Globular Structures of a Helix-Coil Copolymer: Self-Consistent Treatment

A self-consistent field theory was developed in the grand-canonical ensemble formulation to study transitions in a helix-coil multiblock globule. Helical and coil parts are treated as stiff rods and self-avoiding walks of variable lengths correspondingly. The resulting field-theory takes, in addition to the conventional Zimm-Bragg (B.H. Zimm, I.K. Bragg, J. Chem. Phys. 31, 526 (1959)) parameters, also three-dimensional interaction terms into account. The appropriate differential equations which determine the self-consistent fields were solved numerically with finite element method. Three different phase states are found: open chain, amorphous globule and nematic liquid-crystalline (LC) globule. The LC-globule formation is driven by the interplay between the hydrophobic helical segments attraction and the anisotropic globule surface energy of an entropic nature. The full phase diagram of the helix-coil copolymer was calculated and thoroughly discussed. The suggested theory shows a clear interplay between secondary and tertiary structures in globular homopolypeptides.Comment: 26 pages, 30 figures, corrected some typo

Intercalation-enhanced electric polarization and chain formation of nano-layered particles

Microscopy observations show that suspensions of synthetic and natural nano-layered smectite clay particles submitted to a strong external electric field undergo a fast and extended structuring. This structuring results from the interaction between induced electric dipoles, and is only possible for particles with suitable polarization properties. Smectite clay colloids are observed to be particularly suitable, in contrast to similar suspensions of a non-swelling clay. Synchrotron X-ray scattering experiments provide the orientation distributions for the particles. These distributions are understood in terms of competing (i) homogenizing entropy and (ii) interaction between the particles and the local electric field; they show that clay particles polarize along their silica sheet. Furthermore, a change in the platelet separation inside nano-layered particles occurs under application of the electric field, indicating that intercalated ions and water molecules play a role in their electric polarization. The resulting induced dipole is structurally attached to the particle, and this causes particles to reorient and interact, resulting in the observed macroscopic structuring. The macroscopic properties of these electro-rheological smectite suspensions may be tuned by controlling the nature and quantity of the intercalated species, at the nanoscale.Comment: 7 pages, 5 figure

Phase behavior of the Confined Lebwohl-Lasher Model

The phase behavior of confined nematogens is studied using the Lebwohl-Lasher model. For three dimensional systems the model is known to exhibit a discontinuous nematic-isotropic phase transition, whereas the corresponding two dimensional systems apparently show a continuous Berezinskii-Kosterlitz-Thouless like transition. In this paper we study the phase transitions of the Lebwohl-Lasher model when confined between planar slits of different widths in order to establish the behavior of intermediate situations between the pure planar model and the three-dimensional system, and compare with previous estimates for the critical thickness, i.e. the slit width at which the transition switches from continuous to discontinuous.Comment: Submitted to Physical Review

Perdeuterated cyanobiphenyl liquid crystals for infrared applications

Perdeuterated 4'-pentyl-4-cyanobiphenyl (D5CB) was synthesized and its physical properties evaluated and compared to those of 5CB. D5CB retains physical properties similar to those of 5CB, such as phase transition temperatures, dielectric constants, and refractive indices. An outstanding feature of D5CB is that it exhibits a much cleaner and reduced infrared absorption. Perdeuteration, therefore, extends the usable range of liquid crystals to the mid infrared by significantly reducing the absorption in the near infrared, which is essential for telecom applications

Grating-coupled excitation of multiple surface plasmon-polariton waves

The excitation of multiple surface-plasmon-polariton (SPP) waves of different linear polarization states and phase speeds by a surface-relief grating formed by a metal and a rugate filter, both of finite thickness, was studied theoretically, using rigorous coupled-wave-analysis. The incident plane wave can be either p or s polarized. The excitation of SPP waves is indicated by the presence of those peaks in the plots of absorbance vs. the incidence angle that are independent of the thickness of the rugate filter. The absorbance peaks representing the excitation of s-polarized SPP waves are narrower than those representing p-polarized SPP waves. Two incident plane waves propagating in different directions may excite the same SPP wave. A line source could excite several SPP waves simultaneously

Entropy-driven enhanced self-diffusion in confined reentrant supernematics

We present a molecular dynamics study of reentrant nematic phases using the Gay-Berne-Kihara model of a liquid crystal in nanoconfinement. At densities above those characteristic of smectic A phases, reentrant nematic phases form that are characterized by a large value of the nematic order parameter $S\simeq1$. Along the nematic director these "supernematic" phases exhibit a remarkably high self-diffusivity which exceeds that for ordinary, lower-density nematic phases by an order of magnitude. Enhancement of self-diffusivity is attributed to a decrease of rotational configurational entropy in confinement. Recent developments in the pulsed field gradient NMR technique are shown to provide favorable conditions for an experimental confirmation of our simulations.Comment: 10 pages, 5 figure

Thermal annealing study of swift heavy-ion irradiated zirconia

Sintered samples of monoclinic zirconia (alpha-ZrO2) have been irradiated at room temperature with 6.0-GeV Pb ions in the electronic slowing down regime. X-ray diffraction (XRD) and micro-Raman spectroscopy measurements showed unambiguously that a transition to the 'metastable' tetragonal phase (beta-ZrO2) occurred at a fluence of 6.5x10^12 cm-2 for a large electronic stopping power value (approx 32.5 MeV $\mu$m-1). At a lower fluence of 1.0x10^12 cm-2, no such phase transformation was detected. The back-transformation from beta- to alpha-ZrO2 induced by isothermal or isochronal thermal annealing was followed by XRD analysis. The back-transformation started at an onset temperature around 500 K and was completed by 973 K. Plots of the residual tetragonal phase fraction deduced from XRD measurements versus annealing temperature or time are analyzed with first- or second-order kinetic models. An activation energy close to 1 eV for the back-transformation process is derived either from isothermal annealing curves, using the so-called "cross-cut" method, or from the isochronal annealing curve, using a second-order kinetic law. Correlation with the thermal recovery of ion-induced paramagnetic centers monitored by EPR spectroscopy is discussed. Effects of crystallite size evolution and oxygen migration upon annealing are also addressed

