Contamination of Honeybee (Apis mellifera L.) Royal Jelly by Pesticides and Sample Preparation Methods for Its Determination: A Critical Appraisal.

Pesticides can easily enter the food chain, harming bee populations and ecosystems. Exposure of beehive products to various contaminants has been identified as one of the factors contributing to the decline in bee populations, and multiple food alerts have been reported. Despite this fact, royal jelly, a valuable bee product with nutritional and functional properties, has received less attention in this context. Pesticide residues of different chemical class can contaminate royal jelly when foraging bees collect pollen or nectar from pesticide-treated flowers, or in some cases, due to its frequent and inappropriate use in the treatment of mites in beehives. To monitor this issue and also make it more reliable, it is crucial to develop effective sample preparation methods for extracting pesticides from royal jelly for subsequent analysis. In this context, this review provides information about sample preparation methods (solid-phase extraction, solvent extraction, and QuEChERS-quick, easy, cheap, effective, rugged and safe) and analytical methods that have been validated or improved to extract and analyze pesticides, respectively, in royal jelly samples of different origins. Finally, future perspectives are discussed. With this background, we aim to provide data that can guide future research related to this topic.

Determination of acaricides in honeys from different botanical origins by gas chromatography-mass spectrometry.

An analytical method has been proposed and validated to determine seven acaricides (atrazine, chlorpyrifos, chlorfenvinphos, α-endosulfan, bromopropylate, coumaphos, and τ-fluvalinate) in honeys from different botanical origins (multifloral, heather and rosemary) by means of gas chromatography-mass spectrometry. An efficient and simple sample treatment was proposed that involved a solvent extraction with an ethyl acetate and cyclohexane (50:50, v/v) mixture. Chromatographic analysis (<25 min) was performed in a DB-5MS column under programmed temperature conditions. The method was validated in terms of selectivity, limits of detection (0.2-2.0 µg kg-1) and quantification (0.5-7.6 µg kg-1), linearity (limit of quantification-700 (heather) or 800 (multifloral and rosemary) µg kg-1), matrix effect (<20 % in most cases), trueness (recoveries between 81 % and 108 %), and precision (relative standard deviation < 15 %). Finally, of the seven acaricides investigated in several honey samples only τ-fluvalinate residues (

Analysis of flavonoids in Rubus erythrocladus and Morus nigra leaves extracts by liquid chromatography and capillary electrophoresis

AbstractThis study uses high performance liquid chromatography and capillary electrophoresis as analytical tools to evaluate flavonoids in hydrolyzed leaves extracts of Rubus erythrocladus Mart., Rosaceae, and Morus nigra L., Moraceae. For phytochemical analysis, the extracts were prepared by acid hydrolysis and ultrasonic bath and analyzed by high performance liquid chromatography using an ultraviolet detector and by capillary electrophoresis equipped with a diode-array detector. Quercetin and kaempferol were identified in these extracts. The analytical methods developed were validated and applied. Quercetin and kaempferol were quantified in R. erythrocladus, with 848.43 ± 66.68 μg g-1 and 304.35 ± 17.29 μg g-1, respectively, by HPLC-UV and quercetin, 836.37 ± 149.43 μg g-1, by CE-DAD. In M. nigra the quantifications of quercetin and kaempferol were 2323.90 ± 145.35 μg g-1 and 1446.36 ± 59.00 μg g-1, respectively, by HPLC-UV and, 2552.82 ± 275.30 μg g-1 and 1188.67 ± 99.21 μg g-1, respectively, by CE-DAD. The extracts were also analyzed by ultra-performance liquid chromatography coupled with a diode-array detector and mass spectrometer (MS), UPLC-DAD/MS.

Diguanoside tetraphosphate (Gp4G) is an epithelial cell and hair growth regulator.

