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Analysis of phenolic acids and flavonoids in honey

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Abstract

Honey is rich in phenolic acids and flavonoids, which exhibit a wide range of biological effects and act as natural antioxidants. The analysis of polyphenols has been regarded as a very promising way of studying floral and geographical origins of honeys. This review surveys recent literature on determination of these active compounds in honey. The analytical procedure to determine individual phenolic compounds involves their extraction from the sample matrix, analytical separation and quantification. We pay particular attention to sample pre-treatment and separation techniques (e.g., high-performance liquid chromatography and electrophoresis).

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... Honey is a bee-derived natural food item and the nutritive value of this supersaturated natural product as well as its prophylactic medicinal value have been known for many years (Kassim et al. 2010;Mohamed et al. 2010). This unique food product is rich in minerals, carbohydrates, organic acids, phenolic acids, flavonoids, vitamins, enzymes and other proteins (Pyrzynska and Biesaga 2009;Lachman et al. 2010). Its phenolic acids and flavonoids act as natural antioxidants (Pyrzynska and Biesaga 2009;Lachman et al. 2010). ...
... This unique food product is rich in minerals, carbohydrates, organic acids, phenolic acids, flavonoids, vitamins, enzymes and other proteins (Pyrzynska and Biesaga 2009;Lachman et al. 2010). Its phenolic acids and flavonoids act as natural antioxidants (Pyrzynska and Biesaga 2009;Lachman et al. 2010). Due to its composition, honey is important for human nutrition and traditional medicine (Al-Mamary 2002). ...
... The results of in vitro antibacterial activity assays (AWD, MIC and MBC) are given in Ta-ble 4. Bobiş et al. (2013) reported that antimicrobial activity of unifloral honey samples lies between 0 mm and 12 mm for Escherichia coli. The analysis of pollen types can be helpful in determining the flower and geographical origins of honeys (Pyrzynska and Biesaga 2009). In another study with 24 honey samples collected from the Siirt region, the average pollen value was found 22 506 and the total pollen number between 2 086 and 55 710, and the pollen composition of the honey samples was defined as relatively rich (Gürbüz et al. 2019). ...
Article
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Honey is an important functional food for human health and nutrition that is collected by honey bees and stored in the honeycombs. In this study, total phenolic content, antioxidant activity and volatile compounds of 13 different honey samples collected from various districts of Malatya province were investigated. As a result of this study, it was determined that the total phenolic content varied between 8.50 mg GAE 100 g<sup>–1</sup> and 73.90 mg GAE 100 g<sup>–1 </sup>and it was observed that the honey samples were rich in aldehydes, aliphatic acid and esters, alcohols, hydrocarbons, carboxylic acid esters, ketones, terpenes, fatty acids and esters. In addition, the antibacterial effects of honey samples were determined against 18 different pathogenic bacteria using agar well diffusion (AWD) method, minimum inhibitory concentration (MIC) and minimum bactericidal concentration (MBC). In AWD assay, it was recorded that inhibition zone diameters varied between 9 mm and 14 mm and honey samples were found to have a partial inhibitory effect against selected target pathogens.
... Honey, being used for nutritional and functional properties since ancient times (Isla et al., 2011), could establish itself as a potential substitute to the common sugars. Honey is a rich source of several health-beneficial constituents and many of these constituents like polyphenols have antioxidative properties (Pyrzynska & Biesaga, 2009). However, the processing of complex mixtures like honey for invariable product quality and providing an improved product appeal has remained a real challenge for the processing industries. ...
... The loss in TPC was, however, relatively less (about 19%) at the 15% honey level when ET was increased from 120 to 180°C at 14%FM. This reduction in TPC loss could be attributed to the contribution of phenolics from increased addition of honey as honey contains significant amounts of phenolic compounds(Isla et al., 2011;Pyrzynska & Biesaga, 2009). Results of this investigation outline that extrusion of WWF-honey at 180°C is highly detrimental for phenolic substances.3.7.2 | Antioxidant activityHoney level and ET both significantly (p < .05) ...
... AOA of snacks increased by about 38% and 45% with an increase in honey level from 5% to 15% when extrusion was performed at 120 and 180°C temperature, respectively. This improvement in AOA due to the increased addition of honey establishes that honey is a rich source of phenolics and contributes to AOA of foods incorporated with it as many studies(Isla et al., 2011;Pyrzynska & Biesaga, 2009) have reported in past. Contrarily,Bhat et al. (2019) reported a significant decrease in DPPH radical scavenging activity during extrusion of lycopene-enriched WWF which could be due to thermal-induced destruction of heat-labile lycopene. ...
Article
This investigation aimed to evaluate extrusion conditions and honey on whole wheat flour-based functionally expanded snacks using response surface methodology with feed moisture (FM), temperature (ET), and honey level as independent processing variables. Mathematical models with high statistical significance were obtained by fitting data in second-order polynomial equations. Honey addition reduced sectional expansion ratio (SER), increased bulk density (BD), and hardness of snacks. FM and ET had a curvilinear effect on SER, BD, and hardness. Lightness value decreased while redness and yellowness increased with increasing honey level and ET. Honey addition beyond the threshold level suppressed the snack's overall acceptability. The optimized conditions obtained by numerical optimization were 16.50% FM, 151.33°C ET, and 12.83% honey level. Honey addition increased the total phenolic content and antioxidant activity (AOA) of extruded snacks, while ET had a detrimental effect. Extrusion processing enhanced the AOA and augmented the formation of hydroxymethyl furfurals with honey addition.
... One important group of biologically active molecules in honey is polyphenols [6], which have a broad spectrum of biological activity and are natural antioxidants [7]. Phenolic compounds, including phenolic acids, are secondary metabolites of plants and fungi that protect against environmental factors such as UV radiation, viruses and bacteria. ...
... The phenol composition of honey depends primarily on its botanic origin [2], and the quantity of phenolic compounds can vary depending on the season of the year, climatic conditions and processing factors [16]. Comparison of results obtained for the polyphenol composition of honey can be difficult due to its complex matrix, the low concentrations of these compounds and differences in their analysis and presentation [7]. The results presented here are consistent with those obtained by Wilczyńska [17], who noted the highest content of p-hydroxybenzoic acid (12.99 mg/kg) and p-coumaric acid (6.20 mg/kg) in buckwheat honey. ...
Article
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The study compared the content of eight phenolic acids and four flavonoids and the antioxidant activity of six Polish varietal honeys. An attempt was also made to determine the correlations between the antioxidant parameters of the honeys and their polyphenol profile using principal component analysis. Total phenolic content (TPC), total flavonoid content (TFC), antioxidant activity (ABTS) and reduction capacity (FRAP) were determined spectrophotometrically, and the phenolic compounds were determined using high-performance liquid chromatography (HPLC). The buckwheat honeys showed the strongest antioxidant activity, most likely because they had the highest concentrations of total phenols, total flavonoids, p-hydroxybenzoic acid, caffeic acid, p-coumaric acid, vanillic acid and chrysin. The principal component analysis (PCA) of the data showed significant relationships between the botanic origin of the honey, the total content of phenolic compounds and flavonoids and the antioxidant activity of the six Polish varietal honeys. The strongest, significant correlations were shown for parameters of antioxidant activity and TPC, TFC, p-hydroxybenzoic acid, caffeic acid and p-coumaric acid. Analysis of four principal components (explaining 86.9% of the total variance), as a classification tool, confirmed the distinctiveness of the Polish honeys in terms of their antioxidant activity and content of phenolic compounds.
... Association zone 16 (26,703,951-27,146,370 bp) linked to 1-phenylethyl acetate (R) contains two candidate genes coding for: a "Chalcone synthase 2" and a "3-ketoacyl-CoA thiolase 2, peroxisomal." Chalcone synthases participate in the flavonoid and isoflavonoid biosynthesis pathway that follows the degradation of phenylalanine to CA (Pyrzynska and Biesaga, 2009). A ketoacyl-Coa thiolase is required for the synthesis of benzoyl-CoA (Amano et al., 2018), which can be the basis for phenylbenzoate synthesis. ...
... 2-hydroxyisoflavanone is part of the isoflavonoid biosynthesis pathway. Its transformation could compete with the synthesis of compounds known to have a floral taste such as acetophenone or 2-phenylethanol (Pyrzynska and Biesaga, 2009). The association zone 18 (28,257,730-28,352,788 bp) linked to 1-phenylethyl acetate (R) contains a gene coding for a "Probable aldo-keto reductase 1." ...
