Enhanced removal of chiral emerging contaminants by an electroactive biofilter.

50% of pharmaceuticals and 25% of herbicides used worldwide are chiral. Each enantiomer has a unique toxicity and biodegradation profile, affecting differently to organisms. Chirality plays a key role in the behavior of these emerging contaminants (ECs) in terms of their pharmacological or herbicidal activity, but this peculiarity is often overlooked in environmental research.

Chiral Analysis of Pesticides and Emerging Contaminants by Capillary Electrophoresis-Application to Toxicity Evaluation.

Chiral analysis is a very relevant topic in environmental chemistry. This is due to the different properties of the stereoisomers of chiral compounds. In the case of agrochemicals, the desired activity, degradation rate, or toxicity, among other characteristics, may differ between stereoisomers, and the same is true for emerging contaminants, such as pharmaceuticals and cosmetics.

Enantioseparation and ecotoxicity evaluation of ibrutinib by Electrokinetic Chromatography using single and dual systems.

In this work, two chiral methods enabling the separation of ibrutinib enantiomers were developed by Electrokinetic Chromatography. A cyclodextrin (CD) or a mixture of the CD and a chiral ionic liquid (CIL) was used as chiral selector. Using the single CD system, seven neutral and six anionic CDs were tested in a formate buffer at pH 3.

Simultaneous microextraction of pesticides from wastewater using optimized μSPEed and μQuEChERS techniques for food contamination analysis.

Food contamination with pesticides poses significant risks to consumer safety and undermines confidence in food supply chains. Detecting pesticides in food samples is a challenging task that requires efficient extraction techniques. This study aims to compare and validate two microextraction techniques, μSPEed and μQuEChERS-dSPE, for the simultaneous extraction of eight pesticides (paraquat, thiabendazole, asulam, picloram, ametryn, atrazine, linuron, and cymoxanil) from wastewater samples.

First eco-toxicological evidence of ivabradine effect on the marine bacterium Vibrio fischeri: A chiral view.

Ivabradine (S-ivabradine) is a contemporary antihypertensive drug designed and commercialized for cardiovascular diseases treatment over the world. In this work the enantiomer-specific stability and acute toxicity of ivabradine to the marine bacterium Vibrio fischeri as well as the potential mechanism of action were investigated for the first time. With this aim, real concentrations of ivabradine enantiomers under abiotic and biotic conditions were determined by Capillary Electrophoresis (CE) with cyclodextrins (CDs) as chiral selectors.

Stereoselective separation of dimethenamid by cyclodextrin electrokinetic chromatography using deep eutectic solvents.

An Electrokinetic Chromatography (EKC) method was developed in this work enabling for the first time the separation of the four stereoisomers of the acetamide herbicide dimethenamid. A screening of different anionic cyclodextrins (CDs) revealed that the use of a single CD system did not allow the separation of the four dimethenamid stereoisomers while dual systems improved the chiral separation. The combination of 15 mM (2-carboxyethyl)-β-CD (CE-β-CD) with 10 mM methyl-γ-CD (M-γ-CD) originated the partial separation of dimethenamid stereoisomers.

Simultaneous Enantiomeric Separation of Carfentrazone-Ethyl Herbicide and Its Hydrolysis Metabolite Carfentrazone by Cyclodextrin Electrokinetic Chromatography. Analysis of Agrochemical Products and a Degradation Study.

The different activity and toxicity that the enantiomers of agrochemicals may have requires the development of stereoselective analytical methodologies enabling the individual determination of each enantiomer. The aim of this work was to develop the first Electrokinetic Chromatography methodology enabling the simultaneous enantiomeric separation of carfentrazone-ethyl herbicide and its hydrolysis metabolite carfentrazone. The use of an anionic cyclodextrin as chiral selector (captisol at 2.

Stereoselective separation of sulfoxaflor by electrokinetic chromatography and applications to stability and ecotoxicological studies.

An Electrokinetic Chromatography method was developed for the stereoselective analysis of sulfoxaflor, a novel sulfoximine agrochemical with two chiral centers. A screening with fourteen negatively charged CDs was performed and Succinyl-β-CD (Succ-β-CD) was selected. A 15 mM concentration of this CD in a 100 mM borate buffer (pH 9.

Enantiomeric separation of prothioconazole and prothioconazole-desthio by Capillary Electrophoresis. Degradation studies in environmental samples.

