol(-1) > 5000, gamma/kJ mol(-1) cm = 10(-7) AI(2IN(A))(1/3) and delta/kJ mol(-1) = 0 where A is the general electrostatic conversion factor (A = 121.4 kJ mol(-1)), I is the ionic strength = 1/2 the sum of n(i)z(i)(2), and N(A) is Avogadro's constant.     

Phase separation behavior of aqueous solutions of a thermoresponsive polymer

Cloud‐point and binodal curves of the LCST type were obtained for aqueous solutions of a thermoresponsive polymer, poly [2‐(2‐ethoxy)ethoxyethyl vinyl ether], poly(EOEOVE). The cloud‐point curve obtained was very flat except in a dilute region, that is the cloud‐point temperature was insensitive to the polymer concentration, resembling the cloud‐point curve for aqueous solutions of poly(N‐isopropylacrylamide). On the other hand, the binodal curve obtained was parabolic, and located within the two‐phase region of the cloud‐point curve. Accompanied with the phase separation, a sharp endothermic peak was observed in a region including the cloud‐point and binodal temperatures. The reciprocal of the osmotic compressibility ?Π/?c obtained by sedimentation equilibrium indicated that water changes from a good to poor solvent for poly(EOEOVE) with increasing temperature. Analyzing the ?Π/?c data by a thermodynamic perturbation theory, we determined the interchain interaction parameters, the hard‐core diameter d and the depth ε of the square‐well potential. Theoretical binodal and endothermic curves calculated by the perturbation theory using the estimated interaction parameters reproduced experimental ones semiquantitatively, but the theoretical binodal disagreed with the experimental flat cloud‐point curve. The disagreement at high concentrations was in the opposite direction to that expected from the sample polydispersity in the molecular weight. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 2937–2949, 2005     

Surface charge density on spherical silica particles in aqueous alkali chloride solutions

The results of a systematic investigation on the influence of different alkali ion species on the surface charge density, ₀, of spherical silica particles (AEROSIL 300) in the pH range between 4 and 8 and with electrolyte concentrations from 0.005 M to 0.3 M are presented. The accuracy of the data may be described by a residual deviation,s( ₀ ^m ), including at least four single measurements:s( ₀ ^m )>0.2C/cm². The alkali sequence found for the spherical particles is in agreement with data for porous silica published by other authors.     

Mixtures of mucin and oppositely charged surfactant aggregates with varying charge density. Phase behavior, association, and dynamics

The nonionic surfactant Tween80 is a commonly used excipient in drug formulations containing an active substance with low aqueous solubility. Model drug vehicles with varying charge density were obtained by mixing Tween80 (PS-80) with the cationic surfactant Tetradecyltrimethylammonium chloride (TTAC), thus forming mixed micelles. The micelles were mixed with the negatively charged polyelectrolyte mucin, which is a component in the protective mucus layer covering epithelial cell linings. Depending on the composition of the mixture, complex-formation could be followed by precipitation. Using X-ray diffraction, it was found that the precipitate contained a lamellar phase with properties sensitive to the proportion of PS-80. Higher amounts of PS-80 were found to oppose phase separation. Further analysis in the one-phase region, or alternatively of the supernatant of two-phase samples, by (1)H NMR, HPLC, and diffusion measurements with PGSE-NMR led to the conclusions that at low proportion of PS-80 aggregates composed of mixed (PS-80 and TTAC) micelles and mucin were formed, whereas increased concentrations of PS-80 favored the dissolution of the precipitate and limited the interactions between mixed micelles and the polymer.     

The effects of charge transfer on the aqueous solvation of ions

Ab initio-based charge partitioning of ionic systems results in ions with non-integer charges. This charge-transfer (CT) effect alters both short- and long-range interactions. Until recently, the effects of CT have been mostly neglected in molecular dynamics (MD) simulations. The method presented in this paper for including charge transfer between ions and water is consistent with ab initio charge partitioning and does not add significant time to the simulation. The ions of sodium, potassium, and chloride are parameterized to reproduce dimer properties and aqueous structures. The average charges of the ions from MD simulations (0.900, 0.919, and -0.775 for Na(+), K(+), and Cl(-), respectively) are consistent with quantum calculations. The hydration free energies calculated for these ions are in agreement with experimental estimates, which shows that the interactions are described accurately. The ions also have diffusion constants in good agreement with experiment. Inclusion of CT results in interesting properties for the waters in the first solvation shell of the ions. For all ions studied, the first shell waters acquire a partial negative charge, due to the difference between water-water and water-ion charge-transfer amounts. CT also reduces asymmetry in the solvation shell of the chloride anion, which could have important consequences for the behavior of chloride near the air-water interface.     

Viscosity behavior of benzoic acid and benzoate ion in aqueous solution

Relative viscosities of aqueous solutions of benzoic acid and benzoates of lithium, sodium, potassium, and ammonium are measured. In the temperature range 25–35°C, the Jones-Dole viscosityB coefficients of the benzoate ion decrease with increasing temperature, indicating a net structure-making effect. The somewhat larger value of theB coefficient for the benzoate ion than that for the benzoic acid molecule confirms similar behavior for the acetate ion and acetic acid in aqueous solutions although the effect is much smaller.     

Polyelectrolyte–particle complex formation. Polyelectrolyte linear charge density and ionic concentration effects. Monte Carlo simulations

The influence of the linear charge density (LCD) of a polyelectrolyte on its adsorption on an oppositely charged colloidal particle is investigated by Monte Carlo simulations. Adsorption characteristics are studied at different linear charge densities and ionic concentrations and for a given polyelectrolyte/particle size ratio so that particle curvature has full effect. The isolated polyelectrolyte goes through a smooth transition from a collapsed structure to an extended rod-like conformation with increasing the linear charge density in the low ionic concentration regime. In the high ionic concentration regime, the polyelectrolyte is less sensitive to the increase in the linear charge density and adopts a coil conformation. We found that complex formation is promoted by decreasing the ionic concentration and increasing the linear charge density and that large changes in the polymer dimensions are observed at the adsorption-desorption limit. By adjusting the linear charge density and ionic strength, we demonstrate that the adsorption-desorption limit corresponds to a sharp transition from non-adsorbed to adsorbed conformations and that the mean adsorption energy per monomer has to be less than -0.4 kT to achieve adsorption. We calculated that the linear charge density at the adsorption-desorption limit is related to the Debye-Hückel length according to LCD^crit ~3². At small values of the linear charge density and low ionic strength (no adsorption is observed at high ionic strength), a large amount of monomers are present in loops and tails. By increasing LCD, the amount of monomers in trains reaches a maximum value and the polyelectrolyte adopt flat conformation at the surface of the particle.