Ultrasound-assisted extraction of isoflavones from soy beverages blended with fruit juices

A new method for the fast determination of isoflavones from soy beverages blended with fruit juices without the need of freeze-drying the sample was developed. During the method development, several parameters were studied: solvent (methanol and ethanol), sample:solvent ratio (5:1 to 0.2:1), temperature (10-60 °C) and extraction time (5-30 min). The most important parameter for the extraction of isoflavones from soy drinks was the sample:solvent ratio. The optimized method consists of extracting the sample with ethanol with a sample:solvent ratio of 0.2:1 on an ultrasound bath at 45 °C during 20 min. Also, samples were freeze-dried, extracted using conventional method and compared with the optimized method and no significant difference was observed on total and individual isoflavone concentration. The most representative samples from the Spanish market, with a wide variation of isoflavone concentration were analyzed using the optimized method. Differences between manufacturers reached an almost 10 times fold variation. Overall isoflavone concentration ranged from 6.7 to 58.2 mg L⁻¹.     

Chromatographic determination of the mycotoxin patulin in fruit and fruit juices

Patulin is a mycotoxin produced by several fungal species of the genera Penicillium and Aspergillus, but principally by Penicillium expansum on fruit such as apples. The occurrence of patulin as a natural contaminant of apple juice is a worldwide problem and international recommendations and regulations have been made for maximum levels permitted in consumer products. This paper reviews currently available analytical methods for its determination in fruit and fruit juices. Of these, HPLC with ultraviolet or, preferably, photodiode array detection is most widely used, although GC and TLC methods have also been described.     

Determination of pesticides in fruit and fruit juices by chromatographic methods. An overview

In order to combat a variety of pests, pesticides are widely used in fruits. Several extraction procedures (liquid extraction, single drop microextraction, microwave-assisted extraction, pressurized liquid extraction, supercritical fluid extraction, solid-phase extraction, solid-phase microextraction, matrix solid-phase dispersion, and stir bar sorptive extraction) have been reported to determine pesticide residues in fruits and fruit juices. The significant change in recent years is the introduction of the Quick, Easy, Cheap, Effective, Rugged, and Safe (QuEChERS) methods in these matrices analysis. A combination of techniques reported the use of new extraction methods and chromatography to provide better quantitative recoveries at low levels. The use of mass spectrometric detectors in combination with liquid and gas chromatography has played a vital role to solve many problems related to food safety. The main attention in this review is on the achievements that have been possible because of the progress in extraction methods and the latest advances and novelties in mass spectrometry, and how these progresses have influenced the best control of food, allowing for an increase in the food safety and quality standards.     

The use of stable isotopes ratios for authentication of fruit juices

The determination of the content of stable isotopes, ¹⁸O and ²H, respectively, in juice water facilitates the distinction between authentic juices and juices made from concentrates by redilution with tap water. At the same time, the detection of C₄ cane or corn-derived sugar syrups in fruit juices which are produced from C₃ fruit types is thus facilitated by the characteristic differences in ¹³C/¹²C, expressed as δ ¹³C (‰) values due to photosynthetic CO₂ assimilation via the C₃₋, C₄₋, and crassulacean acid metabolism pathways. In this study, the quantitative determination of water added to an authentic juice, on the basis of δ ¹⁸O, and δ ²H values, respectively, was successfully performed. Also, the δ ¹⁸O, and δ ²H of juice water and δ ¹³C of the whole juice in 18 samples were also determined. The results obtained provided us with the possibility of distinguishing between authentic fruit juices and those obtained by redilution of concentrated fruit juices and the detection of C⁴ type added sugar.     

Spectrophotometric determination of ascorbic acid in pharmaceutical preparations and fruit juices

Conditions were established for the determination of ascorbic acid using phsophovanadotungstic acid as reagent. The method was applied to the determination of ascorbic acid in pure form, pharmaceutical preparations and fruit juices. The method is sensitive (2-24 micrograms ml-1 of ascorbic acid) and rapid and tolerates the presence of common ingredients usually found in fruit juices. The results obtained with the proposed method showed good agreement with those given by the standard method.     

Polarographic determination of sorbic acid in fruit juices and soft drinks

A simple differential-pulse polarographic method using a laboratory-built hanging mercury drop electrode as the working electrode was developed for the determination of sorbic acid in fruit juices and soft drinks. Sorbic acid was extracted from the samples with diethyl ether. After reduction of the ethereal solution to a small volume by direct evaporation, the residual ether was dissolved in the supporting electrolyte (25 ml of acetonitrile + 1 ml of 0.06 M acetic acid + 0.8 g of tetraethylammonium bromide). Peak current was measured at -1.7 V. The working range of the method, without dilution or pre-concentration of the samples, was from 4 to 229 p.p.m. for the original juice and drink samples. The validity of the method was confirmed by parallel determinations using the method of the Association of Official Analytical Chemists and by recovery tests on a large variety of juice samples. Satisfactory recoveries and agreement in results from the two methods were obtained. The recovery and precision (relative standard deviation) of the method were 97 +/- 4 and 100 +/- 3%, respectively, for blackcurrant juice for five determinations.     

