Scattering from solutions of star polymers

We study the scattering intensity of dilute and semi-dilute solutions of star polymers. The star conformation is described by a model introduced by Daoud and Cotton. In this model, a single star is regarded as a spherical region of a semi-dilute polymer solution with a local, position dependent screening length. For high enough concentrations, the outer sections of the arms overlap and build a semi-dilute solution (a sea of blobs) where the inner parts of the actual stars are embedded. The scattering function is evaluated following a method introduced by Auvray and de Gennes. In the dilute regime there are three regions in the scattering function: the Guinier region (low wave vectors, ) from where the radius of the star can be extracted; the intermediate region () that carries the signature of the form factor of a star with f arms: ; and a high wavevector zone () where the local swollen structure of the polymers gives rise to the usual q ^-5/3 decay. In the semi-dilute regime the different stars interact strongly, and the scattered intensity acquires two new features: a liquid peak that develops at a reciprocal position corresponding to the star-star distances; and a new large wavevector contribution of the form q ^-5/3 originating from the sea of blobs. Received: 3 September 1997 / Revised: 13 January 1988 / Accepted: 31 March 1998     

Comment on “Growth of Molecular Superlattice in Fully Hydrated Dipalmitoylphosphatidylcholine during Subgel Phase Formation Process” by H. Takahashi, K. Hatta and I. Hatta

This comment shows that data recently reported [#!ref1!#] as being seemingly in conflict with earlier data [#!ref2!#] are, in fact, in excellent agreement. Together, both studies confirm that the kinetics of the subgel phase transformation in dipalmitoylphosphatidylcholine (DPPC) lipid bilayers obeys Kolmogorov-Avrami (K-A) theory [#!ref3!#,#!ref4!#] with an anomalously low effective dimensionality. Received: 11 December 1997 / Accepted: 28 January 1998     

Phase diagram of randomly polymerized membrane

Using a replica formalism, a generalization of a recent mean field model corresponding to the observed wrinkling transition in randomly polymerized membranes is presented. In this model we study the effects of global fluctuations of the surface normals to the flat membrane, which can be introduced by a random local field. In absence of these global fluctuations, we show that, the model exhibits both continuous and discontinuous transitions between flat and wrinkled phases, contrary to what has been predicted by Bensimon et al. and Attal et al. Phase diagrams both in replica symmetry and in breaking of replica symmetry in sense of Almeida and Thouless are given. We have also investigated the effects of global fluctuations on the replica symmetry phase diagram. We show that, the wrinkled phase is favored and the flat phase is unstable. For large global fluctuations, the transition between wrinkled and flat phases becomes first order. Received: 3 December 1997 / Revised: 31 March 1998 / Accepted: 3 August 1998     

Fluctuation-magnification of non-equilibrium membranes near a wall

Membranes in thermal equilibrium are well known to exhibit Brownian motion type shape fluctuations. Membranes containing active force centers -- such as chemically active membrane proteins -- suffer additional non-equilibrium shape fluctuations due to the activity of these force centers. We demonstrate, using scaling arguments, that non-equilibrium shape fluctuations are in general greatly amplified by the presence of a nearby wall or membrane due to the absence of a fluctuation-dissipation theorem. For adhesive membranes, this fluctuation magnification effect may facilitate the establishment of bonding. For non-adhesive membranes, fluctuation magnification produces a long-range repulsive pressure which can exceed the well known Helfrich repulsion due to purely thermal fluctuations. Received: 1 September 1997 / Accepted: 3 December 1997     

Structure factor of a lamellar smectic phase with inclusions

Motivated by numerous X-ray scattering studies of lamellar phases with membrane proteins, amphiphilic peptides, polymers, or other inclusions, we have determined the modifications of the classical Caillé law for a smectic phase as a function of the nature and concentration of inclusions added to it. Besides a fundamental interest on the behavior of fluctuating systems with inclusions, a precise characterization of the action of a given protein on a lipid membrane (anchoring, swelling, stiffening ...) is of direct biological interest and could be probed by way of X-ray measurements. As a first step we consider three different couplings involving local pinching (or swelling), stiffening or curvature of the membrane. In the first two cases we predict that independent inclusions induce a simple renormalization of the bending and compression moduli of the smectic phase. The X-ray experiments may also be used to probe correlations between inclusions. Finally we show that asymmetric coupling (such as a local curvature of the membrane) results in a modification of the usual Caillé law. Received 10 March 2000 and Received in final form 30 August 2000     

