A scattering study on intermicellar interactions and structures of polymeric micelles

The micellar structure is usually considered to be composed of a hard sphere (liquid) core and a heavily solvated corona. Therefore, the correction for intermicellar interactions at finite concentrations can be relatively complicated. In this article, small-angle neutron scattering of a copolymer, known as Pluronic L64 (PEO₁₃PPO₃₀PEO₁₃), in o-xylene in the presence of D₂O is used to demonstrate that, based on the hard sphere approximation, intermicellar interactions can be corrected by representing the micellar size as having an equivalent hard sphere radius. The procedure remains valid even if the micellar shape becomes asymmetric, with axial ratios of 3 ? 4. For the present system, the equivalent hard sphere radius corresponds to the micellar core radius plus one-half of the micellar shell thickness. With the equivalent hard sphere approach, the scattering behavior of the micelle could be described by using a core-shell structure. © 1994 John Wiley & Sons, Inc.     

Liquid-crystalline ordering in two-dimensional systems with discrete symmetry

The mean-field theories of liquid-crystalline (nematic) ordering developed for three-dimensional systems are applied to describe two-dimensional systems of both geometrically anisotropic and anisotropically interacting particles. Systems with discrete symmetry (lattice models) for which long-range order is possible are considered on the base of the Landau free-energy expansion. It is shown that the Hamiltonian describing the energy of intermolecular interactions may be written in a common form for lyotropic and thermotropic systems. The mean-field theory gives a continuous phase transition (second-order phase transition) for a square lattice, whereas for a triangular lattice it gives a phase transition with latent heat (first-order phase transition) like for three-dimensional systems. These results are compared with results of the exact theories (two-dimensional Ising and Potts models). It is concluded that for realistic two-dimensional models the orientational in-plane ordering is not sharper than a second-order phase transition.     

Smectic ordering in athermal systems of rodlike triblock copolymers

The phase behavior of the system of parallel rigid triblock copolymers is examined using the second virial density functional theory. The triblock particle consists of two identical infinitely thin hard rods of finite lengths on the opposite ends of one central hard cylinder with nonzero length and diameter. Stability analyses and free energy calculations show that the system of parallel particles can form not only uniform nematic and smectic A phases but also a smectic C phase. The stability and structure of the tilted structure are controlled by only the diameter and the length of the central cylinder segment. Interestingly, the diameter affects only the layer tilting and the periodicity, but not the packing fraction of the nematic to smectic-C transition. For all values of cylinder length the usual smectic A and smectic C transitions compete with each other and no nematic-columnar transition is observed. At low and high cylinder lengths the smectic A phase is stabilized first, while the smectic C is the most stable for intermediate length values.     

Micellization and intermicellar interactions in aqueous sodium dodecyl benzene sulfonate solutions

Quasielastic light scattering was used to investigate the size and shape of sodium dodecyl benzene sulfonate (SDBS) micelles in aqueous solutions. Measurements were made as a function of temperature and NaCl and SDBS concentrations. Light scattering data indicate that the micelles are spherocylinders with a semiminor axis of 22 Å. The length of the micelles increases strongly with salt concentration and decreases with temperature. The minimum micelle has an aggregation number of n⁰ = 28 and a hydrodynamic radius of R = 22 Å. Diffusion coefficient and intensity data were analyzed using a thermodynamic theory of micellar aggregation and a model based on DLVO theory of interactions.     

Kinetic pathways of phase ordering in lipid raft model systems

We studied kinetic pathways of order-order transitions in bilayer lipid mixtures using a time-dependent Ginzburg-Landau (TDGL) approach. During the stripe-to-hexagonal phase transition in an incompressible two-component system, the stripe phase first develops a pearl-like instability along the phase boundaries, which grows and drives the stripes to break up into droplets that arrange into a hexagonal pattern. These dynamic features are consistent with recent experimental observations. During the disorder-to-hexagonal phase transition in an incompressible three-component system, the disordered state first passes through a transient stripelike structure, which eventually breaks up into a hexagonal droplet phase. Our results suggest experiments with synthetic vesicles where the stripelike patterns could be observed.     

Atoms-in-molecules study of intra- and intermolecular bonding in the pentaerythritol tetranitrate crystal

Chemical bonding in the pentaerythritol tetranitrate crystal based on the experimental electron density obtained from X-ray diffraction data at 100 K and theoretical calculations at the experimental molecular geometry have been analyzed in terms of the Quantum Theory of Atoms in Molecules. Features of the intra- and intermolecular bond critical points and the oxygen atom lone-pair locations are discussed. Numerous intermolecular bonding interactions, including O...H and O...O, have been found and characterized. Atomic charges and atomic energies were integrated and compared with those for similar compounds. The N-O topological bond orders have been calculated for the first time, and the PETN atomic valences have been estimated.     

