CNDO/2 study of benzene-chlorine complex

We have carried out CNDO/2 calculations for the benzene-chlorine complex in a number of configurations. In order to obtain reasonable complexation energies, it was necessary to exclude chlorine 3d-orbitals from the basis set. When onlys- andp-orbitals were included, we found maximum stability for the complex for an unsymmetrical geometry. The calculated complexation energy was ?3.5 kcal/mole. Configuration-interaction calculations predicted a wavelength of about 270 nm for the charge-transfer band. Most, but not all, geometries were found to produce stable complexes.     

Detector for particulate polycyclic aromatic hydrocarbons in water

It is estimated that most polycyclic aromatic hydrocarbons (PAHs) in environmental water are not dissolved but rather in particulate form. Nevertheless, the currently available optical detectors are not suited for proper sampling of solid PAHs. A new setup for direct sampling and quantification of suspended particulate PAHs in water is suggested. It is based on a polymeric film that has the capability of dissolving PAH particulates, coupled to a traditional laser-induced fluorescence probe. Kinetics and performance of two sampling modes have been studied: bulk sampling, by immersing the probe into the water, and surface sampling, by laying the film on the water surface. The latter method has proved to be more sensitive; however, it is diffusion-limited. Linear calibration plots have provided quantification over a wide concentration range with detection limits in the ppb range (these could be improved by using a modified probe). The effects due to other particulates in water have been studied and only little interferences have been observed. The possibility of analysis of PAH mixtures has been addressed and it has been concluded that multivariate analysis is needed.     

Efficiency of separating amine 5,7-dinitrobenzofurazane derivatives

The influence of eluent nature and polarity, water concentration in an aqueous-organic mixture, and its pH on the retention of 5,7-dinitrobenzofurazane derivatives of a number of aromatic amines under the conditions of RP HPLC is revealed. A procedure is developed for the separation of a mixture of six aromatic amines on a column ZORBAX SB-C18.     

Bootstrap classification and point-based feature selection from age-staged mouse cerebellum tissues of matrix assisted laser desorption/ionization mass spectra using a fuzzy rule-building expert system

A bootstrap method for point-based detection of candidate biomarker peaks has been developed from pattern classifiers. Point-based detection methods are advantageous in comparison to peak-based methods. Peak determination and selection are problematic when spectral peaks are not baseline resolved or on a varying baseline. The benefit of point-based detection is that peaks can be globally determined from the characteristic features of the entire data set (i.e., subsets of candidate points) as opposed to the traditional method of selecting peaks from individual spectra and then combining the peak list into a data set. The point-based method is demonstrated to be more effective and efficient using a synthetic data set when compared to using Mahalanobis distance for feature selection. In addition, probabilities that characterize the uniqueness of the peaks are determined.This method was applied for detecting peaks that characterize age-specific patterns of protein expression of developing and adult mouse cerebella from matrix assisted laser desorption/ionization (MALDI) mass spectrometry (MS) data. The mice comprised three age groups: 42 adults, 19 14-day-old pups, and 16 7-day-old pups. Three sequential spectra were obtained from each tissue section to yield 126, 57 and 48 spectra for adult, 14-day-old pup, and 7-day-old pup spectra, respectively. Each spectrum comprised 71,879 mass measurements in a range of 3.5-50 kDa. A previous study revealed that 846 unique peaks were detected that were consistent for 50% of the mice in each age group (C. Laurent, D.F. Levinson, S.A. Schwartz, P.B. Harrington, S.P. Markey, R.M. Caprioli, P. Levitt, Direct profiling of the cerebellum by MALDI MS: a methodological study in postnatal and adult mouse, J. Neurosci. Res. 81 (2005) 613-621.).A fuzzy rule-building expert system (FuRES) was applied to investigate the correlation of age with features in the MS data. FuRES detected two outlier pup-14 spectra. Prediction was evaluated using 100 bootstrap samples of 2 Latin-partitions (i.e., 50:50 split between training and prediction set) of the mice. The spectra without the outliers yielded classification rates of 99.1 ± 0.1%, 90.1 ± 0.8%, and 97.0 ± 0.6% for adults, 14-day-old pups, and 7-day-old pups, respectively. At a 95% level of significance, 100 bootstrap samples disclosed 35 adult and 21 pup distinguishing peaks for separating adults from pups; and 8 14-day-old and 15 7-day-old predictive peaks for separating 14-day-old pup from 7-day-old pup spectra. A compressed matrix comprising 40,393 points that were outside the 95% confidence intervals of one of the two FuRES discriminants was evaluated and the classification improved significantly for all classes. When peaks that satisfied a quality criterion were integrated, the 55 integrated peak areas furnished significantly improved classification for all classes: the selected peak areas furnished classification rates of 100%, 97.3 ± 0.6%, and 97.4 ± 0.3% for adult, 14-day-old pups, and 7-day-old pups using 100 bootstrap Latin partitions evaluations with the predictions averaged. When the bootstrap size was increased to 1000 samples, the results were not significantly affected. The FuRES predictions were consistent with those obtained by discriminant partial least squares (DPLS) classifications.     

