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At present, dietary supplements are commercially available products, globally consumed as an addition to the usual diet. Considering that dietary supplements are a source of nutrients, they are widely utilized to improve human health and prevent various diseases; therefore they are expected to be safe. There is still no common definition regarding the role of supplements which cannot be considered functional foods nor drugs. Dietary ingredients in supplements are exempt from food additives or drugs regulations. For this reason, these supplements are marketed without any data on identity, including ingredient information, effectiveness, toxicology and safety. Therefore, efficacy and safety are necessary claims required to preserve consumer health. To face this imperative challenge, sensitive and selective analytical techniques capable of providing a full characterization of the supplements in terms of their components are needed. In the last decades, Capillary Electrophoresis (CE) has shown to be a powerful tool that offers solutions to almost any analytical issue arising in several application fields. Due to its simplicity of operation and versatility, it has become a complementary separation tool to other separation techniques such as gas and liquid chromatography in the analysis of dietary supplements. This chapter aims to give a comprehensive overview of the most important applications of CE for the analysis of dietary supplements in terms of their main key components.

Unknown extraction recovery from solid matrix samples leads to meaningless chemical analysis results. It cannot always be determined, and it depends on the complexity of the matrix and properties of the extracted substances. This paper combines a mathematical model with the machine learning method - neural networks that predict liquid extraction recovery from solid matrices. The prediction of the three-stage extraction recovery of polycyclic aromatic hydrocarbons from a wooden railway sleeper matrix is demonstrated. Calculation of the extraction recovery requires the extract's volume to be measured and the polycyclic aromatic hydrocarbons' concentration to be determined for each stage. These data are used to calculate the input values for a neural network model. Lowest mean-squared error (0.014) and smallest retraining relative standard deviation (20.7%) were achieved with the neural network setup 6:5:5:4:1 (six inputs, three hidden layers with five, five, and four neurons in a layer, and one output). To train such a neural network, it took less than 8000 steps - less than a second - using an average-performance laptop. The relative standard deviation of the extraction recovery predictions ranged between 1.13 and 5.15%. The three-stage recovery of the extracted dry sample showed 104% of three different polycyclic aromatic hydrocarbons. The extracted wet sample recovery was 71, 98, and 55% for phenanthrene, anthracene, and pyrene, respectively. This method is applicable in the environmental, food processing, pharmaceutical, biochemical, biotechnology, and space research areas where extraction should be performed autonomously without human interference.

In this paper, a portable instrument for surface tension measurements, characterization and applications is described. The instrumentation is operated wirelessly, and samples can be measured in situ. The instrument has changeable different size probes; therefore, it is possible to measure samples from 1 ml up to 10 ml. The response of the measured retraction force and the concentrations of measured surfactant is complex. Therefore, two calibration methods were proposed: (i) the conditional calibration using polynomial and logarithmic fitting and (ii) the neural network trained model prediction of the surfactant concentration in samples. Calibrating the instrument, the neural network trained model showed a superior coefficient of determination (0.999), comparing it to the conditional calibration using polynomial (0.992) and logarithmic (0.991) fit equations.

Sodium lauryl ether sulphate (SLES) is the main chemical component in several lubricant products used for soil conditioning in the mechanized excavation industry using Earth Pressure Balance-Tunnel Boring Machines. During the tunnelling process, huge amounts of excavated soil are produced and the SLES presence can affect the subsequent re-use of this material as a by-product. Currently, there is still no regulatory indication of reliable and sensitive bioassays for monitoring soil quality during the excavation process. The main objective of this work was to verify if the Vibrio fischeri screening test was suitable as a consistent and precautionary tool for this specific purpose. Firstly, the ecotoxicity (EC20 and EC50) of the SLES standard solution and three commercial products (SLES content from 10 to 50%) were evaluated to select the most environmental friendly product. Subsequently, soil samples from about 2 years of tunnelling in a real construction site, conditioned with the selected product, were evaluated for their environmental compatibility with the prescriptions of an Italian site-specific protocol. The latter established 2 mg/L as a threshold value for SLES concentration in soil water extracts and a no toxic response (2 mg/L. The toxicity was directly related to SLES concentration, indicating that the V. fischeri test and the SLES analyses are suitable tools for assessing excavated soil as a by-product, ensuring its safe reuse in accordance with a green production process (circular economy).

