María Ángeles García

Chiral separation of agricultural fungicides

Fungicides are very important and diverse environmental and agricultural concern species. Their determination in commercial formulations or environmental matrices, requires highly efficient, selective and sensitive methods. A significant number of these chemicals are chiral with the activity residing usually in one of the enantiomers. The different toxicological and degradation behavior observed in many cases for fungicide enantiomers, results in the need to investigate them separately. For this purpose, separation techniques such as GC, HPLC, supercritical fluid chromatography (SFC) and CE have widely been employed although, at present, HPLC still dominates chromatographic chiral analysis of fungicides. This review covers the literature concerning the enantiomeric separation of fungicides usually employed in agriculture grouping the chiral separation methodologies developed for their analysis in environmental, biological, and food samples.

Spectrophotometric and conductimetric determination of the critical micellar concentration of sodium dodecyl sulfate and cetyltrimethylammonium bromide micellar systems modified by alcohols and salts

Determination of the critical micellar concentration of some modified micellar systems used as mobile phases in micellar liquid chromatography and micellar electrokinetic chromatography has been achieved. Sodium dodecyl sulfate (SDS) and cetyltrimethylammonium bromide (CTAB) were used as surfactants, n-propanol and n-butanol as modifiers, and phosphate buffer was included in some of the micellar systems.

Characteristics and enantiomeric analysis of chiral pyrethroids

Pyrethroids are synthetic pesticides that originated from the modification of natural pyrethrins to improve their biological activity and stability. They are a family of chiral pesticides with a large number of stereoisomers. Enantiomers of synthetic pyretroids present different insecticidal activity, toxicity against aquatic invertebrates and persistence in the environment so the development of rapid and sensitive chiral methods for the determination of different enantiomers is necessary. Several techniques have been employed for this purpose including gas chromatography, high performance liquid chromatography or more recently capillary electrophoresis and sub or supercritical fluid chromatography. A general view on the different chiral separation methods applied to the analysis of pyrethroids and the most important information about these pesticides is provided in this review.

Evaluation of new cellulose-based chiral stationary phases Sepapak-2 and Sepapak-4 for the enantiomeric separation of pesticides by nano liquid chromatography and capillary electrochromatography.

Two novel polysaccharide-based chiral stationary phases (CSPs), known as Sepapak-2 (cellulose tris(3-chloro-4-methylphenylcarbamate)) and Sepapak-4 (cellulose tris(4-chloro-3-methylphenylcarbamate)), have been evaluated in this work for the chiral separation of a group of 16 pesticides including herbicides, insecticides and fungicides. The optimization of the mobile phase employed in nano-liquid chromatography (nano-LC) enabled the chiral separation of seven pesticides on Sepapak-2 and of nine pesticides on Sepapak-4. Due to the fact that Sepapak-4 gave better results, this column was selected to compare nano-LC and capillary electrochromatography (CEC) under the same conditions that consisted in the use of a 90/9/1 (v/v/v) ACN/H₂O/ammonium formate (pH 2.5) background electrolyte (BGE). As expected, both the efficiency and the chiral resolution obtained in CEC experiments were higher than in nano-LC for all the analyzed compounds. The analytical characteristics of the CEC developed methodology were evaluated in terms of linearity, LODs, LOQs, precision, selectivity, and accuracy allowing its application to the quantitation of metalaxyl and its enantiomeric impurity in a commercial fungicide product marketed as enantiomerically pure (metalaxyl-M) and in soil and tap water samples after solid phase extraction (SPE). The determined amount of metalaxyl-M was found to be a 26% above the labeled content and it contained an enantiomeric impurity of a 3.7% of S-metalaxyl was determined.

Recent advances in CE analysis of antibiotics and its use as chiral selectors.

Antibiotics are a class of therapeutic molecules widely employed in both human and veterinary medicine. This article reviews the most recent advances in the analysis of antibiotics by CE in pharmaceutical, environmental, food, and biomedical fields. Emphasis is placed on the strategies to increase sensitivity as diverse off‐line, in‐line, and on‐line preconcentration approaches and the use of different detection systems. The use of CE in the microchip format for the analysis of antibiotics is also reviewed in this article. Moreover, since the use of antibiotics as chiral selectors in CE has grown in the last years, a new section devoted to this aspect has been included. This review constitutes an update of previous published reviews and covers the literature published from June 2011 until June 2013.

