Local order in polycarbonate glasses by 13C{19F} rotational‐echo double‐resonance NMR

Nearest‐neighbor chain packing in a homogeneous blend of carbonate ¹³C‐labeled bisphenol A polycarbonate and CF₃‐labeled bisphenol A polycarbonate has been characterized using a shifted‐pulse version of magic‐angle spinning ¹³C{¹⁹F} rotational‐echo double‐resonance (REDOR) NMR. Complementary NMR experiments have also been performed on a polycarbonate homopolymer containing the same ¹³C and ¹⁹F labels. In the blend, the ¹³C observed spin was at high concentration, and the ¹⁹F dephasing or probe spin was at low concentration. In this situation, an analysis in terms of a distribution of isolated heteronuclear pairs of spins is valid. A comparison of the results for the blend and homopolymer defines the NMR conditions under which higher concentrations of probe labels can be used and a simple analysis of the REDOR results is still valid. The nearest neighbors of a CF₃ on one chain generally include a carbonate group on an adjacent chain. A direct interpretation of the REDOR total dephasing for the polycarbonate blend indicates that at least 75% of carbonate‐carbon ¹³C ··· F₃ nearest neighbors are separated by a narrow distribution of distances 4.7 ± 0.3 Å. In addition, analysis of the variations in REDOR spinning‐sideband dephasing shows that most of the ¹³C ··· F₃ dipolar vectors have a preferred orientation relative to the polycarbonate mainchain axis. This combination of distance and orientational constraints is interpreted in terms of local order in the packing of the carbonate group of one polycarbonate chain relative to the isopropylidene moiety in a neighboring chain. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 2760–2775, 2006     

The random planar graph process

We consider the following variant of the classical random graph process introduced by Erd?s and Rényi. Starting with an empty graph on n vertices, choose the next edge uniformly at random among all edges not yet considered, but only insert it if the graph remains planar. We show that for all ε > 0, with high probability, θ(n²) edges have to be tested before the number of edges in the graph reaches (1 + ε)n. At this point, the graph is connected with high probability and contains a linear number of induced copies of any fixed connected planar graph, the first property being in contrast and the second one in accordance with the uniform random planar graph model. © 2007 Wiley Periodicals, Inc. Random Struct. Alg., 2008     

Simulation of femtosecond pulse propagation in air

We present numerical simulations of the propagation of intense spatio-temporal fields propagating in air. Characteristic parameters of the propagation like peak intensities, plasma densities and diameters of the plasma channels are obtained. The evolution of the spectral content of the pulses is investigated and, in agreement with recent experiments, white-light supercontinuum generation is observed. We show in which areas of the pulse the supercontinuum is generated and conclude that self-phase modulation is responsible for the spectral broadening. Furthermore we investigate azimuthal instabilities of intense rotationally symmetric pulsed beams propagating in air. Although the spatial-temporal evolution of the field is strongly influenced by the onset of plasma generation, the instabilities are basically caused by the Kerr effect. We conclude that calculations assuming rotational symmetry become unrealistic due to the fast growth of azimuthal instabilities in the focal region.     

[{LiCH(CH2CH2OMen)SO2Ph}4] (OMen = Menthyl): Synthesis and First Structure of a Chiral Solvent Free Lithiated Sulfone with a Direct Li–C Bond

R*OCH₂CH₂CH₂SO₂Ph (R*OH = MenOH, (–)‐menthol, ( 3a ); BorOH, (1S)‐(–)‐borneol, ( 3b )) were found to react with n‐BuLi in n‐pentane/n‐hexane and toluene/n‐hexane under deprotonation yielding LiCH(CH₂CH₂OR*)SO₂Ph (R* = Men, ( 4a ); Bor, ( 4b )) which reacted with n‐Bu₃SnCl forming the requisite tri(n‐butyl)tin compounds n‐Bu₃SnCH(CH₂CH₂OR*)SO₂Ph (R* = Men, ( 5a ); Bor, ( 5b )) as diastereomeric mixtures. The identities of 5a and 5b were unambiguously proved by ¹H, ¹³C and ¹¹⁹Sn NMR spectroscopic measurements. Solutions of 4a afforded crystals of [{LiCH(CH₂CH₂OMen)SO₂Ph}₄] ( 4a′ ) for which the structure was determined by single‐crystal X‐ray crystallography. Complex 4a′ crystallized in a tetrameric structure without any additional solvent molecules. There were found direct Li–C bonds (Li1–C1/Li2–C20 2.231(9)/2.236(9) Å). The tetrahedral donor set of Li is completed by three oxygen atoms. One oxygen atom comes from the OMen substituent via intramolecular coordination and two oxygen atoms come from SO₂ groups of neighboured LiCH(CH₂CH₂OMen)SO₂Ph moieties. Thus, a heterocubane structure with a Li₄S₄ core is built up.     

A note on the Undirected Rural Postman Problem polytope

This note refers to the article by G. Ghiani and G. Laporte ``A branch-and-cut algorithm for the Undirected Rural Postman Problem', Math. Program. 87 (2000). We show that some conditions for the facet-defining property of the basic non-trivial inequalities are not sufficient and that the Rural Postman Problem polytope is more complex even when focusing on canonical inequalities only.