Wooden sleepers used in railways are impregnated with preservatives with fungicidic and bactericidic properties, which contain a large amount of harmful polycyclic aromatic hydrocarbons (PAHs). The aim of this research was to reveal the type of fungi in the rhizosphere of plants, which tolerate pollutants and can be involved in bioremediation process of creosote-contaminated used wooden railway sleepers. Tagetes patula grown in the substrate with 12.5% creosote impregnated used wooden sleepers chips additive is characterized by the most intensive root development and the biggest population of active fungi, therefore it is recommended for further investigation. Number of colonies of fungi in the rhizosphere of investigated plants decreased in many cases by increasing the amount of sleepers chips additive in substrate, however it was greater in the substrates with creosote treated wooden sleepers chips additives (12.5, 25 and 37.5% wooden sleepers chips) than in the pure substrate and various substrates with additives of pure Pinus sylvestris chips. This is a pioneering study searching for the local fungi species in Lithuania, which can be further utilized for the bioremediation of PAHs.

A wide use of foaming agents as lubricants is required in mechanized tunneling. Their main component, the anionic surfactant sodium lauryl ether sulphate (SLES), can remain in residual concentrations in soil debris, influencing their potential reuse as by-product. This study aimed at evaluating the environmental fate and effects of a foaming product used for conditioning soils collected from real excavation sites, in the presence/absence of an anti-clogging polymer, both containing SLES. Soil microcosm experiments were set-up and incubated for 28 days. Over time, soils and their water extracts (elutriates) were collected to perform both ecotoxicological tests (Vibrio fischeri, Lepidium sativum, Eisenia foetida, Hetereocypris incongruens, Danio rerio) and SLES analysis. The results showed that, just after conditioning, SLES did not exert any hazardous effect on the organisms tested except for the bacterium V. fischeri, which was the most sensitive to its presence. However, from day seven the toxic effect on the bacterium was never observed thanks to the SLES decrease in the elutriates (&lt, 2 mg/L). SLES degraded in soils (half-lives from 9 to 25 days) with higher disappearance rates corresponding to higher values of microbial abundances. This study highlights the importance of site-specific studies for assessing the environmental reuse of spoil materials.

Landfill leachate is a highly polluted and toxic waste stream harmful to the environment and human health, its biological treatment, even if challenging, offers the opportunity of recovering valuable resources. In this study, we propose the application of an extractive membrane bioreactor equipped with a polymeric tubing, made of Hytrel, as an innovative device able to remove specific organic toxic compounds of the leachate and, at the same time, to produce an effluent rich in valuable chemicals suitable for recovery. The leachate treatment consists in a two-step process: the extraction of specific toxic compounds through the polymeric tubing based on the affinity with the polymer, and their subsequent biodegradation in controlled conditions in the bulk phase of the extractive membrane bioreactor, thus avoiding the direct contact of the microbial consortium with the toxic leachate. Three synthetic streams simulating leachates produced by landfills of typical industrial/hazardous waste, mixed municipal and industrial solid waste, and oil shale industry waste, whose toxic fraction is mainly constituted by phenolic compounds, have been tested. Successful performance was achieved in all the tested conditions, with high removal (≥98%) and biodegradation efficiencies (89-95%) of the toxic compounds. No mass transfer limitations across the tubing occurred during the operation and a marginal accumulation (in the range of 4-7%) into the polymer has been observed. Furthermore, volatile fatty acids and inorganic compounds contained in the leachates were fully recovered in the treated effluent. Feasibility study confirmed the applicability of the proposed bioreactor as a powerful technology able to achieve high toxic removal efficiency in leachate treatment and facilitate resource recovery.

Alkylethoxysulfate (AES) surfactants are the main component of most commercial products used for soil conditioning in the excavation industry, in particular as lubricants for mechanized tunnelling. Huge amounts of soil debris are produced during the excavation process and their possible re-use as by-products (e.g. land covering) or discharge as waste is a critical question in civil engineering. There can be an environmental impact from the potential ecotoxicity of the residual chemical mixture occurring in the foam-conditioned excavated soil. Chemical analyses are not able on their own to assess the potential hazards for the ecosystem ascribable to inadequate management of this kind of conditioned soil. Ecotoxicological tests, on the other hand, provide useful overall information about the potential effects of conditioned debris on soil and aquatic biota, including synergic ones, whether or not there is a detailed knowledge of the chemical composition of all the components of the commercial foaming products. In this context, the objective of this work was to evaluate the overall ecotoxicity of excavated soil conditioned with two common foaming products containing sodium lauryl ether sulphate (SLES) as the main component, in order to verify their possible re-use as by-products. For this purpose, two soils with different geopedological characteristics were conditioned with the commercial foaming agents at the concentrations utilised for mechanized tunnelling and then used for microcosm laboratory experiments. Soil sub-samples were collected at different times (0, 7, 14, 28 days) of incubation and soil elutriates were produced to assess the effects of the foaming agents on five test species (Pseudokirchneriella subcapitata, Daphnia magna, Danio rerio, Vibrio fischeri and Lepidium sativum). The results of the tests were then compared with SLES residual concentrations in the elutriates, determined with the MBAS (methylene blue active substances) spectrophotometric method. Finally, the data were combined in a battery index, which proved effective at evaluating the overall ecotoxicity in a real-life situation of two different excavated soils conditioned with the two products analysed.