In this work, two analytical methodologies by Capillary Electrophoresis were developed. The first one enabled the rapid and cost-effective enantioseparation of prothioconazole and was applied to the analysis of prothioconazole-based commercial agrochemical formulations. The second methodology enabled the simultaneous enantioseparation of prothioconazole and its metabolite prothioconazole-desthio and was applied to degradation studies of both compounds in soil and sand samples.

Natural radioactivity and total K content in wild-growing or cultivated edible mushrooms and soils from Galicia (NW, Spain).

The radioactive isotope, K, of naturally occurring potassium (0.012%) is present in the Earth's crust in a low percentage of all potassium, leading to its presence in almost all foodstuffs. The impact of K activity concentrations was assessed in wild and cultivated edible mushrooms and in growing substrates.

Enantiomeric separation of panthenol by Capillary Electrophoresis. Analysis of commercial formulations and toxicity evaluation on non-target organisms.

The first CE methodology enabling the enantiomeric separation of panthenol was developed in this work. Electrokinetic chromatography with cyclodextrins (CD-EKC) was the CE mode employed for this purpose. The effect of different experimental variables such as the nature and concentration of the cyclodextrin, the temperature and the separation voltage was investigated.

Villari Effect at Low Strain in Magnetoactive Materials.

Magnetic composites of soft magnetic FeGa particles embedded in a silicone matrix have been synthesized. The Villari effect has been studied depending on the size and concentration of the particles and on the magnetic state of the composite. The results indicate a decrease in the Villari effect when the concentration of the magnetic particles increases.

Enantiomeric Determination of Drugs in Pharmaceutical Formulations and Biological Samples by Electrokinetic Chromatography.

Chirality is a relevant issue in the pharmaceutical field due to the different biological activity that enantiomers of a chiral drug can show. In fact, the desired biological or pharmaceutical activity might be present in only one of the enantiomers, while the other enantiomer(s) may have different biological activity, be inactive or even toxic. This has motivated in recent years the development of drugs marketed as pure enantiomers to avoid exposing the organism to the action of enantiomers that may not be active or even harmful to health.

Modeling-based optimization of the simultaneous enantiomeric separation of multicomponent mixtures of phenoxy acid herbicides using dual cyclodextrin systems by Capillary Electrophoresis.

In this work, the Dubsky's model proposed for Capillary Electrophoresis (CE) enantioseparation systems with a mixture of chiral selectors was applied to the rapid optimization of the simultaneous enantiomeric separation of a multicomponent mixture of six phenoxy acid herbicides using a dual system of two cyclodextrins (CDs), (2-hydroxypropyl)-β-CD (HP-β-CD) and heptakis(2,3,6-tri-O-methyl)-β-CD (TM-β-CD). Simply by carrying out a small number of individual experiments separately with each CD, the Dubsky's model enabled to foresee the results that could be obtained for any possible combination of concentrations and relative proportion of both CDs in the mixture. Results obtained in this work demonstrated that the model was successful by improving the previous results experimentally obtained by the trial and error method for the simultaneous enantiomeric separation of the six phenoxy acid herbicides studied in this work.

Enantiomeric separation of ivabradine by cyclodextrin-electrokinetic chromatography. Effect of amino acid chiral ionic liquids.

A chiral methodology was developed for the first time to ensure the quality control of ivabradine, a novel anti-ischemic and heart rate lowering drug commercialized as a pure enantiomer. With this aim, electrokinetic chromatography (EKC) was employed and the enantiomeric separation of ivabradine was investigated using different anionic and neutral cyclodextrins (CDs) and amino acid-based chiral ionic liquids (CILs) as sole chiral selectors. Baseline separation was only achieved with sulfated CDs, and the best enantiomeric resolution was obtained with sulfated-γ-CD.

Enantiomeric analysis of pyrethroids and organophosphorus insecticides.

The use of pesticides has increased sharply in the last decades, not only in agriculture, but also in industry, public health, and other areas. Pyrethroids and organophosphorus insecticides are among the most employed pesticides. These chemicals usually contain asymmetric chiral atoms; thus, they are characterized by stereoisomerism.

Stability and toxicity studies for duloxetine and econazole on Spirodela polyrhiza using chiral capillary electrophoresis.

