Flavonoids in Meliponinae honeys from Venezuela related to their botanical, geographical and entomological origin to assess their putative anticataract activity

 Honey was collected from 24 stinglessbee nests in Venezuela. The flavonoid compounds in the phenolic extracts were analysed and related to the botanical, geographical and entomological origin of the honey. Honeys produced in savannas were richer in flavonoids compared with honeys from the forests. It was found that phenolic extracts of honey of the same geographical origin had similar flavonoid profiles, whereas the same could not be said of honeys of the same entomological origin, although the botanical origin of the samples was variable. It is proposed that analysis of stinglessbee honey eyedrops in terms of their flavonoid content can be used as a basis of authenticating and controlling for their geographical origin. Received: 28 July 1997     

Unifloral honeys of the province of Buenos Aires,Argentine

Samples of 63 unifloral honeys of the province of Buenos Aires, Argentina, from Eucalyptus spp, Lotus spp, Helianthus annuus, Melilotus albus, Brassicaceae, clovers other than Lotus and Melilotus, and Sagittaria montevidensis, were obtained by cold extraction at the laboratory. The frequencies of occurrence of pollen types, and the moisture, hydroxymethylfurfural, ash, acidity and proline contents were determined. Electrical conductivity, pH and colour were also analysed. Honey presented a high percentage (about 40%) of unifloral honey. The most frequent unifloral honeys were from Eucalyptus spp, Lotus spp and Helianthus annuus. Samples had a low pollen diversity with six to 19 pollen types, the most important nectariferous taxa being those that characterized the unifloral honeys. All samples presented moisture, hydroxymethylfurfural, ash and free acidity contents according to international standards. The colour of the honey was from water white to light amber, and all samples had a very low ash content. Significant differences at the 5% level in the hydroxymethylfurfural content, electrical conductivity, colour and proline content were observed among honeys from different floral origins. However, a high variability between samples from the same floral origin was observed, indicating that other factors such as accompanying pollen and geographical origin affect the physicochemical characteristics of honey. Copyright © 2005 Society of Chemical Industry     

Physico chemical and bioactive properties of honeys from Northwestern Argentina

Honey is used for its nutritional and functional properties. The Argentinean Northwest is a region with a growing potential for honey production, but up to now, few physicochemical and biological studies have been carried out. The aim of this study is to characterize monofloral (Prosopis sp and Citrus lemon) and multifloral honey samples from the Argentinean Northwest from a physicochemical and functional standpoint. The results showed that the honeys had good properties of stability and freshness. The highest content of flavonoid and phenolic compounds correspond to multifloral honeys. A positive correlation was observed between colour intensity and flavonoid or phenolic compounds content (R² = 0.98 and R² = 0.92, respectively). The flavonoids, chrysin and pinocembrin were present in all samples analyzed, while hesperidin and hesperetin were numerically more important in lemon honey (>1 mg/kg), providing a valuable marker of botanical origin.The highest antioxidant activity against ABTS radical cation was detected in the darkest honey samples. All tested honeys showed antibacterial activity with MIC values between 0.10 and 0.25 g/mL on Gram-positive and Gram-negative antibiotic resistant bacteria. Neither pH nor osmolarity affected bacterial growth. The phenolic compounds and hydrogen peroxide were responsible for antimicrobial activity by bioautographic assays.The antioxidant and antimicrobial properties found in honeys from the Argentinean Northwest make them products of high added value and excellent quality.     

Antioxidant properties and phenolic content of sulla (Hedysarum spp.) honeys from Southern Italy

The geographical origin greatly influences the qualitative and nutraceutical characteristics of honey. In this study, a total of twenty‐four sulla honeys from eight different geographical areas of Southern Italy have been examined for total phenolic content (Folin–Ciocalteu method), antioxidant activity (FRAP and DPPH assays), colour intensity (ABS₄₅₀), and identification and quantification of phenolic acids (RP‐HPLC/UV‐VIS method). The total phenolic content ranged from 47.9 (Potentino honeys) to 248.3 mg GAE per kg honey (Penisola Sorrentina honeys). The antioxidant activity ranged from 47.06% (Basso Pollino honeys) to 88.25% (Penisola Sorrentina honeys), and from 98.26 μM Fe (II) (Potentino honeys) to 786.53 μm Fe (II) (Tarantino honeys) for DPPH and FRAP assays, respectively. Major phenolic acids identified in analysed samples were gallic, caffeic and ferulic acids. Correlations between the parameters analysed were statistically significant (P < 0.05). The results of the study showed that the parameters studied are greatly affected by the peculiarities of their production area.     

