Honeydew honey is increasingly being valued by consumers and the food industry worldwide, particularly bracatinga honeydew honey (Bhh) obtained from honeydew of plant-sucking insects (Tachardiella ...sp.) that infest the tree species bracatinga (Mimosa scabrella Bentham) from Santa Catarina State (SC), Brazil. Due to mixture between honeys, authentication is an important aspect of quality control and its regard with the origin guarantee in terms of source and geographical documentation needs to be determined. We therefore determined the free amino acids (FAA) by GC-MS to elucidate the contribution of plant-sucking insects (Tachardiella sp.) and Apis mellifera bees to the Bhh in order to classify this honey from five different geographic areas of Santa Catarina, using chemometric approach. The results showed that proline is provided exclusively by Apis mellifera bees, and this honey could be differentiated into geographic regions based on the FAA profile. Principal component analysis identified the main FAA responsible for clustering of the samples in these regions (the sum of the first 2 principal components account for 82% of the total variance) and provided a similar discrimination of the geographical location map, particularly with regard to the northern and southern geographical orientations. This method is therefore a reliable analytical strategy for the authentication of this honey.
•Free amino acids were determined in bracatinga honeydew honeys and honeydew.•Results evidenced that proline is provided exclusively by bee to the honeydew honey.•High concentrations of free amino acids were observed.•Bracatinga honeydew honeys from a mesoregion were discriminated geographically.•Free amino acids can be an analytical strategy for authentication of honeydew honey.
Th e aim of this study was to investigate the composition and quality of Serbian honeydew honey. For this purpose, the physicochemical characteristics of 14 honeydew samples were analyzed. Th e ...physicochemical characteristics of all honeydew honeys from Serbia analyzed in this research can be considered to be within the parameters prescribed for honeydew in general. Th e sum value of glucose and fructose, the content of sucrose, water, hydroxymethylfurfural, acidity, and diastase activity were in line with European and national regulations for honey, for all investigated honeydew samples. Out of a total of 14 tested honey samples, 1 sample did not comply with the national regulations for honey regarding electrical conductivity. According to our results, in most of investigated samples the fructose/glucose (F/G) ratio was greater than 1.11 and glucose/water (G/W) ratio was close to 2. Th is means that they can be categorized as medium-crystallizing honeys. Th e results obtained in this study indicate excellent quality, absence of undesirable fermentation, acceptable freshness and proper manipulation of Serbian honeydews.
A simple, reproducible and sensitive method has been optimized and validated for simultaneous determination of 32 phenolic compounds in bracatinga (Mimosa scabrella Benth.) with the diluted-and-shoot ...approach, without the need of any additional clean-up steps. It has been based on high performance liquid chromatography coupled with triple quadrupole tandem mass spectrometry and electrospray ionization (HPLC-ESI-MS/MS). The chromatography conditions were optimized, and due to the selectivity provided by MRM monitoring, LC separation required only 9min. The developed method was validated on the basis of Eurachem and European Commission Decision 2002/657/EC guidelines. Mean recoveries ranged from 70.4 to 110%. Intra-day and inter-day precision with RSD (relative standard deviations) from 0.14 to 18.9% and 0.34 to 20.0%, respectively were achieved. Limits of detection (LOD) and quantification (LOQ) ranged from 0.03 to 3.20μgL−1 and 0.20–12.8μgL−1. Finally, the method was applied to samples and 20 phenolic compounds were quantified in all the samples analyzed, representing a contribution to the characterization and quantification of phenolic compounds from bracatinga (M. scabrella Bentham) honeydew honey.
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•The bracatinga (Mimosa scabrella Benth.) honeydew honey is a source of phenolic compounds•A validated LC-MS/MS method for the analysis of 32 phenolic compounds was developed•A simple, environmentally friendly dilute-and-shoot approach was performed•20 phenolic compounds were identified among the samples analyzed•Presence of 6 phenolic compounds was reported for the first time in this study
Honey is classified in blossom honey (nectar of plants) or honeydew honey (secretions of living parts of plants or excretions of plant-sucking insects on plants). The antioxidant and antibacterial ...properties of honeydew honey are higher than those of most blossom honeys.
Therefore it is important to determine the kind of honey to avoid adulterations. In this work, studies carried out to differentiate honeys according their botanical origin (blossom or honeydew) have been reviewed.
Honeydew honey is generally characterized by higher values of electric conductivity, pH, acidity and ash content, darker colour, higher oligosaccharides content and lower content of monosaccharides than blossom honey. FT-NIR and FT-MIR spectroscopy have been proposed for the honey authentication. These techniques also allowed the simultaneous determination of sugars and physicochemical parameters used in routine quality control of honey. The trisaccharide melezitose was regarded as a characteristic feature of honeydew honey. A diacylglycerilether was identified as a biochemical marker for honeydew honey. As conclusion, nowadays frauds can be avoid because honeydew and blossom honeys can be classified correctly.