Tilt model of inverted amphiphilic mesophases

We present an alternative model of structure and energetics of the inverted amphiphilic mesophases. The previous studies of the inverted hexagonal, H_II, and inverted micellar cubic, Q_II, phases considered the amphiphilic monolayers to be homogeneously bent. In contrast, we assume a unit cell of an inverted mesophase to consist of flat fragments of monolayer. Hence, the unit cells of the H_II and Q_II phases are represented by a hexagonal rod and a polyhedron, respectively. Our model is motivated by Turner and Gruner's X-ray diffraction reconstruction of structure of the H_II phase. The only deformation of the amphiphilic monolayers we consider is tilt of the hydrocarbon chains with respect to the monolayer surface, determined by the packing constraints imposed in the mesophases. Applying our recent model for the elastic energy of tilt in liquid membranes [#!ref23!#], we show that: i) tilt accounts in a natural way for the frustration energy of mesophases resulting from filling by the hydrocarbon chains the corners of the unit cells, ii) the energy of tilt variation along the membrane surface is analogous to the bending energy. We compute the energetics of the H_II, Q_IIsc and Q_IIfcc phases and obtain a hypothetical phase diagram in terms of the elastic constants of monolayers. Moreover, we calculate the structural dimensions of the mesophases. We verify the model showing that the obtained phase diagram describes the recent data for the glycolipids/water systems; the predicted dimensions of the Q_II phase are in accord with the measured values; the model treats quantitatively the structural features observed for the H_II phase. Received: 9 February 1998 / Revised: 4 June 1998 / Accepted: 3 July 1998     

Dielectric relaxation spectrum of poly (ε-caprolactone) networks hydrophilized by copolymerization with 2-hydroxyethyl acrylate

The dielectric relaxation spectrum of polycaprolactone (PCL) networks hydrophilized with different amounts of 2-hydroxyethyl acrylate (HEA) is investigated. PCL is a semicrystalline polyester with a complex relaxation spectrum that includes the main α relaxation and two secondary modes (β, γ) at lower temperatures. The overlapping of the different relaxational modes was split by using several Havriliak-Negami functions. Crosslinking the material modifies the dynamics of the main relaxation process as reflected by the parameters that characterize the Vogel behavior of the process and the dynamic fragility. The incorporation of HEA units in the network results in a material with microphase separation: two α processes are detected, the one corresponding to the PCL chains and the new one associated to nanometric regions that contain different amount of both comonomers. The incorporation of the HEA units in the system involves the presence of a new β_sw relaxation due to the link of two side chains by water molecules through hydrogen bonding.     

On biomembrane electrodiffusive models

Two models are used in the literature, to study the electric behaviour of cellular membranes such as in protein aggregates, excitable media or ionic currents for examples. The first one is the Electroneutral Model based on Nernst-Planck and Poisson equations with a specific condition of microscopic electroneutrality. The second one is the Cable Model valid for long wavelengths based on an analogy between an electric cable and a cell. Convincing experiments have justified the Cable equation. First, we show that these two models are in contradiction. More precisely the assumption of electroneutrality is not considered in the Cable Model. The main difference between the two models is highlighted by the analysis of the well known voltage instability due to a negative differential conductance. Then, we derive a new semi-microscopic model (the Biomembrane Electrodiffusive Model, called BEM) valid for phenomena at any wavelength. The BEM is based on Nernst-Planck and Poisson equations but, doesn't imply microscopic electroneutrality. It reveals the capacitive behaviour of the membrane. In the limit of long wavelengths, one recovers the behaviour described within the Cable framework, as shown precisely in the study of the negative differential conductance analysis. Finally, we demonstrate the intimate link between the last models: the Cable Model appears as the limit of the BEM for large wavelengths with some prerequisites which are discussed. The effects of geometry and asymmetrical media are introduced. Received: 8 November 1996 / Revised: 23 July 1997 and 8 December 1997 / Accepted: 23 January 1998     

Parametrization of the hybrid potential for pairs of neutral atoms

The hybrid form is a combination of the Rydberg potential and the London inverse-sixth-power energy. It is accurate at all relevant distance scales and simple enough for use in all-atom simulations of biomolecules. One may compute the parameters of the hybrid potential for the ground state of a pair of neutral atoms from their internuclear separation, the depth and curvature of their potential at its minimum, and from their van der Waals coefficient of dispersion C₆.     