A comparative study on phenolic profile,vitamin C content and antioxidant activity of Italian honeys of different botanical origin

The aim of our study was to identify and quantify the phenolic acids, flavonoids and vitamin C and to evaluate the antioxidant activity in ninety Italian honeys of different botanical origins (chestnut, sulla, eucalyptus, citrus and multifloral). The results showed that total phenolic and flavonoid contents varied from 11.08 to 14.26 mg GAE per 100 g honey and from 5.82 to 12.52 mg QE per 100 g honey, respectively. HPLC–UV analysis showed a similar but quantitatively different phenolic profile of the studied honeys. Vitamin C is present in all samples. Multifloral honey showed the highest amount of the detected total phenolic compounds and the highest vitamin C content. The DPPH value varied from 55.06 to 75.37%. Among the unifloral honeys, chestnut honey presented the highest levels of phenolic acids, flavonoids and vitamin C, which are closely associated with its high antioxidant activity. The results show that honey contains high amount of biologically active compounds, which play an important role in defining the nutraceutical quality of the product, and that the distribution of these compounds is influenced by the botanical origin.     

Geographical discrimination of honeys through antioxidant capacity,mineral content and colour

The assessment of geographical origin of honey is economically important for producers and consumers as every region may present particular quality characteristics. In this study, honeys from the seven different regions of Buenos Aires province (Argentina) were characterised by their antioxidant capacity (DPPH, FRAP), total phenolic content (TPC), mineral composition, colour and ash. Honeys showed significant differences among their antioxidant capacity (DPPH), ash, colour and mineral content (P ≤ 0.05). Besides, a good antioxidant activity and low amounts of Cu and Zn (<1.0–1.5 and 0.7–1.8 mg kg^?1, respectively) were found in the samples. Significant Pearson's correlations (P ≤ 0.05) among the different parameters were found. Moreover, the linear discriminant analysis allowed the classification of honeys in their original groups with a prediction success of 98%. The present results suggest that honeys could be correctly classified by their geographical origin through their TPC, colour, ash and mineral concentrations.     

Phenolic profile and antioxidant properties of Polish honeys

The phenolic components of honeys have great participation in their nutritional value and antioxidant activity. Moreover, phenolic components are promising markers for the determination of botanical and geographical origin of honey. The purpose of the present work was to study the antioxidant activity and profiles of phenolic acids and flavonoids of honeys of various origins. The total phenolic content of honeys varied from 4.46 to 15.04 mg of gallic acid equivalents per 100 g of product and the total phenolic acid content determined chromatographically varied from 201.05 to 2089.08 μg per 100 g of product. Buckwheat honey exhibited the highest antioxidant activity and contained the highest total phenolic amount, whereas rape honey exhibited the lowest values in this respect. Moreover, the buckwheat honey contained the highest amount of phenolic acids. There were significant linear correlations between total phenolic content and antioxidant activity of honey extracts in the reaction with DPPH^? (1,1‐diphenyl‐2‐picrylhydrazyl) and ABTS^{? +} (2,2′‐azinobis‐(3‐ethylbenzothiazoline‐6‐sulfonic acid)) free radicals. In most samples, p‐coumaric acid was the dominant phenolic acid (39.1–677.2 μg per 100 g). The honeys also contained considerable amount of gallic acid (6.0–913.8 μg per 100 g). Among flavonoids naringenin was predominant in the most studied honey samples.     

Antioxidant activity of Portuguese honey samples: Different contributions of the entire honey and phenolic extract

The antioxidant activity of Portuguese honeys was evaluated considering the different contribution of entire samples and phenolic extracts. Several chemical and biochemical assays were used to screen the antioxidant properties of entire honeys with different colour intensity and phenolic extracts: reducing power, 2,2-diphenyl-1-picrylhydrazyl (DPPH) radical-scavenging capacity, and inhibition of lipid peroxidation using the β-carotene linoleate model system and the thiobarbituric acid reactive substances (TBARS) assay. The amounts of phenols, flavonoids, ascorbic acid, β-carotene, lycopene and sugars present in the samples were also determined. The highest antioxidant contents and the lowest EC₅₀ values for antioxidant activity were obtained in the dark honey. An analysis of variance was carried out to evaluate the influence of the colour intensity and extraction method in the antioxidant properties and phenolic contents. A discriminant analysis was also performed, giving satisfactory results once the six samples were clustered in six individual groups obtained through the definition of two discriminant analysis dimensions.     