•The main parameters to classify honeydew and blossom honeys were review.•FT-NIR and FT-MIR spectroscopy have been proposed for the honey authentication.•Melezitose and a diacylglycerilether were identified as characteristic features of honeydew honey.•Spectroscopy did not allow a good determination of HMF and enzyme activities.•Frauds can be avoid because honeydew and blossom honeys can be classified correctly.
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•Comprehensively profiled the chemical composition of New Zealand honeydew honey.•First study to produce a quantitative amino acid profile for New Zealand honeydew honey.•First study ...to quantify the flavonoid sakuranetin in any variety of honeydew honey.•Antioxidant activity of New Zealand honeydew honey was compared to Manuka honey.
Demand for honeydew honey (HDH) is growing, both from consumers and the food industry, due to its potential antimicrobial, anti-inflammatory, and antioxidant properties. However, information on the chemical profile of HDH remains scant, particularly on New Zealand honeydew honey (NZHDH). This paper aims to provide a comprehensive chemical analysis of NZHDH produced from honeybees, which feed on nectar exuded by the scale insect Ultracoelostoma assimile. This insect feeds on most species of the Southern Beech (Nothofagus spp.). The proximate composition, mineral profile, sugar profile, phenolic profile, amino acid profile, and antioxidant activity of NZHDH was determined and compared to results for HDH and other varieties of honey previously reported in literature. It was determined that the antioxidant activity of NZHDH is comparable to several studies on Manuka honey, which is widely considered as the “gold standard” for its antioxidant activity. This demonstrated that NZHDH indeed had excellent antioxidant properties. This study was the first time that a quantitative amino acid profile has been produced for NZHDH. The major amino acids were proline, L-aspartic acid, L-glutamic acid, L-alaine, and L-phenylalanine. The major phenolic compounds were pinocembrin, abscisic acid, and pinobanksin. Of the phenolic compounds quantified in this study, only p-hydroxybenzoic acid has previously been quantified in NZHDH.
•Echimidine and lycopsamine are commonly found in honey.•Echimidine, acetylechimidine, lycopsamine and their N-oxides are frequent in pollen.•1 g of pollen/day exceeds the recommended maximum daily ...intake (MDI) of PA by an adult 60 kg.•13 g of honey/day normally exceeds the recommended MDI of PA by an adult 60 kg.•PA levels in propolis and royal jelly are low, but studies of this order are scarce.
Pyrrolizidine alkaloids (PA) are secondary metabolites of plants, which are mostly found in the genus Senecio, Echium, Crotalaria, and Eupatorium. The presence of 1,2-unsaturated PA in foods is a concern to food regulators around the world because these compounds have been associated to acute and chronic toxicity, mainly in the liver. The intake foods with PA/PANO usually occur through accidental ingestion of plants and their derivatives, besides to products of vegetal-animal origin, such as honey. PA/PANO are transferred to honey by their presence in nectar, honeydew, and pollen, which are collected from the flora by bees. In addition to honey, other beekeeping products, such as pollen, royal jelly, propolis, and beeswax, are also vulnerable to PA contamination. In this context, this review provides information about chemical characteristics, regulation, and toxicity, as well as summarizes and critically discusses scientific publications that evaluated PA in honeys, pollens, royal jelly, and propolis.
Pesticides are known to cause numerous negative effects on the health of humans and animals, either through direct contact or through the consumption of contaminated food. In Brazil, mainly due to ...the many pesticides allowed for use, these substances are commonly found in different food matrices, such as honeys. Due to these aspects and the nonexistence of information about pesticides in Brazilian honeydew honey, this study was conducted to determine seven pesticide residues in Mimosa scabrella honeydew honey (MHH) from the southern region of Brazil by gas chromatography-mass spectrometry (GC-MS). No pesticide residues were found in honey samples from the Paraná state. On the other hand, in six of the fifteen samples analyzed from Santa Catarina state, atrazine was determined at levels below 9 µg kg−1. These values were lower than the current maximum residue limits (MRLs; 0.05 mg kg−1) for honeys. Moreover, τ-fluvalinate was detected in one sample with a content lower than the limit of quantification. Thus, the MHH evaluated were free or with low levels of the seven pesticides investigated, and in all cases, concentrations were below the established MRLs. In addition, these results also confirmed that the analyzed MHH can be exported to other countries since the samples comply with the limits for the evaluated pesticides.
