Validated dispersive liquid-liquid microextraction for analysis of organophosphorous pesticides in water

Dispersive liquid-liquid microextraction (DLLME) combined with gas chromatography and mass spectrometry (GC-MS) was applied to the determination of six organophosphorous pesticides (OPPs) in water samples. The analytes included in this study were prophos, diazinon, chlorpyrifos methyl, methyl parathion, fenchlorphos and chlorpyrifos. Several extraction and dispersion solvents were tested for dispersive liquid-liquid microextraction of these analytes and the best results were obtained using chloroform as extraction solvent and 2-propanol as dispersion solvent. Calibration curves of the analytes in water samples were constructed in the concentration range from 100 to 1100 ng/L for prophos, diazinon and methyl parathion and in the range from 100 to 1000 ng/L for chlorpyrifos methyl, fenchlorphos and chlorpyrifos. Limits of detection (LODs) were in the range of 1.5-9.1 ng/L and limits of quantification (LOQs) were in the range of 5.1-30.3 ng/L, below the maximum admissible level for drinking water. Relative standard deviations (RSDs) were between 6.5 and 10.1% in the concentration range of 100-1000 ng/L. The relative recoveries (%RRs) of tap, well and irrigation water samples fortified at 800 ng/L were in the range of 46.1-129.4%, with a larger matrix effect being detected in tap water.     

On the calculation of disjoining pressure isotherms for nonaqueous films

A review of the methods of London and Hamaker and of Lifshitz for calculating disjoining pressure isotherms of nonaqueous liquid films is presented. The disjoining pressure isotherms for films of n-octane and of three triglycerides (tributyrin, tricaprylin, and triolein) on glass were calculated using both methods. The disjoining pressure isotherms for films on silanized glass were calculated using only the London-Hamaker approach. The refractive indices and static dielectric constants, necessary for the calculations, were measured. The silanized glass was considered to be the original glass covered by a layer with the same characteristic frequency as the underlying glass and a smaller limiting value of the dielectric constant epsilon(0). The limiting dielectric constant epsilon(0) and the thickness of the surface layer were taken as adjustable parameters. The disjoining pressure isotherms indicate that all films are stable on glass. In contrast, the stability of the films formed on silanized glass was found to depend mainly on the value of epsilon(0) and, less strongly, on the thickness of the surface layer. The stability of the films decreased with the decrease of epsilon(0) and, for each value of epsilon(0), was maximal for the thinnest surface layer.     

Wetting films of polar and nonpolar liquids

Disjoining pressure isotherms for water and n-octane films on glass obtained using a recently developed apparatus, based on the interferometric technique, are compared with other values reported in the literature. Our method, including a simple cleaning procedure, yields experimental results in excellent agreement both with other experimental results and with theoretical predictions. An error analysis was made which quantifies the uncertainty of our results and simultaneously allows the minimization of the errors.     

Trajectory Modeling of Robot Manipulators in the Presence of Obstacles

This paper presents two different strategies for the problem of the optimal trajectory planning of robot manipulators in the presence of fixed obstacles. The first strategy is related to the situation where the trajectory must pass through a given number of points. The second strategy corresponds to the case where only the initial and final points are given. The optimal traveling time and the minimum mechanical energy of the actuators are considered together to build a multiobjective function. The trajectories are defined using spline functions and are obtained through offline computation for online operation. Sequential unconstrained minimization techniques (SUMT) have been used for the optimization. The obstacles are considered as three-dimensional objects sharing the same workspace performed by the robot. The obstacle avoidance is expressed in terms of the distances between potentially colliding parts. Simulation results are presented and show the efficiency of the general methodology used in this paper.     

Some remarks on dualisability and endodualisability

The fundamental problem of dualisability and the particular problem of endodualisability are discussed. It is proved tha every finite generating algebra of a quasi-variety generated by a finite dualisable algebra D is also dualisable. The corresponding result for endodualisability is true when D is subdirectly irreducible. Under special conditions, it is also proved that a finite algebra M is endodualisable if and only if any finite power M ⁿ of M is endodualisable. Received January 27, 1999; accepted in final form September 17, 1999.     

Ageing effects on the wettability behavior of laser textured silicon

In the present work we investigate the ageing of acid cleaned femtosecond laser textured 〈1 0 0〉 silicon surfaces. Changes in the surface structure and chemistry were analysed by Rutherford backscattering spectrometry (RBS) and X-ray photoelectron spectroscopy (XPS), in order to explain the variation with time of the water contact angles of the laser textured surfaces. It is shown that highly hydrophobic silicon surfaces are obtained immediately after laser texturing and cleaning with acid solutions (water contact angle > 120°). However these surfaces are not stable and ageing leads to a decrease of the water contact angle which reaches a value of 80°. XPS analysis of the surfaces shows that the growth of the native oxide layer is most probably responsible for this behavior.     

Adhesion forces in liquid media: effect of surface topography and wettability

This work was motivated by the unexpected values of adhesion forces measured between an atomic force microscopy tip and the hydrophobic surface of ultra-high-molecular-weight polyethylene. Two types of samples with different roughness but similar wettability were tested. Adhesion forces of similar magnitude were obtained in air and in polar liquids (water and Hank's Balanced Salt Solution, a saline solution) with the rougher sample. In contrast, the adhesion forces measured on the smoother sample in air were much higher than those measured in water or in the aqueous solution. Those experimental results suggested the presence of nanobubbles at the interface between the rough sample and the polar liquids. The existence of the nanobubbles was further confirmed by the images of the interface obtained in noncontact tapping mode. The adhesion forces measured in a nonpolar liquid (hexadecane) were small and of the same order of magnitude for both samples and their values were in good agreement with the predictions of the London-Hamaker approach for the van der Waals interactions. Finally, we correlate the appearance of nanobubbles with surface topography. The conclusion of this work is that adhesion forces measured in aqueous media may be strongly affected by the presence of nanobubbles if the surface presents topographical accidents.