Size control of surfactant vesicles made by a mixture of cationic surfactants and organic derivatives.

Spontaneous size-controllable vesicles that are prepared by a mixture of surfactants with different alkyl chain lengths (n-alkyltrimethylammonium bromide, C(n)TAB) and an organic derivative (5-methyl salicylic acid, 5mS) in aqueous solution have been investigated. When the organic derivative 5mS is mixed with the C(n)TAB surfactants in aqueous solution, the surfactant vesicles are spontaneously formed above a certain 5mS concentration. Small angle neutron scattering reveals that the core radius of surfactant vesicles is clearly increased from ca. 31 nm to ca. 97 nm with the alkyl chain length of surfactants while the bilayer thickness of the vesicles is nearly constant. The structure of surfactant vesicles maintains against temperature change ranging from 30 degrees C to 45 degrees C, showing no structural change. These results can provide thermally stable surfactant vesicles with various sizes and constant bilayer thickness that may possess a different permeability and may allow the surfactant vesicle to be used in gene or drug delivery for a variety of goods.

Microphase separations of the fluids with spherically symmetric competing interactions.

A density functional perturbation theory has been developed for studying the phase behaviors of a competing system in the spherical pores. The pore size as well as the intensity of competing interactions exerts a strong influence on the vapor-liquid, vapor-cluster, and cluster-liquid transitions of a competing system. The microdomain spacing (D) of the cluster is commensurate with the periodicity of modulation in the particle density distributions of a competing system in a spherical pore with the pore radius (R). For the cluster phase, we find that the multi-vaporlike void is formed depending on the periodicity of modulation by finite-size artifacts. For R < D, the competing system only shows the vapor-liquid transition at a high amplitude. For R > D, the vapor-cluster and cluster-liquid transitions are found at a high amplitude, whereas at a low amplitude, the cluster-liquid transition only occurs. The competing system exhibits two tricritical points, which are joined to one another by the line of second-order transitions at the low and high densities. A comparison with the result of a slit pore shows that (i) the tricritical points in a spherical pore, which has the highest symmetry, occur at a low amplitude compared with that of a slit pore because of the geometrical properties of the pores, and that (ii) the slit pore relatively shows the wide vapor-cluster and cluster-liquid coexistence regions compared with that of a spherical pore: the geometrical symmetry of a pore results in a weaker tendency for phase separation.

Nonadditive penetrable mixtures in nanopores: surface-induced population inversion.

We investigate the surface-induced population inversion of the nonadditive penetrable mixtures which exhibits the fluid-fluid demixing transition of the bulk system due to the confinement effect. The result shows that the population inversions are strongly affected by the extra repulsion between unlike species, the mole fraction of species, the width of nanopores, and the nonadditive walls. The extra repulsion between unlike species in a confined system increases the contact density of both species at the wall and promotes the population inversion in nanopores. The population inversion is the typical shift first-order fluid-fluid demixing transition due to the confinement effect in nanopores. The population inversions are only observed in nanopores with finite widths. The population inversion line is shifted toward a higher fluid density with decreasing width of the nanopores and lies slightly in lower density compared with the coexistence curves of the bulk system. The nonadditive wall for the big particles leads to the population inversion in lower density compared with that of the nonadditive wall for the small particles. The population inversion line is terminated at a lower mole fraction.

Structure and thermodynamics of hard-core Yukawa fluids: thermodynamic perturbation approaches.

The thermodynamic perturbation theories, which are based on the power series of a coupling constant (λ-expansion), have been proposed for studying the structural and thermodynamic properties of a hard-core Yukawa (HCY) fluid: one (A1-approximation) is the perturbation theory based on the hard-sphere repulsion as a reference system. The other (A2-approximation) is the perturbation theory based on the reference system which incorporates both the repulsive and short-range attractive interactions. The first-order mean-spherical approximation (FMSA) provided by Tang and Lu [J. Chem. Phys. 99, 9828 (1993)] has been employed for investigating the thermodynamic properties of a HCY fluid using the alternative method via the direct correlation function. The calculated results show that (i) the A1 and A2 approximations are in excellent agreements with previous computer simulation results in the literature and compare with the semi-empirical works of Shukla including the higher-order free energy terms, (ii) the A1 and A2 approximations are better than the FMSA and the mean-spherical approximation, (iii) the A2-approximation compares with the A1-approximation, even though the perturbation effect of an A2-approximation is much smaller than that of an A1-approximation, and that (iv) the FMSA study is particularly of advantage in providing the structure and thermodynamics in a simple and analytic manner.