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•First study that evaluated pesticides in honeydew honey from Brazil.•Atrazine was found in six of the twenty-eight samples evaluated (<LOQ - 9 µg kg−1).•τ-fluvalinate was determined in only one sample but with a content below LOQ.•No analyzed honey sample exceeded the established maximum residue limits.
•Authenticity assessment of 64 honeydew honey samples of specific botanical origin.•UHPLC-LTQ OrbiTrap MS and UHPLC-DAD MS/MS analysis of phenolic compounds.•Identification of a total of 52 phenolic ...compounds and quantification of 25 of them.•Evaluation of the antioxidant capacity by spectroscopic and electrochemical methods.•Cyclic voltammetry for determination of biological activity of honeydew honey.
Concerning the particular nutritive value of honeydew honey compared to blossom honey, and small number of studies defining botanical origin of honeydew honey, comprehensive analysis of phenolic profile of 64 honeydew honey samples of specific botanical origin was performed. Two advanced techniques of liquid chromatography hyphenated with mass spectrometry were used for identification of a total of 52 compounds and quantification of 25 of them. Pattern recognition analysis applied on data on phenolic compounds content confirmed that quercetin, naringenin, caffeoylquinic acid, hydroxyphenylacetic acid, apigenin and genistein, could be considered as potential markers of botanical origin of honeydew honey. Spectroscopic and electrochemical approaches were applied for the evaluation of the antioxidant capacity. Quercus sps. samples, Quercus frainetto and Quercus ilex, showed high biological activity and specific chemical composition. Additionally, cyclic voltammetry profiles were used for characterization and natural clustering of honeydew honey for the first time.
•Aliphatic organic acids (AOA) can be used to verify honey authenticity.•Bracatinga honeydew honeys (BHH) were differentiated from blossom honeys using AOA.•Different harvests do not influence the ...profile and content of AOA in BHH.•The classification model proposed was effective in verifying the BHH authenticity.•Four commercial BHH were proposed as adulterated samples.
This study aimed to differentiate bracatinga (Mimosa scabrella Bentham) honeydew honey (BHH) from blossom honeys and BHH intentionally adulterated, all of them from three harvests, associating data of aliphatic organic acids (AOA) determined by capillary electrophoresis and chemometric analyses. The profile and concentration of AOA in pure BHH were similar between harvests, but distinct from blossom honeys. Succinic, glycolic, glutaric, malic, acetic, gluconic, and lactic acids were responsible for the differentiation between these two types of honey since they were the dominant variables (r > 0.80) in the principal component analysis. Based on this, the classification and regression trees method was used to develop a classification model considering these AOA. The proposed method needed only six of these AOA and adequately classified all blossom honeys and almost all pure and adulterated BHH. Therefore, the proposed model proved to be promising and reliable for verifying authenticity and fraud detection in BHH.
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•First screening of bracatinga honeydew honey (BHH) quality by using marker peptides.•Major royal jelly proteins (MRJP) identified by untargeted LC-ESI-Triple-TOF-MS/MS.•LC-QqQ-MS/MS ...method optimized for quantification of MRJP peptide markers in BHH.•Selection of suitable peptides is essential to avoid modification.•QNIDVVAR from MRJP 4 could be used to differentiate BHH from floral honeys.
Honey traceability is an important topic, especially for honeydew honeys, due to the increased incidence of adulteration. This study aimed to establish specific markers to quantify proteins in honey. A proteomics strategy to identify marker peptides from bracatinga honeydew honey was therefore developed. The proteomics approach was based on initial untargeted identification of honey proteins and peptides by LC-ESI-Triple-TOF-MS/MS, which identified the major royal jelly proteins (MRJP) presence. Afterwards, the peptides were selected by the in silico digestion. The marker peptides were quantified by the developed targeted LC-QqQ-MS/MS method, which provided good linearity and specificity, besides recoveries between 92 and 100% to quantify peptides from bracatinga honeydew honey. The uniqueness and high response in mass spectrometry were backed by further complementary protein analysis (SDS-PAGE). The selected marker peptides EALPHVPIFDR (MRJP 1), ILGANVK (MRJP 2), TFVTIER (MRJP 3), QNIDVVAR (MRJP 4), FINNDYNFNEVNFR (MRJP 5) and LLQPYPDWSWTK (MRJP 7), quantified by LC-QqQ-MS/MS, highlighted that the content of QNIDVVAR from MRJP 4 could be used to differentiate bracatinga honeydew honey from floral honeys (p < 0.05) as a potential marker for its authentication. Finally, principal components analysis highlighted the QNIDVVAR content as a good descriptor of the analyzed bracatinga honeydew honey samples.
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