Testing for linearity in retention time — Carbon number plots for n-alkanes

Summary Multiparametric, least-squares, regression treatment of G.C. data is extended to describe deviations from the usual linear model. Through statistical evaluation of results, four parameters models are generally found adequate and the use of higher degree empirical models is discouraged.     

Relative characterization of rosemary samples according to their geographical origins using microwave-accelerated distillation, solid-phase microextraction and Kohonen self-organizing maps

For centuries, rosemary (Rosmarinus officinalis L.) has been used to prepare essential oils which, even now, are highly valued due to their various biological activities. Nevertheless, it has been noted that these activities often depend on the origin of the rosemary plant and the method of extraction. Since both of these quality parameters can greatly influence the chemical composition of rosemary oil, an original analytical method was developed where "dry distillation" was coupled to headspace solid-phase microextraction (HS-SPME) and then a data mining technique using the Kohonen self-organizing map algorithm was applied to the data obtained. This original approach uses the newly described microwave-accelerated distillation technique (MAD) and HS-SPME; neither of these techniques require external solvent and so this approach provides a novel "green" chemistry sampling method in the field of biological matrix analysis. The large data set obtained was then treated with a rarely used chemometric technique based on nonclassical statistics. Applied to 32 rosemary samples collected at the same time from 12 different sites in the north of Algeria, this method highlighted a strong correlation between the volatile chemical compositions of the samples and their origins, and it therefore allowed the samples to be grouped according to geographical distribution. Moreover, the method allowed us to identify the constituents that exerted the most influence during classification.     

Effect of high temperature in determination of the mathematical dead time and the constants of the n-alkane retention time curve in gas chromatography

In gas liquid chromatography, the column dead time and the constants of the n-alkane retention time curve are calculated by the multiparametric least-squares regression iterative method at high temperature between 180 and 270°C. The method was applied to two types of columns. The first group includes eight packed columns (seven OV polymethylphenylsiloxane and Apolane-87), while the second includes five glass capillary columns (four methylsilicone with different film thicknesses and Apolane-87). The calculated tM and b values were compared with those obtained by Guardino's, Grobler's, and Kaiser's methods. The influences of coating thickness and temperature thereon were investigated.     

A numerical interpolation of Kováts indices without dead time correction

Summary Comparison with normal procedures shows that numerical interpolation of the logarithms of gross retention times generates quite useful Kováts indices for gas chromatographic analysis. The dead time concept is not used in the interpolation.     

Alpha-benzoinomixe: Extracting agent for uranium(VI), tungsten(VI), molybdenum(VI) and some transition metals of the iron family

The effect of pH on the percent extraction of vanadium(V), iron(II), cobalt(II), nickel(II), copper(II), molybdenum(VI), tungsten(VI) and uranium(VI) by -benzoinoxime in different solvents has been studied. The maximum recovery is not appreciably affected by the nature of the solvent, but occurs at different pH values for different metals. The pH corresponding to maximum extraction increases with increasing hydrolysis pK of the species in aqueous solution, and decreases with increasing stability constant of the complexes formed. Alpha-benzoinoxime allows the separation of these metal ions into three groups: V(V), Mo(VI) and W(VI) are extracted at pH=2, U(VI) at pH=5, Fe(II), Cu(II), Co(II) and Ni(II) at around pH=10.     

Comparison of Retention Indices of Some Explosives and Related Compounds Calculated by Different Mathematical Methods in Reversed-Phase Liquid Chromatography

In reversed phase liquid chromatography, the retention indices of some neutral and acidic explosives and related compounds (nitramines, nitroaromatics, aminoaromatics, and nitrophenols) based on the alkan-2-one, alkyl aryl ketone, and 1-nitroalkane retention index standards have been determined by the application of a new mathematical adaptation method, viz. a multiparametric least-squares regression iterative method. This method was applied to two types of columns. The first group includes six octadecyl-C₁₈ columns with different packing materials and obtained from different manufacturers, while the second group comprises one octyl-C₈ column. The retention indices have been extensively studied using either methanol-water or methanol-phosphate buffer mobile phase systems. The calculated multiparametric retention indices values were compared with those obtained by Guardino's, Grobler's, and Kovàts' methods. The influences of the concentration of the organic modifier in the mobile phase, aqueous mobile phase pH, and the column packing material on the retention indices of the explosives were also investigated. Good agreement was observed between the retention indices calculated by the use of the four mathematical methods for both neutral and acidic explosives.     

Gas chromatographic behaviour of monosubstituted benzenes,benzaldehydes and acetophenones on OV polymethylphenylsilicone stationary phases

Summary The retention indices of some monosubstituted benzenes, benzaldeyhdes and acetophenones have been determined on seven OV polymethylphenylsiloxane liquid phases. The interactions and forces that affect the separation of the isomers and their elution sequences are discussed, taking into account mesomeric and inductive effects of the substituents in the benzene ring and the dipole moments of these solutes. These phases are not very selective for the separation or the accurate assessment of the effect of substituent over the benzene nucleus. This may be explained by the presence of the considerable number of benzene nuclei integral to the structure of these phases.     

Comparison of mathemical methods for the calculation of retention indices at high temperature in gas chromatography

The retention indices of three homologous series (2-alkanones, 1-alkanols, cycloalksanones) have been determined at high temperature by the application of two new adaptation methods: A multiparametric least-squares regressions iterative method based on the dertermination of the adjusted retention times and a cubic interpolation directly using the uncorrected retention times without dead time correction. The two methods were applied to two types of columns. The first group includes eight packed columns (seven OV polymethylphenylsiloxane and Apolane-87 stationary phases), while the second includes five glass capillary columns (four methyl-silicons with different film thicknesses and Apolane-87 stationary phases). The retention indices obtained with a multiparametric and a cubic interpolation methods were compared with each other and with those calculated by Grobler's, Guardino's, Kaiser's and Kovàts' methods. The influence of coating, film thickness, and temperature on them was investigated.     

Kinetic Study of Microwave Extraction of Essential Oil of Nigella sativa L. Seeds

The Nigella sativa L. is widely cultivated in the Algerian Sahara and primarily used for its health benefits. Extraction experiments were carried out by a microwave energy, performed at atmospheric pressure with a small quantity of water for 10 min. This method enabled a best yield (0.54–0.57%) and a high amount of the volatile fraction with a shorter extraction time and a reduction of energy consumption. The kinetic study of essential oils extraction was quantitatively studied. Thus, the qualitative and quantitative composition of the essential oils extracted for 10 min and in different periods was examined by capillary gas chromatography and by gas chromatography-mass spectrometry. The percentage of the main constituents such as p-cymene, thymoquinone, α-thujene, 4-terpineol and carvacrol was reported. The family classes present a significant variation according to the extraction time. Kinetic and extraction rate profile of microwave process (yield) showed that it is possible to reduce the extraction time.