Article
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Nacional is a variety of cocoa tree known for its "Arriba" aroma characterised mainly by fruity, floral, and spicy aromatic notes. In this study, the genetic basis of the fruity aroma of modern Nacional cocoa was investigated. GWAS studies have been conducted on biochemical and sensorial fruity traits and allowed to identify a large number of association zones. These areas are linked to both the volatile compounds known to provide fruity flavours and present in the beans before and after roasting, and to the fruity notes detected by sensorial analysis. Five main metabolic pathways were identified as involved in the fruity traits of the Nacional population: the protein degradation pathway, the sugar degradation pathway, the fatty acid degradation pathway, the monoterpene pathway, and the L-phenylalanine pathway. Candidate genes involved in the biosynthetic pathways of volatile compounds identified in association areas were detected for a large number of associations.
... Association zone 16 (26,703,951 -27,146,370bp) linked to 1-phenylethyl acetate (R) contains two candidate genes coding for: a "Chalcone synthase 2" and a "3-ketoacyl-CoA thiolase 2, peroxisomal". Chalcone synthases participate in the flavonoid and isoflavonoid biosynthesis pathway that follows the degradation of phenylalanine to cinnamic acid (Pyrzynska and Biesaga, 2009). A ketoacyl-Coa thiolase is required for the synthesis of benzoyl-CoA (Amano et al., 2018). ...
... 2-hydroxyisoflavanone is part of the isoflavonoid biosynthesis pathway. Its transformation could compete with the synthesis of compounds known to have a floral taste such as acetophenone or 2-phenylethanol (Pyrzynska and Biesaga, 2009 (Hao et al., 2014). This function may explain the associations with acetophenone, which requires a common benzyl alcohol precursor for synthesis. ...
Thesis
Theobroma cacao est un arbre originaire des régions tropicales humides d’Amérique latine. Il est cultivé pour ses fèves qui permettent la production de chocolat. Le Nacional, originaire d’Equateur, est une variété de cacao fin connue pour ses arômes floraux et épicées, appelée saveur « Arriba ». Les mécanismes de la synthèse de ses arômes restent peu connus. Les travaux de cette thèse ont porté sur l’étude des déterminants génétiques et biochimiques des arômes des cacaos fins équatoriens afin d’initier de contribuer aux connaissances dans ce domaine.Une première partie de l’étude a été réalisée à partir d’une population de cacaoyer de type Nacional moderne, qui est la variété de Nacional actuellement cultivée. Des études d’associations ont été réalisées sur l’ensemble du génome (GWAS) et ont porté sur l’analyse des composés volatils relatifs aux arôme floraux et fruités (fruits frais et fruits secs) contenus dans les fèves, avant et après torréfaction, ainsi que, sur des résultats d’analyses sensorielles de liqueurs. Cette première étude a pu montrer que les arômes floraux du Nacional étaient principalement synthétisés grâce à deux voies de biosynthèse: celle des monoterpènes et la voie de dégradation du L-phénylalanine. Les résultats relatifs aux arômes fruités ont permis de mettre en lumière cinq voies métaboliques majeures: la voie de biosynthèse des monoterpènes, les voies de dégradations du L-phénylalanine, des sucres, des acides gras et des protéines. Des gènes candidats codant pour des enzymes impliqués dans ces voies métaboliques ont été identifiés dans les zones d’associations correspondantes.La variété Nacional moderne est issue de diverses générations de croisements entre des Trinitario (hybrides Amelonado/Criollo) et le Nacional ancestral, mettant ainsi en jeu 3 ancêtres contrastés. L’effet de cette étape de domestication récente sur les arômes de la variété Nacional moderne a été étudié. Grâce aux données de génotypage des trois ancêtres de référence et aux résultats des GWAS portant sur l’ensemble des caractères de qualité (composés volatils et non-volatils, analyses sensorielles), il a été possible de déterminer l’origine des allèles ayant un effet positif sur les arômes dans les différentes zones d’associations. Cette étude a montré que l’ensemble des ancêtres fondateurs ont apporté des allèles favorables à la synthèse d’arômes de qualité (floraux, fruités, …) mais aussi à la synthèse de défauts (amertume, astringence, …). Nous avons pu montrer que les zones d’associations en lien avec les arômes de qualité et celles avec les défauts n’étaient pas liées génétiquement. Il est donc possible de sélectionner les zones d’intérêts pour les arômes tout en contre-sélectionnant les zones apportant des défauts.La deuxième partie de cette étude a porté sur l’analyse des arômes d’une population de cacaoyers natifs d’Amazonie et issus de la zone d’origine de la variété Nacional ancestral. Dans cette étude, des analyses GWAS ont également été effectuées sur l’ensemble des caractères de qualité analysés précédemment. Quatre vingt dix sept gènes candidats sont communs aux deux populations analysées. De nouveaux composés volatils ainsi que de nouvelles zones d’associations ont également été détectées montrant ainsi une plus grande diversité et richesse aromatique de ces nouvelles ressources génétiques et leur intérêt pour la création de nouvelles variétés aromatiques adaptées à l’Amazonie.Enfin, une étude GWAS sur les composés non-volatils, les caractères sensoriels liés à l’amertume et à l’astringence, ainsi que la teneur en matière grasse et en protéines, a également été réalisée sur les deux populations. Des gènes candidats en lien avec la voie de biosynthèse de la caféine et celle des polyphénols, ou en lien avec la voie de biosynthèse des acides gras ont pu être observés dans les zones d’associations.
... From a compositional point of view, honey is a highly concentrated solution of complex mixture of sugars: fructose (38%), glucose (31%), water (17%), maltose (7%), as well as trisaccharides, other higher carbohydrates, sucrose, minerals, vitamins, and enzymes. Its composition depends strongly on the plant species from which the nectar or the honeydew was collected, and other factors, such as postharvest treatments, geographical, environmental or climate conditions [2,3]. Honey is among the top ten foods with the highest adulteration rate in the European Union, that implies a detrimental to its quality and consumers safety [4]. ...
... Phenolic compounds are secondary metabolites of plants generally involved in their defense against ultraviolet radiation or pathogens and have been recognized as the main responsible for the antioxidant activity of honey [11][12][13]. The most abundant phenol-types in honey are flavonoids, especially flavones and flavanols, as well as phenolic acids derived from benzoic and cinnamic acids [2,14]. ...
Article
Honey is a natural product well known for its beneficial properties. It contains phytochemicals, a wide class of nutraceuticals found in plants, including compounds with highly demonstrated antimicrobial and antioxidant capacities as phenolic compounds and flavonoids. The main goal of this work is the development of a miniaturized and environmentally friendly methodology to obtain the phenolic profile of Galician honeys (Northwest Spain) from different varieties such as honeydew, chestnut, eucalyptus, heather, blackberry and multi-floral. The total phenolic content (TPC) and antioxidant activity (AA) were also evaluated. As regards sample preparation, miniaturized vortex (VE) and ultrasound assisted extraction (UAE) employing aqueous-based solvents were performed. Individual quantification of 41 target phenolic compounds was carried out by liquid chromatography-tandem mass spectrometry (LC-MS/MS). Results revealed the presence of 25 phenolic compounds in the 91 analyzed samples, reaching concentrations up to 252 µg g-1. Statistical tools such as analysis of variance (ANOVA) and principal component analysis (PCA) were employed to obtain models that allowed classifying the different honeys according to their botanical origin. Obtained results, based on TPC, AA and ∑phenolic compounds showed that significant differences appeared depending on the honey variety, being several of the identified phenol compounds being responsible of the main differentiation.
... Phenolic compounds (phenolic acids and flavonoids) are the secondary components of plants [9] that transfer to honey through nectar, pollen, or propolis by bees [10]. ey are responsible for the most antioxidant activity in honey [11]. ...
... e scavenging activities of the honey samples were measured by DPPH assay as described by Meda et al. [21] with slight modifications. A 400 mg of honey sample was mixed with different amounts of methanol (3,6,9,12, and 15 mL) separately. en, 0.75 mL of honey in methanol was mixed with 1.5 mL of DPPH solution. ...
