Retention characteristics of alkylated polycyclic aromatic hydrocarbons in normal phase liquid chromatography

Summary Retention characteristics of series of polymethyl and mono-n-alkyl derivatives of benzene and pyrene, and also of parent polycyclic aromatic hydrocarbons (PAH), were studied using silica and aminopropyl- and cyanopropyl-modified silica. Differences in the selectivities for the studied compound groups were found between the three phases. Deviations from linear behaviour in plots of log (k′)vs. carbon number were observed for the methyl series. These are explained in terms of differences in π-electron delocalisation within the aromatic ring systems. Further, the effect of methyl substitution on selectivity decreased with an increasing number of aromatic rings. Results were obtained which indicated that the primary adsorption site in a cyano column used in normal phase mode, at least for PAH molecules, is the cyano group.     

Systematic Encoding and Shortening of PAC Codes

Polarization adjusted convolutional (PAC) codes are a class of codes that combine channel polarization with convolutional coding. PAC codes are of interest for their high performance. This paper presents a systematic encoding and shortening method for PAC codes. Systematic encoding is important for lowering the bit-error rate (BER) of PAC codes. Shortening is important for adjusting the block length of PAC codes. It is shown that systematic encoding and shortening of PAC codes can be carried out in a unified framework.     

Electronic Relaxation in Indium Oxide Films Studied with Perturbed Angular Correlations

The electronic relaxation due to the ¹¹¹In → ¹¹¹Cd electron capture process was studied by measuring perturbed γγ-angular correlations after ¹¹¹In-ion implantation into indium oxide films of various compositions and thicknesses and deposited on different substrates. X-ray diffraction, Rutherford backscattering and secondary ion mass spectrometry were used to characterize the microstructure and composition of the samples. The film thickness and type of substrate were found to have much less influence on the after effect than the deposition parameters and impurities.     

Identification of phenyl-substituted polycyclic aromatic compounds in ring furnace gases using GC-MS and GC-AED

Summary The ring furnace baking process is an intermediate step in the production of graphite electrodes. In this process coal tar pitch is pyrolized to form amorphous carbon and volatile aromatic and polycyclic aromatic compounds (PACs). These gaseous ring furnace emissions were analysed by GC-MS and GC-AED. As a result of the pyrolytic reactions taking place, several phenyl-substituted PACs are generated, which were identified by their chromatographic retention indices and mass spectra. Pure reference compounds were analysed for verification if available. A number of phenyl-PACs are reported to be present in coal tar-related material, including phenylpyridines and phenyldibenzofurans previously unreported. A formation scheme for phenyl-dibenzofurans on the basis of a radical mechanism is proposed. Dedicated to Prof. Dr. Wolfgang Meyer zu Reckendorf, Münster, on the occasion of his 65th birthday. Presented at the 21^st ISC held in Stuttgart, Germany, 15^th–20^th September, 1996     

Fluorescence spectroscopy of polynuclear aromatic compounds in environmental monitoring

The occurrence of polynuclear aromatic compounds (PAC) in the environment and experimental techniques suitable for the detection of PAC in environmental compartments are briefly reviewed. The specific requirements for on-site andin situ environmental analysis are outlined. Particular emphasis is given to fluorescence spectroscopic techniques for the investigation of humic acid- and soil-containing samples. Some examples of studies in the literature on Shpol'skii and jet spectroscopy and on laser-induced fluorescence (OF) measurements of PAC and mineral oils are highlighted. Contaminants in the environment are usually encountered as multicomponent mixtures in very complex matrices. Total fluorescence analysis in combination with the chemometrical technique of rank annihilation factor analysis (RAFA) was employed for the evaluation of a six-component PAC mixture in toluene. It was shown that even in the presence of strong spectral overlap the qualitative identification of all compounds and the reliable quantification of five substances was possible. Results are presented from our stationary and time-resolved fluorescence investigations of the interactions between pyrene and humic acid in water. The Stern-Volmer analysis showed a significant effect of pH on the static quenching efficiency which can be explained by the pH-dependent macromolecular structure of humic acids. Preliminary results from studies of the deactivation of triplet PAC and quenching of delayed fluorescence by humic acid are reported. LIF measurements of mineral oils directly from soil surfaces and of a model oil in a soil column were performed with a fiber-optic coupled multichannel spectrometer. The fluorescence intensity/ concentration relationships were established for a crude and a fuel oil; the corresponding lower limits of detection (LOD) were determined to be 0.025 and 0.125% m/m (mass/mass percentages). These detection limits are compared with realistic oil contaminations of soils. In a soil column designed to mimic fixed-bed bioreactors the distributions of fluorescence signal intensities from a perylene-doped model oil before and after water flooding were determined. These results fromin situ measurements can provide a quantitative basis for the modelling of temporal and spatial contaminants' distributions in reactor design.     