Calculation of scattering from stretched copolymers using the tube model: a generalisation of the RPA

There are many experimental situations in which polymer chains are constrained or localised into a small region of space (e.g. melt chains confined to a “tube”, network chains pinned by crosslinks). We show that detailed consideration of the quenched variables is vital in these experiments. This paper provides a crucial link between microscopic models with localising constraints and scattering patterns by a generalisation of the Random Phase Approximation (RPA) which allows for quenched translational variables. A method is developed which deals with correlations between the quenched variables brought about by incompressiblity (for example, in a polymer melt there are correlations between tubes because of the interaction between chains). As an example, the generalised RPA is applied to models based on the Warner-Edwards picture of the tube. Theoretical results for a melt of H-shaped copolymers are compared with experimental scattering. Early results suggest that to fit the scattering we may be forced to relax one of the central assumptions of the tube model; that the tube deforms affinely, that all chains retract by the same amount or that the tube diameter does not couple to the strain. Received 26 October 1998 and Received in final form 19 March 1999     

Perylene hexafluoroantimonate: Suppression of the Peierls transition by anion-chain disorder

Crystal growth and X-ray structural analysis are reported for the new quasi-one-dimensional organic conductor perylene hexafluoroantimonate. Due to deviation from exact 4:3 stoichiometry and anion-chain disorder the three-dimensional Peierls transition is suppressed to temperatures below 30 K in spite of a molecular field transition temperature of 330 K. Anisotropy of the microwave conductivity exceeds 3000:1 at room temperature. Curie paramagnetic defects with comparatively small electron spin resonance line width predominate at low temperature. Thermally activated paramagnetic defects, giving rise to pronounced Overhauser shift, are separated in the 30-100 K range. They are explained by neutral Perylene intra-stack defects, whose concentration can be reduced by both aging and annealing. The angular and temperature dependence of the conduction electron spin resonance line is analysed in detail, exhibiting the influence of intra-stack dipole interaction growing with temperature. Restricted diffusion of the conduction electron spins with diffusion coefficient of about 6 cm²/s parallel to the stacking direction is detected by fixed gradient pulsed electron spin resonance at room temperature. Received 17 July 1998     

Structural study of the ferroelectric instability in SnPSe

The structural change occurring in between the paraelectric and the ferroelectric phases is investigated by means of X-ray diffraction. Details of the structure in both phases are obtained and the role of the lone pair is discussed in the light of structural data. In agreement with the 2/ m to m symmetry lowering, polar displacements are found within the m plane away from a particular crystallographic direction but antiparallel displacements occur also. These results are discussed in the frame of the phenomenological theory which predicts a particular temperature dependence of the dielectric polarization in this crystal. Received: 10 July 1998     

Analysis of infrared reflectivity of conducting polymers: example of camphor-sulphonic-acid-doped polyaniline

The reflectivity spectrum of a polyaniline CSA-doped in presence of m-cresol has been measured over the wide wavenumber range of 15- 9 000 cm ^-1 (0.002-1.1 eV) at room temperature. Experimental data compare well with similar experiments performed by another group. The conductivity spectrum of this conducting polymer has been deduced from the reflectivity spectrum by means of two methods, Kramers-Kronig transformation and best fit of an “extended Drude” model to the reflectivity spectrum. Whereas the deviation from Drude behavior was interpreted in terms of Anderson localization or by inhomogeneous disorder by other groups, it is shown here that a different model developed for conducting oxides that also exhibit non-Drude behavior, applies very well to this example of conducting polymer. Received 11 February 1999 and Received in final form 26 April 1999     

Molecular dynamics in nanophase-separated comb-like poly( $ \upalpha$- n-alkyl $ \upbeta$-L-aspartate)s

A series of poly( -n-alkyl -L-aspartates) which are nanophase self-assembled comb-like polymers has been studied by dielectric spectroscopy in a broad frequency range ( 10^-23×10⁶ Hz), with n-alkyls side chains of various lengths, 10n18. In every member of the series the same relaxations were identified after the decomposition of the experimental isothermal trace in up to three peaks with relaxation times distributions. The strength, width and average relaxation time for all the relaxation modes were determined for each material. Besides the local low temperature, Arrhenius modes, two relaxation modes, and , present a cooperative character whose dynamics are not affected by the side chains melting. The relaxation is a polyethylene-like glass transition of the amorphous side chains and its dynamics is strongly dependent on the n value due to the increasing restrictions imposed by the self-assembled confinement. The strength of the relaxation mode increases as the lateral chains loose their 2D order. The restricted chopstick motion of the rigid rods is thought to be the origin of the mode; this motion is hindered at temperatures where the cage size decreases as a result of the increasing disorder with temperature.     