Article
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Stingless bee honey is a good source of antioxidants, which is attributed to the phenolic compounds. The type and concentration of phenolic compounds in honey can be affected by botanical origin. Therefore, in this study, Heterotrigona itama honey from three botanical origins (gelam, acacia, and starfruit) was evaluated for its antioxidant activity and profile of phenolic compounds. Apis mellifera honey was used as a comparison. Antioxidant activity and profile of phenolic compounds in honey were determined using spectrophotometric and chromatographic methods, respectively. The total phenolic content (TPC), total flavonoids content (TFC), free radical scavenging activity (IC50), and ferric reducing antioxidant power (FRAP) of H. itama were ranged between 52.64 and 74.72 mg GAE/100 g honey, 10.70–25.71 mg QE/100 g honey, 11.27–24.09 mg/mL, and 77.88–164.88 µmol FeSO4.7H2O/100 g honey, respectively. The findings showed that the antioxidant activity and phenolic and flavonoid contents in H. itama honey were significantly higher than Apis honey. Benzoic acid and taxifolin were found as the predominant phenolic acid and flavonoid in all samples. However, chrysin was significantly highest in Apis honey than stingless bee honey. This result suggested that chrysin can be used as a chemical marker to distinguish Apis honey from stingless bee honey. Gallic acid and ellagic acid were found as the chemical marker for gelam honey, salicylic acid, benzoic acid, and 4-hydroxybenzoic acid for starfruit honey while ferulic acid for acacia honey.
... Association zone 16 (26,703,951-27,146,370 bp) linked to 1-phenylethyl acetate (R) contains two candidate genes coding for: a "Chalcone synthase 2" and a "3-ketoacyl-CoA thiolase 2, peroxisomal." Chalcone synthases participate in the flavonoid and isoflavonoid biosynthesis pathway that follows the degradation of phenylalanine to CA (Pyrzynska and Biesaga, 2009). A ketoacyl-Coa thiolase is required for the synthesis of benzoyl-CoA (Amano et al., 2018), which can be the basis for phenylbenzoate synthesis. ...
... 2-hydroxyisoflavanone is part of the isoflavonoid biosynthesis pathway. Its transformation could compete with the synthesis of compounds known to have a floral taste such as acetophenone or 2-phenylethanol (Pyrzynska and Biesaga, 2009). The association zone 18 (28,257,730-28,352,788 bp) linked to 1-phenylethyl acetate (R) contains a gene coding for a "Probable aldo-keto reductase 1." ...
Article
Full-text available
Theobroma cacao is the only source that allows the production of chocolate. It is of major economic importance for producing countries such as Ecuador, which is the third-largest cocoa producer in the world. Cocoa is classified into two groups: bulk cocoa and aromatic fine flavour cocoa. In contrast to bulk cocoa, fine flavour cocoa is characterised by fruity and floral notes. One of the characteristics of Nacional cocoa, the emblematic cocoa of Ecuador, is its aromatic ARRIBA flavour. This aroma is mainly composed of floral notes whose genetic and biochemical origin is not well-known. This research objective is to study the genetic and biochemical determinism of the floral aroma of modern Nacional cocoa variety from Ecuador. Genome-Wide Association Study (GWAS) was conducted on a population of 152 genotypes of cocoa trees belonging to the population variety of modern Nacional. Genome-Wide Association Study was conducted by combining SSR and SNP genotyping, assaying biochemical compounds (in roasted and unroasted beans), and sensory evaluations from various tastings. This analysis highlighted different areas of association for all types of traits. In a second step, a search for candidate genes in these association zones was undertaken, which made it possible to find genes potentially involved in the biosynthesis pathway of the biochemical compound identified in associations. Our results show that two biosynthesis pathways seem to be mainly related to the floral note of Nacional cocoa: the monoterpene biosynthesis pathway and the L-phenylalanine degradation pathway. As already suggested, the genetic background would therefore appear as largely explaining the floral note of cocoa.
... De acuerdo con Bertoncelj (2011), los perfiles de flavonoides de mieles están determinados por su origen botánico y geográfico, así como por las condiciones climáticas de la zona. Por lo tanto, la identificación y cuantificación de sustancias fenólicas, podría ser no solamente un marcador del origen floral sino también un indicador potencial de su calidad biológica no sólo por sus propiedades antibacteriana, antiinflamatoria, anti-oxidante, anti-cancerígena, anti-trombótica y anti-hiperlipidémica (Pyrzynska et al., 2009;Rao et al., 2016), sino también como aditivo que permita mantener la inocuidad y prevenir el deterioro de los alimentos, disminuyendo con ello los casos de enfermedades transmitidas por alimentos (ETA), así como la pérdida y desperdicio alimentario. Sin embargo, a menos que los componentes responsables de cualquiera de estas propiedades sean identificados y estandarizados, entonces cualquier resultado obtenido no podrá atribuirse a este producto en general (Molan, 2012). ...
... Phenolic compounds of honey behave as antioxidants in a variety of ways, including the direct trapping of reactive oxygen species (ROS), inhibition of enzymes responsible for producing superoxide anions, chelation of transition metals involved in the process of forming radicals, and prevention of the peroxidation process by reducing alkoxyl and peroxyl radicals (Pyrzynska & Biesaga, 2009). Several studies observed a correlation between total phenolic content (TPC) and antioxidant activity, suggesting that phenolic compounds are the main compounds responsible for that bioactive property. ...
Article
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Honey is a natural food of worldwide economic importance. Over the last decades, its potential for food, medical, cosmetical, and biotechnological applications has been widely explored. One of the major safety issues regarding such applications is its susceptibility to being contaminated with bacterial and fungi spores, including pathogenic ones, which may impose a hurdle to its consumption in a raw state. Another factor that makes this product particularly challenging relies on its high sugar content, which will lead to the formation of hydroxymethylfurfural (HMF) when heated (due to Maillard reactions). Moreover, honey's bioactivity is known to be affected when it goes through thermal processing due to its unstable and thermolabile components. Therefore, proper food processing methodologies are of utmost importance not only to ensure honey safety but also to provide a high‐quality product with low content of HMF and preserved biological properties. As so, emerging food processing technologies have been employed to improve the safety and quality of raw honey, allowing, for example, to reduce/avoid the exposure time to high processing temperatures, with consequent impact on the formation of HMF. This review aims to gather the literature available regarding the use of conventional and emergent food processing technologies (both thermal and nonthermal food processing technologies) for honey decontamination, preservation/enhancement of honey biological activity, as well as the sensorial attributes.
... In addition, melanoidins, products of the Maillard reaction, were described as the main components responsible for the radical-scavenging capacity of honey [61,62]. These substances reduce the adverse effects of reactive oxygen species (ROS) and reactive nitrogen species (RNS), inhibit the enzymes responsible for producing superoxide anions, act as metal chelators, and interfere in the chain reactions of free radicals and can play a preventative role in the process of their formation [63]. Through these antioxidant mechanisms, honey contributes to wound and burn healing by interfering with abnormal inflammatory response [6]. ...
Article
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Honey is a natural product rich in several phenolic compounds, enzymes, and sugars with antioxidant, anticarcinogenic, anti-inflammatory, and antimicrobial potential. Indeed, the development of honey-based adhesives for wound care and other biomedical applications are topics being widely investigated over the years. Some of the advantages of the use of honey for wound-healing solutions are the acceleration of dermal repair and epithelialization, angiogenesis promotion, immune response promotion and the reduction in healing-related infections with pathogenic microorganisms. This paper reviews the main role of honey on the development of wound-healing-based applications, the main compounds responsible for the healing capacity, how the honey origin can influence the healing properties, also highlighting promising results in in vitro and in vivo trials. The challenges in the use of honey for wound healing are also covered and discussed. The delivery methodology (direct application, incorporated in fibrous membranes and hydrogels) is also presented and discussed.
... (Hermanns et al., 2020) Numerous compounds contribute to the marked antioxidant and anti-inflammatory activity, such as flavonoids, phenolic acids, tocopherols, ascorbic acid, and enzymes, including catalase (CAT) or superoxide dismutase (SOD) and Maillard reaction like products, such as MGO. (Al-Mamary et al., 2002;Brudzynski and Miotto, 2011;Pyrzynska and Biesaga, 2009) Components of honey can act as a danger signal and activate the immune system via TLR4 signaling. Exposure of macrophages to honey promotes pro-inflammatory cytokines release, unrelated to possible LPS contamination. ...
Article
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Hospital-acquired infections and treatment-related wound complications constitute a tremendous burden for the health care system, particularly given the serious increase in multidrug resistant pathogens. Imagine that a large part of nosocomial infections can be prevented using a simple treatment. In this respect, honey is used mainly in topical cutaneous wound care because of its potent broad-spectrum antibacterial and wound healing activities. However, therapeutic use outside this scope has been limited. The current review provides an in-depth view of studies using honey outside the conventional wound care indications. Non-conventional routes of honey application include subcutaneous, intra-socket, abdominal, and oral administration in novel indications, such as post colon surgery, mucositis, and tooth extraction. Honey consistently demonstrates beneficial therapeutic activities in these novel applications, orchestrating antimicrobial and prophylactic activity, reducing inflammation and wound dehiscence, and inducing healing, epithelialization, and analgesic activity. Several molecular mechanisms are responsible for these beneficial clinical effects of honey during the course of wound healing. Pro-inflammatory effects of honey, such as induction of iNOS, IL-1β, and COX-2, are mediated by TLR4 signaling. In contrast, honey's anti-inflammatory actions and flavonoids induce anti-inflammatory and antioxidant pathways by inducing NRF2 target genes, including HO-1 and PRDX1. The molecular and biochemical pathways activated by honey during the different phases of wound healing are also discussed in more detail in this review. Variation between different honey origins exists, and therefore standardized medical-grade honey may offer an optimized and safe treatment. Honey is a valuable alternative to conventional antimicrobial and anti-inflammatory therapies that can strongly reduce nosocomial infections.
