Roles of rhenium diimine complexes as metal‐ion probes and photosensitizers in functional polyurethanes

Polyurethanes incorporated with rhenium diimine complexes were synthesized. The polymers exhibited interesting morphologies and solution properties. Results from gel permeation chromatography suggested the formation of polymer aggregates in solutions. The polymers could act as probes for metal ions. The addition of metal ions to polymer solutions led to significant changes in the electronic absorption properties of the polymer solutions. This was attributed to the interactions between the polyether moieties and metal ions. The metal complexes could also act as efficient photosensitizers. After doping with charge‐transport viologens, the photoconductivity of the polymers was greatly enhanced. The experimental quantum efficiency was simulated with Onsager's theory. The thermalization distances and the primary yields were typically 12–14 Å and 10^?3, respectively. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 1708–1715, 2003     

On Levels in Arrangements of Curves, II: A Simple Inequality and Its Consequences

We give a surprisingly short proof that in any planar arrangement of n curves where each pair intersects at most a fixed number (s) of times, the k-level has subquadratic (O(n^2-1/2s) complexity. This answers one of the main open problems from the author’s previous paper [DCG 29, 375-393 (2003)], which provided a weaker upper bound for a restricted class of curves only (graphs of degree-s polynomials). When combined with existing tools (cutting curves, sampling, etc.), the new idea generates a slew of improved k-level results for most of the curve families studied earlier, including a near-O(n^3/2 bound for parabolas.     

Synthesis of highly condensed heterocycles using radical reactions

Using radical chemistry novel highly condensed heterocycles have been synthesized. The mechanism for their formation is discussed.     

Least‐squares meshfree method for incompressible Navier–Stokes problems

A least‐squares meshfree method based on the first‐order velocity–pressure–vorticity formulation for two‐dimensional incompressible Navier–Stokes problem is presented. The convective term is linearized by successive substitution or Newton's method. The discretization of all governing equations is implemented by the least‐squares method. Equal‐order moving least‐squares approximation is employed with Gauss quadrature in the background cells. The boundary conditions are enforced by the penalty method. The matrix‐free element‐by‐element Jacobi preconditioned conjugate method is applied to solve the discretized linear systems. Cavity flow for steady Navier–Stokes problem and the flow over a square obstacle for time‐dependent Navier–Stokes problem are investigated for the presented least‐squares meshfree method. The effects of inaccurate integration on the accuracy of the solution are investigated. Copyright © 2004 John Wiley & Sons, Ltd.     

Behavior and surface energies of polybenzoxazines formed by polymerization with argon,oxygen, and hydrogen plasmas

Polybenzoxazine (PBZZ) thin films can be fabricated by the plasma‐polymerization technique with, as the energy source, plasmas of argon, oxygen, or hydrogen atoms and ions. When benzoxazine (BZZ) films are polymerized through the use of high‐energy argon atoms, electronegative oxygen atoms, or excited hydrogen atoms, the PBZZ films that form possess different properties and morphologies in their surfaces. High‐energy argon atoms provide a thermodynamic factor to initiate the ring‐opening polymerization of BZZ and result in the polymer surface having a grid‐like structure. The ring‐opening polymerization of the BZZ film that is initiated by cationic species such as oxygen atoms in plasma, is propagated around nodule structures to form the PBZZ. The excited hydrogen atom plasma initiates both polymerization and decomposition reactions simultaneously in the BZZ film and results in the formation of a porous structure on the PBZZ surface. We evaluated the surface energies of the PBZZ films polymerized by the action of these three plasmas by measuring the contact angles of diiodomethane and water droplets. The surface roughness of the films range from 0.5 to 26 nm, depending on the type of carrier gas and the plasma‐polymerization time. By estimating changes in thickness, we found that the PBZZ film synthesized by the oxygen plasma‐polymerization process undergoes the slowest rate of etching in CF₄ plasma. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 4063–4074, 2004     

Gray code for derangements

We give a Gray code and constant average time generating algorithm for derangements, i.e., permutations with no fixed points. In our Gray code, each derangement is transformed into its successor either via one or two transpositions or a rotation of three elements. We generalize these results to permutations with number of fixed points bounded between two constants.     

