Mesomorphic structure peculiarities of two mix-substituted phthalocyanines of the A3B type

Mesomorphic properties and structures of two mix-substituted lipophilic phthalocyanine derivatives of the A₃B type, with a different ratio of electron-donating (hexadecyloxy-) and electron-withdrawing (Cl-) substituents on the isoindol fragments ‘A’ and ‘B’, correspondingly, were studied by polarising optical microscopy, differential scanning calorimetry and small-angle X-ray scattering. Both compounds display columnar mesophases, and the type of organisation of the columns in the mesomorphic state was found to strongly depend on the number of peripheral chlorine substituents in the molecule. The di-chloro-substituted phthalocyanine forms a solid pasty lamellar phase at room temperature, which on heating undergoes successive transitions to two large-lattice columnar mesophases (2D-Col_h and 3D-M_Col) arising from the aggregation of several phthalocyanine-containing piles. On the contrary, aggregation of columns does not occur for the tetra-chloro-substituted phthalocyanine, which forms a nematic columnar mesophase of single phthalocyanine piles (1D-N_Col). While the di-chloro-compound partly crystallises on cooling, the nematic phase of the tetra-chloro-compound freezes at room temperature. The reasons for this different self-organisation behaviour are not yet fully understood, but some hints may be deduced from the proposed supramolecular models.     

Formation and structure of chitosan–poly(sodium methacrylate) complex nanoparticles

Interpolyelectrolyte complex (IPEC) dispersions were prepared from chitosan and poly(sodium acrylate), NaPMA, by mixing their solutions, at different carboxyl-to-aminium molar ratios, r_CA. Gyration radius was determined by small angle x-ray scattering (SAXS) and showed that, as r_CA was increased, IPEC dimensions decreased and reached a minimum at r_CA?=?0.75, which was considered the ratio at which IPEC cluster dimensions were minimum, following collapse, phase segregation, nucleation, and growth of larger particles. Pair distance distributions, P(r), became narrower up to r_CA?=?0.75, increasing its width from this point. Relaxation-related parameters from dynamic light scattering (DLS) intensity correlation functions (ICFs) identified three main relaxation processes. The fast process, related to free polyelectrolyte molecules random motion disappeared as r_CA, was increased. The other two relaxation processes also were a function of r_CA and presented marked changes at r_CA?=?0.75. At the same value of r_CA, the energy of activation for the average relaxation rate showed the occurrence of a clear change in the nature of IPEC-related interactions. As hydrodynamic diameter, determined by DLS, was much larger than the gyration radius determined by SAXS, IPEC particles could be described as being composed by a core, rich in segregated, insoluble material, enveloped by IPEC soluble clusters, possibly in the form of water-rich gels.     

Mechanically robust conductive carbon clusters confined ethylene methyl acrylate–based flexible composites for superior shielding effectiveness

Arresting of conducting carbon black into polymeric matrix to develop flexible and light weight composite has been a widely practiced platform. Extensive development of telecommunication creates a major vexations regarding radiation pollution. Thereafter, we have been motivated to develop low‐cost, flexible composites of specialty carbon black VXC (Vulcan XC 72)–filled ethylene methyl acrylate (EMA) by mechanical mixing technique. Developed composite has significant conductivity (6.67 × 10⁻⁴ S cm⁻¹) with promising mechanical and thermal properties. Dispersion of high‐structured carbon blacks in EMA was investigated by small angle X‐ray scattering to reflect the dependency of conducting mesh formation on dispersion. Interconnected filler network development has been visualized by field emission scanning electron microscope and high‐resolution transmission electron microscope. Electromagnetic interference shielding value in the X band has calculated to be 30.8 dB. Such features can make this EVXC (EMA‐Vulcan XC 72) composite a useful alternate for flexible electromagnetic interference shielding material.     

Modification of membrane heterogeneity by antipsychotic drugs: an X-ray diffraction comparative study

Lipid mixtures are used to mimic biological membranes as they allow characterization of lipid lateral domains defined by their specific lipid molecular organization. Therapeutic agents such as antipsychotic drugs (AP) that may interact with lipids arrangement are likely to modify membrane biological properties. The present study describes the effect of 2 typical and 5 atypical antipsychotic drugs on an aqueous co-dispersion of a lipid mixture made of egg phosphatidylcholine (PC)/brain sphingomyelin (SM)/cholesterol (1/1/1 mol/mol/mol). Lamellar liquid-ordered (Lo) and liquid-disordered (Ld) phase coexistence was identified in the control and antipsychotic-added mixtures at 37 degrees C using synchrotron small-angle X-ray scattering methods (XRD). Intensity of the Bragg peaks was used to generate electron density profiles (EDP) allowing bilayer thickness calculation. All antipsychotic except from amisulpride induced a Lo phase bilayer thickness (d(pp)) decrease. Chlorpromazine, haloperidol, amisulpride and 9-0H-risperidone induced a Ld d(pp) increase while ziprazidone, risperidone and clozapine induced a Ld d(pp) decrease, indicating that antipsychotic atypicality is not associated with a specific d(pp) modification on our lipid model mixture. Results are discussed in terms of competition of antipsychotic compounds with cholesterol and mode of reorganization of lateral domains. A pharmacological relevance of these changes is also discussed.     