A molecular model for the line tension of lipid membranes

The line tension of a symmetric, lipid bilayer in its liquid-crystalline state is calculated on the basis of a molecular lipid model. The lipid model extends the opposing forces model by an expression for the conformational free energy of the hydrocarbon chains. We consider a membrane edge that consists of a perturbed bilayer covered by a section of a cylinder-like micelle. The structural rearrangement of the lipids implies an excess free energy which we minimize with respect to the cross-sectional shape of the membrane edge, including both the micellar and the bilayer region. The line tension is derived as a function of molecular lipid properties, like the lipid chain length or the head group interaction strength. We also relate it to the spontaneous curvature of the lipid layer. We find the line tension to become smaller for lipid layers that tend to curve more towards the hydrophobic core. Our predictions for the line tension and their relation to experimentally derived values are discussed. Received 2 January 2000     

Random phase approximation of the spin-wave excitation for quasi-one-dimensional magnetic polymer

Based on a theoretical model proposed for quasi-one-dimensional organic polymer ferromagnets, the ground state and low-lying magnetic excitation are studied. Within Hartree-Fock approximation, the ground state of the system is shown to be a stable ferromagnetic state due to the electron-electron correlation and topological structure of the system. The random-phase approximation is employed to explore the magnon excitation and the excitation spectrum is obtained, including an acoustic mode and four optical modes. It is found that the acoustic mode possesses the characteristic of the ferromagnetic magnon. Received 9 July 1999     

Water droplets in a spherically confined nematic solvent: A numerical investigation

Recently, it was observed that water droplets suspended in a nematic liquid crystal form linear chains [Poulin et al., Science 275, 1770 (1997)]. The chaining occurs, e.g., in a large nematic drop with homeotropic boundary conditions at all the surfaces. Between each pair of water droplets a point defect in the liquid crystalline order was found in accordance with topological constraints. This point defect causes a repulsion between the water droplets. In our numerical investigation we limit ourselves to a chain of two droplets. For such a complex geometry we use the method of finite elements to minimize the Frank free energy. We confirm an experimental observation that the distance d of the point defect from the surface of a water droplet scales with the radius r of the droplet like .When the water droplets are moved apart, we find that the point defect does not stay in the middle between the droplets, but rather forms a dipole with one of them. This confirms a theoretical model for the chaining. Analogies to a second order phase transition are drawn. We also find the dipole when one water droplet is suspended in a bipolar nematic drop with two boojums, i.e., surface defects at the outer boundary. Finally, we present a configuration where two droplets repel each other without a defect between them. Received 11 December 1998     

Miscibility in poly(L-lactide)- b -poly( $ \upvarepsilon$ -caprolactone) double crystalline diblock copolymers

Thermally stimulated depolarization currents, TSDC, wide-angle X-ray scattering, WAXS, differential scanning calorimetry, DSC, and polarized light optical microscopy, PLOM, have been used to examine poly(L-lactide)-b -poly( -caprolactone) diblock copolymers in a wide composition range. Both components are crystallizable and the miscibility in the amorphous phase has been determined from the behavior of the primary relaxations which are the dielectric manifestation of the glass transition, and also from the superstructural morphology revealed by PLOM and the compositional dependence of the melting points as determined by DSC. Distinct segmental mobilities in the amorphous phase which can be well resolved by TSDC are present; the mode of the slower component shifts to lower temperatures as the PCL content increases while the glass transition of neat PCL is present for all compositions. A relaxation times bimodal distribution is apparent for PCL-rich copolymers. The composition dependence of the multiple glass transitions detected in these weakly segregated copolymers are predicted by the self-concentration model for a miscible blend made of components with a large T_g contrast.     

Chain length dependence of anomalous swelling in multilamellar lipid vesicles

Using small-angle X-ray scattering, the repeat distance vs. temperature is measured for a homologous series of multilamellar vesicles of lecithins with varying acyl chain length in excess water condition around the lipid main transition. A systematic chain length dependence is found which is in accordance with a bending rigidity renormalization and critical unbinding of the lamellae close to the transition, as previously suggested in H?nger et al. [Phys. Rev. Lett. 72, 3911 (1994)]. Received 13 January 1999 and Received in final form 6 September 1999     

Charge carriers bulk recombination instead of electroplex emission after their tunneling through hole-blocking layer in OLEDs

Charge carriers bulk recombination instead of forming electroplex after their tunneling through a hole-blocking layer, i.e. 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP), in organic electroluminescence (EL) device ITO/poly-(N-vinyl-carbazole)(PVK)/BCP/tris(8-hydroxyquinoline) aluminum (Alq₃)/Al is reported. By changing the thickness of BCP layer, one can find that high electric fields enhance the tunneling process of holes accumulated at the PVK/BCP interface into BCP layer instead of forming “electroplex emission” as reported earlier in literatures. Our experimental data show that charge carriers bulk recombination takes place in both PVK layer and BCP layer, and even in Alq₃ layer when BCP layer is thin enough. Further, it is suggested that PVK is the origin of the emission shoulder at 595 nm in the EL spectra of trilayer device ITO/PVK/BCP/Alq₃/Al.