Novel determination of polychlorinated naphthalenes in water by liquid chromatography-mass spectrometry with atmospheric pressure photoionization.

This study presents the development, optimization, and validation of a novel method for the determination of polychlorinated naphthalenes (PCNs) by liquid chromatography-atmospheric pressure photoionization (APPI), using toluene as dopant. The mass spectra of PCN 52, 54, 66, 67, 73, and 75 were recorded in negative ionization. The base ions corresponded to [M-Cl+O](-), where M is the analyte molecule. A strategy, which includes designs of experiments, for the development, the evaluation, and the optimization of the LC-APPI-MS/MS methods is also described. Finally, a highly sensitive method with low instrumental limits of detection (LoDs), ranging from 0.8 pg for PCN 75 to 16 pg for PCN 54 on column, was validated. A Thermo Hypersil Green PAH (100 mm × 2.1 mm, 3 µm) column was used with acetonitrile/water/methanol as mobile phase. The method was applied for the determination of the selected PCNs in surface and tap water samples. A simple liquid-liquid extraction method for the extraction of PCNs from water samples was used. Method LoQs ranged from 29 ng L(-1), for PCN 73, to 63 ng L(-1), for PCN 54, and the recoveries ranged from 97 to 99%, for all congeners. This is the first LC-APPI-MS/MS method for the determination of PCNs in water samples.

Quantification of Hydrogen Peroxide in Cretan Honey and Correlation with Physicochemical Parameters.

The aim of the present study is to quantify hydrogen peroxide, generated from various types of honey produced in Crete, as a potent antimicrobial agent, and establish any correlation with their physicochemical parameters. The basic physicochemical parameters (diastase activity, HMF content, moisture, electrical conductivity, color, and sugars) of 30 authentic honey samples were determined. The concentration of hydrogen peroxide in all samples was found to be within the range 0.010-0.092 mM. The known correlation between the electrical conductivity and the color of honey was confirmed in this study. Univariate and multivariate statistics applied to the results indicate that the results can be used to discriminate honey sample groups of different botanical origins.

Validated method for the simultaneous determination of methadone and its main metabolites (EDDP and EMDP) in plasma of umbilical cord blood by gas chromatography-mass spectrometry.

A sensitive and specific GC/MS method for the determination of methadone (MDN) and its two main metabolites, 2-ethylidene-1,5-dimethyl-3,3-diphenylpyrrolidine (EDDP) and 2-ethyl-5-methyl-3,3-diphenylpyrroline (EMDP), in plasma samples obtained from venous and arterial umbilical cord blood and maternal blood has been developed, optimized and validated. Specimen preparation includes protein precipitation with acetonitrile and simultaneous solid-phase extraction of the three analytes. Methadone-d9 was used as internal standard for the determination of MDN and EMDP, while EDDP-d3 for EDDP. Limits of detection were 0.6 microg/L for MDN and 0.3 microg/L for EDDP and EMDP, while limits of quantification were 2.0 microg/L for MDN and 1.0 microg/L for EDDP and EMDP. The calibration curves were linear up to 2000 microg/L for MDN and up to 1000 microg/L for EDDP and EMDP. Absolute recovery ranged from 94.8 to 99.7% for all three analytes. Intra- and interday accuracy was less than 5.3 and 5.5%, respectively, while intra- and interday precision was less than 3.5 and 5.0%, correspondingly, for all analytes. The method proved suitable for the determination of MDN and its two main metabolites in plasma samples obtained from umbilical cord and maternal blood of a woman participating in a MDN maintenance program, during the prenatal and postpartum period.

Development and validation of an EI-GC-MS method for the determination of methadone and its major metabolites (EDDP and EMDP) in human breast milk.