... Ferulic acid (FA) is considered an ubiquitous phytochemical molecule that plays a key role in the rigidity of plant wall cells [7,8]. Moreover, these two phenolic acids are widely present in fruits [9], vegetables [10], olive oil [11], microalgae [12], propolis [13] and honey [14]. Also, microorganisms, such as yeasts, have been metabolically engineered to synthesize these dietary phenolic acids in order to improve their production [15]. ...
Article
Polyvinylpyrrolidone (commonly known as povidone or PVP) rapidly dissolves in water. This significantly hinders its use in sustained release formulations developed for the biomedical field. Electrospun fibers of PVP dissolve even faster due to larger surface to volume ratio. In this work, we propose a way to circumvent this problem by developing and using functional fibrous materials in hydrogel form. In particular, we demonstrate that ethanolic solutions of PVP containing two hydroxycinnamic acid derivatives, namely p-coumaric and ferulic acids could be electrospun into functional hydrogel fiber mats. After electrospinning, the formed composite mats were first thermally treated at 130°C for 20 hours and subsequently were immersed in aqueous media, where they turned into hydrogels. Thermal annealing did not degrade hydroxycinnamic acid derivatives, preserving their functionality. We propose these hydrogel fiber mats as potential wound dressings and to that end, in vitro tests showed up to 8 days of antioxidants’ release, and consequent protection of A549 epithelial cells against oxidative stresses. Biocompatibility tests using human red blood cells and A549 and HaCaT cell lines indicated no adverse effects. Model studies of mice skin burns induced by UV-B radiation showed that the hydrogel fiber dressings significantly reduced the levels of matrix metallopeptidase, (MMP-9), and glutathione peroxidase 1 (GPX-1), which are usually upregulated by reactive oxidative species on burnt skin. Finally, ex-vivo human skin investigations demonstrated skin regeneration and control of the inflammatory phase as indicated by low levels of pro-inflammatory cytokines (IL-6 and IL-8). Therefore, our outcomes indicate that the developed PVP-based fiber hydrogels, produced using a simple protocol, are promising candidates for active wound dressings.
... Myriad enzymes are also commonly detected in honey, such as diastase (amylase), invertase and glucose oxidase, which contribute to the therapeutic effect of honey [5,8,13]. Antioxidant compounds such as flavonoids (quercetin and kaempferol) and phenolic acids (vanillic acid, gallic acid and syringic acid) contribute to the antioxidative property of honey [14] by quenching of reactive oxygen species (ROS), thereby preventing free radical formation [15,16]. Oxidative stress (OS) is neutralised following HS as it increases the glutathione peroxidase (GPx), reduces glutathione (GSH), superoxide dismutase (SOD) and nitric oxide (NO) levels [17]. ...
Article
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Phytochemical contents of honey are presumed to be beneficial to the female reproductive system (FRS). However, the biological effects of honey supplementation (HS) in vivo on the FRS remain unclear. This review aims to investigate the current literature on the effects of HS on the FRS, particularly on the sex hormone profile and reproductive organs (uterus and vagina). A systematic literature search using Scopus, MEDLINE via Ovid and Cochrane Library databases was conducted. Records were screened and identified for preclinical and clinical studies addressing the effects of HS on the FRS. Data on populations, interventions, outcomes and methodological quality were extracted. Studies were synthesised using tables and written summaries. Of the 198 identified records, six fulfilled the inclusion criteria. All six records were used for data extraction: two experimental studies using rats as the model organism and four human clinical studies of honey on female reproductive health. HS elevated the progesterone levels, restrained body weight increase, prevented uterine and vaginal atrophies in ovariectomised rats, attenuated symptoms of candidiasis and improved oxidative status in patients. Current evidence shows that short-term HS following surgical or physiological menopause exerts an oestrogenic, antioxidant and anti-inflammatory effect on the FRS. However, insufficient long-term studies preclude any definitive conclusions.
... In addition, honey is a natural source of flavonoids and phenolic acids, which are important organic compounds distinguishing honey from edible syrup. The polyphenols are regarded as the potential markers of studying the origins of honeys [2]. Although different kinds of honey exhibit wide variations in their compositions, all the honey is primarily composed of sugar and water (more than 90% in total). ...
Article
The laser-induced fluorescence (LIF) technique, which has been widely used for food testing, can be combined with various algorithms to classify and recognize different kinds of honey. This paper proposes the Kolmogorov-Smirnov test-Gaussian mixture model (KS-GMM) algorithm, which is coupled with the LIF technique to realize accurate classification and recognition of different types of pure honey. The experiments are designed and carried out to obtain a set of LIF spectrum data from various honey and syrup samples. The proposed KS-GMM algorithm is applied for classification and recognition, with GMM, k-nearest neighbor (kNN), and decision tree algorithms as cross-validation methods. By comparing recognition results of training sets containing different amounts of data, it is found that the KS-GMM algorithm exhibits a maximum recognition accuracy of 96.52%. The research results prove that the KS-GMM algorithm outperforms, to the best of our knowledge, the other three algorithms in classifying and recognizing the honey types.
... Because of the limitations of pollen analysis, attempts have been made to predict the botanical origin of honeys and eventually to classify them by analysing their physicochemical parameters [4][5][6][7][8][9] or by combining the pollen analysis with the sensory control and the physicochemical analysis. [10][11][12][13][14][15] Several authors have also determined volatile markers to authenticate monofloral honeys, such as the compound methyl anthranilate for citrus honeys, [16][17][18] while others have used non-volatile compounds, such as phenolic compounds [19][20][21] and amino acids. 17 Lastly, multivariate analysis has been proved to be a useful statistical tool for the characterization and classification of honeys, both botanically and geographically. ...
Article
BACKGROUND Although the main method for monofloral honeys’ authentication is pollen analysis, other classification approaches have been also applied. However, the majority of the existing classification models so far have utilised a few honey types or a few honey samples of each honey type, which can lead to inaccurate results. Aiming at addressing this, the present study's goal was to create a classification model by analysing in total 250 honey samples from 15 different monofloral honey types in ten physicochemical parameters and then, multivariate analysis (MANOVA, PCA and MDA) was applied in an effort to distinguish and classify them. RESULTS Electrical conductivity and colour were found to have the highest discriminative power, allowing the classification of monofloral honey types, such as oak, knotgrass and chestnut honey, as well as the differentiation between honeydew and nectar honeys. The classification model had a high predictive power, as the 84.4% of the group cases was correctly classified, while for the cases of chestnut, strawberry tree and sunflower honeys the respective prediction was correct by 91.3%, 95% and 100%, allowing further determination of unknown honey samples. CONCLUSION It seems that the characterisation of monofloral honeys based on their physicochemical parameters through the proposed model can be achieved and further applied on other honey types. The results could contribute to the development of methodologies for the determination of honey's botanical origin, based on simple techniques, so that these can be applied for routine analysis. This article is protected by copyright. All rights reserved.
... Flavonoids are the key phenolic compounds found in honey: pinobanksin, quercetin, pinocembrin, galangin, chrysin, kaempferol, and luteolin. (Pyrzynska & Biesaga, 2009;Saranraj & Sivasakthi, 2018). ...