Theory of ordering in three-dimensional polymer systems with local orientational-deformational interactions

The spontaneous ordering of a three-dimensional polymer system composed of flexible segments with a fixed mean-square length in the presence of local intra- and interchain orientational-deformational interactions was considered. The fixation of the segment chain length on average is possible only during relatively weak interchain interactions or at high temperatures, i.e., in the isotropic state. The three-dimensional model, unlike its two-dimensional version, suggests the existence of the critical point at which a second-order phase transition from the isotropic state to an ordered state takes place. The critical behavior of the multichain model is described by the spherical approximation for an anisotropic Heisenberg ferromagnetic. The dependence of the critical point and the parameters of short- and long-range dipole and quadrupole orientational orders on the chain rigidity and magnitude of interchain interactions was determined. In the isotropic state, orientation correlations of segments decline according to the Ornstein-Zernike law, as in the 3D model of Gaussian subchains without fixation of their mean-square length. In the ordered state, the correlation functions tend to a finite limiting value corresponding to the presence of long-range order, as in the case of the multichain model of rigidchain segments in the strong-order approximation. A comparison of the short-range and long-range orders in the model of chains composed of segments with a fixed mean-square length and undeformable (rodlike) elements in the mean-field approximation, on the one hand, and multichain models, on the other hand, showed their equivalence, especially at high degrees of ordering.     

Incorporating intermicellar interactions in the fitting of SANS data from cationic wormlike micelles

Small-angle neutron scattering (SANS) from cationic wormlike micellar solutions composed of hexadecyltrimethylammonium bromide (CTABr) and hexadecylpyridinium bromide (CPyBr) in deuterated water was studied at 40 degrees C as a function of surfactant and salt concentrations. Two scattering functions of semiflexible chains incorporating excluded volume effects, with and without the intermicellar interactions, were used in SANS data model fitting. Two needed changes were made in the well-accepted models. Extensive and systematic SANS data analysis suggests the robustness of these corrected scattering functions when the intermicellar interactions are included. The influence of the headgroups and ionic strength on the contour length and micellar flexibility of these two systems was demonstrated on the basis of the quantitative structural information obtained from the model fitting. Micellar flexibility was found to depend on surfactant concentration, even when intermicellar interactions were taken into account, despite predictions to the contrary.     

Compound formation and solvent (dis)ordering in syndiotactic polystyrene/benzylmethacrylate systems

In-situ small- and wide-angle X-ray scattering (SAXS and WAXS) experiments combined with Raman spectroscopy have been performed to study the phase behaviour of syndiotactic polystyrene (sPS) and benzylmethacrylate (BzMA). In the quenched gels, sPS adopts a helical conformation which is stabilised by the solvent molecules, in fact compound formation occurs. From the combined experimental data it was concluded that two different structural modifications exist within the solvent-included helical δ-phase, respectively the δ' phase in which the solvent molecules are intercalated and ordered between the phenyl rings of sPS and a δ” phase where this solvent ordering is lost.     

Pressure-induced ordering in adamantane: a Monte Carlo simulation study

Isothermal-isobaric ensemble Monte Carlo simulation of adamantane has been carried out with a variable shape simulation cell. The low-temperature crystalline phase and the room-temperature plastic crystalline phases have been studied employing the modified Williams potential. We show that at room temperature, the plastic crystalline phase transforms to the crystalline phase on increase in pressure. Further, we show that this is the same phase as the low-temperature ordered tetragonal phase of adamantane. The high-pressure ordered phase appears to be characterized by a slightly larger shift of the first peak toward a lower value of r in C-C, C-H, and H-H radial distribution functions as compared to the low-temperature tetragonal phase. The coexistence curve between the crystalline and plastic crystalline phase has been obtained approximately up to a pressure of 4 GPa.     

IR dichroism study of orientational ordering of liquid-crystalline acrylates

Orientational ordering of four liquid-crystalline acrylates induced by the surface of KBr plates over a wide temperature range was studied by the IR dichroism technique. IR spectra of homogeneously aligned samples were used to calculate the angles between the direction of the transition moment for a series of vibrations of the mesogenic fragment and its long axis. A method for calculation of the homeotropic orientation parameter of molecules was proposed. The orientation parameters of homogeneously and homeotropically aligned samples in the nematic, smectic (A), and chiral smectic (I andH) phases were calculated. Thein situ photopolymerization of acrylates in the smectic phases occurs with retention of the orientational ordering in the polymer films formed. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 319–323, February, 1999.     

