Determination of organic compounds from wood combustion aerosol nanoparticles by different gas chromatographic systems and by aerosol mass spectrometry

Organic compounds in atmospheric nanoparticles have an effect on human health and the climate. The determination of these particles is challenged by the difficulty of sampling, the complexity of sample composition, and the trace-level concentrations of the compounds. Meeting the challenge requires the development of sophisticated sampling systems for size-resolved particles and the optimization of sensitive, accurate and simple analytical techniques and methods. A new sampling system is proposed where particles are charged with a bipolar charger and size-segregated with a differential mobility analyzer. This system was successfully used to sample particles from wood pyrolysis with particle sizes 30–100 nm. Particles were analyzed by four techniques: comprehensive two-dimensional gas chromatography–time-of-flight mass spectrometry, gas chromatography–time-of-flight mass spectrometry, gas chromatography–quadrupole mass spectrometry, and aerosol mass spectrometry (aerosol MS). In the chromatographic techniques, particles were collected on a filter and analyzed off-line after sample preparation, whereas in the aerosol MS, particle analysis was performed directly from the particle source. Target compounds of the samples were polyaromatic hydrocarbons and n-alkanes. The analytical techniques were compared and their advantages and disadvantages were evaluated. The sampling system operated well and target compounds were identified in low concentrations.     

Binary‐offset‐carrier modulation techniques with applications in satellite navigation systems

An important aspect in designing the modulation scheme for various satellite systems, such as the modernized GPS and Galileo, is to obtain good spectral properties and suitable spectral shaping. For example, in the future satellite navigation systems, some of the main goals are: low interference with the existing GPS signals, good root‐mean‐square (RMS) bandwidth, good time resolution (in order to allow the separation between channel paths and to decrease the synchronization errors) etc. Starting from the recently proposed cosine‐ and sine‐BOC modulation families for GPS and Galileo systems, we introduce a new, generalized family, denoted here by double‐BOC (DBOC) modulation. We derive and analyze the properties of the power spectral densities (PSD) and autocorrelation functions (ACF) of the DBOC modulation with various orders, we show its relationship with BPSK, sine‐ and cosine‐BOC modulations, and we illustrate via several examples how to choose optimally the parameters of this new modulation family, according to different optimization criteria. The examples are targeting at applications such as the design of suitable modulations for Galileo open service (OS) and public regulated service (PRS) signals, but the authors believe that the DBOC concept might be useful to other satellite‐based applications, when the available bandwidth is large enough. Copyright © 2006 John Wiley & Sons, Ltd.     

High‐molar‐mass polypropene with tunable elastic properties by hafnocene/borate catalysts

Elastic polypropene has gained growing industrial and academic interest as a thermoplastic elastomer. In this study, “rac”‐ and “meso”‐dimethylsilyl(3‐benzylindenyl)(2‐methylindenyl)hafnium dichloride complexes (Hfr and Hfm, respectively), activated with [NHMe₂Ph][B(C₆F₅)₄]/triisobutyl aluminum, were used in propene polymerization. Using these catalyst systems, we obtained polymers with high molar masses, up to 550 kg/mol, and moderate isotacticities between 34 and 52%. By varying the polymerization conditions, we could modify the polymer microstructure and molar mass. ¹³C NMR was used to calculate the polymer pentad sequence distributions. The crystalline parts of the polymers were analyzed with the differential scanning calorimetry successive self‐nucleation and annealing (SSA) technique. The SSA thermograms revealed that Hfr produced polypropene with a more uniform lamellar structure than Hfm. The mechanical properties were tested with dynamic mechanical analysis creep‐recovery tests. In the series, the polymers with the lowest isotacticities and therefore lowest crystallinities showed the best elastic properties. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 4743–4751, 2006     

HXeOBr in a xenon matrix

We report on a new noble-gas molecule HXeOBr prepared in a low-temperature xenon matrix from the HBr and N(2)O precursors by UV photolysis and thermal annealing. This molecule is assigned with the help of deuteration experiments and ab initio calculations including anharmonic methods. The H-Xe stretching frequency of HXeOBr is observed at 1634 cm(-1), which is larger by 56 cm(-1) than the frequency of HXeOH identified previously. The experiments show a higher thermal stability of HXeOBr molecules in a xenon matrix compared to HXeOH.     

Decomposition of arborescent linear programs

We apply what we call sequential projection to reformulate certain linear programs as recursive optimization problems. We then apply the standard idea of approximating the return function at each stage of the recursion by using inner (or outer) linearization, and iteratively refining the approximation until the original linear program has been solved. The contribution of the paper lies in its unification of existing decomposition approaches and in showing that they can be generalized to apply to what we call arborescent linear programs.     

Two levels are as good as any

The asymptotic expected efficiency of distributive sorting is studied showing that for “smooth” key distributions it suffices to consider 2-level methods. The expected cost of sorting n such keys satisfies asymptotically: C(n) ? Kn, where K does not depend on the distribution.