Crystalline polymers in real space

Recent work has resolved uncertainties as to how polymers develop their melt-crystallized textures and brought a unified context to the subject. Spherulites form because of the long molecular length not because of its polydispersity. When a molecule is only partly attached to a growing lamella the unattached portions will occupy adjacent space and exert a short-range repulsive pressure on any neighbouring lamella at a branch point. This is confirmed by monodisperse long n-alkanes forming spherulites only with chainfolded lamellae not when crystallizing as extended chains. An additional textural element, cellulation, is superposed on regular spherulitic growth beyond a certain radius (in linear-low-density polyethylenes) when there is sufficient fractional crystallization of segregated species which lower the local equilibrium melting temperature and thence the isothermal supercooling and growth rate, the last declining continuously to an asymptotic limit. First results show that both the radius to cellulation and the cell width are effectively independent of growth velocity; neither scales with the diffusion length. A possible explanation is proposed for this novel situation which has no precedent in either polymeric or non-polymeric systems.     

Head-to-Head Polymers

Head-to-head polymers of α-olef ins, vinyl and acrylic monomers synthesized by indirect methods have shown similarities and differences in some of their behavior when compared to their counterparts of the common head to tail polymers. Head-to-head polyole-fins, such as polystyrene or polypropylene, were prepared by 1,4-polymerization of the corresponding 2,3-disubstituted butadienes-1,3 followed by hydrogenation of the remaining double bonds, polyacrylates by alternating copolymerization of ethylene and maleic anhydride, followed by esterification of the polymer. Head-to-head polyacrylates were reduced to poly(allyl alcohols) which were then acrylated to the acetates and benzoates. Head-to-head polyvinyl halides) were obtained from 1,4-polybutadiene by chlorination or bromination. The head-to-head polymers were characterized by spectroscopic analysis, some molecular weight characterization was done, and their thermal behavior was studied. The blending behavior with the corresponding head-to-tail polymers was studied in some cases; in others (head-to-head polystyrene), the blending with other polymers was investigated and the codegradation of the polymers was evaluated.     

Fully fluorinated imidodiphosphinate shells for visible- and NIR-emitting lanthanides: hitherto unexpected effects of sensitizer fluorination on lanthanide emission properties

In this paper we demonstrate that the effect of aromatic C--F substitution in ligands does not always abide by conventional wisdom for ligand design to enhance sensitisation for visible lanthanide emission, in contrast with NIR emission for which the same effect coupled with shell formation leads to unprecedented long luminescence lifetimes. We have chosen an imidodiphosphinate ligand, N-{P,P-di(pentafluorophinoyl)}-P,P-dipentafluorophenylphosphinimidic acid (HF20tpip), to form ideal fluorinated shells about all visible- and NIR-emitting lanthanides. The shell, formed by three ligands, comprises twelve fully fluorinated aryl sensitiser groups, yet no-high energy X--H vibrations that quench lanthanide emission. The synthesis, full characterisation including X-ray and NMR analysis as well as the photophysical properties of the emissive complexes [Ln(F20tpip)3], in which Ln=Nd, Sm, Eu, Gd, Tb, Dy, Er, Yb, Y, Gd, are reported. The photophysical results contrast previous studies, in which fluorination of alkyl chains tends to lead to more emissive lanthanide complexes for both visible and NIR emission. Analysis of the fluorescence properties of the HF20tpip and [Gd(F20tpip)3] reveals that there is a low-lying state at around 715 nm that is responsible for partially quenching of the signal of the visible emitting lanthanides and we attribute it to a pi-sigma* state. However, all visible emitting lanthanides have long lifetimes and unexpectedly the [Dy(F20tpip)3] complex shows a lifetime of 0.3 ms, indicating that the elimination of high-energy vibrations from the ligand framework is particularly favourable for Dy. The NIR emitting lanthanides show strong emission signals in powder and solution with unprecedented lifetimes. The luminescence lifetimes of [Nd(F20tpip)3], [Er(F20tpip)3] and [Yb(F20tpip)3] in deuteurated acetonitrile are 44, 741 and 1111 micros. The highest value observed for the [Yb(F20tpip)3] complex is more than half the value of the Yb ion radiative lifetime.     

Neuropeptide delivery to the brain: a von Willebrand factor signal peptide to direct neuropeptide secretion

Background  

Multiple neuropeptides, sometimes with opposing functions, can be produced from one precursor gene. To study the roles of the different neuropeptides encoded by one large precursor we developed a method to overexpress minigenes and establish local secretion.     

Deviatoric stress: a nuisance or a gold mine?

Both synchrotron radiation and deviatoric stress were once considered to be nuisances. Now synchrotron radiation is one of the most important tools available to scientists of all disciplines and deviatoric stress is one of the most useful aspects of x-ray diffraction at extreme conditions. Samples in high-pressure devices are under true hydrostatic pressure only when surrounded by a fluid, thus limiting true hydrostatic pressure studies at ambient temperatures to pressures below about 11?GPa. Elevated temperature is able to extend this limit but has rarely been used for this purpose. Instead, noble gases have been used as pressure media as their solids are especially soft. Deviatoric stress and resultant anisotropic elastic strain in solid samples and solid media have led to many subtle errors in determinations of elastic properties and crystal structures, especially in the days before it was realized that they could be measured and were potentially a valuable source of information. In recent years, measuring anisotropic elastic strain by x-ray diffraction has provided new insights into materials strength, elastic properties, crystal structures, mechanisms of phase transitions, slip systems, lattice preferred orientation, and, of course, ways to make corrections when deviatoric stress is indeed a nuisance.     

An investigation of permanganic etching of linear low-density polyethylene

Permanganic etching is a technique of removing material selectively to reveal lamellae in crystalline polymers. It is generally found that populations of lamellae with different thicknesses are removed to different depths. In linear poly-ethylene we have previously shown that this discrimination is not an inherent property but a consequence of differential deformation during cutting to expose the surface prior to etching. The work is now extended to linear low-density polyethylene to test whether the changed basis of molecular segregation (with more branched molecules crystallizing later) alters the etching behavior. It is shown that thinner lamellae are etched at a faster rate which is only slightly reduced after removing damage due to cutting. This intrinsic differentiation between crystal thicknesses accompanies faster etching rates than for the linear material. It is inferred that this is due to faster chain scission at fold surfaces which are more penetrable for the linear low-density than for the linear polymer; however, chain scission remains slow compared to stem removal. Fold stems are probably removed as entities rather than incrementally, but it is evident that a fold surface region needs to be etched away before a stem can be removed.     

Optical study of H2O ice to 120 GPa: dielectric function, molecular polarizability, and equation of state

The refractive index of H2O ice has been measured to 120 GPa at room temperature using reflectivity methods. The refractive index increases significantly with pressure on initial compression and exhibits small changes with pressure at previously identified phase transitions. Pressure dependencies of the molecular polarizability show changing slopes in different pressure regions. A general molar refractivity analysis of this change in slope reveals features at 60 GPa due to the onset of the ice VII-X transition. Band gap closure in H2O ice is constrained by the dispersion data using a single oscillator dielectric model. Sample thickness measurements obtained from interference patterns yield pressure-volume relations in excellent agreement with those measured by x-ray diffraction.