Determination of phenolic acids in fruit juices by isocratic column liquid chromatography

A simple and rapid analytical method of five phenolic acids, gallic, chlorogenic, caffeic, ellagic and ferulic acid, which are naturally occurring bioactives, were determined in fruit juices by isocratic LC using photodiode array UV detection. The sample was pre-treated by solid-phase extraction (a combination of Sep-Pak Plus tC18 and Bond Elut PSA).     

Direct surface plasmon resonance immunosensing of pyraclostrobin residues in untreated fruit juices

A surface plasmon resonance (SPR) immunoassay for on-line detection of the strobilurin fungicide pyraclostrobin in untreated fruit juices is presented. The analysis of pyraclostrobin residues is accomplished in apple, grape, and cranberry samples by monitoring the recognition events occurring separately in a two-channel home-made SPR biosensor. Covalent coupling of the analyte derivative results in a reversible method, enabling more than 80 measurements on the same sensor surface. Optimization of the immunoassay conditions provides limits of detection as low as 0.16?μg?L^?1. The selectivity and reproducibility of the analysis is ensured by studying both non-specific interactions with unrelated compounds and inter-assay coefficients of variation. Excellent recovery ranging from 98 to 103?% was achieved by a simple 1:5 dilution of fruit juice with assay buffer before the analysis. The lack of previous cleaning and homogenization procedures reduces the analysis time of a single food sample to only 25?min, including the regeneration cycle.

Determination of thiabendazole in fruit juices by a new monoclonal enzyme immunoassay

A competitive, indirect enzyme-linked immunosorbent assay (ELISA) for thiabendazole has been developed and applied to the analysis of fruit juices spiked with this fungicide. The immunoassay is based on a new monoclonal antibody derived from a hapten functionalized at the nitrogen atom in the 1-position of the thiabendazole structure. To our knowledge, such a structure has not been previously used to obtain antibodies to thiabendazole. The I50 value and the detection limit of the ELISA for standards were 0.2 and 0.05 ng/mL, respectively. Fruit juices were analyzed by diluting samples in assay buffer, without extraction or cleanup. Samples were not even centrifuged or filtered to remove fruit pulp. Under these conditions, the immunoassay was able to accurately determine thiabendazole down to 1 ng/mL in orange and grapefruit juices, down to 5 ng/mL in banana juice, and down to 20 ng/mL in apple and pear juices. Sensitivity differences of the ELISA were caused by the minimum dilution required by each juice to minimize matrix effects: 1/10 for orange and grapefruit juices, 1/50 for banana juice, and 1/100 for apple and pear juices. In an attempt to further increase the sensitivity of the immunoassay for matrixes showing the strongest interferences, apple and pear juices spiked with thiabendazole at low levels (1-20 ng/mL) were extracted with ethyl acetate before analysis. This simple procedure entailed a significant reduction of matrix effects, which in fact allowed us to determine accurately as low as 5 ng/mL thiabendazole in apple and pear juices. Irrespective of whether samples were analyzed by the direct dilution method or after extraction, the simplicity, sensitivity, and sample throughput of this monoclonal immunoassay makes it a very convenient method for the routine monitoring of thiabendazole residues in fruit juices.     

Development of immunoaffinity columns for pyraclostrobin extraction from fruit juices and analysis by liquid chromatography with UV detection

Pyraclostrobin belongs to a new generation of fungicides widely used to preserve high valuable crops. In the present study, three monoclonal antibodies with different affinities to this modern strobilurin have been evaluated for their usefulness in the production of immunoaffinity columns suitable for the solid-phase extraction, concentration, and clean-up of residues from food commodities. Different immunosorbents were produced and characterized in terms of antibody immobilization efficiency, immunosorbent binding capacity, optimum elution conditions, and reusability. Covalent coupling of the antibodies to Sepharose-CNBr gel took place with high yield (over 90%), whereas the immunosorbent efficacy to retain the analyte (from 28 to 68%) was shown to depend on the amount and type of antibody immobilized on the support. As a matter of fact, columns prepared with the monoclonal antibody PYs5#14 were able to selectively bound up to 53 μg of pyraclostrobin per gram of beads. Acetonitrile solutions were preferred over methanolic ones for analyte elution, and some immunosorbents could be reused at least 4-6 times provided that the amount of pyraclostrobin and the volume of sample did not overload the column. Effectiveness of the selected immunoaffinity column was evidenced by the development of an extraction procedure for pyraclostrobin residues from fruit juices and further determination by high-performance liquid chromatography with UV detection. A concentration factor of 50 times was achieved with the developed immunoaffinity column, which eventually resulted in a limit of quantification of 0.01 mg L(-1). Finally, quantitative recoveries were obtained on apple juice and red grape must samples spiked with pyraclostrobin from 0.01 to 1 mg L(-1).     