A chilled margin of komatiite and Mg-rich basaltic andesite in the western Bushveld Complex, South Africa

A chill sequence at the base of the Lower Zone of the western Bushveld Complex at Union Section, South Africa, contains aphanitic Mg-rich basaltic andesite and spinifex-textured komatiite. The basaltic andesite has an average composition of 15.2 % MgO, 52.8 % SiO2, 1205 ppm Cr, and 361 ppm Ni, whereas the komatiite has 18.7 % MgO, 1515 ppm Cr, and 410 ppm Ni. Both rock types have very low concentrations of immobile incompatible elements (0.14–0.72 ppm Nb, 7–31 ppm Zr, 0.34–0.69 ppm Th, 0.23–0.27 wt% TiO2), but high PGE contents (19–23 ppb Pt, 15–16 ppb Pd) and Pt/Pd ratios (Pt/Pd 1.4). Strontium and S isotopes show enriched signatures relative to most other Lower Zone rocks. The rocks could represent a ~20 % partial melt of subcontinental lithospheric mantle. This would match the PGE content of the rocks. However, this model is inconsistent with the high SiO2, Fe, and Na2O contents and, in particular, the low K2O, Zr, Hf, Nb, Ta, Th, LREE, Rb, and Ba contents of the rocks. Alternatively, the chills could represent a komatiitic magma derived from the asthenosphere that underwent assimilation of the quartzitic floor accompanied by crystallization of olivine and chromite. This model is consistent with the lithophile elements and the elevated Sr and S isotopic signatures of the rocks. However, in order to account for the high Pt and Pd contents of the magma, the mantle must have been twice as rich in PGE as the current estimate for PUM, possibly due to a component of incompletely equilibrated late veneer

41Ca in tooth enamel. part I: A biological signature of neutron exposure in atomic bomb survivors

The detection of 41Ca atoms in tooth enamel using accelerator mass spectrometry is suggested as a method capable of reconstructing thermal neutron exposures from atomic bomb survivors in Hiroshima and Nagasaki. In general, 41Ca atoms are produced via thermal neutron capture by stable 40Ca. Thus any 41Ca atoms present in the tooth enamel of the survivors would be due to neutron exposure from both natural sources and radiation from the bomb. Tooth samples from five survivors in a control group with negligible neutron exposure were used to investigate the natural 41Ca content in tooth enamel, and 16 tooth samples from 13 survivors were used to estimate bomb-related neutron exposure. The results showed that the mean 41Ca/Ca isotope ratio was (0.17 ± 0.05) × 10-14 in the control samples and increased to 2 × 10-14 for survivors who were proximally exposed to the bomb. The 41Ca/Ca ratios showed an inverse correlation with distance from the hypocenter at the time of the bombing, similar to values that have been derived from theoretical free-in-air thermal-neutron transport calculations. Given that γ-ray doses were determined earlier for the same tooth samples by means of electron spin resonance (ESR, or electron paramagnetic resonance, EPR), these results can serve to validate neutron exposures that were calculated individually for the survivors but that had to incorporate a number of assumptions (e.g. shielding conditions for the survivors).Fil: Wallner, A.. Ludwig Maximilians Universitat; Alemania. Universitat Technical Zu Munich; Alemania. Universidad de Viena; AustriaFil: Ruhm, W.. Helmholtz Center Munich German Research Center For Environmental Health; Alemania. Ludwig Maximilians Universitat; AlemaniaFil: Rugel, G.. Ludwig Maximilians Universitat; Alemania. Universitat Technical Zu Munich; AlemaniaFil: Nakamura, N.. Radiation Effects Research Foundation; JapónFil: Arazi, Andres. Universitat Technical Zu Munich; Alemania. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Faestermann, T.. Universitat Technical Zu Munich; AlemaniaFil: Knie, K.. Universitat Technical Zu Munich; Alemania. Ludwig Maximilians Universitat; AlemaniaFil: Maier, H. J.. Ludwig Maximilians Universitat; AlemaniaFil: Korschinek, G.. Universitat Technical Zu Munich; Alemani

Unified algebraic treatment of resonance

Energy resonance in scattering is usually investigated either directly in the complex energy plane (E-plane) or indirectly in the complex angular momentum plane (L-plane). Another formulation complementing these two approaches was introduced recently. It is an indirect algebraic method that studies resonances in a complex charge plane (Z-plane). This latter approach will be generalized to provide a unified algebraic treatment of resonances in the complex E-, L-, and Z-planes. The complex scaling (rotation) method will be used in the development of this approach. The resolvent operators (Green's functions) are formally defined in these three spaces. Bound states spectrum and resonance energies in the E-plane are mapped onto a discrete set of poles of the respective resolvent operator on the real line of the L- and Z-planes. These poles move along trajectories as the energy is varied. A finite square integrable basis is used in the numerical implementation of this approach. Stability of poles and trajectories against variation in all computational parameters is demonstrated. Resonance energies for a given potential are calculated and compared with those obtained by other studies.Comment: 15 pages, 1 Table, 7 Figures (6 are snapshots of videos