The antischistosomal prodrug oxamniquine is activated by a sulfotransferase (SULT) in the parasitic flatworm Schistosoma mansoni. Of the three main human schistosome species, only S. mansoni is sensitive to oxamniquine therapy despite the presence of SULT orthologs in Schistosoma hematobium and Schistosoma japonicum. The reason for this species-specific drug action has remained a mystery for decades. Here we present the crystal structures of S. hematobium and S. japonicum SULTs, including S. hematobium SULT in complex with oxamniquine. We also examined the activity of the three enzymes in vitro; surprisingly, all three are active toward oxamniquine, yet we observed differences in catalytic efficiency that implicate kinetics as the determinant for species-specific toxicity. These results provide guidance for designing oxamniquine derivatives to treat infection caused by all species of schistosome to combat emerging resistance to current therapy.

Mechanized excavation of tunnels with Earth Pressure Balance-Tunnel Boring Machines requires the use of foaming agents. The latter contain the anionic surfactant sodium lauryl ether sulphate (SLES) as the main compound. The re-use as a by-product of excavated soil containing foaming agents (spoil material) can pose a risk for soil and particularly for aquatic ecosystems if they are close to the spoil material final destination site. This work reports the chemical results (SLES residual concentrations) and ecotoxicological effects (battery of five tests) of 28 day-mesocosm studies performed at a tunnelling construction site. The soil mesocosms were set up with two different lithologies, which contained four different foaming agent products at the highest amounts used for excavation. The decrease in SLES concentrations and the ecotoxicological tests were performed in soil and its water extract (elutriate) at different times (0, 7, 14, 28 d). Elutriates were prepared in order to simulate a possible SLES leaching from soil to water. The results showed a decrease in SLES over time and different ecotoxicological responses depending not only on the initial amount of each product, but also on the soil lithology and organism tested (aquatic or terrestrial). This study showed how only site-specific ecotoxicological evaluations can ensure a safe management of the spoil material, making possible the re-use of soil and avoiding production of waste.

In order to identify new aromatase enzyme inhibitors, thirty aryl sulfonamide derivatives containing an indole nucleus have been synthesized. The enzyme inhibition assay showed that four compounds inhibit aromatase in the sub-micromolar range. Loading concentrations of these four compounds were afterwards tested for cell viability and cytotoxicity on MCF7 human breast cancer cells, revealing a time- and dose-dependent decrease of active metabolizing cells over the time of the culture (0–72 h), starting from a concentration of 100 μM. Likewise LDH released raised up to 40% at early time of exposures (24 h). Finally, the docking study showed that the best active compounds efficiently bound in the active site of the aromatase; high values of HBD and low levels of HBA are the principal requirement evidenced by the QSAR model.

Currently, dietary supplements are widely consumed over the world for health-related reasons. Even though, most of these supplements are beneficial for human health, they can also have side effects due to an excess of one of the supplement ingredients or to the presence of contaminants. It is then important to ensure their efficacy and safety. Recently, miniaturized separation techniques have emerged as popular analytical tools in several application fields. Rapid separations, low consumption of both samples and reagents, as well as high efficiency and reduction of production costs are some of the requirements of research laboratories and manufacturing companies. The aim of this review is to give an overview of the electromigration and miniaturized chromatographic methods for the analysis of dietary supplements. Applications for the determination of supplements related molecules including amino acids, peptides, selenium, vitamins, phenethylamines, nanomaterials, polyphenols, biomolecules, other components as contaminants and pharmaceutical drugs are described. (C) 2018 Elsevier B.V. All rights reserved.