Methadone is used extensively for the maintenance of opioid-addicted pregnant women. Because methadone and the two major metabolites, 2-ethylidene-1,5-dimethyl-3,3-diphenylpyrrolidine (EDDP) and 2-ethyl-5-methyl-3,3-diphenylpyrroline (EMDP), are excreted into breast milk, a sensitive and specific gas chromatographic-mass spectrometric method has been developed, optimized, and validated for their quantitative determination in human breast milk. The procedure combined protein precipitation with acetonitrile and solid-phase extraction, using Isolute Confirm HCX mixed-mode SPE columns, with minimal matrix effect. The optimum extraction conditions for all three analytes were evaluated using spiked human breast milk, and the recovery exceeded 93.0%. This assay uses methadone-d(9) as internal standard for the determination of methadone and EMDP, and EDDP-d(3) for the determination of EDDP. Calibration curves were linear within the range of 2.00-1000 microg/L for methadone (R(2) > 0.995) and 1.00-500 microg/L for EDDP (R(2) >0.997) and EMDP (R(2) > 0.991). Intra- and interday accuracy and precision were within the range of 0.8-5.7% and 1.3-5.2%, respectively, for all analytes. The stability study was assessed by fortifying human breast milk with methadone and its metabolites at two different concentrations and keeping the samples at different temperature conditions. The analytes were found to be stable in breast milk at room temperature for at least 4 h and at -20 degrees C for at least one month. The method was used for the determination of methadone and its major metabolites in human breast milk samples obtained from women in the postpartum period participating in a methadone maintenance program.

An evaluation study of different methods for the production of ß-D-glucan from yeast biomass.

ß-Glucan is a proven beneficial and valuable molecule for human and animal health systems. It can be incorporated as an ingredient in various functional foods and beverages. ß-Glucan has been isolated from various biological sources, fungi, mushrooms, algae, plants, and bacteria. The yeast cell wall comprises a suitable target for the extraction and purification of ß-glucan. Although there are various extraction techniques, significant differences are observed as the technique used affects the final yield and purity, molecular weight, biological activity, solubility, quality, and other biological and functional properties of the extracted ß-glucan. The aim of this review is the evaluation of different extraction methods for the production of ß-glucan from yeast biomass. Furthermore, the use of industrial spent yeast waste from breweries and the wine industry for biotechnological ß-glucan production and the concept of green wineries and breweries are discussed.

A Squaraine Derivative for Cost-Effective, Quick, and Highly Sensitive Determination of Mercury and Thiols and pH Sensing.

The introduction of innovative sensing approaches is of increasing interest in the development of analytical platforms and methodologies for the colorimetric, fluorimetric, and/or optical detection of important analytes. Herein, the synthesis of a novel squaraine derivative is reported, as well as its successful utilization in the colorimetric and fluorimetric determination of thiols. The reported squaraine was also evaluated as a pH sensor. In addition, a promising paper-based colorimetric method for mercury detection was developed and evaluated.

Response surface methodology toward the optimization of high-energy carotenoid extraction from Aristeus antennatus shrimp.

High-energy assisted extraction techniques, like ultrasound assisted extraction (UAE) and microwave assisted extraction (MAE), are widely applied over the last years for the recovery of bioactive compounds such as carotenoids, antioxidants and phenols from foods, animals and herbal natural sources. Especially for the case of xanthophylls, the main carotenoid group of crustaceans, they can be extracted in a rapid and quantitative way with the use of UAE and MAE. Response surface methodology (RSM) is used for the optimization of extraction methodologies, also being applied to optimize high energy techniques. Three independent variables, namely extraction time, ultrasound or microwave power and solvent/material ratio, were investigated for both methods by employing a 16-run three-level Box-Behnken design (BBD). Considering the extraction efficiency for carotenoids from Aristeus antennatus shrimp, the selected conditions for UAE were 5 min, 600 W and 10:1 mL g(-1). Acetone was the solvent of choice for the extraction procedure. For MAE, the best experimental values were 7 min, 30 W and 20:1 mL g(-1) using n-hexane:acetone:ethanol 2:1:1 (v/v/v) as extraction solvent. The determination of total carotenoid yield was carried out using the spectophotometric calibration curve (A=0.1646(±0.0061)C-0.005(±0.022), R(2)=0.996, n=3) of a standard mix solution of canthaxanthin, zeaxanthin and lutein at 452.1 nm. Under the selected conditions, the yield of total carotenoids for UAE was 23.4(±2.3) and 6.73(±0.56) mg of carotenoids per 100 g dry sample for the head and the body of shrimp, while for MAE was 23.92(±0.63) and 13.3(±1.1) mg of carotenoids per 100g dry sample, respectively. The recovery of both methods was calculated between 60 and 105%. The results indicate that high-energy extraction techniques are faster, less laborious, more repeatable and reproducible methods than the conventional approaches for the quantitative recovery of sensitive bioactive compounds. Moreover, the recovery of a high-added value group of bioactive molecules from natural sources, such as carotenoids, can constitute a profitable and valuable commercial alternative, as these compounds can be used as dietary supplements, food color enhancers and additives in animal feeds, functional foods, preservatives, pharmaceuticals and cosmetics.

