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.     

The inclusion of electrostatic and dispersion interactions into potentials of mean torque for solutes dissolved in uniaxial liquid crystal solvents

A potential of mean torque is derived for a solute at infinite dilution in a uniaxial liquid crystal solvent, which contains terms originating from the dispersion interaction, and the electrostatic interaction between quadrupole moments on both molecules. It is shown that the electrostatic term is non-zero only if the solute-solvent vectors are distributed with lower than spherical symmetry. If this distribution has cylindrical symmetry then both the electrostatic and dispersion terms in the potential of mean torque are shown to depend on order parameters for the orientational distribution of the solute-solvent vectors, as well as on the order parameters of the solvent molecules.     

Electronic phase separation in a low-temperature tetragonal phase of lanthanum-strontium cuprates according to 139La NQR data

A nonuniform electron density distribution is observed in La_{1−x− y} Nd_ySr_xCuO₄ and La_1−x−y Eu_ySr_xCuO₄, and long-lived magnetic fluctuations in these compounds are studied. The dynamics of the magnetic fluctuations depends strongly on the magnetic properties of the rare-earth ions, which stabilize the low-temperature tetragonal phase. Pis’ma Zh. éksp. Teor. Fiz. 67, No. 5, 344–349 (10 March 1998)     

Anomalous anisotropies and field dependencies of the muon Knight shift and the relaxation rate in monocrystalline Bi

The angular dependence of the muon Knight shift,K _μ, and the muon relaxation rate in Bi at 11 K were measured in external magnetic fields up to 1 T. BothK _μ and the second moment,M ₂, are field dependent and involveP ₄ ⁰(cos θ) andP ₄ ³(cos θ) terms in the angular dependence. The Knight shift behaviour is discussed in terms of the dipole-dipole interaction and the de Haas-van Alphen effect, a consistent interpretation was not achieved in either case. The field dependence ofM ₂ is in complete contrast to the second moment calculations and points to a field dependent redistribution of the charge distribution around the interstitial site.     

Energy transfer between the flavin chromophores of electron-transferring flavoprotein fromMegasphaera elsdenii as inferred from time-resolved red-edge and blue-edge fluorescence spectroscopy

Both a mode-locked argon-ion laser and synchrotron radiation were used as excitation sources to obtain time-resolved polarized fluorescence of the two FAD cofactors in electron transferring flavoprotein fromMegasphaera elsdenii. Red-edge excited and blue-edge detected fluorescence anisotropy decay curves did not contain a fast relaxation process which was observed upon mainband excitation and detection. This relaxation was assigned to homo-energy transfer between the two FAD cofactors. Failure of energy transfer as observed with edge spectroscopy on this protein excludes restricted reorientational motion of the flavins as a possible mechanism of depolarization. From the global analysis of the fluorescence anisotropy decay surface obtained at multiple excitation and detection wavelengths, the distance between and the relative orientation of the flavins could be estimated. The methodology described has general applicability in other multichromophoric biopolymers and has the potential to acquire accurate geometrical parameters in these systems.     

Change in the nature of the Ni diffusion mechanism on the Si(111) surface with adsorption of Co atoms

The diffusion of Ni on a Si (111) surface is investigated by LEED and Auger electron spectroscopy. It is found that, in contrast to the process on the initially clean Si (111)−7×7 surface, on Si (111) surfaces with submonolayer Co coverages the nature of the Ni transport mechanism changes at a temperature of about 750 °C, and the Ni surface diffusion coefficients increase sharply below this temperature. Pis’ma Zh. éksp. Teor. Fiz. 66, No. 9, 611–614 (10 November 1997)     

Pseudo-billiards

A new class of Hamiltonian dynamical systems with two degrees of freedom and kinetic energy of the form T = c₁|p₁| + c₂|p₂| (called “pseudo-billiards”) is studied. For any kind of interaction, the canonical equations can always be integrated on sequential time intervals; i.e. in principle all the trajectories can be found explicitly.

Depending on the potential, a dynamical system of this class can either be completely integrable or behave just as a usual non-integrable Hamiltonian system with two degrees of freedom: in its phase space there exist invariant tori, stochastic layers, domains of global chaos, etc. Pseudo-billiard models of both the types are considered.

If a potential of a pseudo-billiard system has critical points (equilibria), then trajectories close to these points (“loops”) can exist; they can be treated as images of self-localized objects with finite duration. Such a model (with quartic potential) is also studied.     

Intra-cavity spectroscopy with diode lasers

A multi-mode diode laser with an external cavity is studied experimentally and theoretically for its application to intra-cavity spectroscopy. One facet of a typical Ga_0.89Al_0.11As laser diode was antireflection-coated by deposition of HfO₂ such that 10^–3 residual reflectivity was left over. This diode was placed in an external optical cavity. The emission spectrum of this diode laser is highly sensitive to any frequency-dependent loss in the cavity, and the detectivity of such a loss grows with the pump rate. Even close to threshold, the absorption at 780 nm of Rb atoms with a density of 5×10¹⁰ cm^–3 has been detected. An adequate model for diode lasers based on rate equations and including frequency-dependent gain saturation is developed and applied to the calculations of output spectra. The sensitivity of these spectra to intra-cavity absorption is determined by the overall cavity loss — which is rather high — and the fraction of spontaneous emission in the total emission, in contrast with dye lasers where it is limited by nonlinear mode coupling. Various criteria for the sensitivity are suggested. The smallest detectable absorption with a perfectly antireflection-coated laser is 10^–6 cm^–1. Improvement of the characteristics of the laser diode would increase the sensitivity.     

Certification of the sulphur content of three rapeseed reference materials

Summary The sulphur content of three rapeseed reference materials has been certified on the basis of measurements made by inductively coupled plasma-optical emission spectroscopy, isotope-dilution mass spectrometry and ion chromatography. Their suitability for the calibration of x-ray fluorescence spectrometers used for measuring sulphur in rapeseed samples was established.