The studies were carried out in the period of 2013–2014 in experiment developed during plant vegetation, cultivating five plant species in the vegetative pots with the substrate contaminated with used sleepers (US) and uncontaminated substrate fertilised with nitrogenous fertilisers. The objective of the research is to analyse the morphological features of aboveground and underground parts of herbaceous plants and determine the dependence of the number of fungi and bacteria colonies in the rhizosphere of these plants and the substrate contaminants and the impact of nitrogenous fertiliser concentration; with reference to that, determine the feasibility of these plants for phytoremediation. A tolerant plant was found, i.e. Tagetes patula L. as a phytoremediator, which adapted to grow in the condition of contaminated and fertilised substrate with nitrogen, and suitable for cultivating it in similar edaphic conditions. An intolerant plant, i.e. Trifolium repens L. as a phytoindicator, is a perennial, herbaceous plant of Fabaceae Lindl. Family, the rhizosphere of which contains the maximum number of fungi and bacteria colonies in the occurrence of the maximum concentration of nitrogenous fertilisers and contaminants. These bacteriological and mycological processes, as well as the excess of nitrogen, have negative impact on the growth of aboveground and underground parts of Trifolium repens.DOI: http://dx.doi.org/10.5755/j01.erem.72.4.17493

The increasing worldwide consumption of pharmaceuticals and personal care products such as ibuprofen (IBU) is leading to the widespread and persistent occurrence of these chemicals and their transformation products in soils and waters. Although at low concentrations, the continuous discharge of these micropollutants and the incomplete removal by the actual wastewater treatments can provoke accumulation in the environment with risks for the trophic chain. Non-target organisms as duckweed can be used for the environmental monitoring of pharmaceutical emerging contaminants. In this work, plants of Lemna gibba L. were exposed to high (0.20 and 1mgL-1) and environmentally relevant (0.02mgL-1) concentrations of IBU to investigate their removal and metabolization capacity. The main oxidized IBU metabolites in humans (hydroxy-IBU and carboxy-IBU) were determined in the intact plants and in the growth solutions, together with non-destructive physiological parameters and phytotoxic indicators. The IBU uptake increased with the increasing of IBU concentration in the medium, but the relative accumulation of the pharmaceutical and generation of hydroxy-IBU was higher in presence of the lower IBU treatments. Carboxy-IBU was not found in the plant tissue and solutions. The changes observed in growth and photosynthetic performances were not able to induce phyto-toxic effects. Apart from a mean physical-chemical degradation of 8.2%, the IBU removal by plants was highly efficient (89-92.5%) in all the conditions tested, highlighting the role of L. gibba in the biodegradation of emerging contaminants.

A group of 36 fungal strains, belonging to the Lithuanian mycobiota, was collected and isolated from different locations, habitats, and matrices, including creosote-treated wood in storage yards for crosstie wastes. The eight most perspective strains selected according to preliminary assessment of tolerance to coal tar were subsequently identified combining taxonomical evaluation and molecular techniques. The tolerance of the eight identified fungal species (five basidiomycetes and three ascomycetes) to the presence of various concentrations of coal tar, and for the four most perspective fungal strains (Pleurotus sp., Schizophyllum sp., Irpex lacteus, Bjerkandera adusta) to polycyclic aromatic hydrocarbons was evaluated. The ligninolytic enzymatic activity assay of the isolated strains resulted in a good correspondence between the tolerance to pollutants and the capability to produce ligninolytic enzymes indicating that this group of white-rot fungi is perspective for further investigation and eventual usage for mycoremediation of polycyclic aromatic hydrocarbons polluted substrates.

Tolerance of wood decay fungi of the genera Agrocybe, Armillaria, Auricularia, Daedalea, Pleurotus, Trametes to the presence of various amounts of creosote-treated wood (CTW) in the growth medium was compared. In the case of the most tolerant strain, Pleurotus ostreatus SMR 684, extracellular laccase and peroxidase specific activities were monitored during growth in the presence of CTW. Degradation of various creosote-constituting polycyclic aromatic hydrocarbons by this strain was evaluated by GC-MS and the ecotoxicity of treated and untreated CTW was compared by Microtox test.

