Stability of bioactive polyphenols from honey during different extraction methods

The LC–MS/MS technique was applied to the stability study of several flavonoids and phenolic acids in honey samples during the ultrasonic extraction (USE) and microwave-assisted extraction (MAE). Phenolic compounds from the standard mixture were stable under ultrasounds action with the mean recovery of (90.4% ± 7.1%), but during microwave-assisted extraction the benzoic acid derivatives and aglycones of flavonoids showed lower recovery (70–80%). In honey matrix, the phenolic acids and the glycosides exhibited the high stability for MAE and USE treatments. However, the recoveries of tested aglycones were below 10%. In the presence of an artificial sugar matrix, flavonols were almost completely degraded after successive treatment under MAE and USE conditions. The obtained results indicated that standard addition method for flavonoids quantification in honey samples should not be recommended. Application of the USE conditions provided higher and/or similar extraction yields for phenolic acids than usually applied shaking with solvent. It also allowed shortening the time required for the whole sample preparation procedure. Phenolic acids and glycosides such as quercetrin, rutin and hesperidin appeared to be stable under such conditions.     

Tracing the geographical origin of honeys based on volatile compounds profiles assessment using pattern recognition techniques

The goal of this study was to examine the possibility of verifying the geographical origin of honeys based on the profiles of volatile compounds. A head-space solid phase microextraction (SPME) combined with comprehensive two-dimensional gas chromatography–time-of-flight mass spectrometry (GC × GC–TOFMS) was used to analyze the volatiles in honeys with various geographical and floral origins. Once the analytical data were collected, supervised pattern recognition techniques were applied to construct classification/discrimination rules to predict the origin of samples on the basis of their profiles of volatile compounds. Specifically, linear discriminant analysis (LDA), soft independent modeling of class analogies (SIMCA), discriminant partial least squares (DPLS) and support vector machines (SVM) with the recently proposed Pearson VII universal kernel (PUK) were used in our study to discriminate between Corsican and non-Corsican honeys. Although DPLS and LDA provided models with high sensitivities and specificities, the best performance was achieved by the SVM using PUK. The results of this study demonstrated that GC × GC–TOFMS combined with methods like LDA, DPLS and SVM can be successfully applied to detect mislabeling of Corsican honeys.     

Characterization of Eucalyptus Globulus Honeys Produced in the Eurosiberian Area of the Iberian Peninsula

The characterization of thirty-one honey samples using melisopalynological and physicochemical characteristics as diastase activity, invertase activity, pH, moisture, electrical conductivity, hydroxymethylfurfural content, and color, as well as phenolic and flavonoid content, mineral composition, and sugar content was performed. All the samples were produced in the Eurosiberian area of the Iberian Peninsula. Relationships between certain pollen types and the selected physicochemical parameters have been found using a Spearman rank correlation analysis. The principal component analysis of data set was an important tool for the determination of the variables used to characterize this honey type.     

蜜罐系统模型的有限自动机

蜜罐系统作为一种主动响应的安全技术,利用诱骗技术吸引入侵,对网络数据进行捕捉和控制,及时获取攻击信息并记录入侵过程,研究攻击手段和过程。对该技术的研究已成为目前信息安全领域的研究热点。本文通过确定性有限自动机理论对蜜罐系统模型进行描述,根据确定性有限自动机状态转换图模拟捕捉攻击行为的全过程,为蜜罐系统的设计和部署提供有力的理论依据和论证。     

Degradation of erythromycin in honey and selection of suitable marker residues for food safety analysis

Extra-label use of veterinary medications in apiculture is a practice which is known to result in the presence of drug residues in honey. Erythromycin has been used by some beekeepers in an attempt to control foulbrood diseases in honey bees. It is recognised that erythromycin degrades in acidic aqueous solutions to yield predominantly anhydroerythromycin. Honey is an acidic medium in which erythromycin should also degrade. Three degradation products with a molecular weight of 715 Da (anhydroerythromycin, erythromycin enol ether, and an unidentified but suspected related isomer) have been confirmed to be formed in honey. Erythromycin was found to degrade rapidly in honey at typical hive temperature with a half-life of less than one day. Based on these results, it is recommended that food safety laboratories include degradation products in analytical testing protocols when examining honey for erythromycin residues.     

Physico-chemical properties of multi-floral honey from the West Bank,Palestine

Honey is a nutritious product that is produced by honey bees. Its nutritional value and genuine quality is of great importance to consumers. The present study aimed at evaluating the physico-chemical properties of Palestinian multi-floral honey from the West Bank. For this purpose, a total of 33 honey samples were collected directly from honey beekeepers in different geographic regions of the West Bank and analyzed for pH, moisture, relative density, total sugars, reducing sugars, sucrose, fructose, proteins, ash, hydroxymethylfurfural, and mineral content. The mean physico-chemical contents were: pH = 3.44, moisture = 16.53%, relative density = 1.424, reducing sugars = 78.86%, sucrose = 4.10%, fructose = 38.29%, proteins = 0.33%, ash = 0.14%, and hydroxymethylfurfural = 12.32 mg/kg. Cd and Pb were below detection limits in all samples analyzed. Honey samples were rich in K, Na, Ca, Pb, and Mg with concentrations ranging between 183.86 mg/kg (K) and 22.74 mg/kg (Mg). Other trace elements (Fe, Li, B, Mn, Ba, Zn, Cu, Cr, and Ni) were found in much smaller concentrations between 5.21 mg/kg (Fe) and 0.08 mg/kg (Ni). In conclusion, the results of physico-chemical analysis of Palestinian multi-floral honey indicated purity and good quality that meet the international honey standards.     

