Rotenone and rotenoids in cubè resins, formulations, and residues on olives

Rotenone and rotenoids (deguelin, beta-rotenolone (12a beta-hydroxyrotenone), tephrosin (12a beta-hydroxydeguelin), 12a alpha-hydroxyrotenone, and dehydrorotenone) were determined in cubè resins and formulations. Cubè resins from Lonchocarpus contain large quantities of deguelin (ca. 21.2%) and smaller quantities of tephrosin (ca. 3.5%) and beta-rotenolone (ca. 3.0%). The composition of commercial formulations may present very different rotenoid contents depending on the extracts used to prepare them. Because these rotenoids also present insecticide activity, the efficacy of these formulations may be very different. The storage stability and photodegradation of some rotenone formulations were studied. Rotenone and rotenoids are very sensitive to solar radiation, which degrades them rapidly, with half-lives in the order of a few tens of minutes. Some formulations show greater disappearance rates than that of cubè resin, indicating that not much attention has been paid to protecting the active ingredients from photodegradation in the formulation. A study on the residues on olives was also carried out to assess not only the rotenone content, but also that of the main rotenoids. At harvest, the residues of deguelin, tephrosin, and beta-rotenolone were 0.10, 0.06, and 0.10 mg/kg, respectively, very similar to rotenone (0.08 mg/kg), and though a few data indicate similar acute toxicity values for deguelin, only rotenone is taken into consideration in the legal determination of the residue.     

Influence of postharvest hot water treatment on nutritional and functional properties of kumquat (Fortunella japonica Lour. Swingle Cv. Ovale) fruit

The present study investigated the influence of a hot water dip (HWD) for 2 min at 50 degrees C, a standard and effective treatment for postharvest decay control of citrus fruit, on the nutritional and health-related properties of kumquats. The results show that most of the parameters examined, including titratable acidity, soluble solids content, maturity index, glucose, fructose, sucrose, ascorbic acid, dehydroascorbic acid, alpha- and gamma-tocopherols, beta-carotene, zeaxantin, rhoifolin, and antioxidant activity, were not significantly affected by treatment. The levels of beta-cryptoxanthin, narirutin, and total flavonoids increased after HWD, whereas lutein and total phenols decreased. The concentration of the essential oil and the relative percentage of the individual components of the essential oil were not affected by HWD except for the minor compound p-menta-1,5-dien-1-ol, which increased after HWD. After storage, lower levels of glucose, total sugars, beta-carotene, beta-cryptoxanthin and lutein were recorded in HWD fruit. A decrease in antioxidant activity and increases in alpha-tocopherol and total vitamin E were found both in control and HWD fruit. The influence of HWD at 50 degrees C for 2 min on individual nutraceuticals and health-related properties was thus generally low and may depend on storage conditions.     

Enrichment of higher molecular weight fractions in inulin

Inulin (general formulas GFn and Fm, with G = anhydroglucose and F = anhydrofructose) naturally occurs as a homologous series of oligo- and polysaccharides with different chain lengths. For reasons of growing interest in the food and pet food industries, the short chain inulins have to be separated from their long chain analogues because their properties (digestibility, prebiotic activity and health promoting potential, caloric value, sweetening power, water binding capacity, etc.) differ substantially. To study these properties in relation to the number average degree of polymerization (DPn), ultrafiltration, specific crystallization from aqueous solution, and precipitation from solvent/water mixtures were used to enrich native chicory and dahlia inulin in the higher molecular weight fractions. Depending on the membrane module used, the DPn of chicory inulin (DPn = 8.1) and dahlia inulin (DPn = 29) could be increased by ultrafiltration to a maximum value of, respectively, 22 and 43. With crystallization from aqueous solutions (25 degrees C), similar results were obtained but at a much higher yield. Finally, long chain inulin could be precipitated from aqueous solutions in the presence of high concentrations of methanol, ethanol, and acetone. Acetone demonstrated to be the best solvent system to increase the DPn, followed by ethanol and methanol. However, for safety reasons and food purposes, ethanol was evaluated to be the best choice. With ethanol, the DPn could be raised to 25 for chicory inulin and up to 40 for dahlia inulin.     

Residue study of ivermectin in plasma,milk, and mozzarella cheese following subcutaneous administration to buffalo (Bubalus bubalis)

The distribution of ivermectin in buffalo plasma and milk after administration of a single subcutaneous dose (0.2 mg kg(-)(1) b.w.) was studied. Ivermectin reached the maximal concentration in plasma (28.5 +/- 1.7 ng mL(-)(1)) and milk (23.6 +/- 2.6 ng mL(-)(1)) after 2.4 +/- 0.32 and 2.8 +/- 0.44 days, respectively. The drug showed a parallel disposition in milk and plasma, with a ratio of 1.12 +/- 0.16. Ivermectin concentrations were detected in mozzarella cheese obtained from milk collected on days 1, 3, 4, and 20 following administration. The highest values (81.4 +/- 3.26 ng g(-)(1)) were found in the cheese produced on day 3 and were 4-fold higher than those present in the milk.     

Determination of acequinocyl and hydroxyacequinocyl on fruits and vegetables by HPLC-DAD

A method for determining residues of the new reduced-risk pesticide acequinocyl and its deacetylated derivative hydroxyacequinocyl on fruits and vegetables (grapes, lemons, pears, and tomatoes) by HPLC is described. The pesticides were extracted from the fruits and vegetables with hexane and ethyl acetate solution (1:1, v/v), determined by HPLC-DAD at 250 nm and confirmed by LC/MS. No cleanup was necessary. This method is characterized by recoveries (0.01-4 mg/kg) > 77%, while the coefficient of variation was determined to be less than 11%. The limit of quantitation for both acequinocyl and hydroxyacequinocyl was 0.01 mg/kg for all matrixes.     