The miniaturization and optimization of a white rot fungal bioremediation experiment is described in this paper. The optimized procedure allows determination of the degradation kinetics of anthracene. The miniaturized procedure requires only 2.5 ml of culture medium. The experiment is more precise, robust, and better controlled comparing it to classical tests in flasks. Using this technique, different parts, i.e., the culture medium, the fungi, and the cotton seal, can be analyzed. A simple sample preparation speeds up the analytical process. Experiments performed show degradation of anthracene up to approximately 60 % by Irpex lacteus and up to approximately 40 % by Pleurotus ostreatus in 25 days. Bioremediation of anthracene by the consortium of I. lacteus and P. ostreatus shows the biodegradation of anthracene up to approximately 56 % in 23 days. At the end of the experiment, the surface tension of culture medium decreased comparing it to the blank, indicating generation of surfactant compounds.

The lipophilicity of some cardiovascular drugs was determined by capillary electrophoresis (CE). Mexiletine, amlodipine and indapamide, the drugs considered, were in contact with liposomial vescicles for 2, 4 or 6 h. After the contact time the drugs, penetrated into liposomial vesicles, were determined by CE using phosphate buffer (pH 6.3 or 7.4) or borate buffer (pH 9). The lipophilicity of three drugs was determined considering the drug percentage penetrated into liposomial vesicles. The found lipohilicity order was amlodipine > mexiletine > indapamide.

The lipophilicity of pipemidic, nalidixic and oxolinic acids was determined by forming phospholipidic micelles directly in an electrophoretic capillary. Phosphatidylcholine derivatives, namely l -α-dilauroyl phosphatidylcholine (DLPC) or l -α-dimiristoyl phosphatidylcholine (DMPC), were added in the run buffer (50 mM phosphate buffer at pH 7.4). To obtain a mixed micelle, phospholipidic derivatives and sodium cholate were together added in the run buffer. Considering the increasing of migration time when phosphatidylcholine derivative is added in the run buffer, Ks can be determined and then quinolones lipophilicity.

Midodrine hydrochloride is a peripheral α1-adrenoreceptor agonist that induces venous and arterial vasoconstriction. Midodrine, after oral or intravenous administration, undergoes enzymatic hydrolysis and releases deglymidodrine, a pharmacologically active metabolite. Midodrine and deglymidodrine have a chiral carbon in the 2-position. To investigate the bioactivity of racemates and enantiomers of the drug and metabolite, three chromatographic chiral stationary phases, Chiralcel OD-H, Chiralcel OD-R, and α1-AGP, were evaluated for enantiomeric resolution. Good enantioseparation of midodrine racemate was obtained using the Chiralcel OD-H column. This stationary phase was then used to collect separately the midodrine enantiomers. By alkaline hydrolysis of rac-midodrine and each separated enantiomer, rac-deglymidodrine and its enantiomers were prepared. The control of the enantiomeric purity was carried out by α1-AGP stationary phase, while the hydrolysis of rac-midodrine and its enantiomers was controlled by capillary electrophoresis using trimethyl-β-cyclodextrin as chiral selector. The pharmacological activity of the two racemates and the two enantiomeric pairs was tested in vitro on a strip of rabbit descending thoracic aorta. The tests continued that the activity of the drug and metabolite is due only to the (−)-enantiomer because neither of the (+)-enantiomers is active. Chirality 16:356–362, 2004. ©2004 Wiley-Liss, Inc.

Mycoremediation is a form of bioremediation that uses fungal mycelia to return an environment contaminated by pollutants to a less contaminated state. One of the primary role of fungi in the ecosystem is decomposition which is performed by the mycelium. White-rot fungi secrete extracellular enzymes and acids that breakdown lignin and cellulose, the two main building blocks of plant fiber. The ligninolytic enzymes have low substrate specificity and that permits them the degradation of organic xenobiotic compounds with different origin, scarcely susceptible to bacterial attack. The key to mycoremediation is determining the right fungal species to target a specific pollutant. In IBAF laboratories a fungal germplasm bank is present (International Bank of Edible Saprophytic Mushrooms), containing about 530 samples of wood-degrading fungi, mainly Pleurotus. Fungi belonging to Pleurotus genus have been used for the treatment of polluted waste for many years. In particular, olive mill waste waters were used as growth medium for P. ostreatus, with the result of an abundant mycelium growth and the decrease of COD and phenols in the waste waters. P. ostreatus was able to grow in a mixture containing wood treated with creosote (CTW) and wheat straw, totally degrading phenols and reducing the 65-70% of polycyclic aromatic hydrocarbons and heterocyclic compounds. To clarify the degradation of polyciclic aromatic hydrocarbons (PAH), a study was performed in batch on fluoranthene, one of the principal PAH contained in creosote. The results pointed out that this compound was totally absorbed by the mycelium (15 days) and then degraded by 50% in 40 days. Also the antibiotic Oxytetracycline, that enters the environmental compartments as a consequence of animal waste disposal, disappeared in P. ostreatus culture medium as early as the third day of exposure onwards, with an almost complete removal after 14 days.