FInite torsion of slightly compressible rubberlike circular cylinders∗

A regular perturbation procedure and the Rayleigh-Ritz method are used to study the finite torsion of cylinders made of slightly compressible neo-Hookean materials. Two cases are considered: 1. the length of the cylinder is not permitted to change during torsion and 2. the net axial force on the cylinder vanishes. The perturbation procedure fails for certain constitutive relations whereas, in principle, the Rayleigh-Ritz method has general applicability. When it works, the success of the perturbation procedure depends on prior knowledge of the problem for an incompressible material (the zeroth order nonlinear problem). The solution of problem 2. is considerably more complicated than the solution of problem 1. since the complete approximation of order n for problem 2. requires extensive work on the approximation of order (n + 1).     

Reversed-phase liquid chromatographic determination of isoniazide in human urine as a test of the genetically predetermined type of biotransformation by acetylation

A new method of determination of genetically predetermined type of biotransformation by acetylation rate using reversed-phase liquid chromatography (RP-HPLC) was described. The method is based on determination of isonicotinic hydrazide (INH) which is excreted with the patient's urine during 24 h period after oral administration of 0.4 g of the drug. INH is used as pharmacogenetic marker. Precolumn derivatization of 4-chloro-5,7-dinitrobenzofurazan is used at RP-HPLC determination of INH and a new drug phosphabenzide (diphenylphosphinylacetic hydrazide, DPPAH) with specrtophotometric detection in urine. The limit of INH detection was 0.27 mug ml(-1) and the one of DPPAH was 0.82 mug ml(-1). As a result of pharmacokinetic investigation it was discovered that bimodal distribution by acetylation rate for DPPAH is less apparent than in the case of INH. It is shown, that immunomodulator xymedone (N-(beta-oxyethyl)-4,6-dimethyldihydropirimidon-2) is the acetylation inductor of xenobiotics.     

Natural radiative lifetimes in the1 P 1 and1 F 3 sequences of Sr I

We have measured radiative lifetimes in the 5s n p ¹ P ₁ (n=5–29) and 5s n f ¹ F ₃ (n=4–11) Rydberg series in neutral strontium. The measurements were performed with single-step laser excitation starting from the ground state or from a metastable state populated by collisions. The decay photons were detected using delayed coincidence technique or a transient recorder. The presence of configuration interaction in the 5s n p ¹ P ₁ series can be observed aroundn=8. The perturbation in the 5s n f ¹ F ₃ series is not reflected in the behaviour of the lifetime values.     

Measurements of vacuum field emission from bio-molecular andsemiconductor-metal eutectic composite microstructures

Designs, calculations, and initial data are presented from a program investigating the use of biomolecular and eutectic composite microstructures as vacuum field-emission cathodes. Calculations, supported by the initial data, indicate that these electron sources should be capable of macroscopic beam current densities, J⩾100 A/cm², without the formation of a surface plasma. The absence of a plasma allows these cathodes to operate as a long-pulse to DC electron sources. The designs avoid the formation of surface plasma by forcing the current emitted from the tips to transit a thin layer of silicon. The natural high-field current-limiting nature of the silicon serves to prevent the ablation of tip structures and the subsequent formation of cathode plasma. Initial data obtained with these microstructures has demonstrated Fowler-Nordheim characteristic emission. Coated bio-molecular composite cathodes have demonstrated stable DC current densities of ~100 mA/cm², and the eutectic composite cathodes have demonstrated similarly stable DC current densities of ~1 A/cm²     

Free vibrations of skirt supported pressure vessels — an engineering application of timoshenko beam theory

Timoshenko beam theory is applied to the study of the free vibrations of skirt supported pressure vessels in this paper; such systems are used in the process and power generation industries as well as aboard nuclear powered vessels. It is shown that the analysis is not significantly more complicated than the analysis of skirt-vessel combinations by Euler-Bernoulli beam theory. This latter analysis is provided in an appendix. Two sets of boundary conditions are considered: namely, the cases of (a) a cantilevered system and (b) a fixed-pinned system. The first two natural frequencies of nine typical cases are calculated and compared with the corresponding results obtained from Euler-Bernoulli beam theory. The numerical differences are significant so that if a beam theory is adequate to model the system, it is clear that Timoshenko beam theory is the appropriate one to use. In addition, the first two mode shapes for a particular case are presented for comparison with the corresponding mode shapes predicted by Euler-Bernoulli beam theory. Finally, some comments on the modeling and analysis of specific, real systems are made. It is emphasized that the purpose of the paper is to demonstrate that Timoshenko beam theory is not unduly difficult to apply to problems of engineering interest when a beam theory model is suitable.