Structure and phase behavior of a confined nanodroplet composed of the flexible chain molecules.

A polymer density functional theory has been employed for investigating the structure and phase behaviors of the chain polymer, which is modelled as the tangentially connected sphere chain with an attractive interaction, inside the nanosized pores. The excess free energy of the chain polymer has been approximated as the modified fundamental measure-theory for the hard spheres, the Wertheim's first-order perturbation for the chain connectivity, and the mean-field approximation for the van der Waals contribution. For the value of the chemical potential corresponding to a stable liquid phase in the bulk system and a metastable vapor phase, the flexible chain molecules undergo the liquid-vapor transition as the pore size is reduced; the vapor is the stable phase at small volume, whereas the liquid is the stable phase at large volume. The wide liquid-vapor coexistence curve, which explains the wide range of metastable liquid-vapor states, is observed at low temperature. The increase of temperature and decrease of pore size result in a narrowing of liquid-vapor coexistence curves. The increase of chain length leads to a shift of the liquid-vapor coexistence curve towards lower values of chemical potential. The coexistence curves for the confined phase diagram are contained within the corresponding bulk liquid-vapor coexistence curve. The equilibrium capillary phase transition occurs at a higher chemical potential than in the bulk phase.

Adsorption of the heteronuclear AB diblock copolymers confined in the slitlike pores.

A density functional perturbative theory, which is based on both the modified fundamental measure theory for the spheres and the Wertheim's first-order perturbation theory for the chain connectivity, has been proposed for investigating the structure of the heteronuclear AB diblock copolymers. It has been applied for studying the adsorption of the heteronuclear AB diblock copolymers confined in the hard slit pores and the walls via the Lennard-Jones (3-9) potential. The theoretical calculation shows that the structure of the confined heteronuclear AB diblock copolymer are strongly affected by the size ratio of the beads composed of the block as well as the chain lengths of the blocks composed of the copolymer. The surface-binding potential, which has different affinity with regard to the walls, plays an important role for the structure and phase behaviors of the heteronuclear AB diblock copolymer such as the selective adsorption of the homogeneous AB diblock copolymer immersed in the solvent.

Structure of penetrable sphere fluids and mixtures near a slit hard wall: a modified bridge density functional approximation.

The modified density functional theory, which is based both on the bridge density functional and the contact value theorem, has been proposed for the structural properties of penetrable sphere fluids and their mixtures near a slit hard wall. The Verlet-modified bridge function proposed by Choudhury and Ghosh [J. Chem. Phys. 119, 4827 (2003)] for one-component system has been extended for fluid mixtures. The radial distribution functions obtained from the Verlet-modified bridge function are in excellent agreement with computer simulations over a wide range of density and temperature and better than those obtained from the standard integral theories including the Percus-Yevick and hypernetted-chain closures. The calculated particle density distributions confined in a slit pore are also found to be reasonably good compared to the simulation data. Even for high density systems the accuracy of the hypernetted-chain and the mean-field approximation functionals increase with increasing temperature. However, the agreement between theory and simulation slightly deteriorates in the systems of low temperature.

Depletion interactions in two-dimensional colloid-polymer mixtures: molecular dynamics simulations.

The depletion interactions acting between two hard colloids immersed in a bath of polymers, in which the interaction potentials include the soft repulsion/attraction, are extensively studied by using the molecular dynamics simulations. The collision frequencies and collision angle distributions for both incidental and reflection conditions are computed to study the dynamic properties of the colloidal mixtures. The depletion effect induced by the polymer-polymer and colloid-polymer interactions are investigated as well as the size ratio of the colloid and polymer. The simulated results show that the strong depletion interaction between two hard colloids appears for the highly asymmetric hard-disc mixtures. The attractive depletion force at contact becomes deeper and the repulsive barrier becomes wider as the asymmetry in size ratio increases. The strong polymer-polymer attraction leads to the purely attractive depletion interaction between two hard colloids, whereas the purely repulsive depletion interaction is induced by the strong colloid-polymer attraction.