Degradation of 2-chlorophenol was studied using a laccase-based catalyst immobilized, for the first time, with a natural clinoptilolite as solid support. The optimal conditions for the enzyme immobilization were determined together with pH and temperature stability. The biocatalyst containing 1 U of laccase was able to remove 0.73 micromoles di 2-chlorophenol.

The organochlorine pesticide γ-hexachlorocyclohexane (γ-HCH, lindane) and its non-insecticidal isomers α-, β-, and δ- continue to pose serious environmental and health concerns, although their use has been restricted or completely banned for decades. The present study reports the first results on the ability of two Arthrobacter strains, not directly isolated from a HCH-polluted site, to grow in a mineral salt medium containing α-, β-, or γ-HCH (100 mgl(-1)) as sole source of carbon. Growth of cultures and HCHs degradation by Arthrobacter fluorescens and Arthrobacter giacomelloi were investigated after 1, 2, 3, 4, and 7 days of incubation by enumerating colony forming units and GC with ECD detection, respectively. Both bacteria are able to metabolize the HCHs: A. giacomelloi is the most effective one, as after 72 h of incubation it produces 88 % degradation of α-, 60 % of β-, and 56 % of γ-HCH. The formation of possible persistent compounds was studied by GC/MS and by HPLC analysis. Pentachlorocyclohexenes and tetrachlorocyclohexenes have been detected as metabolites, which are almost completely eliminated after 72 h of incubation, while no phenolic compounds were found.

A bioremediation system for creosote-treated wood is proposed, based on the detoxifying capability of Pleurotus ostreatus, a ligninolythic fungus. Non-sterilized chipped contaminated wood was mixed at various ratios with wheat straw on which Pleurotus mycelia was grown. At 1:2 initial ratio contaminated wood:wheat straw, chemical analyses demonstrated an almost complete degradation of creosote oil components after 44 days, also confirmed by a significant reduction of ecotoxicity. Lower ratios, i.e. higher amount of contaminated wood, lower system efficiency, although a better creosote degradation was obtained by a stepped up wood addition.

Humic acids are able to interact with a wide range of pollulants and can influence their solubility, transport and bioavailability. In order to study the interaction between polar aromatic hydrocarbons and these macromolecules an affinity capillary electrophoretic method, the Hummel-Dreyer in its modified version, has been used. Two acidic metabolites of Phenanthrene:1-hydroxy-2-naphthoic acid (1-HNA) and 3,4-dihydroxybenzoic acid (3,4-DBA) were studied. The analysis for the binding studies were carried out by injecting a solution of HA in 25 mM ammonium hydrogen carbonate buffer (pH 9) into an uncoated fused silica capillary, filled with buffer solutions of 1-HNA or 3,4-DBA in varying and increasing amounts. The results obtained indicate that both compounds bind to HA, as had been confirmed by dialysis experiments and literature data. Capillary Electrophoresis proved to be a useful technique for investigating the link between xenobiotics and environmental macromolecules.

Diltiazem (DTZ) is an optically active calcium channel blocker having a benzodiazepine structure. The drug used in therapy is (+)-cis-diltiazem with configuration (2S,3S). To describe the analytical profile of DTZ different stationary phases (RP-18, RP-8, monolithic support) were tested. The best separation of DTZ from A, B, E and F was obtained using as stationary phase a RP-8 or a monolithic RP-18. The characterization of impurities was carried out using two analytical systems, HPLC and HPLC/MS.

Pethidine, predominantly a u-receptor agonist, is a phenyl-piperidinic synthetic drug. It is used in the management of moderate to several pain. A possible hydrolytic degradation of an ester group can generate a very toxic compound, the N-methyl-4-1,2,3,6 tetrahydropyridine (MPTP) which contaminates the drug. Because of the toxicity of MPTP a suitable method for its determination must be selective and sensitive. Afterwards we propose simple methods to determine pethidine and MPTP by capillary electrophoresis (CE), MECK and RP-high performance liquid chromatography (HPLC) looking at the limit of detection obtained using these three techniques. CE was carried out using as running buffer ammonium acetate (pH 8.3). MECK was performed with a borate buffer (pH 8.3) containing sodium dodecylsulphate and trimethyl-beta-cyclodextrins. RP-HPLC was carried out on a RP18 stationary phase, using as mobile phase a mixture of phosphate buffer (ph7) containing acetonitrile and 1% of diethylamine. 2003 Elsevier Science B.V. All rights reserved.

