Determination of aromatic amines in environmental water samples using solid-phase extraction modified with sodium dodecyl sulphate and micellar liquid chromatography

Extraction and determination of seven aromatic amines in environmental water samples were performed with solid-phase extraction (SPE) and micellar liquid chromatography (MLC) using experimental design. Extraction of aromatic amines was carried out with a C₁₈ cartridge modified with sodium dodecyl sulphate (SDS). The washing solution and elution solvent for extraction of aromatic amines were aqueous solution containing 5% (v/v) acetonitrile and 5% (v/v) acetone and 3 mL methanol, respectively. The chemometrics approach was applied for the separation optimisation of these compounds using MLC. Different mobile phase compositions were used for modelling based on retention times to obtain the best separation using central composite design. The optimum mobile phase composition for separation and determination of analytes in water samples was 69 mM SDS, 9% v/v 1-propanol and pH = 6.4. Recoveries were between 84.8–93.5% with relative standard deviation (RSD) less than 5.8% (n = 5). Limits of detection and linear range were 1–4.5 and 3.1–125.0 µg/L, respectively. The proposed method was applied to determine the aromatic amines in real samples (river and well waters). Amount of 4-nitroaniline and 3-nitroaniline in river water sample were 2.15 and 1.91 µg/L, respectively.     

Utilization of water-contained surfactant-based ultrasound-assisted microextraction followed by liquid chromatography for determination of polycyclic aromatic hydrocarbons and benzene in commercial oil sample

In this work, a microextraction method, water-contained surfactant-based ultrasound-assisted, followed by high-performance liquid chromatography (HPLC) was developed for determination of five polycyclic aromatic hydrocarbons (PAHs) and benzene in commercial oil samples. During the microextraction method, a micellar solution as the only extraction solvent was injected into the oil sample in a conical bottom glass tube and formed a cloudy solution. The dispersion process was accelerated by applying ultrasound irradiation. Phase separation was done by centrifugation and then the lower sediment phase was directly analyzed by HPLC. A chemometrics approach was applied for the optimization of the extraction condition. Under the optimum conditions, the proposed method showed good linearity within the different ranges for different analytes (e.g., 0.10–200 ng mL^?1 for phenanthrene), the square of the correlation coefficient was higher than 0.999 and the appropriate limit of detection was in the range of 0.04–0.41 ng mL^?1. The recoveries in all cases were above 95 %.     

Removal of chromate from aqueous solution by reduction with nanoscale Fe–Al layered double hydroxide

Nanoscale layered double hydroxides of Fe^II and Al^III (Fe–Al LDH) have been applied for removal of chromate (Cr^VI) from aqueous solution. Given the reaction stoichiometry, Cr^VI was completely reduced to Cr^III and coprecipitated with Fe^III and Al^III oxyhydroxides. The extent of Cr^VI removal decreased with increasing initial pH and decreasing molar ratio of Cr^VI/structural Fe^II in the LDH. The chromate reduction rate at different initial concentrations of Cr^VI was well described by the pseudo-second-order model with reaction rate constant ranging from 197.4 to 13.53 (mmol min)^?1. Initial pH and substitution of various amounts of Fe^III in the LDH structure had little effect on the reaction rate. Backtransformation of Cr^III to Cr^VI by birnessite Mn oxide (δ-MnO₂) after 40 days of reaction was less than 1% of the initial Cr (as Cr^III solid), indicating high stability of the final reaction products and high efficiency of nanoscale Fe–Al LDHs for removal of chromate from aqueous solution.     

Response surface methodology and support vector machine for the optimization of separation in linear gradient elution

Experimental design methodology was used to optimize the linear gradient elution chromatography. The effect of initial mobile phase composition (φ_in), initial isocratic time (t_in), and gradient time (t_G) on the retention times of phenyl thiohydantoin aminoacids (PTH‐amino acids) was investigated. The experiments were performed according to Box–Behnken experimental design to map the chromatographic response surface. Then multiple linear regression and support vector machine (SVM) methods were used to fit the retention times of solutes. Results shows the SVM models have better ability to predict retention time and used for grid search in factor space. The SVM models were verified, as good agreement was observed between the predicted and experimental values of retention time in the optimal condition.     

Planar Hypohamiltonian Graphs on 40 Vertices

A graph is hypohamiltonian if it is not Hamiltonian, but the deletion of any single vertex gives a Hamiltonian graph. Until now, the smallest known planar hypohamiltonian graph had 42 vertices, a result due to Araya and Wiener. That result is here improved upon by 25 planar hypohamiltonian graphs of order 40, which are found through computer‐aided generation of certain families of planar graphs with girth 4 and a fixed number of 4‐faces. It is further shown that planar hypohamiltonian graphs exist for all orders greater than or equal to 42. If Hamiltonian cycles are replaced by Hamiltonian paths throughout the definition of hypohamiltonian graphs, we get the definition of hypotraceable graphs. It is shown that there is a planar hypotraceable graph of order 154 and of all orders greater than or equal to 156. We also show that the smallest planar hypohamiltonian graph of girth 5 has 45 vertices.     