Molecular identification of honey entomological origin based on bee mitochondrial 16S rRNA and COI gene sequences

The increasing recognition and production of stingless bee honey has raised the needs to develop rapid, sensitive and accurate methodologies for honey identification through bees' species from the DNA of bees present in honey. Genetic identification of raw honeys produced by different bee species from Malaysia was performed based on mitochondrial DNA sequences and phylogenetic analysis by means of forensically informative nucleotide sequencing (FINS) technique. The 300 bp of mitochondrial large subunit ribosomal RNA (16S rRNA) gene region and mitochondrial cytochrome c oxidase subunit I (COI) gene region were the gene markers used to classify and identify honey produced by Apis honey bees and Trigona stingless bees. The genetic identities of honey origin from Apis dorsata, Apis mellifera, Apis cerana, and Heterotrigona itama were accurately identified. Kelulut honey sourced from the stingless bee was distinguishable from other Apis type of honeys in phylogenetic analyses. This FINS technique is a specific and reliable method for identification of honey origin via its bee source that can be used to overcome the issue of false declaration of honey origin and mislabelling.     

Entomological authentication of stingless bee honey by 1H NMR-based metabolomics approach

The high value of stingless bee honey, better known as pot-honey, offers an incentive to fraud and requires new analytical methods to guarantee the entomological origin. In this research, Geotrigona-Trigona, Melipona, Scaptotrigona, and Apis mellifera Ecuadorian honeys were analyzed. Orthogonal projection to latent structure-discriminant analysis (OPLS-DA) built on ¹H NMR data obtained by both water dilution and chloroform extracts spectra, conveyed to successful entomological discrimination. The metabolic fingerprints of these different types of honeys are unique. The most important findings are specific marker signals of entomological origin in chloroform extracts: metabolites deriving from the cerumen secreted by the same bees are present and may be considered as the bee species signature on honey. Furthermore, the endogenous diacylglyceryl ether is recognized as the key marker of pot-honey adulteration with Apis mellifera honey.     

Uncertainties in the determination of pyrrolizidine alkaloid levels in naturally contaminated honeys and comparison of results obtained by different analytical approaches

The contamination of honey with hepatotoxic pyrrolizidine alkaloids (PAs) is a well-known hazard for food safety. While management strategies and controls of the honey industry aim to reduce the PA levels, uncertainties remain with regard to the safety of regionally produced and marketed honey. In addition, a previous study showed large differences of results obtained after various periods of storage and apparent differences between the analytical results of different laboratories. Therefore, this study aimed at examining these uncertainties by monitoring the impact of storage on the PA and PA N-oxide (PANO) content of two freshly harvested honeys and on possible demixing effects caused by pollen settling. Additionally, three analytical approaches – target analysis with matrix-matched calibration or standard addition and a sum parameter method – were applied for a comparative analysis of 20 honeys harvested in summer 2016. All samples originated from Schleswig-Holstein in Northern Germany where the PA plant Jacobaea vulgaris is currently observed on a massive scale. The results of the time series analyses showed that PANO levels markedly decreased within a few weeks and practically reached the LOD 16 weeks after harvest. Tertiary PAs, by contrast, remained stable and did not increase as a consequence of PANO decrease. The experiments on a putative demixing, which may result in a heterogeneous distribution of PAs/PANOs, revealed that there was no such effect during storage of up to 12 weeks. A comparison of the PA/PANO levels obtained by different analytical approaches showed that in some cases the sum parameter method yielded much higher levels than the target approaches, whereas in other cases, the target analysis with standard addition found higher levels than the other two methods. In summary, the results of this study highlight uncertainties regarding the validity and comparability of analytical results and consequently regarding health risk assessment.     

Crystallization of Honey at −20°C

Honeys from different regions of the province of Buenos Aires were stored at ?20°C, and factors that affect crystallization were analyzed. Crystals were observed by light microscopy. Firmness, adhesivity and viscosity of the samples were measured. Honey was characterized by determining the water activity, turbidity, moisture, fructose, and glucose contents. Results show that the viscous characteristics of the samples depend on the number, size, and disposition of crystals. Various honey samples exhibited Newtonian, pseudoplastic, and thixotropic behaviors. Crystallization was favored at higher moisture contents, suggesting that the parameters that affect honey crystallization at room temperature have a different effect at freezing temperatures. Honey that presented higher values of firmness had a moisture content lower than 17%, and a linear inverse relationship was observed between the adhesivity and firmness of honey samples.