Liquid chromatography-electrospray ionization-tandem mass spectrometry method for the determination of epoxidized soybean oil in food products

Epoxidized soybean oil (ESBO) is widely used as a plasticizer and stabilizer in such polymers [poly(vinyl chloride) in particular] commonly adopted for manufacturing of gaskets of the lids for glass jars and plastic films for food packaging. Human exposure to ESBO and its derivatives is likely to occur over a lifetime with a significant variation according to life stage. A reversed phase liquid chromatography interfaced with electrospray ion trap tandem mass spectrometry method for the determination of ESBO in foods was developed. A simple sample treatment procedure entailing the use of an extraction step with dichloromethane without any further cleanup was proved. Chromatographic separation was performed using two C18 columns with an aqueous acetic acid-acetone-acetonitrile mixture as the mobile phase under gradient conditions. The method was validated in terms of detection limits (4 mg kg(-1)), quantitation limits, linearity (established over 2 orders of magnitude), recovery (good mean recoveries, higher than 90% for all of the signals detected), precision (RSD% < 8), and trueness. The applicability of the method to the determination of ESBO in different food matrices (in particular those rich in edible oil) was demonstrated, and the performances were compared to those reachable by the commonly well-known gas chromatography-mass spectrometry procedure.     

Synergetic effect of organic solvents and paraoxon on the immobilized acetylcholinesterase

The toxicity of organophosphorus pesticides is attributed to their ability to inhibit acetylcholinesterase (AChE), which catalyses the hydrolysis of the neurotransmitting agent acetylcholine (ACh). A simple, reproducible and stable AChE-based amperometric bioelectrode was used, for measuring the enzyme activity before and after the incubation with paraoxon dissolved in organic solvents.The inhibition percentage induced by a paraoxon in organic solvent solutions increases in the following sequence: acetonitrile < water < hexane, suggesting that the paraoxon repartition between the organic solvent and the essential water for enzyme activity plays an important role in establishing the analytical and kinetic parameters of the bioelectrode. Considering the AChE denaturation, induced only by the organic solvent, as a pseudo-inhibition process, the kinetic treatment of the bioelectrode response revealed that it follows a mixed competitive/non-competitive mechanism, while the inhibition due to a non-aqueous solution of paraoxon corresponds to a non-competitive/uncompetitive mechanism. In the last case, the synergetic effect of denaturation and inhibition of enzyme was dominated by the inhibitor presence.     

Phenolics of Arbutus unedo L. (Ericaceae) fruits: identification of anthocyanins and gallic acid derivatives

Arbutus unedo L., the strawberry tree (Ericaceae family), is an evergreen shrub or small tree, typical of the Mediterranean fringe and climate. The aim of the present study was to evaluate the profile of the phenolic constituents of A. unedo fruits. Seven compounds were purified by Sephadex LH-20 column chromatography of the MeOH extract followed by HPLC and were characterized as arbutin, beta-D-glucogalline, gallic acid 4-O-beta-D-glucopyranoside, 3-O-galloylquinic acid, 5-O-galloylquinic acid, 3-O-galloylshikimic acid, and 5-O-galloylshikimic acid, by means of NMR and ESI-MS analyses. Moreover, LC-PDA-MS analysis of the red pigment of A. unedo fruits revealed the presence of three anthocyanins recognized as cyanidin 3-O-beta-D-galactopyranoside, delphinidin 3-O-beta-D-glucopyranoside, and cyanidin 3-O-beta-D-arabinopyranoside. These pigments were also quantified.     

GC-ITMS determination and degradation of captan during winemaking

Captan and its metabolite tetrahydrophthalimide (THPI) were determined in grapes, must, and wine by GC-ITMS. Pesticides were extracted with acetone/petroleum ether (50:50 v/v). Because of the high selectivity of the ITMS detector, no interferent was found and cleanup was not necessary. Recoveries from fortified grapes, must, and wines ranged between 90 and 113% with a maximum coefficient of variation of 11%. Limits of quantitation were 0.01 mg/kg for both compounds. In model systems, captan and its metabolites, THPI, cis-4-cyclohexene-1,2-dicarboxylic acid, and 1,2,3,6-tetrahydrophthalamic acid, were determined by HPLC. The degradation of captan during winemaking was studied. Captan degraded in must, giving 100% THPI, and at the end of fermentation, only THPI was found in wine. The degradation of captan to THPI was due to the acidity in must and wine. This metabolite was present at low levels on grapes, and, unlike captan, it had no negative effect on the fermentative process. Model systems showed that the mechanism of disappearance of captan in grapes was due to photodegradation and codistillation.     

Effect of sunscreen and antioxidant on the stability of pyrethrin formulations

The stability of pyrethrins in formulations containing different combinations of antioxidant and sunscreen was studied with model system experiments. The mechanism of disappearance of pyrethrins was mainly due to photodegradation, but some loss by codistillation can occur. In formulations, the presence of mineral oil and emulsifiers determined a decrease on codistillation losses. The presence of the antioxidant in formulations even at high concentrations did not affect pyrethrin photodegradation rates, but rising amounts of sunscreen determined a progressive increase on half-life times of pyrethrins. A combination of sunscreen and antioxidant at low concentrations provided an effective protection against sunlight similar to that obtained by high amounts of sunscreen alone.