Geographical characterisation of multifloral honeys from the Marche region (Italy) according to their antioxidant activity and colour using a chemometric approach

Multifloral honeys produced in the Marche region (Italy) were analysed leading to the antioxidant and colour characterisation of this type of regional honeys: the antioxidant activity was determined measuring total phenolic content (TPC), and using ABTS and DPPH assays. The elaboration of data with multivariate analyses enabled differentiation of the geographical origin of honey samples, namely as coming from the Mid/Coastal Hilly or from the High Hilly/Submountain belt of the Marche region. The cluster analysis applied to a selection of samples divided honeys belonging to the Mid/Coastal Hilly belt into three groups showing low, medium and high antioxidant activity and in part located in different areas of the region. Finally, using data of unifloral honeys from the Marche region previously determined, it was possible to have an indication of the prevalent nectar contained in most of the multifloral honey samples harvested in 2012 in the Marche region.     

Flavonoid profile of Robinia honeys produced in Croatia

In this work specific pollen content, selected physicochemical parameters and flavonoid profile of 40 Croatian Robinia honeys from two production seasons were analysed. Results showed good compliance with national and international regulatory requirements, as well as with values typical for Robinia monofloral honey. All analysed samples showed same, typical flavonoid profile. Flavonoid content was different for two seasons, but rates of individual compounds remained unchanged. Higher concentrations of flavonoids were found in samples produced during dry season with high temperatures.     

Phenolic acid composition and antioxidant properties of Malaysian honeys

Abstract: The phenolic acid and flavonoid contents of Malaysian Tualang, Gelam, and Borneo tropical honeys were compared to those of Manuka honey. Ferric reducing/antioxidant power assay (FRAP) and the 1,1‐diphenyl‐2‐picryl‐hydrazyl (DPPH) radical‐scavenging activities were also quantified. All honey extracts exhibited high phenolic contents (15.21 ± 0.51– 42.23 ± 0.64 mg/kg), flavonoid contents (11.52 ± 0.27– 25.31 ± 0.37 mg/kg), FRAP values (892.15 ± 4.97– 363.38 ± 10.57 μM Fe[II]/kg), and high IC₅₀ of DPPH radical‐scavenging activities (5.24 ± 0.40– 17.51 ± 0.51 mg/mL). Total of 6 phenolic acids (gallic, syringic, benzoic, trans‐cinnamic, p‐coumaric, and caffeic acids) and 5 flavonoids (catechin, kaempferol, naringenin, luteolin, and apigenin) were identified. Among the Malaysian honey samples, Tualang honey had the highest contents of phenolics, and flavonoids, and DPPH radical‐scavenging activities. We conclude that among Malaysian honey samples, Tualang honey is the richest in phenolic acids, and flavonoid compounds, which have strong free radical‐scavenging activities.     

单花蜂蜜多酚类物质的抗氧化活性

以5种中国单花原蜜,不同产地的42个样本通过Amberlite XAD-2吸附树脂得到的多酚提取物为原料,采用分光光度法,测定总酚酸和总黄酮含量、还原能力、抗氧化活性(清除DPPH自由基、O2－ ·能力),评估蜂蜜多酚类物质抗氧化活性及蜂蜜品种、颜色和地域差异对清除自由基的影响。结果表明：样本总黄酮含量为(9.41±0.18)～(92.76±0.13)mg/kg;总酚酸含量为(9.10±0.05)～(149.57±0.14)mg/100g;深色枣花蜜抗氧化能力最强,对DPPH自由基、O2－ ·清除作用分别为EC50＝(0.042±0.014)g/mL和EC50＝(0.038±0.009)g/mL。提示蜂蜜的多酚类物质影响抗氧化活性,酚酸、黄酮含量与抗氧化能力呈现正相关系;色深原蜜的酚酸、黄酮含量高于色浅原蜜,抗氧化能力也强于浅色原蜜。     

The determination of phenolic profiles of Serbian unifloral honeys using ultra-high-performance liquid chromatography/high resolution accurate mass spectrometry