29Si NMR study of structural ordering in aluminosilicate geopolymer gels

A systematic series of aluminosilicate geopolymer gels was synthesized and then analyzed using 29Si magic-angle spinning nuclear magnetic resonance (MAS NMR) in combination with Gaussian peak deconvolution to characterize the short-range ordering in terms of T-O-T bonds (where T is Al or Si). The effect of nominal Na2O/(Na2O + K2O) and Si/Al ratios on short-range network ordering was quantified by deconvolution of the 29Si MAS NMR spectra into individual Gaussian peaks representing different Q4(mAl) silicon centers. The deconvolution procedure developed in this work is applicable to other aluminosilicate gel systems. The short-range ordering observed here indicates that Loewenstein's Rule of perfect aluminum avoidance may not apply strictly to geopolymeric gels, although further analyses are required to quantify the degree of aluminum avoidance. Potassium geopolymers appeared to exhibit a more random Si/Al distribution compared to that of mixed-alkali and sodium systems. This work provides a quantitative account of the silicon and aluminum ordering in geopolymers, which is essential for extending our understanding of the mechanical strength, chemical and thermal stability, and fundamental structure of these systems.     

Integration of intra- and extravasation in one cell-based microfluidic chip for the study of cancer metastasis

Most studies of cancer metastasis focus on cancer cell invasion utilizing adhesion assays that are performed independently, and are thus limited in their ability to mimic complex cancer metastasis on a chip. Here we report the development of an integrated cell-based microfluidic chip for intra- and extravasation that combines two assays on one chip for the study of the complex cascade of cancer metastasis. This device consists of two parts; one is an intravasation chamber for the three-dimensional (3-D) culture of cancer cells using a Matrigel matrix, and the other is an extravasation chamber for the detection of metastasized cancer cells by adhesion molecules expressed by epithelial cells. In this novel system, the intravasation and extravasation processes of cancer metastasis can be studied simultaneously using four screw valves. Metastatic LOVO and non-metastatic SW480 cells were used in this study, and the invasion of LOVOs was found to be higher compared to SW480. In contrast, invasion of cells treated with metalloproteinase (MMP) inhibitors decreased within the intravasation chamber. Degraded cancer cells from the intravasation chamber were detected within the extravasation chamber under physiological conditions of shear stress, and differences in binding efficiency were also detected when CA19-9 antibody, an inhibitor of cancer cell adhesion, was used to treat degraded cancer cells. Our results support the potential usefulness of this new 3D cell-based microfluidic system as a drug screening tool to select targets for the development of new drugs and to verify their effectiveness.     

Theory of nematic ordering in supramolecular systems: Self-assembly of mesogenic groups and self-organization of the system

The behaviors of two systems are considered: a low-molecular system (a binary mixture of low-molecular components) and a polymer system (mixture of a macromolecules and a low-molecular dopant) whose components reversibly bind to form dimers capable of liquid-crystal ordering. The general theory of binary-mixture structuring, where two processes occur—self-assembly of mesogenic dimers of the mixture components and their self-organization—is presented. The theory demonstrates general laws of the behavior of low-molecular and polymer systems as well as differences related to the features of polymer thermodynamics.     

Simulation of structure formation in disperse systems

The main rules governing the redistribution of microparticles in disperse systems were revealed by computer simulation. These rules predetermine the character and properties of the structure being formed, which opens up the possibility to control the properties of disperse materials, including sorbents and catalysts based on high-dispersity solid phases.     

Energetics of intra- and intermolecular bonds in ω-alkanediols

The enthalpies of combustion and vaporization at 298.15 K of the-alkanediols were determined with a CRMT rocking calorimeter equipped with a micro-bomb and a Tian-Calvet calorimeter equipped with a Knudsen effusion cell, respectively. The enthalpies of formation in the condensed and gaseous phases and the enthalpies of atomization are calculated. They depend linearly on the number of carbon atoms. Furthermore, the results permit derivation of the enthalpy of an intermolecular hydrogen bond in liquid-alkanediols and calculation of mean enthalpies of the C-C and C-OH bonds. All these thermochemical quantities are discussed in relation to the structural particulars of the molecules.