Contactless conductivity detection of sodium monofluoroacetate in fruit juices on a CE microchip

Rapid and quantitative determination of sodium monofluoroacetate in diluted fruit juices (dilution 1:9 v/v in deionized water) and tap water was performed by microchip CE, using contactless conductivity detection. A separation buffer consisting of 20 mM citric acid and histidine at pH 3.5 enabled the detection of the monofluoroacetate (MFA) anion in diluted apple juice, cranberry juice, and orange juice without lengthy sample pretreatments. The analyte was very well separated from interfering anionic species present in juices and tap water. LODs in diluted juices and tap water were determined to be 125, 167, 138, and 173 microg/L for tap water, apple juice, cranberry juice, and orange juice, respectively, based upon an S/N of 3:1. Taking into account the dilution factor, the LODs for juice samples range from 1 to 2 mg/L, which is adequate for monitoring the toxicity of MFA in these juice beverages and tap water. The calibration curves for MFA in diluted fruit juices were linear over the range of 500 microg/L to 80 mg/L. The total analysis time for detecting the MFA anion in fruit juices was less than 5 min, which represents a considerable reduction in analysis time compared to other analytical methods currently used in food analysis.     

Gas-liquid chromatographic determination of ethanol in “Alcohol-Free” beverages and fruit juices

Summary A rapid, sensitive and direct method is described for the detemination of ethanol in Alcohol-Free beverages and fruit juices. A known amount of internal standard is added to the sample and a 0.1 mm³ aliquot is injected directly into a gas chromatograph. Ethanol concentrations as low as 0.005% v/v can be detected and quantitatively determined. Five brands of beer, seven brands of grape juice and four brands of apple juice; all labelled Alcohol-Free were analyzed. Ethanol in concentrations ranging from 0.009% v/v to 0.385% v/v was found. These findings indicate that these products are not actually Alcohol-Free but alcohol-low or alcohol-poor.     

The determination of organotin compounds in fruit juices using gas chromatography-atomic absorption spectrometry

A method for extracting butyl-, cyclohexyl-, octyland phenyl-tin compounds in fruit juices was developed using 0.05% tropolone in 25% pentane/diethyl ether. Methyl derivatives formed by Grignard reaction were quantified by gas chromatography-atomic absorption spectrometry. Several fruit juices contained low ng cm^?3 levels of butyl- and octyl-tins. Gas chromatography-mass spectrometry, used for the confirmation of the butyl- and octyl-tins, also detected phenyl- and cyclohexyl-tin compounds at levels below the GC AA detection limits (0.03–0.05 ng Sn cm^?3).     

Determination of Gallic acid by differential pulse polarography: Application to fruit juices

Phenolic compounds possess antioxidant, antitumor, antimutagenic, antibacterial and anticarcinogenic properties. Gallic acid (2,3,4-trihydroxybenzoic acid) is a natural phenolic compound; therefore, determination of trace gallic acid is very important. In this work, a novel, sensitive and reliable method was developed using differential pulse polarography. The most suitable buffer system was found to be Britton-Robinson (B-R) buffer, pH 10.0. The gallic acid peak in this medium appeared at about ?160 mV, it responded well to standard additions, and high reproducibility was obtained. The calibration graph was linear in the concentration range of gallic acid from 1.0–50.0 μM with a correlation coefficient of 0.999. The limit of detection (LOD) and limit of quantification (LOQ) were obtained as 0.3 and 1.0 μM, respectively. The proposed method was successfully applied to the determination of gallic acid in fruit juices. The influences of some other commonly found inorganic and organic salts on the determination were also examined. Some interferiences were eliminated by using complexing agents, e.g. EDTA.     

Determination of titratable acidity and ascorbic acid in fruit juices in continuous-flow systems

Summary Two continuous-flow systems for the determination of titratable acidity and ascrobic acid in fruit juice samples are described. The assemblies permit on-line dialysis of analytes prior to the reaction step, thus improving selectivity and performing sample dilution. Flow systems are built with a channel carrying the donor phase (sample in both determinations) and another channel carrying an acceptor phase, both of them entering the dialyser. The outcoming stream transporting the dialysed sample fills the valve loop, permitting its injection into a carrier stream which continuously passes through the spectrophotometric detector. For the titratable acidity, acceptor phase and carrier are distilled water, the reagent merged with the carrier channel being a buffered solution of bromothymol blue (pH 7). The analytical signal obtained is then monitored at 616 nm. For ascorbic acid, the acceptor phase was a Fe(III) solution, which reacts with the dialysed analyte to form Fe(II). A buffered solution of o-phenanthroline (pH 4.5) is used as carrier, reacting with Fe(II) to give the analytical signal, which is monitored at 510 nm. Chemical and physical parameters are optimized for both systems. The analytical features of the determination are established. Finally, the proposed procedures are compared with the official volumetric AOAC methods for both parameters. The FIA methods turn out to be suitable for a rapid and accurate control of fruit juice samples, compared with the reference methods; additionally they compete advantageously with the volumetric methods in the case of turbid and highly coloured samples.