Polyphenolic profiles of 44 unifloral Serbian honeys were analyzed using ultra-high-performance liquid chromatography (UHPLC) coupled with hybrid mass spectrometer which combines the Linear Trap Quadrupole (LTQ) and OrbiTrap mass analyzer. Rapid UHPLC method was developed in combination with a high sensitivity accurate mass scan and a simultaneous data dependent scan. The honey samples were of different botanical origin: acacia (Robinia pseudoacacia), sunflower (Helianthus annuus), linden (Tilia cordata), basil (Ocimum basilicum), buckwheat (Fagopyrum esculentum), oilseed rape (Brassica napus), and goldenrod (Solidago virgaurea). The presence of 43 compounds, mainly flavonoids, was proven in all honey samples by their characteristic mass spectra and fragmentation pattern. Relatively high amounts of chrysin, pinocembrin and galangin were identified in all honey extracts. p-Coumaric acid was not detected in basil, buckwheat and goldenrod honey extracts. A larger amount of gallic acid (max value 1.45 mg/kg) was found in the sunflower honey, while a larger amount of apigenin (0.97 mg/kg) was determined in the buckwheat honey in comparison with other honeys. The samples were classified according to the botanical origin using pattern recognition technique, Principal Component Analysis (PCA). The LTQ OrbiTrap technique was proven to be reliable for the unambiguous detection of phenolic acids, their derivatives, and flavonoid aglycones based on their molecular masses and fragmentation pattern.     

Characterization of honeys by their botanical and geographical origins based on physico-chemical properties and chemo-metrics analysis

Honey, because of its nutritional and medicinal values, is in high demand and has become one of the important commodities. However, the issue of its quality and authenticity remain as important factors in consumption and marketing of honey. To assess the possibility of discriminating honeys by their geographical and botanical origins; 30 fresh honey samples of different botanical and geographical origins were collected and their major physico-chemical properties such as: total dissolved sugar (TDS), total ash, sugar profile, acidity, metallic ions and electric conductivity (EC) were investigated. The data was subjected to different chemo-metric (Hierarchical Cluster, Principal components and stepwise discriminant) analysis. Among the 23 characters used in the analysis; only 11 (TDS, EC, acidity, total ash, colour, and some specific metallic ions) characters have showed significant variations among different origin honeys. According to the stepwise discriminant analysis; 11 variables confirmed the grouping of the honey samples into four cluster groups based on their botanical and geographical origins. The clustering of the honeys associated with dominant plant source & climatic conditions of their origins. The study generally revealed the successful discrimination of honeys into their botanical and geographical provenances using fewer physico-chemical characters supported with melissopalynological data through applying suitable chemo-metric analysis.     

Minerals content in Basilicata region (southern Italy) honeys from areas with different anthropic impact

The aim of this study was to examine the minerals content (toxic elements, macro-elements and trace elements) of Basilicata region (southern Italy) honeys and compare the mineral profile of honeys classified as rural, industrial and urban according to anthropic characteristics of geographical origin. Overall, Ca, Na, Mg, Fe, Al, Zn and Mn were the most abundant elements detected in honeys, with average contents exceeding 1 ppm, whereas heavy metals content was lower than the maximum limit established for honey. Statistical analysis revealed significant differences (P < 0.05) among honeys as function of anthropic characteristics of geographical origin, with the exception for Se, Co and Ag content. Industrial honeys were characterised by the highest Zn, Cr, Sn, Cd and Pb content, urban honeys showed the highest As, Fe, Ni, Mn, Na, Mg and Ca content, whereas rural honeys showed the highest Cu, Al and Ba content (P < 0.05). The findings of this study highlighted that honeys mineral profile is closely related to different content of elements in environment, which is affected by anthropogenic activities.     

Characterization of Spanish honeys with protected designation of origin "Miel de Granada" according to their mineral content

Honey attributes such as geographical origin or specified botanical sources often command a premium price due to their organoleptic or pharmacoactive properties. "Miel de Granada" is a highly quality product with protected designation of origin (PDO) which includes six monofloral honeys and two multifloral honeys. Our objective was the characterization of "Miel de Granada" according to their metal content. Metal content was specific enough and allowed discrimination from honeys of different botanical and geographical origins and confirmed the authenticity of PDO labelling as Granada product with the determination of only five elements (K, Na, Ca, Mg and Zn). Chemometric techniques as cluster analysis and ANOVA were used to classify honeys according to their botanical and geographical origin in the metal data. Metal content marks the differences in honey samples and can be used as a tool to assess the quality of honeys. ANOVA showed significant differences among rosemary honeys from different geographical areas despite the botanical factor weight. Our research contributes to the groundwork studies to determine the geographical origin of Spanish honeys.     