Our goal was to study the effect of Gp4G on skin tissues and unravel its intracellular action mechanisms. The effects of Gp4G formulation, a liposomic solution of Artemia salina extract, on several epidermal, depmal, and hair follicle structures were quantified. A 50% increase in hair length and a 30% increase in the number of papilla cells were explained by the changes in the telogen/anagen hair follicle phases. Increasing skin blood vessels and fibroblast activation modified collagen arrangement in dermal tissues. Imunohistochemical staining revealed expressive increases of versican (VER) deposition in the treated animals (68%). Hela and fibroblast cells were used as in vitro models. Gp4G enters both cell lines, with a hyperbolic saturation profile inducing an increase in the viabilities of Hela and fibroblast cells. Intracellular ATP and other nucleotides were quantified in Hela cells showing a 38% increase in intracellular ATP concentration and increases in the intracellular concentration of tri- , di- , and monophosphate nucleosides, changing the usual quasi-equilibrium state of nucleotide concentrations. We propose that this change in nucleotide equilibrium affects several biochemical pathways and explains the cell and tissue activations observed experimentally.

The chameleon-like nature of zwitterionic micelles: the intrinsic relationship of anion and cation binding in sulfobetaine micelles.

The rate of specific hydrogen ion-catalyzed hydrolysis of 2-( p-heptoxyphenyl)-1,3-dioxolane and acid-base equilibrium of 4-carboxy-1-n-dodecylpyridinium in zwitterionic micelles of SB3-14, C14H29NMe2+(CH2)3SO3(-) are controlled by NaClO4, which induces anionic character and uptake of H3O+ in the micelles. Other salts, e.g., NaF, NaCl, NaBr, NaNO3, NaI, NaBF4, have similar, but smaller, effects on the uptake of H3O+. Salt effects upon zeta potentials of SB3-14 micelles, estimated by capillary electrophoresis, are anion specific, and the anion order is similar to that of the rates of acid hydrolysis and of acid-base equilibria. Fluorescence quenching shows that the micellar aggregation number is not very sensitive to added salts, consistent with electrophoretic evidence. These specific anion effects follow the Hofmeister series and are related to anion hydration free energies.

Radical acetylation of 2'-deoxyguanosine and L-histidine coupled to the reaction of diacetyl with peroxynitrite in aerated medium.

Diacetyl, like other alpha-dicarbonyl compounds, is reportedly cytotoxic and genotoxic. A food and cigarette contaminant, it is related with alcohol hepatotoxicity and lung disease. Peroxynitrite is a potent oxidant formed in vivo by the diffusion-controlled reaction of the superoxide radical anion with nitric oxide, which is able to form adducts with carbon dioxide and carbonyl compounds. Here, we investigate the nucleophilic addition of peroxynitrite to diacetyl forming acetyl radicals, whose reaction with molecular oxygen leads to acetate. Peroxynitrite is shown to react with diacetyl in phosphate buffer (bell-shaped pH profile with maximum at 7.2) at a very high rate constant ( k 2 = 1.0 x 10 (4) M (-1) s (-1)) when compared with monocarbonyl substrates ( k 2 < 10 (3) M (-1) s (-1)). Phosphate ions (100-500 mM) do not affect the rate of spontaneous peroxynitrite decay, but the H 2PO 4 (-) anion catalyzes the nucleophilic addition of the peroxynitrite anion to diacetyl. The intermediacy of acetyl radicals is suggested by a three-line spectrum ( a N = a H = 0.83 mT) obtained by EPR spin trapping of the reaction mixture with 2-methyl-2-nitrosopropane. The peroxynitrite reaction is accompanied by concentration-dependent oxygen uptake. Stoichiometric amounts of acetate from millimolar amounts of peroxynitrite and diacetyl were obtained under nonlimiting conditions of dissolved oxygen. In the presence of either l-histidine or 2'-deoxyguanosine, the peroxynitrite/diacetyl system afforded the corresponding acetylated molecules identified by HPLC-MS ( n ). These studies provide evidence that the peroxynitrite/diacetyl reaction yields acetyl radicals and raise the hypothesis that protein and DNA nonenzymatic acetylation may occur in cells and be implicated in aging and metabolic disorders in which oxygen and nitrogen reactive species are putatively involved.