Hydroxylation-induced modifications of the Al2O3/NiAl(0 0 1) surface at low water vapour pressure

STM, STS, LEED and XPS data for crystalline θ-Al₂O₃ and non-crystalline Al₂O₃ ultra-thin films grown on NiAl(0 0 1) at 1025 K and exposed to water vapour at low pressure (1 × 10⁻⁷-1 × 10⁻⁵ mbar) and room temperature are reported. Water dissociation is observed at low pressure. This reactivity is assigned to the presence of a high density of coordinatively unsaturated cationic sites at the surface of the oxide film. The hydroxyl/hydroxide groups cannot be directly identify by their XPS binding energy, which is interpreted as resulting from the high BE positions of the oxide anions (O_1s signal at 532.5-532.8 eV). However the XPS intensities give evidence of an uptake of oxygen accompanied by an increase of the surface coverage by Al³⁺ cations, and a decrease of the concentration in metallic Al at the alloy interface. A value of ∼2 for the oxygen to aluminium ions surface concentration ratio indicates the formation of an oxy-hydroxide (AlO_xOH_y with x + y ∼ 2) hydroxylation product. STM and LEED show the amorphisation and roughening of the oxide film. At P(H₂O) = 1 × 10⁻⁷ mbar, only the surface of the oxide film is modified, with formation of nodules of ∼2 nm lateral size covering homogeneously the surface. STS shows that essentially the valence band is modified with an increase of the density of states at the band edge. With increasing pressure, hydroxylation is amplified, leading to an increased coverage of the alloy by oxy-hydroxide products and to the formation of larger nodules (∼7 nm) of amorphous oxy-hydroxide. Roughening and loss of the nanostructure indicate a propagation of the reaction that modifies the bulk structure of the oxide film. Amorphisation can be reverted to crystallization by annealing under UHV at 1025 K when the surface of the oxide film has been modified, but not when the bulk structure has been modified.     

Optical bistability in an all-optical fiber nonlinear fabry-perot resonator with linear absorption

An all-optical fiber nonlinear Fabry-Perot resonator is proposed. The steady-state model for describing this resonator is developed. The transmission and refection bistabilities are shown numerically. Our results show that the bistability in this system is similar to that in a normal nonlinear Fabry-Perot etalon, except that the characteristics of the bistability can be changed not only by the cavity length but also by the phase shifts of the fiber loop mirrors.     

Fluorination of diamond — C4F9I and CF3I photochemistry on diamond (100)

The radiation-induced decomposition of C₄F₉I and CF₃I overlayers at 119 K on diamond (100) surfaces has been shown to be an efficient route to fluorination of the diamond surface. X-ray photoelectron spectroscopy has been used for photoactivation as well as for studying the photodecomposition of the fluoroalkyl iodide molecules, the attachment of the photofragments to the diamond surface, and the thermal decomposition of the fluoroalkyl ligands. Measured chemical shifts agree well with ab initio calculations of both C 1s and F 1s binding energies. It is found that chemisorbed CF₃ groups on diamond (100) decompose by 300 K whereas C₄F₉ groups decompose over the range 300 to 700 K and this reactivity difference is rationalized on steric grounds. Both of these thermal decomposition processes produce surface C---F bonds on the diamond. The surface C---F species thermally decompose over a wide temperature range extending up to 1500 K. Hydrogen passivation of the diamond surface is ineffective in preventing free radical attack from the photodissociated products of the fluoroalkyl iodides; I atoms produced photolytically abstract H from surface C---H bonds to yield hydrogen iodide at 119 K allowing diamond fluorination. The attachment of chemisorbed F species to the diamond (100) surface causes band bending as the surface states are occupied as a result of chemisorption. This results in a shift to higher binding energy of the diamond-related C 1s levels present in the surface and subsurface regions which are sampled by XPS on the diamond. The use of photoactivation of fluoroalkyl iodides for the fluorination of diamond surfaces provides a convenient route compared to other methods involving the action of atomic F, molecular F₂, XeF₂ and F-containing plasmas.