Stability and toxicity studies for duloxetine and econazole were achieved using individual solutions and their mixtures. Stability of drugs racemates and enantiomers was investigated under abiotic and biotic conditions. Toxicity was evaluated for the first time on Spirodela polyrhiza.

Enantiomer stability and combined toxicity of duloxetine and econazole on Daphnia magna using real concentrations determined by capillary electrophoresis.

Enantiomer stability was investigated in this work for the first time for duloxetine and econazole in individual solutions and their mixtures under the standardized ecotoxicity test experimental conditions for Daphnia magna and abiotic conditions. Real (and not nominal) enantiomer concentrations were employed for calculations since their determination was achieved by Capillary Electrophoresis. Relevant differences were found in stability profiles for both drugs in any case.

Cationic amine-bridged periodic mesoporous organosilica materials for off-line solid-phase extraction of phenoxy acid herbicides from water samples prior to their simultaneous enantiomeric determination by capillary electrophoresis.

Two novel materials based on periodic mesoporous organosilica (PMO) with cationic amine-bridged ligands, (styrylmethyl)bis(triethoxysilylpropyl)ammonium chloride (PMO-STPA) and bis(3-triethoxysilylpropyl)amine (PMO-TEPA), were synthesized in this work to obtain materials with reverse-phase/strong anionic exchange mixed-mode or strong anionic exchange retention mechanism, respectively. The resulting materials were comprehensively characterized and showed functionalization with cationic amine-bridged ligands, and values of surface areas characteristic of mesoporous materials (higher than 100m/g). These materials were evaluated for the off-line solid-phase extraction (SPE) of a mixture of six phenoxy acid herbicides (fenoprop, mecoprop, dichlorprop, 2-(4-chlorophenoxy)propionic acid (4-CPPA), 2-(3-chlorophenoxy)propionic acid (3-CPPA), 2-phenoxypropionic acid (2-PPA)) from water samples previous to their analysis by CE with diode-array detection using a dual chiral selector system (20mM of heptakis(2,3,6-tri-O-methyl)-β-CD (TM-β-CD) and 7mM of (2-hydroxypropyl)-β-CD (HP-β-CD) dissolved in 50mM phosphate buffer, pH 7.

Periodic mesoporous organosilica materials as sorbents for solid-phase extraction of drugs prior to simultaneous enantiomeric separation by capillary electrophoresis.

Two novel periodic mesoporous organosilica materials were synthesized with a neutral phenylene-bridged ligand, 1,4-bis(trimethoxysilylethyl)benzene, one of them using tetraethyl orthosilicate as additional silica source (PMO-TMSEB-1 and PMO-TMSEB-2). A third material was also synthesized with 1,4-bis(triethoxysilyl)benzene ligand (PMO-TESB-1) which use has scarcely been reported. The three materials were evaluated as solid-phase extraction (SPE) sorbents for the off-line extraction of a mixture of seven drugs of different nature (duloxetine, terbutaline, econazole, propranolol, verapamil, metoprolol, and betaxolol) from water samples.

Analysis of antibiotics by CE and CEC and their use as chiral selectors: An update.

Natural, synthetic or semisynthetic antibiotics are highly used to prevent or treat diseases in humans and animals, and to promote animal growth. This fact makes that antibiotics residues or their transformation products may be present in food or in the environment after human or animal excretion. For this reason, it is imperative to develop reliable and sensitive analytical methodologies for their analysis.

Enantiomeric separation of the antiuremic drug colchicine by electrokinetic chromatography. Method development and quantitative analysis.

Two analytical methodologies were developed by CE enabling the enantiomeric separation of colchicine, an antiuremic drug commercialized as pure enantiomer. Succinyl-γ-CD and Sulfated-γ-CD were selected as chiral selectors after a screening with different anionic CDs. Under the optimized conditions, chiral resolutions of 5.

Citrate versus acetate-based dialysate in on-line haemodiafiltration. A prospective cross-over study.

Background And Aims: A bicarbonate dialysate acidified with citrate (CD) has been reported to have local anticoagulant effect and improves biocompatibility. This study examines the effect of CD on dialysis efficiency, coagulation, acid-base status, electrolytes, and inflammation in patients in on-line hemodiafiltration (OL-HDF).

Methods: 35 patients in OL-HDF were enrolled in a prospective, cross-over study for a 24-week period and two phases alternating CD and acetate dialysate fluid (AD).