Selective and sensitive detection of organic contaminants in water samples by on-line trace enrichment–gas chromatography–mass spectrometry

Liquid chromatographic (LC) type trace enrichment is coupled online with capillary gas chromatography (GC) with mass spectrometric (MS) detection for the analysis of aqueous samples. A volume of 1–10 ml of an aqueous sample is preconcentrated on a trace-enrichment column packed with a polymeric stationary phase. After cleanup with HPLC-grade water the precolumn is dried with nitrogen and subsequently desorbed with ethyl acetate. A fraction of 60 μl is introduced on-line into a diphenyltetramethyldisilazane-deactivated retention gap under partially concurrent solvent evaporation conditions and using an early solvent vapor exit. The analytes are separated and detected by means of GC–MS. The potential of the LC–GC–MS system for monitoring organic pollutants in river and drinking water is studied. Target analysis is carried out with atrazine and simazine as model compounds; the detection limits achieved under full-scan and multiple ion detection conditions are 30 pg and 5 pg, respectively. Identification of unknown compounds (non-target analysis), is demonstrated using a river water sample spiked with 168 pollutants varying in polarity and volatility.     

Retention in coupled capillary column supercritical fluid chromatography with lipids as model compounds

Summary We have investigated to which extent retention data, acquired on single capillary columns, can be used for predicting retention factors in a coupled column system. For this purpose we utilized a model mixture of 18 lipid components with widely different vapor pressures and polarities. The sample was chromatographed on two columns, SB-biphenyl-30 (70% methyl-30% biphenylpolysiloxane) and SB-cyanopropyl-50 (50% methyl-50% cyanopropylsiloxane). Experimental retention factors, acquired in coupled column systems with two columns connected in different order, were thus compared with values calculated from runs on each single column. The agreement between calculated and experimental values generally was better than 5% without any pressure drop correction.To study the possibility of predicting retention behavior in a wide pressure range from a limited number of experiments, we also investigated the relation between solute retention and mobile phase density. We found that all data could be fitted to second order equations, which gives the possibility to optimize the resolution with respect to pressure from a limited number of runs at different pressures.     

Computer-aided selection and optimization of chromatographic columns and conditions for multicolumn analysis procedures

Clearly, the usefulness of a computer-aided column design program will depend on its ability to predict quickly and accurately, a design which will yield chromatograms closely approximating those obtained experimentally. Such a computer model for designing and specifying operating conditions for optimum performance of either single or serially coupled columns with different stationary phases is described herein. Tests have been performed in order to verify the accuracy of the model. In addition to single column optimization and the design of column combinations which can be used to achieve separations difficult or impossible on a single phase alone, the model has proven quite useful as an aid to the design and development of multicolumn analysis procedures that involve critical timing of valve-switching sequences.     

On-line solvent evaporator for coupled LC systems

The mobile phase of a fraction eluted from a first LC column is removed by an on-line evaporator in order to reconcentrate the solute material or to exchange the eluent before performing a subsequent LC separation. Evaporation essentially occurs by concurrent evaporation, i.e. the solvent evaporates at a rate equal to the flow rate of the incoming eluent, and is driven by the overflow principle, i.e. vapors leave the tube as a result of the expansion resulting from evaporation. The liquid is introduced into a small tube (e.g., 4 cm × 1.3 mm i.d.) which is packed, e.g., with a coarse silica gel. The outlet of the evaporator is connected to vacuum in order to enable evaporation at reduced temperature and to increase retention of the volatile components. With normal phase eluents, evaporation rates may approach 1 ml/min; n-dodecane was the most volatile n-alkane fully retained by the evaporator.     

Nonequilibrium fluctuations in μ space

The properties of fluctuations in space in or outside thermal equilibrium are obtained by solving hierarchies of equations derived either from the Liouville or the Master equation. In particular we study the one-, two-, etc., time correlation functions that describe the spatial and temporal behavior of the fluctuations in space. Explicit solutions are obtained for a dilute gas. The Langevin approach is briefly discussed. Our results are compared with those obtained in the extensive literature, which is reviewed in some detail.     

Application of a hybrid meshless technique for natural frequencies analysis in functionally graded thick hollow cylinder subjected to suddenly thermal loading

A hybrid meshless technique based on composition of meshless local Petrov–Galerkin method (for spatial variables) and Newmark finite difference method (for time domain) is developed for natural frequencies analysis of thick cylinder made of functionally graded materials (FGMs). The FG cylinder is assumed to be under suddenly thermal loading, axisymmetric and plane strain conditions. The dynamic behaviors and time history of displacements are obtained in time domain using Green–Naghdi (GN) theory of coupled thermo-elasticity (without energy dissipation). Using fast Fourier transform (FFT) technique, the displacements are transferred to frequency domain and all natural frequencies are illustrated for various grading patterns of FGMs. The variations of mechanical properties in FG thick hollow cylinder are considered to be in nonlinear volume fraction law through radial direction. The presented hybrid meshless technique furnishes a ground to analyze the effects of various grading patterns of FGMs on natural frequencies, which are obtained employing GN coupled thermo-elasticity governing equations. Also, the frequency history and natural frequencies are illustrated for various grading patterns at several points across thickness of cylinder.     

Exact solutions of functionally graded piezoelectric material sandwich cylinders by a modified Pagano method

The three-dimensional (3D) coupled analysis of simply-supported, functionally graded piezoelectric material (FGPM) circular hollow sandwich cylinders under electro-mechanical loads is presented. The material properties of each FGPM layer are regarded as heterogeneous through the thickness coordinate, and obey an exponent-law dependent on this. The Pagano method is modified to be feasible for the study of FGPM sandwich cylinders. The modifications are as follows: a displacement-based formulation is replaced by a mixed formulation; a set of the complex-valued solutions of the system equations is transferred to the corresponding set of real-valued solutions; a successive approximation method is adopted to approximately transform each FGPM layer into a multilayered piezoelectric one with an equal and small thickness for each layer in comparison with the mid-surface radius, and with the homogeneous material properties determined in an average thickness sense; and a transfer matrix method is developed, so that the general solutions of the system equations can be obtained layer-by-layer, which is significantly less time-consuming than the usual approach. A parametric study is undertaken of the influence of the aspect ratio, open- and closed-circuit surface conditions, and material-property gradient index on the assorted field variables induced in the FGPM sandwich cylinders.     

A class of solvable coupled nonlinear oscillators with amplitude independent frequencies

Existence of amplitude independent frequencies of oscillation is an unusual property for a nonlinear oscillator. We find that a class of N coupled nonlinear Liénard type oscillators exhibit this interesting property. We show that a specific subset can be explicitly solved from which we demonstrate the existence of periodic and quasiperiodic solutions. Another set of N coupled nonlinear oscillators, possessing the amplitude independent nature of frequencies, is almost integrable in the sense that the system can be reduced to a single nonautonomous first order scalar differential equation which can be easily integrated numerically.     

The Ablowitz–Ladik hierarchy integrability analysis revisited: the vertex operator solution representation structure

A regular gradient-holonomic approach to studying the Lax type integrability of the Ablowitz–Ladik hierarchy of nonlinear Lax type integrable discrete dynamical systems in the vertex operator representation is presented. The relationship to the Lie-algebraic integrability scheme is analyzed and the connection with the τ-function representation is discussed.     

一种一致性排序标度方法

针对层次分析法判断矩阵一致性问题,提出了一种新的排序标度方法,证明了采用新方法形成的判断矩阵具有一致性,最后通过实例运用说明了此方法的可行性和有效性.