Thesis
The health benefits of honey as an oral therapeutic agent for the treatment of diarrhea caused by Shigella sonnei, Escherichia coli and Salmonella typhimurium depend on their ability to withstand human gastrointestinal conditions. Most of the previous studies regarding the antibacterial potential of honey against enteric pathogens were performed in agar well diffusion assays or dilution assays using standard media. However, no studies are available regarding the survival and susceptibility of Shigella sonnei to honey in gastrointestinal simulated conditions. To address this, we initially evaluated the survival of Shigella sonnei in human gastric simulated conditions (GSC) and intestinal simulated conditions (ISC) with food and without food source at 60 and 120 minutes intervals, mimicking the early and late gastric and intestinal emptying. This is followed by the determination of susceptibility of Shigella Sonnei to New Zealand based medically graded Manuka and Saudi Talah honey in such conditions. Colony-forming units (CFU) of Shigella sonnei and minimum inhibitory concentrations (MICs) were calculated at different dilutions for both honeys at 60 and 120 minutes intervals. We, also, determined the antibacterial activity of honeys against bacteria tested by agar well diffusion assay and micro-broth dilution assay in standard media with and without catalase for comparison. Shigella sonnei was unable to survive in the acidic environment of the stomach without the food matrix. However, it survived in the stomach when inoculated with a food source and exhibited (1.5±0.2) ×105colony forming units (CFU) at 60 minutes interval and (1.7±0.3 )×105 (CFU) at 120 minutes incubation when CFU of suspension was 1±×107. However, in intestinal simulated conditions, it survived in both food and without food matrix at the same CFU (1.2×107 ±0.4) at 60 minutes interval and 1.7×107 ±0.2 at 120 minutes interval. No growth of Shigella sonnei was observed in the gastric environment in the presence of both honey at different concentrations without a food source. In the presence of food source, the Manuka honey inhibited the growth of Shigella sonnei at 10% v/v and Talah honey at 20% v/v dilutions in GSC. In ISC, Manuka honey completely inhibited the growth of Shigella sonnei at 15% and 20 % v/v dilutions, whereas Talah honey inhibited at 20% v/v and 25% dilutions without food and with food source respectively. In comparison with a standard in vitro conditions, Manuka honey inhibited the growth of Shigella sonnei at 9% v/v and Talah honey at 20% v/v without enteric simulated conditions and without catalase solution. In the catalase solution, Manuka honey inhibited S. sonnei at 11% v/v and Talah honey at 22% v/v dilutions. We have demonstrated in this study that S. sonnei can survive in the acidic environment of the stomach when inoculated onto the solid food source, whereas the same level of acidity is completely inhibitory to bacteria in a standard acidified broth environment without a food source. Intestinal simulated conditions were not inhibitory to bacterial growth. Both Manuka and Talah honeys inhibited the growth of S. sonnei in gastric and intestinal simulated conditions. However, Manuka honey inhibited the growth of S. sonnei at lower concentrations as compared to Talah honey. The results indicate that the oral administration of honey for the treatment of infectious diarrhea caused by MDR Shigella sonnei could be an effective and safe alternative. However, the percentage of honey required to inhibit the bacterial growth in the human gastrointestinal tract would be slightly higher in comparison with standard media. Further studies are required to evaluate the effectiveness of honey in an in vivo model of infectious diarrhea.
... Along with this, downregulation of Yes-associated protein expression in pancreatic cancer and extrinsic and intrinsic pathway triggering are other mechanisms for its anticancer action [58,59]. In vivo studies of flavonoids like apigenin and chrysin and luteolin found in honey control the proliferation of pancreatic, glioma and aortic vascular smooth muscle cells in rats respectively [60][61][62]. ...
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Background Natural plants and plant-derived formulations have been used by mankind from the ancient period of time. For the past few years, many investigations elaborated the therapeutic potential of various secondary chemicals present in the plants. Literature revealed that the various secondary metabolites, viz. phenolics and flavonoids, are responsible for a variety of therapeutic action in humans. Main body In the present review, an attempt has been made to compile the exploration of natural phenolic compounds with major emphasis on flavonoids and their therapeutic potential too. Interestingly, long-term intake of many dietary foods (rich in phenolics) proved to be protective against the development and management of diabetes, cancer, osteoporosis, cardiovascular diseases and neurodegenerative diseases, etc. Conclusion This review presents an overview of flavonoid compounds to use them as a potential therapeutic alternative in various diseases and disorders. In addition, the present understanding of phenolics and flavonoids will serve as the basis for the next scientific studies.
... Meliponines make great contribution to environmental conservation, as they perform pollination of native plant species and contribute to a reduction in deforestation and environmental damage [4,7]. In addition, they are commercially known for their role in the production of natural products, such as honey, wax, royal jelly, propolis, and geopropolis and accumulation of pollen [3,4,8,9]. ...
... Meliponines make great contribution to environmental conservation, as they perform pollination of native plant species and contribute to a reduction in deforestation and environmental damage [4,7]. In addition, they are commercially known for their role in the production of natural products, such as honey, wax, royal jelly, propolis, and geopropolis and accumulation of pollen [3,4,8,9]. ...
Article
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Cancer is one of the major maladies affecting humankind and remains one of the leading causes of death worldwide. The investigation of the biological activities of stingless bee products, especially propolis and geopropolis, has revealed promising therapeutic properties, especially in the research on new antineoplastic agents. This literature review of preclinical trials, involving biological assays of antitumor activity and identification of the chemical composition of propolis and geopropolis of stingless bee species, describes the cytotoxicity in tumor lineages (breast, lung, ovarian, liver, mouth, pharynx, larynx, colon, stomach, colorectal, cervix, kidney, prostate, melanoma, human glioblastoma, canine osteosarcoma, erythroleukemia, human chronic myelocytic leukemia, and human promyelocytic leukemia) of propolis and geopropolis of 33 species of stingless bees. The chemical composition of propolis and geopropolis was identified, indicating that these belong to the chemical classes of phenolic acids, flavonoids, coumarins, benzophenones, anthraquinones, alkaloids, terpenes, steroids, saponins, fatty acids, and carbohydrates and are possibly responsible for the cytotoxicity in tumor cells. Apoptosis was one of the main mechanisms of cytotoxicity of extracts and substances isolated from stingless bee products. Although the results found are encouraging, other preclinical studies and clinical trials are essential for the discovery of new anticancer agents.
... The issue is that a number of these compounds are known to act as antioxidants (i.e., polyphenols (flavonoids and non-flavonoids), organic acids, vitamins (ascorbic acid), and enzymes (glucose oxidase and catalase)). Many of the honey flavonoids and phenolic acids are known to have antioxidant activity [29]. The amount and type of flavonoids vary depending on the flower source (i.e., botanical origin). ...
Article
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Veterinary drugs could contaminate animal-derived food products for human consumption. Some antibiotic residues (e.g., chloramphenicol (CAP), nitrofuran metabolites) are banned in foodstuffs of animal origin (e.g., milk, honey, etc.) in the European Union because of toxicological risks for the consumer. Screening methods applied for food safety monitoring should be sensitive, specific, cheap, quick, and portable for field testing (e.g., self-control). Electrochemical biosensors make it possible to develop a promising and economically interesting approach. An innovative and cheap electrochemical method based on disposable screen-printed carbon electrodes (SPCE), coupled to magnetic beads (MB), that allows the simultaneous detection of three families of antibiotics in milk was published by a Spanish academic team. When the biosensor method was applied to detect CAP residues in honey, two major issues were identified: firstly, the very low levels of residues to reach (i.e., regulatory limits below 1 µg/kg), and secondly, the complexity of the honey matrix; there is not a single honey matrix. Honey composition and color vary considerably depending on the botanical origin. Moreover, some honey ingredients can interfere with the electrochemical detection, especially substances with antioxidant activities (e.g., polyphenols). Therefore, in parallel with the optimization of the electrochemical method, the reduction of matrix effects was a big challenge.
... [7,10] These antioxidant compounds are often the products of secondary metabolites of plants and enter into honey by the action of the bee families (Apis mellifera) visiting those plants. [11,12] Thus, the amount and type of these antioxidant polyphenol components present in honey mainly depend on its floral source or botanical source. However, the diversity of vegetation (floral variety) where honey bees collect the nectar is directly related to the geographical origin having different ecological and climatic features (weather condition, soil type, rainfall, soil mineral content, and the like). ...
Article
The Amhara region of Ethiopia is endowed with honey of diverse varieties and qualities. However, there is a lack of information on its secondary metabolite content and antioxidant nature. For this study, 47 fresh honey samples were collected from seven administrative zones throughout three provinces in the Amhara National Regional State, Ethiopia. The honey samples’ restorative nature was evaluated by the quantitative determination of phenolic content and antioxidant capabilities using standard colorimetric methods. The finding showed that the mean values of total polyphenol content based on gallic acid equivalent (GAE) ranged from 17.03 to 42.04 mg GAE per 100 g of honey. The mean value of the entire flavonoid content using catechin equivalent (CE) was from 3.20 to 7.40 mg CE, and when using quercetin equivalent (QE), it ranged from 1.67 to 5.08 mg QE, per 100 g of honey sample. The ascorbic acid equivalent antioxidant content (AEAC) of the honey samples – ranged from 16.23 to 26.5 9 mg AEAC per 100 g of the honey samples. The percent antioxidant activities (% AA) of the honey samples—ranged from 23.74 to 40.11%. There was a strong positive correlation between phenolic content and antioxidant properties. Amber-colored honey enjoyed the highest value on the stated parameters based on the samples’ colors, while the white-colored samples registered the least value. Based on the findings, it is concluded that the region’s honey has a magnificent therapeutic nature. Using the principal component analysis (PCA) model, the top three principal components described 96.63% of the total variations. The linear discriminant analysis (LDA) model has an average of 68.1% discriminant power. The LDA model was cross-validated by the leave-one-out cross-validation approach, and 70.21% of it clustered adequately. In the biplot analysis, honey sample distribution based on their color clustered better than the geographic origin and climate factors.