HPLC flavonoid profiles as markers for the botanical origin of European unifloral honeys

The HPLC phenolic profiles of 52 selected unifloral honey samples produced in Europe were analysed to detect possible markers for the floral origin of the different honeys. Lime‐tree (five markers), chestnut (five markers), rapeseed (one marker), eucalyptus (six markers) and heather (three markers) honeys had specific markers with characteristic UV spectra. In addition, the flavanone hesperetin was confirmed as a marker for citrus honey, as well as kaempferol for rosemary honey and quercetin for sunflower honey. Abscisic acid, which had been reported to be a possible marker for heather honey, was also detected in rapeseed, lime‐tree and acacia honeys. Ellagic acid in heather honey and the hydroxycinnamates caffeic, p‐coumaric and ferulic acids in chestnut, sunflower, lavender and acacia honeys were also detected. The characteristic propolis‐derived flavonoids pinocembrin, pinobanksin and chrysin were present in most samples in variable amounts. © 2001 Society of Chemical Industry     

Hesperetin: A marker of the floral origin of citrus honey

Seventeen flavonoid aglycones were identified in various experimental and commercial citrus honey samples by HPLC analysis. The flavanone hesperetin was detected in all samples. This flavanone was not detected in any of the honey samples, from diverse floral origin (including rosemary, lavender, sunflower, almond, sweet chestnut, white clover, Erisarum, Robinia, Rhododendron, Tilia, Prosopis, Eucalyptus and Calluna honeys) previously investigated. The analysis of the flavonoids present in orange nectar revealed that the flavanone hesperidin (hesperetin-7-rutinoside) was the major flavonoid detected and, therefore, this should be the main source of the hesperetin found in citrus honey. Hesperetin should be produced by hydrolysis of hesperidin by the bee enzymes present in honey. These results suggest that hesperetin could be used as a marker for the botanical origin of citrus honey.     

天山茶茎黄酮苷元提取工艺优化及其生物活性

为了优化天山茶藨茎5种黄酮苷元（木犀草素、槲皮素、山奈酚、异鼠李素、芹菜素）的酸水解提取工艺,评价其体外抗氧化和α-葡萄糖苷酶抑制活性,本文利用UPLC-MS/MS法测定天山茶藨茎5种黄酮苷元的提取率,通过单因素实验和正交试验优化天山茶藨茎黄酮苷元酸水解提取工艺。利用DPPH、ABTS自由基清除实验测定天山茶藨茎提取物及5种黄酮苷元的抗氧化活性,并测定了其α-葡萄糖苷酶抑制活性。结果表明,5种黄酮苷元的检出限、定量限分别在0.8~1.6、2.9~5.4 μg/L,在3.2~207.0 μg/L范围内具有良好的线性关系（R2≥ 0.9962）,方法的稳定性、精密度和重复性良好（RSD≤4.4%）。确定最佳酸水解提取工艺为:90%甲醇溶液（含5%盐酸）、提取温度:70℃、提取时间:100 min,该条件下,总黄酮苷元提取率为4.06 mg/g,RSD<5%,表明正交试验优化的提取条件稳定可行。天山茶藨茎提取物及5种黄酮苷元均具有一定的α-葡萄糖苷酶抑制活性和抗氧化活性,其中甲醇盐酸提取物与5种黄酮苷元的α-葡萄糖苷酶抑制活性均高于阳性对照阿卡波糖（IC₅₀:53.84±2.41 mg/L）,槲皮素对DPPH自由基的清除活性最好（IC₅₀:（2.94±0.18） mg/L）,木犀草素、山奈酚对ABTS自由基清除活性较好（IC₅₀分别为（5.34±0.10）、（5.55±0.17） mg/L）,它们的抗氧化活性高于阳性对照V_C。本研究建立的UPLC-MS/MS方法灵敏、精确、高效,可以对天山茶藨茎5种黄酮苷元化合物同时进行定量分析。优化的酸水解提取工艺能有效提高天山茶藨茎黄酮苷元的提取率。     

Chemical variability in propolis from Santiago del Estero,Argentina, related to the arboreal environment as the sources of resins

BACKGROUND: Propolis composition is extremely variable and depends on the plant resin sources that grow around the apiary. Polyphenols have been reported to be responsible of its pharmacological and biological properties. The contents of polyphenols and flavonoid aglycones were studied in propolis from different provenances to correlate these contents with the nature of the flora surrounding the hive. RESULTS: Nineteen of these bioactive substances were identified in 30 samples classified into three arboreal categories according to their main species. A noticeable variability was observed in the concentration of each component depending on the plant origin of the samples. Higher amounts were found for pinocembrin (0.2–102.3 g kg^?1), quercetin (0.08–86.6 g kg^?1) and chrysin (0.8–18.8 g kg^?1). Salicylic, 4‐hydroxybenzoic, benzoic, ferulic and gallic acids were other remarkable constituents. CONCLUSION: Statistical significant differences in polyphenol and flavonoid contents were observed among arboreal groups, while very strong linear correlations were found between polyphenol and flavonoid contents for all the samples as well as for all the groups (R²% > 87). Copyright © 2009 Society of Chemical Industry