Large melting point depression of 2–3‐nm length‐scale nanocrystals formed by the self‐assembly of an associative polymer: Telechelic,pyrene‐labeled poly(dimethylsiloxane)

Large melting point depressions for organic nanocrystals, in comparison with those of the bulk, were observed in an associative polymer: telechelic, pyrene‐labeled poly(dimethylsiloxane) (Py‐PDMS‐Py). Nanocrystals formed within nanoaggregates of pyrenyl units that were immiscible in poly(dimethylsiloxane). For 5 and 7 kg/mol Py‐PDMS‐Py, physical gels resulted, with melting points exceeding 40 °C and with small‐angle X‐ray scattering peaks indicating that the crystals were nanoconfined, were 2–3 nm long, and contained roughly 18–30 pyrenyl dye end units. In contrast, 30 kg/mol Py‐PDMS‐PY was not a gel and exhibited no scattering peak at room temperature; however, after 12 h of annealing at ?5 °C, multiple melting peaks were present at 5–30 °C. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3470–3475, 2004     

Structure of a poly(2,5‐benzimidazole)/phosphoric acid complex

As‐cast films of poly(2,5‐benzimidazole) exhibit uniplanar orientation in which the planes of the aromatic rings lie parallel to the film surface. Upon doping with phosphoric acid, the original crystalline order is lost, but the doped film can be stretched to produce films with uniaxial orientation. After thermal annealing at 540 °C, nine Bragg reflections are resolved in the fiber diagram, and these are indexed by an orthorhombic unit cell with the dimensions a = 18.1 Å, b = 3.5 Å, and c = 11.4 Å, containing four monomer units of two chains. The absence of odd‐order 00l reflections points to a 2₁ chain conformation, which is probably planar so that the aromatic units can be stacked along the b axis. The water and phosphoric acid contents of the crystalline structure cannot be determined exactly because of the presence of extensive amorphous regions that probably have different solvation. The best agreement between the observed and calculated intensities is for an idealized structure containing two phosphoric acids and two water molecules per unit cell. However, the phosphoric acid is probably present mainly in the form of pyrophosphoric acid and its higher oligomers. In addition, the X‐ray data are consistent with a more disordered structure containing chains with random (up and down) polarity and a lack of c‐axis registry. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2576–2585, 2004     

Discontinuous travelling wave solutions for certain hyperbolic systems

In an earlier paper on a malignant cell invasion model (Marchantet al., SIAM J. Appl. Math, 60, 2000) we introduced a novelform of discontinuous travelling wave solution. These solutionscould be studied easily by combining behaviour within a phaseplane with the Rankine–Hugoniot shock conditions, whichdescribe properties (such as the ratio of the jump discontinuitiesto the speed of propagation) that solutions may possess. Theseresults were new for several reasons. The shock conditions relateto hyperbolic equations (which the model is) but were appliedin a travelling wave ordinary differential equation phase planeusing techniques that usually apply to parabolic reaction–diffusionsystems. In addition the solutions possess singular behaviournear several points in the phase plane but in spite of thisthere exists a robust and stable family of physically interestingsolutions. In this paper we discuss two previously studied models, oneof detonation theory and one of angiogenesis. We show that eachof these models also possesses a family of discontinuous travellingwave solutions which was not previously discovered. Of particularinterest is the solution which has a blunt interface at thefront of the invading profile. In all three models it is thissolution that is seen to stably evolve from physically relevantinitial data, and for physically relevant parameter values. This work confirms the robustness of these novel travellingwave solutions and their applicability to a wider range of mathematicalmodelling situations.     

A critical review of the chemical kinetics of SF4, SF5, and S2F10 in the gas phase

The gas phase chemical kinetics of SF₄, SF₅, and S₂F₁₀ are reviewed with particular emphasis on relevance to the general problem of the dielectric breakdown of SF₆. Specific reaction systems treated are SF₄ + F₂, SF₅ + SF₅, and the pyrolysis of S₂F₁₀. Computer modeling calculations were carried out to arrive at the best estimates of rate parameters. Based on the results of these calculations, sets of recommended rate parameters are provided. The major discrepancies and problems in establishing the kinetic data base are described. Thermochemical consequences of different model calculations are given.     

Complexation thermodynamics of free and graft oligomers with complementary polymers

The dilute solution complexation equilibrium between linear macromolecules and smaller complementary oligomers is considered when: (1) the oligomers are free in solution; and (2) the oligomers are covalently attached at one end to the polymer. A general statistical mechanical framework is developed and is illustrated using a simple random walk model for polymer conformation. The statistical mechanical partition functions are formulated using a generating function technique, allowing thermodynamic averages in the complexed state to be calculated. Loops, trains, and tails of all possible length are allowed in the conformation of a complexed oligomer. Simulation results for the free oligomer case are compared with those obtained for oligomers covalently attached to the polymeric molecular. The model provides a theoretical explanation for the experimentally observed enhancement of complexation of oligomers grafted to the complementary polymers.