... Our results are in line with those obtained by other authors [61]. Thus, before the administration of the treatment with EOs, the TPC in our honey sample was 110.1 mg-GAE/100 g and increase, after the administration of EOs until 163.95 mgGAE/100 g, in the honey sample treated with basil EO. ...
Article
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Honey is a natural food with pharmacological properties. The present study was focused on the use of essential oils in the supplementary feeding of bee families for three weeks (spring). The purpose was to monitor the effect of essential oils (basil, thyme, juniper, cloves, mint, cinnamon, oregano, rosemary) on the chemical components of the resulting honey. The honey sampling period was carried out before the administration of essential oils in the supplementary feed of the bee families, after the administration of essential oils in the bee feed, respectively, after the first harvest (rapeseed). The honey samples were subjected to chemical analysis to determine humidity, impurities, ash, pH, acidity, total phenolic content (TPC) and flavonoid content (FC), reducing sugar content and antioxidant activity. In addition, the antimicrobial activity against nine strains was tested. We found out that all the essential oils used had a positive effect on the chemical composition of honey, especially the essential oil of oregano, mint, thyme, cinnamon. Experimental variants in which juniper and clove essential oil were introduced reduced the acidity of honey by 28.12% and 35.48%, respectively. Ash content varies between 0.23% and 0.46%, impurities content between 4.11% and 9.11%, while the values for pH were between 3.42 and 4.03. As for the TPC, they have increased considerably in all experimental variants to which essential oil has been added, compared to the batch fed only with sugar syrup, the highest value being recorded for the sample treated with cinnamon after the third harvest (163.94 mg/100 g). The FC values vary between 8.41–44.36 mg/100 g, depending of the treatment applied and the period of harvesting. Regarding the antimicrobial activity, the results highlighted that the essential oils present in the diet of bees produced honey with antimicrobial effect increased after two weeks after administration.
... Honey is well stocked with phenolic acids and flavonoids, which manifest a broad array of its biological effects and serve as naturally occurring antioxidants. The presence of a variety of these compounds makes honey an excellent antioxidant nominee with a similar capacity as many other fruits (Gheldof & Engeseth, 2002;Keskin et al., 2021;Pyrzynska & Biesaga, 2009). ...
... Thereby, the honey is a significant contributor to the phenolic compounds; however, their concentrations depend on the origin and type of honey. At least 5000 flavonoids and phenolic acids have been described in honey using different analytical methods (Pyrzyńska & Biesaga, 2009). The main phenolic compounds in honey include caffeic acid, p-coumaric acid, gallic acid, vanillic acid, syringic acid, chlorogenic acid, and 4-(dimethylamino)benzoic acid; and the dominant flavonoids in honey include apigenin, genistein, pinocembrin, chrysin, quercetin, luteolin, kaempferol, galangin, and pinobanksin (Cianciosi et al., 2018). ...
Article
Background Mead is a traditional alcoholic beverage obtained by fermentation of mead wort and is popularly produced at home and/or in small meaderies. Different types of mead can be distinguished based on honey-to-water ratio, addition of spices and/or fruits, and the method of wort preparation. The consumption of mead has gained popularity in Europe owing to the presence of its natural and high-quality compounds. As a result, mead production has remarkably increased during the past years, and increasing attention has been paid to improve its production parameters. Scope and approach In the first part of this comprehensive review, general aspects of mead production and the characteristic parameters of alcoholic beverages, including organic acid content, pH value, ethanol content, titratable acidity, volatile acidity, and residual sugar content are discussed. In the second part, the aroma profile and sensory acceptability of mead, including parameters that might influence the characteristic aroma of mead, is presented. Key findings and conclusions The flavor of mead mainly depends on the type of honey used for fermentation, and the analysis of odorants is one of the most important criteria in the quality evaluation of mead. In addition, the presence of hydroxymethylfurfural, one of the major Maillard reaction products, and of phenolic compounds is related to the type of honey used. Furthermore, the antioxidant activity of mead significantly correlates with the type and amount of honey used for mead preparation.
... ( White, 1979;Bertoncelj et al., 2007). Fenolik ve flavonoid bileşiklerce zengin olan bal aynı zamanda epidemiyolojik, i kardiyovasküler, ve kanser tedavilerinde de önemli rol oynamaktadır (Al-Habori et al., 2002;Pyrzynska and Biesaga, 2009;Miotto, 2010). ...
... Honey is very rich in polyphenols and the main ones are flavonoids, phenolic acids, and phenolic acid derivatives. These are compounds known to have antioxidant properties (Pyrzynska & Biesaga, 2009). Honey has numerous nutritional and biological effects such as antimicrobial, antiviral, antiparasitic, anti-inflammatory, antimutagenic, anticancer and immunosuppressive activities. ...
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Abstract This review uses an interdisciplinary perspective to examine the eating habits of the Ottomans through the information conveyed in the works of western travelers who came to the Ottoman territory. Travel books, which are the primary sources for Ottoman history, were used to analyze the food consumption habits in Ottoman culinary culture. The impressions of western travelers were taken directly and displayed in quotation marks. Then, within the knowledge of the literature, the Ottoman food culture was interpreted in the context of nutrition and dietetics. During the period of the Ottoman Empire we can see that honey was used as a sweetener in desserts, that barley and rye were preferred in bread making, and half-baked bread, which was traditionally consumed in the Ottoman food culture, was enjoyed. According to the travels books, vegetables, grains, meat, dairy products, and olive oil were among the most consumed foods. The Ottoman Empire incorporated different factors and brought together a unique new culture. As seen, The Ottoman cuisine, which incorporated food from different cultures, owes its wealth to the innovations it developed within its social dynamics. According to travel books, healthy food and nutrition were at the forefront in the Ottoman period.
... It is known that most of the TP compounds (e.g., flavonoids and phenolic acids) in the honey are acidic in character. To date, many phenolic compounds, which are acidic in character, such as gallic acid, chlorogenic acid, caffeic acid, pcoumaric acid, ferulic acid, and ellagic acid were determined in the honey (Pyrzynska and Biesaga, 2009). The acidity of honeys having a high level of TP content can be expected to be high. ...
Article
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In the present study, the physicochemical characteristics and sugar compositions of 14 different honey samples obtained from two different regions of Turkey were analyzed by using multivariate analysis methods. pH, acidity, moisture content (%), total soluble solids (Brix), diastase activity, total phenolic content, and Lugol's reaction analyses of the samples were performed using the physicochemical parameters. Moreover, the fructose, glucose, sucrose, maltose, fructose/glucose, and fructose + glucose values of the samples were determined using HPLC-RI system. It was determined that 1 of 14 samples has been adulterated with maltose syrup and 2 of 14 samples have HMF content higher than the limit set by the law. The honey samples were classified based on their physicochemical characteristics and sugar compositions by making use of the principal component analysis and hierarchical cluster analysis. Moreover, the factors affecting the quality of honey were determined and the relationships between these factors were shown.
Chapter
Honey—an important natural compound and a renowned native food product—is exploited since immemorial times for its medical properties. Its medicinal properties have fascinated the humans so much as it has earned a dominating spot in conventional medicine. Currently more research is going on in exploring the natural compounds present in the honey for promoting human health. Honey contains more than 200 bioactive components besides glucose, fructose, minerals, vitamins, amino acids and enzymes (Da Silva et al., Food Chem 196:309–323, 2016). The composition of honey depends on the type of plants on which honeybee (Apis mellifera) nourishes. Different kinds of phytochemicals present in the honey with high phenolic content, polyphenols and flavonoids mainly contribute to its high medicinal properties including its antioxidant and anticancer action (Iurlina et al., Food Chem 115:1141–1149, 2009; Pyrzynska and Biesaga, TrAC Trends Anal Chem 28:893–902, 2009; Yao et al., Food Chem 81:159–168, 2003). The polyphenolic compounds present in the honey have been found to possesses anti-proliferative effects against various types of cancers (Jaganathan and Mahitosh, J Biomed Biotechnol 2009:830616, 2009). These studies summarized the significant role of the bioactive species present in honey for different diseases. In this review, we critically examine the anticancer properties and molecular mechanisms of different bioactive components present in honey.