Perturbed Angular Correlation Study of Magnetic and Electric Hyperfine Interactions at 111Cd in GdNi2 and SmNi2

The magnetic hyperfine field B _hf of the closed-shell probe nucleus ¹¹¹Cd in the C15 Laves phase RNi₂ (R= Gd, Sm) has been investigated as a function of temperature by perturbed angular correlation (PAC) spectroscopy. The saturation magnetic hyperfine fields at 10 K are B _hf=7.7(2) and 3.9(1) T for GdNi₂ and SmNi₂, respectively. Although the probe nucleus resides on the cubic rare-earth site, a strong axially symmetric electric quadrupole interaction (QI) is observed in the paramagnetic phase at T300 K. The possible relation of this unexpected QI to the structural instability of RNi₂ is discussed.     

Monte Carlo Simulations of PAC-Spectra as a General Approach to Dynamic Interactions

Time Dependent Perturbed Angular Correlations of -rays (PAC) can be used to study hyperfine interactions of a dynamic nature. However, the exact effect of the dynamic interaction on the PAC-spectrum is sometimes difficult to derive analytically. A new approach based on Monte Carlo simulations is therefore suggested, here implemented as a Fortran 90 program for simulating PAC spectra of dynamic electric field gradients of any origin. The program is designed for the most common experimental condition where the intermediate level has spin 5/2, but the approach can equally well be used for other spin states. Codes for 4 different situations have been developed: (1) Rotational diffusion by jumps; used as a test case. (2) Jumps between two states with different electric field gradients, different lifetimes and different orientations of the electric field gradient principal axes. (3) Relaxation of one state to another. (4) Molecules adhering to a surface with random rotational jumps around the axis perpendicular to the surface. To illustrate how this approach can be used to improve data-interpretation, previously published data on ^111mCd-plastocyanin and ¹¹¹Ag-plastocyanin are re-considered. The strength of this novel approach is its simplicity and generality so that other dynamic processes can easily be included by only adding new program units describing the random process behind the dynamics. The program is hereby made publicly available.     

FIR Volterra kernel neural models and PAC learning

The probably approximately correct (PAC) learning theory creates a framework to assess the learning properties of static models for which the data are assumed to be independently and identically distributed (i.i.d.). The present article first extends the idea of PAC learning to cover the learning of modeling tasks with m‐dependent sequences of data. The data are assumed to be marginally distributed according to a fixed arbitrary probability. The resulting framework is then applied to evaluate learning of Volterra Kernel FIR models. © 2002 Wiley Periodicals, Inc.     

Treatment of pulp and paper mill wastewaters with poly aluminium chloride and bagasse fly ash

The present study deals with the use of poly aluminium chloride (PAC) as a coagulant and bagasse fly ash (BFA), which is generated in sugar mills, as an adsorbent for the removal of chemical oxygen demand (COD) and colour of pulp and paper mill effluents. Under optimal conditions of pH 3 and initial PAC dosage of 3 g/l, about 80% COD removal and 90% colour removal were obtained. The optimal conditions for the adsorptive removal of COD and colour with BFA were pH 4 and BFA dosage of 2 g/l. Under these conditions, COD and colour removal were, respectively, 50 and 55%. Adsorptive removal of COD by BFA followed second-order kinetics. Intra-particle diffusion was found to be rate controlling. Freundlich and Langmuir adsorption isotherms were found to fit the equilibrium adsorption data with BFA. Two-stage treatment using PAC (3 g/l) as a coagulant in the first stage and BFA (2 g/l) as an adsorbent in the second stage gave the combined COD and colour removal of nearly 87 and 95%, respectively, for different effluents without any pH adjustment. Two-stage adsorptive treatment using BFA (2 g/l) in both the stages gave a combined COD and colour removal of about 70%. The sludge obtained can be dewatered by centri-clarifiers, dried, briquetted and incinerated to recover its energy content.     

气相色谱分离多环芳香环境污染物用固定相的应用进展

综述了几种气相色谱固定相包括聚硅氧烷、液晶、冠醚、环糊精、离子液体及纤维填充固定相,在分离多环芳香烃(PAHs)、多环芳香化合物(PACs)及多氯联苯(PCBs)等环境污染物中的应用进展,展望了此类固定相的应用前景(引用文献64篇)。