Partial dislocations and stacking faults in cubic SiC

Numerous stacking faults and dislocations (formed by intersection of stacking faults and dislocations limiting nonintersecting stacking faults) in the 3C-SiC films grown by molecular beam epitaxy on a silicon substrate were studied by electron microscopy with the use of weak beams. A procedure for determining any of possible Burgers vectors of the (1/6)〈116〉-type glide dislocations and the (1/6) 〈110〉-and (1/3)〈001〉-type sessile partial dislocations (in face-centered cubic lattices) is developed based on the criterion of the contrast value. The sessile dislocations formed by intersections of stacking faults were shown to have the (1/6)〈110〉-and (1/3)〈001〈-type Burgers vectors. The width of nonintersecting stacking faults corresponds to the stacking-fault energy ranging within 0.1–2 mJ/m².     

Linear rheology of diluted linear, star and model long chain branched polymer melts

We present experiments and theory on the diluted melt dynamics of monodisperse entangled polymers of linear, star and H-shaped architecture. Frequency-dependent rheological data on a series of progressively diluted linear, star and H-polymers are in good agreement with a refined tube-model theory that, for H-polymers, combines star polymer melt behaviour at high frequency, with linear polymer reptation behaviour at low frequencies. Taking into account the effect of dilution via some simple scaling relations, mild polydispersity and by incorporating the high frequency Rouse modes, we are able to model quantitatively the entire frequency range. This work suggests a novel rheological route to analysing long chain branching in polymer melts. Received: 6 April 2000/Accepted: 21 December 2000     

Nonequilibrium Time Reversibility with Maps and Walks

Time-reversible dynamical simulations of nonequilibrium systems exemplify both Loschmidt’s and Zermélo’s paradoxes. That is, computational time-reversible simulations invariably produce solutions consistent with the irreversible Second Law of Thermodynamics (Loschmidt’s) as well as periodic in the time (Zermélo’s, illustrating Poincaré recurrence). Understanding these paradoxical aspects of time-reversible systems is enhanced here by studying the simplest pair of such model systems. The first is time-reversible, but nevertheless dissipative and periodic, the piecewise-linear compressible Baker Map. The fractal properties of that two-dimensional map are mirrored by an even simpler example, the one-dimensional random walk, confined to the unit interval. As a further puzzle the two models yield ambiguities in determining the fractals’ information dimensions. These puzzles, including the classical paradoxes, are reviewed and explored here.     

Nearest neighbor and hard sphere models in continuum percolation

Consider a Poisson process X in R ^d with density 1. We connect each point of X to its k nearest neighbors by undirected edges. The number k is the parameter in this model. We show that, for k = 1, no percolation occurs in any dimension, while, for k = 2, percolation occurs when the dimension is sufficiently large. We also show that if percolation occurs, then there is exactly one infinite cluster. Another percolation model is obtained by putting balls of radius zero around each point of X and let the radii grow linearly in time until they hit another ball. We show that this model exists and that there is no percolation in the limiting configuration. Finally we discuss some general properties of percolation models where balls placed at Poisson points are not allowed to overlap (but are allowed to be tangent). © 1996 John Wiley & Sons, Inc.     

The Crystal and Molecular Structure of Mesomorphic 1,4-Dipentadecanoyloxy-biphenyl (SYM-14)

The compound with the general formula C_nH_2n+1 –COO–C₆H₄–C₆H₄–OOC–C_nH_2n+1, n = 14 (SYM- 14) crystallizes in the triclinic space group P 1 , with a = 5.431(5), b = 9.346(8), c = 39.172(51) Å, α = 92.60(15), β = 90.65(15), γ = 100.364(8)°. The crystal structure was solved by direct methods. Least-squares refinement leads to a final R value of 0.092 for 1575 observed reflections, with I > 2σs(I). The packing arrangement follows the same building principles found recently for the first three members of the well known homologous series of liquid crystalline terephthalylidine-anilines (TBAA-n).     

Fast-atom bombardment and tandem mass spectrometry of macrolide antibiotics

Molecular weights of macrolide antibiotics can be determined from either (M + H)⁺ or (M + Met)⁺, the latter desorbed from alkali metal salt-saturated matrices. The ion chemistry of macrolides, as determined by tandem mass spectrometry (MS/MS), is different for ions produced as metallated than those formed as (M + H)⁺ species. An explanation for these differences is the location of the charge. For protonated species, the charge is most likely situated on a functional group with high proton affinity, such as the dimethylamino group of the ammo sugar. The alkali metal ion, however, is bonded to the highly oxygenated aglycone. As a result, the collision-activated dissociation spectra of protonated macrolides are simple with readily identifiable fragment ions in both the high and low mass regions but no fragments in the middle mass range. In contrast, the cationized species give complex spectra with many abundant ions, most of which are located in the high mass range. The complementary nature of the fragmentation of these two species recommends the study of both by MS/MS when determining the structure or confirming the identity of these biomaterials.     

Optimization of thin film solid phase microextraction and data deconvolution methods for accurate characterization of organic compounds in produced water

The continued rise in the extraction of unconventional oil and gas across the globe poses many questions about how to manage these relatively new waste‐streams. Produced water, the primary waste by‐product, contains a diverse number of anthropogenic additives together with the numerous hydrocarbons extracted from the well. Due to potential environmental hazards, it is critical to characterize the chemical composition of this type of waste before proper disposal or remediation/reuse. In this work, a thin film solid phase microextraction approach was developed and optimized to characterize produced water. The thin film device consisted of hydrophilic‐lipophilic balance particles embedded in polydimethylsiloxane and immobilized on a carbon mesh surface. These devices were chosen to provide broad extraction coverage and high reusability. Various parameters were evaluated to ensure reproducible results while minimizing analyte loss. This optimized protocol, consisting of a 15 min extraction followed by a short (3 s) rinsing step, enabled the reproducible analysis of produced water without any sample pretreatment. Extraction efficiency was suitable for both produced water additives and hydrocarbons. The developed approach was able to tentatively identify a total of 201 compounds from produced water samples, by using one‐dimensional gas chromatography hyphenated to mass spectrometry and data deconvolution.     

Improvements in lipid suppression for 1H NMR-based metabolomics: Applications to solution-state and HR-MAS NMR in natural and in vivo samples

Proton nuclear magnetic resonance (NMR) spectra of intact biological samples often show strong contributions from lipids, which overlap with signals of interest from small metabolites. Pioneering work by Diserens et al. demonstrated that the relative differences in diffusivity and relaxation of lipids versus small metabolites could be exploited to suppress lipid signals, in high-resolution magic angle spinning (HR-MAS) NMR spectroscopy. In solution-state NMR, suspended samples can exhibit very broad water signals, which are challenging to suppress. Here, improved water suppression is incorporated into the sequence, and the Carr-Purcell-Meiboom-Gill sequence (CPMG) train is replaced with a low-power adiabatic spinlock that reduces heating and spectral artefacts seen with longer CPMG filters. The result is a robust sequence that works well in both HR-MAS as well as static solution-state samples. Applications are also extended to include in vivo organisms. For solution-state NMR, samples containing significant amount of fats such as milk and hemp hearts seeds are used to demonstrate the technique. For HR-MAS, living earthworms (Eisenia fetida) and freshwater shrimp (Hyalella azteca) are used for in vivo applications. Lipid suppression techniques are essential for non-invasive NMR-based analysis of biological samples with a high-lipid content and adds to the suite of experiments advantageous for in vivo environmental metabolomics.