Effect of polymer size and chain length on depletion interactions between two colloids.

A density functional theory based on the weighted density has been developed to investigate the depletion interactions between two colloids immersed in a bath of the binary polymer mixtures, where the colloids are modeled as hard spheres and the polymers as freely jointed tangent hard-sphere chain mixtures. The theoretical calculations for the depletion forces between two colloids induced by the polymer are in good agreement with the computer simulations. The effects of polymer packing fraction, degree of polymerization, polymer/polymer size ratio, colloid/polymer size ratio on the depletion interactions, and colloid-colloid second virial coefficient B2 due to polymer-mediated interactions have been studied. With increasing the polymer packing fraction, the depletion interaction becomes more long ranged and the attractive interaction near the colloid becomes deeper. The effect of degree polymerization shows that the long chain gives a more stable dispersion for colloids rather than the short chain. The strong effective colloid-colloid attraction appears for the large colloid/polymer and polymer/polymer size ratio. The location of maximum repulsion Rmax is found to appear Rmax approximately sigmac+Rg2 for the low polymer packing fraction and this is shifted to smaller separation Rmax approximately sigmac+sigmap2 with increasing the polymer packing fraction, where sigmap2 and Rg2 are the small-particle diameter and the radius of gyration of the polymer with the small-particle diameter, respectively.

Effect of hydrostatic pressure on closed-loop phase behavior of block copolymers.

The effect of hydrostatic pressure (P) on closed-loop phase behavior of deuterated polystyrene-block-poly(n-pentyl methacrylate) copolymers [dPS-PnPMA] was investigated by using small-angle neutron scattering and birefringence. For P<20.7 bar, dPS-PnPMA exhibited a lower disorder-to-order transition temperature (T(LDOT)) at 175 degrees C, and then an upper order-to-disorder transition temperature (T(UODT)) at 255 degrees C. With increasing pressure both T(LDOT) and T(UODT) were markedly changed, where dT(LDOT)/dP was 725 degrees C/kbar and dT(UODT)/dP was -725 degrees C/kbar. These are consistent with predictions by the Clausius-Clapeyron equation using measured values of the volume and enthalpy changes of both transitions. The large pressure coefficients imply that the closed-loop phase behavior observed for PS-PnPMA is an entropic-driven phase transition.

Self-organization of amphiphilic polymer in vesicle bilayers composed of surfactant mixtures.

Cryogenic transmission electron microscopy (cryo-TEM) and small angle neutron scattering (SANS) are used to investigate the association of amphiphilic polymers consisting of a double-chain hydrophobic tail attached onto poly(ethylene glycol) (PEG) polymer chains into two different systems of equilibrium vesicles. For cetyltrimethylammonium bromide (CTAB)/sodium perfluorohexanoate (FC(5)) vesicle bilayers, the size distribution of the vesicles slightly becomes narrow in the presence of the polymers, suggesting that the wedge-shaped polymers increase the spontaneous curvature of the vesicles. In contrast, the confinement of polymer molecules inside the CTAB/sodium perfluorooctanoate (FC(7)) vesicles that are stabilized by spontaneous curvature causes an abrupt decrease in the bilayer rigidity. By an analysis of vesicle size distribution, it is found that the membrane elasticity of CTAB/FC(7) vesicles is varied considerably from 6k(B)T to 0.3k(B)T, implying the transition of stabilization mechanism from spontaneous curvature to thermal fluctuation in the presence of polymer. The polymer incorporation mechanism into the bilayers is understood, in the comparison of the vesicle radius and size distribution before and after adding polymer, as that the polymer is anchored into the vesicle bilayer owing to hydrophobic property after the adsorption on the surface of the bilayer.