Article
We have developed a new method for the rapid (2 h) and inexpensive (materials cost < 0.02 €/sample) “2-in-1” determination of the total phenolic content (TPC) and the antioxidant activity (AOX) in honey samples. The method is based on hydrophilic colorimetric films with diazonium groups, which react with phenols rendering highly colored azo groups. The TPC of the sample is correlated to its trolox equivalent antioxidant capacity (TEAC). The intensity of the color allows us to determine both TPC and TEAC of the sample by the analysis of a picture taken with a smartphone that is analysed by the use of the color-definition-parameters (RGB). The controlled light conditions and the systematic use of the same camera avoid the periodical calibration of the system improving the efficiency of the method. Thus, it is a simple method carried out by non-specialized personnel and it involves much lower money and time investment compared to traditional methods.
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Otitis externa (OE) is an external microbial Meatus acousticus (MAE) infection due to damage to the normal MAE serumen skin coat that protects and maintains MAE moisture and temperature. Living in the warm and humid tropics, a decrease in skin pH due to activity in the water including swimming, and excess cerumen cleaning are predisposing factors for OE. The use of antibiotics locally concentrated in OE can not only attack pathogenic microbes but also have an impact on normal flora so that it has the potential to cause resistant microbes. Honey has anti-bacterial properties without the risk of resistance and has even been shown to modulate immunity and inflammation. Various invivo and invitro studies prove that honey has broad spectrum anti-bacterial activity. Honey is proven invitro to modulate immunity by affecting the release of various inflammatory cytokines. This shows that honey has the potential for OE therapy. This article aims to discuss the potential of honey as a topical OE therapy in the hope that it can be an alternative choice of therapy in the management of OE in humans that is safe, effective, and efficient.
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Strawberry-tree (Arbutus unedo L.) honey is expensive and difficult to characterize by melissopalinology. This study aimed to authenticate strawberry-tree (A. unedo L.) honeys from southern Europe, determining arbutin, groups of polyphenols, volatile and semivolatile compounds, as well as biological activities such as trolox equivalent antioxidant capacity, antioxidant activities against both hydroxyl (AOA) and superoxide radicals (SRS), oxygen radical absorbance capacity, anti-inflammatory activity, and antimicrobial activity against 7 microorganisms (Escherichia coli, Streptococcus mutans, Staphylococcus aureus, Aspergillus flavus, Aspergillus niger, Fusarium sp., and Penicillium commune). Arbutin, analyzed using HPLC-UV, was quantified in 83% of the samples. Polyphenols' contents were high. Norisoprenoids and benzene derivatives were the major compounds determined using gas chromatography-mass spectrometry. Theobromine was detected in 67% of samples. 2,6,6-Trimetyl-4-oxo-2-cyclohexen-1-carboxaldehyde, 3,4,5 trimethylphenol and 2-hydroxycyclopent-2-en-1-one were proposed as potential strawberry-tree floral markers. Antioxidant and anti-inflammatory activities were significant. Honeys’ extracts showed higher AOA and SRS, and better antimicrobial activities than the honeys. This study highlights the potential of strawberry-tree honeys and/or their phenolic extracts for food, pharmaceutical and cosmetic uses.
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In this study, aminated graphene oxide functionalized magnetic nanocomposite (AGMN) was facilely synthesized by one-pot hydrothermal approach and acted as the extraction phase of magnetic solid phase extraction (MSPE) of phenolic acids (PAs). Characterization results revealed that the AGMN possessed satisfying saturation magnetism and abundant functional groups. Under the optimal extraction parameters, the proposed AGMN/MSPE presented high enrichment capability to PAs. Sensitive and dependable method for measurement of PAs in wine was proposed by the combination of AGMN/MSPE and HPLC/DAD. Limits of detection and limits of quantification were in the ranges of 0.031-0.23 μg/L and 0.10-0.78 μg/L, respectively, and the RSDs for approach precision varied from 1.8% to 8.9%. Recoveries at low, medium and high fortified levels varied from 84.6% to 116%. The suggested method was used to quantify investigated PAs in ten kinds of Tieguanyin tea-derived wines, and found the contents of PAs in wines were related to the quality of tea-leaves and alcohol content.
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Honey is the principal premier product of beekeeping familiar to Homo for centuries. In every geological era and culture, evidence can be traced to the potential usefulness of honey in several ailments. With the advent of recent scientific approaches, honey has been proclaimed as a potent complementary and alternative medicine for the management and treatment of several maladies including various neurological disorders such as Alzheimer’s disease, Parkinson’s disease, Huntington’s disease, and multiple sclerosis, etc. In the literature archive, oxidative stress and the deprivation of antioxidants are believed to be the paramount cause of many of these neuropathies. Since different types of honey are abundant with certain antioxidants, primarily in the form of diverse polyphenols, honey is undoubtedly a strong pharmaceutic candidate against multiple neurological diseases. In this review, we have indexed and comprehended the involved mechanisms of various constituent polyphenols including different phenolic acids, flavonoids, and other phytochemicals that manifest multiple antioxidant effects in various neurological disorders. All these mechanistic interpretations of the nutritious components of honey explain and justify the potential recommendation of sweet nectar in ameliorating the burden of neurological disorders that have significantly increased across the world in the last few decades.
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The aim of this review article is to provide literature on the grape antioxidants. A very thorough literature search was conducted to describe the bioactive molecules of grapes with antioxidant power. Grape, fruit of wide culture, is very consumed and especially appreciated by the populations of North Africa (Algeria, Morocco, and Tunisia). Grape is a very energetic and refreshing fruit, so it is recommended for the feeding of children and athletes. Not only grape is a tonic provider, but it is also very nutritious because of the elements it contains, such as vitamin C and many group B vitamins. Moreover, grape contains several bioactive molecules with antioxidant character, which have beneficial effects for the human health. Many studies have also shown its effects following the frequent consumption of grapes or grape juice. Keywords: Grape, bioactive molecules, antioxidant, health.
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Background: vegetative diversity is based on different climate and geographical origins. In terms of beekeeping, herbal diversity is strongly correlated to the production of a wide variety of honey. Therefore, based on the existing plant diversity in each country, multiple honey varieties are produced with different health characteristics. While beekeeping potential and consumption preferences are reflected in products’ variety, this leads to an increase in the region’s economy and extensive export. In the last years, monofloral honey has gained interest from consumers and especially in the medicinal field due to the presence of phytochemicals which are directly linked to health benefits, wound healing, antioxidant, anticancer and anti-inflammatory activities. Scope and approach: this review aims to highlight the physicochemical properties, mineral profiles and antioxidant activities of selected monofloral honeys based on their botanical and geographical origin. Moreover, this review focuses on the intercorrelation between monofloral honey’s antioxidant compounds and in vitro and in vivo activities, focusing on the apoptosis and cell proliferation inhibition in various cell lines, with a final usage of honey as a potential therapeutic product in the fight towards reducing tumor growth. Key findings and conclusions: multiple studies have demonstrated that monofloral honeys have different physicochemical structures and bioactive compounds. Useful chemical markers to distinguish between monofloral honeys were evidenced, such as: 2-methoxybenzoic acid and trimethoxybenzoic acid are distinctive to Manuka honey while 4-methoxyphenylacetic acid is characteristic to Kanuka honey. Furthermore, resveratrol, epigallocatechin and pinostrobin are markers distinct to Sage honey, whereas carvacrol and thymol are found in Ziziphus honey. Due to their polyphenolic profile, monofloral honeys have significant antioxidant activity, as well as antidiabetic, antimicrobial and anticancer activities. It was demonstrated that Pine honey decreased the MDA and TBARS levels in liver, kidney, heart and brain tissues, whereas Malicia honey reduced the low-density lipoprotein level. Consumption of Clover, Acacia and Gelam honeys reduced the weight and adiposity, as well as trygliceride levels. Furthermore, the antiproliferative effect of chrysin, a natural flavone in Acacia honey, was demonstrated in human (A375) and murine (B16-F1) melanoma cell lines, whereas caffeic acid, a phenolic compound found in Kelulut honey, proves to be significant candidate in the chemoprevention of colon cancer. Based on these features, the use of hiney in the medicinal field (apitherapy), and the widespread usage of natural product consumption, is gaining interest by each year.