Capillary electrophoresis (CE) and capillary electrochromatography (CEC) have been used to determine losartan and hydrochlorothiazide. The CE separation was carried out in an uncoated capillary filled with a 100 mM sodium borate pH 9 solution containing trimethyl-beta-cyclodextrin. CEC was performed using a capillary packed with a RP-18 stationary phase. The mobile phase was a mixture of 50 mM ammonium acetate pH 7, water and acetonitrile (1/1.5/7.5). By CE and CEC suitable methods to determine simultaneously losartan and hydrochlorothiazide in working standard mixture or pharmaceutical form were obtained. The proposed methods are very simple and both gave accurate and precise results.

The quality control of drugs is generally made by HPLC. This control could be made also by capillary electrochromatography (CEC). In this paper we report the analysis by CEC of ibuprofen, a well-known anti-inflammatory non steroidic drug, and some of its impurities. The analyses were performed in a 100-microm inner diameter (I.D.) fused silica capillary, packed with RP-18 stationary phase. The mobile phase was a mixture of 100 mM formic acid solution (pH 2.5), water and acetonitrile (ACN). The ACN percentage in the mobile phase and the applied voltage were carefully studied to well resolve the drug from each impurity. The results, obtained determining ibuprofen and related compounds by CEC, showed the selectivity and efficiency of the method.

Fenticonazole is a chiral antifungal agent, used in therapy as the racemic mixture. The investigation on the chirality of fenticonazole is reported in this study. rac-Fenticonazole was resolved by HPLC and by capillary electrophoresis (CE). The chiral stationary phase (CSP), used in HPLC, was Daicel OD-H, a commercial phase, which allowed the separate collection of the two enantiomers. The chiral selectors used for CE were some cyclodextrin derivatives. The analysis time required from CE was about the half the HPLC enantioseparation time. The biological activity of the rac-mixture and each individual enantiomer was tested against Cryptococcus neoformans and two Aspergillus nidulans strains. The minimum inhibitory concentration (MIC) evaluation showed that the eutomer was the enantiomer chromatographically more retained and had a longer migration time in the electrophoretic enantioseparation. The CD spectrum of the eutomer showed a positive Cotton effect. © 2002 Wiley-Liss, Inc.

Fenticonazole, a topical antifungal agent containing a stereogenic centre, is used in therapy as a racemic mixture. Five related compounds can be found as impurities in the drug. We propose a HPLC method using as stationary phase a RP-8 column eluted with different gradients of acetonitrile/phosphate buffer (pH 6) for simultaneous determination of the drug and these impurities. We also studied a high performance capillary electrophoresis (HPCE) method for quality control of fenticonazole. The separation of fenticonazole from all its impurities by HPCE was obtained in a relative short capillary (40 cm, effective length 34 cm, 50 μm ID) with a running buffer of 30 mM phosphate (pH 3) containing 8 mM trimethyl-β-cyclodextrin. Under these experimental conditions very good separation of fenticonazole from each individual impurity is obtained in less than 20 minutes. The choice of cyclodextrin added to the running buffer was dictated by the chiral nature of fenticonazole; trimethyl-β-cyclodextrin is mainly used as chiral selector. The optimised HPLC and HPCE methods are compared.

Silybine (SBN), isosilybine (ISBN), silycristine (SCN), silydianine (SDN), and taxifoline (TXF) are the main active flavanoids, generally found in the dried fruits of silybum marianum. The concentrations of these compounds, excepted TXF, are all together usually expressed as silymarine content. In this paper the determination of the silymarine titre was made by high performance liquid chromatography (HPLC), and high performance capillary electrophoresis (HPCE). Two reversed stationary phases, RP-18 and RP-8, were observed comparing the resolutions of all considered flavanoids with each stationary phases. The HPCE was carried out considering the possible improvement in the resolution of SBN, CN, SDN and TXF using, 8-cyclodextrines or organic modifier. The qualitative and quantitative data obtained by HPLC and HPCE were compared.