Analysis of unsteady stagnation‐point flow over a shrinking sheet and solving the equation with rational Chebyshev functions

This paper investigates the nonlinear boundary value problem, resulting from the exact reduction of the Navier–Stokes equations for unsteady laminar boundary layer flow caused by a stretching surface in a quiescent viscous incompressible fluid. We prove existence of solutions for all values of the relevant parameters and provide unique results in the case of a monotonic solution. The results are obtained using a topological shooting argument, which varies a parameter related to the axial shear stress. To solve this equation, a numerical method is proposed based on a rational Chebyshev functions spectral method. Using the operational matrices of derivative, we reduced the problem to a set of algebraic equations. We also compare this work with some other numerical results and present a solution that proves to be highly accurate. Copyright © 2016 John Wiley & Sons, Ltd.     

Screening of adulteration in packaging biocomposites by infrared spectroscopy and chemometrics

Fourier transform infrared spectroscopy coupled with chemometrics was employed to detect packaging polylactic acid-based biocomposite samples adulterated with polypropylene (PP) 30–45% and linear low-density polyethylene 2–10%. Principal component analysis, soft independent modeling of class analogy (SIMCA) and partial least square discriminate analysis (PLS-DA) chemometric techniques were utilized to classify samples in different classes. Totally, 362 samples were modeled in three different classes (two adulterated and one non-adulterated). The obtained results revealed that PLS-DA is the most suitable chemometric approach for prediction of probable adulteration in biocomposite samples with reliable specificity and selectivity. It could provide 99% correct class prediction rate between non-adulterated biocomposite samples and adulterated ones, while SIMCA methods provided 73.33% prediction accuracy in classification.     

Application of dispersive liquid–liquid microextraction with alcoholic solvents followed by HPLC–UV as a sensitive and efficient method for the extraction and determination of citalopram in biological samples using an experimental design

A sensitive and rapid method based on alcoholic-assisted dispersive liquid–liquid microextraction followed by high-performance liquid chromatography for determination of citalopram in human plasma and urine samples was developed. The effects of six parameters (extraction time, stirring speed, pH, volume of extraction and disperser solvents, and ionic strength) on the extraction recovery were investigated and optimized utilizing Plackett–Burman design and Box–Behnken design, respectively. According to Plackett–Burman design results, the volume of disperser solvent, stirring speed, and extraction time had no effect on the recovery of citalopram. The optimized condition was a mixture of 172 µL of 1-octanol as extraction solvent and 400 µL of methanol as disperser solvent, pH of 10.3 and 1% w/v of salt in the sample solution. Replicating the experiment in optimized condition for five times, gave the average extraction recoveries equal to 89.42%. The detection limit of citalopram in human plasma was obtained 4 ng/mL, and the linearity was in the range of 10–1200 ng/mL. The corresponding values for human urine were 5.4 ng/mL with the linearity in the range of 10–2000 ng/mL. Relative standard deviations for inter- and intraday extraction of citalopram were less than 7% for five measurements. The proposed method was successfully implemented for the determination of citalopram in human plasma and urine samples.     

Fischer–Tropsch synthesis over CNT-supported cobalt catalyst: effect of magnetic field

In the present work, the cobalt catalysts supported on carbon nanotubes (CNTs) were prepared by impregnation method in the presence and absence of magnetic field. The prepared catalysts were employed to yield higher hydrocarbons via Fischer–Tropsch synthesis. It is explored that using magnetized water can effectively change the catalyst geometry in impregnation catalyst preparation method. For the preparation of different sizes of cobalt particles on the CNTs support, the physical properties of solvent (water) in impregnation process were changed using the magnetizing process. The results showed that the average particle sizes of impregnated cobalt nanoparticles were decreased by using magnetized water in impregnation step. In addition, in the magnetized treated cobalt catalyst, the cobalt particles mostly dispersed outside the tubes because the capillary forces decreased by reducing water surface tension. Furthermore, the experimental results showed that the probability of chain growth (α) and selectivity to heavier hydrocarbons increased in magnetized water treatment catalysts.     

Tailoring particle shape for enhancing the homogeneity of powder mixtures:Experimental study and DEM modelling

The effect of particle shape modification on the segregation reduction of enzyme granules in laundry detergent powder mixtures was investigated,both experimentally and computationally using Deseret Element Method(DEM).The shape of modified enzyme particles was in such a way that the large and dense enzyme particles were layered by other fine particles in the detergent powder,by means of a process known in the literature as“seeded granulation”.It is found that the homogeneity of modified enzyme particles could be improved significantly comparing to the original spherical enzyme particles in powder mixtures.Overall,the results of this research demonstrated that the segregation-induced properties of the dense/spherical enzyme particles could be lowered by altering their shape,which could enable the enzyme particles to behave almost similar to other ingredients during the pile formation process.