Evaluation of total reducing power of edible oils.

The lipophilicity of untreated edible oils narrows the application of most published methods for the determination of antioxidant activity to hydrophilic extracts of oils. This research addresses the issue of the estimation of the total antioxidant properties of untreated edible oils by modifying two widely applied analytical methods, the Fe-Phenanthroline and the CUPRAC assays, to be used in untreated oils. The modifications pertain to the selection of mixture of solvents (ethanol-butanol in 3:1 v/v ratio), and the optimization of the reaction conditions (reagents concentration and reaction time). The developed methods were applied to a number of hydrophilic and lipophilic standard compounds and different types of commercial edible oils, as well as their corresponding aqueous or organic extracts. This implementation elucidated the differences in the antioxidant content of edible oils. All the results were compared to those of the DPPH and Folin-Ciocalteu methods and the analytical figures of merit for the methods have been estimated. Lastly, it was concluded that the modified CUPRAC assay has higher sensitivity compared to the Fe-Phenanthroline assay.

Development of a generic assay for the determination of total trihydroxybenzoate derivatives based on gold-luminol chemiluminescence.

A selective assay for the determination of one of the most important class of phenolic compounds, namely trihydroxybenzoates (monomeric and polymeric compounds having at least one gallate moiety) based on their enhancing effect on the chemiluminogenic reaction between gold ions and luminol is described for the first time. In the presence of trihydroxybenzoate derivatives, the light emission generated when alkaline luminol is oxidized by gold ions is amplified several orders of magnitude compared to other common phenolic compounds which exhibit minor reactivity or no reactivity at all (e.g. hydroxycinnamates, flavonols, benzenediols). Based on this property, the experimental conditions were optimized in order to enable the determination of total trihydroxybenzoates in complex mixtures without resorting to separation techniques. The method was applied to samples of different composition (teas, herbal infusions and wines) with satisfactory analytical features yielding detection limits at the 10(-7) mol L(-1) level, intra-day precision of 3.1%, inter-day precision less than 10% and recoveries between 88.7 and 97.6%. The strengths and weaknesses of the method were identified and discussed in relation to its application in real samples.

Chemiluminometric determination of vanillin in commercial vanillin products.

Vanillin, ethylvanillin and 4-hydroxy-3-methoxy-benzylalcohol have been found to chemiluminesce by the action of potassium permanganate in sulphuric or polyphosphoric acid media. Both acid media have been compared and sulphuric acid allows the sensitive determination of 0.15-10.0, 0.010-1.0 and 0.0030-0.30microg mL(-1) of vanillin, ethylvanillin and 4-hydroxy-3-methoxy-benzylalcohol with limits of detection equal to 0.045, 0.0030 and 0.00090microg mL(-1), respectively. Recoveries of vanillin from commercial vanillin products are within the range of 95-109%. Comparison with results from the official method shows differences within the range of 0.5-3.0%. The chemiluminogenic reaction mechanism is also discussed.