Chiral separation of metalaxyl and benalaxyl fungicides by electrokinetic chromatography and determination of enantiomeric impurities

The enantiomers of two acylamine fungicides (metalaxyl and benalaxyl) were separated by EKC using CDs as chiral selectors. The use of 15 mM succinyl-γ-CD for metalaxyl and 5 mM succinyl-β-CD for benalaxyl dissolved in a 50 mM 2-morpholinoethanesulfonic acid buffer (pH 6.5), enabled the chiral separation of metalaxyl enantiomers in 11.5 min with a resolution of 3.1 and the enantiomeric separation of benalaxyl in 7.5 min with a resolution close to 15. Under these conditions, the two enantiomers of each of the chiral compound studied were also separated from folpet, very commonly present in fungicide formulations containing metalaxyl or benalaxyl. The analytical characteristics of the two developed methods were studied in terms of precision, linearity, selectivity, limits of detection (LODs) and limits of quantitation (LOQs) showing their suitability for the determination of these compounds in commercial agrochemical formulations. Finally, the development of an in-capillary preconcentration strategy allowed the detection of enantiomeric impurities up to 1.2% in commercial products labeled as enantiomerically pure in metalaxyl-M.

Evaluation of mesoporous silicas functionalized with C18 groups as stationary phases for the solid-phase extraction of steroid hormones in milk

In this work, two mesoporous silicas functionalized with C18 groups (SM‐C18 and SBA‐15‐C18) have been synthesized for their evaluation as stationary phases in SPE for the extraction and preconcentration of seven steroid hormones (estrone, estradiol, estriol, ethinyl estradiol, diethylstilbestrol, testosterone, and progesterone ) from milk. The characterization of both materials by diverse techniques such as transmission electron microscopy, SEM, thermogravimetric analysis, X‐ray diffraction, and adsorption–desorption isotherms showed that the mesoporous silicas had a high surface area, high pore volume, and a homogeneous distribution of the pores and that both silicas presented a similar degree of functionalization. An analytical methodology for the simultaneous separation of the seven selected steroids by HPLC‐DAD was developed. Both silicas were evaluated as stationary phases in SPE for the extraction of the steroid hormones from milk. This HPLC‐DAD method was applied to the analysis of all extracts obtained in the SPE experiments, showing that from the two synthesized mesoporus silicas, SBA‐15‐C18 silica enabled the extraction of the seven compounds with recoveries between 88 and 108% for all except for estriol, for which a recovery of 62% was obtained. The analytical characteristics of this methodology were evaluated, showing good precision and linearity (R2 > 0.994) for all analytes. The comparison of the results obtained with this silica and those obtained with commercial C18 particles and with some other commercial cartridges usually employed in the extraction of steroids showed that SBA‐15‐C18 silica was able to extract the seven steroids with higher recovery values.

Micellar Liquid Chromatography with Hybrid Eluents

Abstract The characteristics of Micellar Liquid Chromatography with hybrid eluents are described. The influence of the addition of an organic modifier to the mobile phase on the retention, eluent strength, efficiency and selectivity is discussed. The application of MLC with hybrid eiuents for predicting solutes hydrophobicity is studied.

Determination of micelle-solute association constants of some benzene and naphthalene derivatives by micellar high-performance liquid chromatography with butanol and sodium chloride additives to mobile phase

SummaryThe interaction between some benzene and naphthalene derivatives and sodium dodecyl sulphate and hexadecyltri-methylammonium bromide in the presence of n-butanol and sodium chloride has been evaluated by high-performance liquid chromatography using micellar mobile phases. Micelle-solute association constants are given for the compounds investigated. The results show that addition of n-butanol to the mobile phase decreases the association constant values relative to those in the absence of any additive. Conversely, when sodium chloride is added to the mobile phase, an increase of the association constant is obtained in most cases. Good correlation between free energy of transfer for water-micelles and for octanol-water has been observed.

Separation of phthalates by cyclodextrin modified micellar electrokinetic chromatography: Quantitation in perfumes

A new CE method has been developed for the simultaneous separation of a group of parent phthalates. Due to the neutral character of these compounds, the addition of several bile salts as surfactants (sodium cholate (SC), sodium deoxycholate (SDC), sodium taurodeoxycholate (STDC), sodium taurocholate (STC)) to the separation buffer was explored showing the high potential of SDC as pseudostationary phase. However, the resolution of all the phthalates was not achieved when employing only this bile salt as additive, being necessary the addition of neutral cyclodextrins (CD) and organic modifiers to the separation media. The optimized cyclodextrin modified micellar electrokinetic chromatography (CD-MEKC) method consisted of the employ of a background electrolyte (BGE) containing 25 mM β-CD-100 mM SDC in a 100 mM borate buffer (pH 8.5) with a 10% (v/v) of acetonitrile, employing a voltage of 30 kV and a temperature of 25 °C. This separation medium enabled the total resolution of eight compounds and the partial resolution of two of the analytes, di-n-octyl phthalate (DNOP) and diethyl hexyl phthalate (DEHP) (Rs~0.8), in only 12 min. The analytical characteristics of the developed method were studied showing their suitability for the determination of these compounds in commercial perfumes. In all the analyzed perfumes the most common phthalate was diethyl phthalate (DEP) that appeared in ten of the fifteen analyzed products. Also dimethyl phthalate (DMP), diallyl phthalate (DAP), dicyclohexyl phthalate (DCP), and di-n-pentyl phthalate (DNPP) were found in some of the analyzed samples.