Coupling solid-phase microextraction and high-performance liquid chromatography for direct and sensitive determination of halogenated fungicides in wine

A solid-phase microextraction (SPME) method coupled to high-performance liquid chromatography with diode array detection (HPLC-DAD) for the analysis of six organochlorine fungicides (nuarimol, triadimenol, triadimefon, folpet, vinclozolin and penconazole) in wine was developed. For this purpose, polydimethylsiloxane-divinylbenzene-coated fibers were utilized and all factors affecting throughput, precision, and accuracy of the SPME method were investigated and optimized. These factors include: matrix influence, extraction and desorption time, percentage of ethanol, pH, salt effect and desorption mode. The performed analytical procedure showed detectability ranging from 4 to 27 microg l(-1) and precision from 2.4 to 14.2% (as intra-day relative standard deviation, RSD) and 4.7-25.7% (as inter-day RSD) depending on the fungicide. The results demonstrate the suitability of the SPME-HPLC-DAD method to analyze these organochlorine fungicides in red wine.     

Differential-pulse adsorptive stripping voltammetry of the herbicides metamitron and isometiozine

Summary A new extract-photometric method is proposed for determining trace amounts of Fe³⁺ based on the formation of a coloured complex with 2-indolehydroxamic acid (2-IHA), that can be extracted into a solution of trioctylmethylammonium chloride solution in toluene. Beer's law was obeyed between 0.06 g/g and 1.25 g/g (minimum error range) of iron in the aqueous phase, with a relative error (p=0.05) of ±0.86%. Molar absortivity at 455 nm was 6500 l mol^–1 cm^–1. The method was applied to the determination of iron in various samples: commercial pharmaceutical nutritional preparations, wine and standard samples of Portland cement and magnesite.     

Accurate evaluation of a polynomial in Chebyshev form

This paper presents a compensated algorithm to accurately evaluate a polynomial expressed in Chebyshev basis of the first and second kind with floating-point coefficients. The principle is to apply error-free transformations to improve the traditional Clenshaw algorithm. The new algorithm is as accurate as the Clenshaw algorithm performed in twice the working precision. Forward error analysis and numerical experiments illustrate the accuracy and properties of the proposed algorithm.     

Liquid crystal binary mixtures of 8OCB + 10OCB. Evidence for a smectic A-to-nematic tricritical point

The two-component system octyloxycyanobiphenyl (8OCB) + decyloxycyanobiphenil (10OCB) has been studied by means of modulated differential scanning calorimetry as well as optical microscopy. The general trends of the phase diagram are similar to the two-component system octylcyanobiphenyl (8CB) + decylcyanobiphenil (10CB), previously published. Evidence for the existence of a TCP have been reported, the molar composition being about 0.33 of 10OCB. Additionally, the smectic mesophase of the 8OCB + 10OCB mixtures has been unmistakably characterized through optical measurements as smectic A for the whole composition range.     

Analytical procedures for the determination of the selective serotonin reuptake inhibitor antidepressant citalopram and its metabolites

The antidepressant citalopram (CIT) is a potent and highly selective serotonin reuptake inhibitor (SSRI) which has been introduced in therapy as a racemic drug. CIT has been used to treat central nervous system affective disorders such as depression, anxiety, obsessive-compulsive disorders, various phobias, borderline personality disorders, bipolar disorders as well as indications wherein inhibition of serotonin reuptake is desired. CIT is demethylated to demethylcitalopram (DCIT) and didemethylcitalopram (DDCIT), which retain considerable activity as SSRIs. Therefore, in recent years, the monitoring of the levels of these analytes in biological fluids for toxicological and therapeutic purposes has been a target worthy of interest. In addition, the differences in activity between CIT enantiomers established the need to assess its behaviour in the field of pharmacological research. It is also necessary to develop analytical methodologies that make it possible to determine the levels of enantiomer concentrations. This review includes most of the published analytical methods for achiral assay of racemic CIT and its metabolites based on high-performance liquid chromatography coupled with UV, fluorescence and mass spectrometry detectors, capillary electrophoresis and gas chromatography with mass spectrometry detectors among others. With regard to the monitoring of enantiomers of CIT and of its metabolites, stereoselective methods based on chiral chromatographic columns, chiral additives in mobile phases and on the derivatization with a chiral reagent are also collected. In addition, different procedures of extraction are mentioned as well as liquid-liquid extraction, solid-phase extraction, solid-phase microextraction, automated online extraction or liquid-phase microextraction in different biological and environmental samples.     

Letter to the editor

This letter shows how the main result contained in a paper recently appeared in the Journal of Multivariate Analysis was in fact a particular case of a more general theorem published three years before.     

Convergence rates of accelerated proximal gradient algorithms under independent noise

Numerical Algorithms - We consider an accelerated proximal gradient algorithm for the composite optimization with “independent errors” (errors little related with historical...