A single parameter determines mesophase transitions in Swollen Liquid Crystals

We report how the control of a single parameter, the co-surfactant, determines the phase transitions of oil-in-water swollen liquid crystals (SLCs) prepared with cetyltrimethylammonium bromide (CTAB), from cubic to hexagonal, lamellar, and finally sponge-like structures. SLCs are complex mixtures (surfactant + co-surfactant + water + salt + oil) usually prepared to form hexagonal mesophases, with cell parameters tunable between 3 and 30 nm. These hexagonal mesophases were successfully used as nanoreactors to prepare a broad range of nanostructured materials. Because the potential of these mesophases as adaptive nanoreactors has not been extended to other liquid crystal geometries than the hexagonal, we studied in a first step the structure evolution of SLCs made with CTAB, cyclohexane, pentanol-1, water and different stabilising salts. We used small-angle X-ray scattering (SAXS), polarised light microscopy and Freeze-Fracture TEM to provide a partial phase diagram and list the different mesophases obtained as a function of composition. We report that the adjustment of a single parameter, the co-surfactant (pentanol-1), determines the phase transition between cubic, hexagonal, lamellar, and sponge-like structures, all other parameters such as the nature and concentration of salt, or amount of oil being constant.     

The influence of halide-mediated oxidation on algae-born adhesives

Adhesive materials extracted from the brown algae Fucus Serratus were studied. These adhesives are composed of cross-linked alginate and polyphenols oxidized in the presence of KI or KBr. All formulations were capable of adhering to a variety of surfaces, however the adhesion properties were influenced by the halide used. SAXS and TEM experiments revealed that oxidized polyphenols self-assemble into chain-like objects, irrespective of the oxidation conditions. Yet, slight differences in the aggregate size were detected. QCM-D results showed that the kinetics of the oxidation was faster with iodide than with bromide. Moreover, oxidation with iodide generates stiffer networks, suggesting that the interaction between the alginate and the polyphenol could be the cause of the reduced adhesion.     

Ordering in Bio-Polyelectrolyte Chitosan Solutions

The scaling of the polyelectrolyte scattering peak in chitosan solutions, as deduced from the relation q_max∼c_p^α was studied by synchrotron SAXS as a function of the charge density of the polymer. We observe a variation in the α exponent corresponding to the limit of the ionic condensation, by varying the degree of acetylation of the polymer. The nature of the solution medium also affects the polyelectrolyte peak, and it is shown that in alcoholic/water mixtures, the lower dissociation of the acid induces a lower charge density, thus influencing the polyelectrolyte ordering.     

Thermoreversible gelation and phase separation in aqueous methyl cellulose solutions

We derived typical phase diagrams for aqueous solutions of methyl cellulose (MC) of different molecular weights via micro‐differential scanning calorimetry, small‐angle X‐ray scattering, and visual inspection. The phase diagrams showed the cooccurrence of gelation and phase separation and qualitatively agreed with the theoretically calculated diagrams. The sol–gel transition line and phase separation line of a lower critical solution point type shifted toward lower temperatures and lower concentrations with an increase in the MC molecular weight. The sol–gel transition line intersected at a temperature higher than the critical point of the phase separation; therefore, both sol–gel phase separation and gel–gel phase separation were possible, depending on the temperature. Specifically, through visual inspection of a high molecular weight MC sample in the critical temperature region, we observed phase separation into two coexisting gels with different polymer concentrations. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 39: 91–100, 2001     

Blends of nylon‐6 with phenol‐containing polymers

The miscibility of nylon‐6 with poly(4‐vinylphenol) (PVPh) or poly(1‐hydroxy‐2,6‐methylphenylene) (p‐Cl‐novolac) was studied with differential scanning calorimetry and small‐angle X‐ray scattering techniques. Both PVPh and p‐Cl‐novolac are miscible with nylon‐6 at the molecular level. The presence of the phenolic polymers affects the crystallization of nylon‐6 and suppresses its melting point. PVPh increases the long space order in crystalline nylon‐6 because it increases the thickness of the amorphous layers. In contrast, a small quantity of p‐Cl‐novolac tends to decrease the long space order. It seems that p‐Cl‐novolac distributed in the amorphous regions introduces more order in these regions and makes the amorphous layers thinner. © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 841–850, 2001     

SAXS study on ionic aggregates of styrene‐isoprene‐sulfonated isoprene terpolymer ionomer

The small‐angle X‐ray scattering profile of styrene‐isoprene‐sulfonated isoprene terpolymer ionomers was studied to clarify the structure of ionic aggregates at ambient temperature as a function of the degree of neutralization of Na or Mg cations. An ionic cluster peak was observed for ionomers with a degree of neutralization greater than 25%. The ionic cluster peak was analyzed by the modified hard sphere model proposed by Yarusso and Cooper [Macromolecules, 1983, 16, 1871], and the size of the ion cluster, the closest approach distance between the clusters, and the average system volume per ion cluster were evaluated by a curve‐fitting method. The size of the ion clusters of the ionomer with monovalent Na cation increased with the degree of neutralization, but for divalent Mg cation slightly changed. The number of ion clusters of the styrene‐isoprene‐sulfonated isoprene ionomer with Na and Mg cations characteristically increased with the neutralization. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 1307–1311, 2000