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Honey is a natural product containing water and different complex compounds such as proteins, sugars, amino acids, vitamins, and minerals. Environmental contaminations and fraud that occur during honey production, endangers consumer health. The aim of this study, investigate and identify the factors that are deliberately or unintentionally present in honey in order to control these factors, the quality of honey and consumer health to be maintained. In the current review study the information achieved by referring to the databases Pubmed, Science Direct, Elsevier, Google Scholar, SID, MagIran, Civilica, World Health Organization, United Nations Food and Drug Administration collected based on keywords honey, physicochemical properties, hygienic quality, public health, heavy metals and pharmaceutical residues during the last 10 years. Factors affecting the hygienic and safety of honey include carbohydrates (fructose-glucose ratio), proline, gluconic acid, citric acid, moisture, ash (especially potassium), 5-hydroxymethylfurfural, diastase activity (alpha and beta amylase), color, electrolytic conductivity, pH, acidity, heavy metals, and pharmaceutical residues. Physicochemical properties, although affecting the quality of honey but not a threat to consumer health, but heavy metals and residual medicines, in addition to honey quality, also endanger consumer health; thus, heavy metals, and pharmaceutical residues, in comparison to physicochemical properties, affect the hygienic quality of honey and public health. Thus heavy metals and pharmaceutical residues than physicochemical properties, the honey quality and consumers public health more endanger. As a result, the identification and control of heavy metals and pharmaceutical residues in honey is more important than physicochemical properties.
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Introduction: Recently, the growing attention of the scientific community has been focused on the threat to health created by environmental pollutants, including pesticides such as chlorpyrifos (CPF), and on the need of finding effective ways to treat and prevent the unfavorable health effects of exposure to them. Particularly promising for CPF, and thus arousing the greatest interest, is the possibility of using various ingredients present in plants, including mainly polyphenol compounds. As the liver is one of the organs for this pesticide and disturbances in the proper functioning of this organ have serious consequences for health, the aim of the present review was to discuss the possibility of using polyphenol‐rich food products as the strategy for the protection against this xenobiotic hepatotoxicity and treatment of this pesticide‐induced liver damage. Methods: A comprehensive search was performed in various databases using specific keywords such as "biologically active compounds", "antioxidants", "Chlorpyrifos/CPF", "environmental exposure", "health effects", "hepatotoxicity", "liver damage", "mechanisms of Chlorpyrifos/CPF action", "oxidative stress", "preventive strategies", "polyphenols", "protection", "risk for health", and "treatment". Results and Conclusion: Due to the ability and the strong antioxidative potential of polyphenols, as well as their abundance in dietary products, it seems to be of high importance to consider the possibility of using polyphenols as potential preventive and therapeutic agents against CPF hepatotoxicity, determined by its strong pro‐oxidative properties. Although most of the data on the effectiveness of polyphenols comes from studies in animals, the fact that some of them are derived from experimental models reflecting human exposure to this pesticide allows us to assume that some polyphenol food products may be promising protective effect against CPF hepatotoxicity in humans.
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High performance liquid chromatography with UV–Vis detection and post-column derivatization with fluorimetric detection was used for analysis of dyes used in Coptic textiles. To obtain the best separation of analyzed compounds composition of mobile phase was optimized. The best results were obtained for 25 mM phosphoric buffer at pH 2.5 with gradient change of methanol concentration (Table 1). As post-column reagents used to enhance fluorescence signal of analyzed compounds, solutions of Al(III), Ga(III), In(III), and Zn(II) were used. The highest increase of fluorescence signal was observed for Ga(III) and 10 mM solution of this ion was used for investigation of plant extracts and extracts from Coptic textiles.
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The concentrations of 23 chemical elements (Al, As, Ba, Ca, Cd, Co, Cr, Cu, Fe, Hg, K, Mg, Mn, Na, Ni, Pb, Sb, Se, Sr, Th, Tl, U, Zn) were determined in 51 honey samples of different botanical origin produced in Siena County (Italy). K, Ca, Na and Mg were the most abundant elements, with mean contents of 1195, 257, 96.6 and 56.7mg/kg, respectively. The Fe, Zn and Sr contents generally ranged from 1 to 5mg/kg. Except for Ba, Cu, Mn and Ni, the trace element contents were below 100μg/kg. The analytical data indicated a good level of quality of the honeys, especially with regard to the concentrations of toxic trace elements, such as As, Cd, Pb and Sb, and suggested a significant influence of the botanical origin on the element composition. Some local geological and geochemical features also seemed to affect the chemistry of the honey.
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An optimization of the OPA method has made feasible separation and quantification of 23 amino acids, which include 5 infrequently searched for. Detection limits ranged from 0.24 to 10.1pmol in honey and from 29.1 to 0.42pmol in bee-pollen; reproducibility (C.V.) ranged from 5.3% to 20.4%; recoveries were above 78.8%. Forty monovarietal honey samples from ilex, oak, heather and chestnut-tree were analyzed for their free amino acid profiles. α-Aminoadipic acid and homoserine are reported for the first time in honeys. Thirty-two samples of Spanish bee-pollen, made of a majority of pellets from Cistus Ladanifer (67.1%) and Echium plantagineum (8.9%), were analyzed for their free and total amino acid profiles. Free γ-aminobutyric acid was extensively found with an average of 0.53mg/g, while Hser and Orn were infrequent. Manually separated monofloral pellets from Cistus ladanifer and Echium plantagineum were analyzed for their free amino acid contents (including proline): 32.46 and 21.87mg/g for the former and 22.18 and 12.23mg/g for the latter. In contrast, the total amino acid percentage (on a dry weight basis) was 13.95% for Cistus ladanifer and 32.22% for Echium plantagineum.
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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
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A GC-MS procedure is described for the simultaneous quantitatation of the minor and major constituents of honeys, as their trimethylsilyl derivatives, from one solution, by one injection. Selected minor components (aliphatic and aromatic carboxylic acids, members of various homologous series, together with o-phosphoric acid, proline and hydroxymethylfurfurol), have been determined on the basis of their characteristic fragment ions, in the presence of extremely high excess of honeysaccharides. Selective fragmentation of these minor compounds in the ion trap detector provided possibilities for distinguishing them. The method permitted the simultaneous quantitation of o-phosphoric, malic, shikimic, citric/isocitric, quinic, margaric, oleic and stearic acids, hydroxymethylfurfurol and proline with the extremely high sugar contents of honeys (fructose, glucose, galacturonic acid, inositol, sucrose, trehalose, turanose, maltose, gentiobiose, isomaltose, raffinose, erlose, melezitose, maltotriose, panose, isomaltotriose) and allowed the fast evaluation of sugar and acid constituents of fifteen honeys from various floral and geological origin. Results revealed that (i) the minor components varied in the concentration range of 0.0001 to 0.43%, and, (ii) together with the saccharides of honeys made up the total of identified and determined constituents from 87.8% to 98.5%. Quantitative evaluation of the minor constituents was performed on the basis of their selective fragment ion values with an average reproducibility of 6.7% (RSD).
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High performance liquid chromatograms of the phenolic fraction of 19 samples of New Zealand manuka honey, some with high levels of non-peroxide antibacterial activity and some with no such activity, were identical, which indicated that phenolic components of this honey are not responsible for the presence or absence of this activity in manuka honey. Similarly, the result showed that geography does not influence the phenolic composition of manuka honey. Antibacterial bee peptides and the antibacterial β-triketone leptospermone were not detected in manuka honey. Methyl syringate constituted approximately 70% w/w of the phenolic fraction of manuka honey and can be regarded as a floral marker for this honey. High performance liquid chromatographic profiles of the phenolic components of manuka, heather, clover and beech honeydew honeys were significantly different and could be used to differentiate honeys if they can be shown to be as consistent as those of manuka honey.
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This review is concerned with analytical methods to prove the authenticity of honey. A special emphasis is put on suitable methods for the detection of the geographical and botanical origin of honey. Whereas the determination of some single parameters, such as 5-hydroxymethylfurfural (HMF), moisture, enzyme activity, nitrogen, mono- and disaccharides, and residues from medicinal treatment or pesticides in honey does not lead to any information about the botanical and geographical origin, there are some suitable methods based on the analysis of specific components or on multi-component analysis. Mostly, such methods give indications of the botanical origin, investigating flavonoids patterns, distribution of pollen, aroma compounds and special marker compounds. There are some other profiles of components which could probably be used for the detection of the geographical origin (e.g. oligosaccharides, amino acids, trace elements). In particular, the combination of methods could be a promising approach to prove authenticity, especially when modern statistical data evaluation techniques will be applied.
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Aroma is an important quality factor in foods. The aroma of bee honey depends on volatile fraction composition, which is influenced by nectar composition and floral origin. Honey of unifloral origin usually commands higher commercial value, thus the floral determination and certification of unifloral honey plays an important role in quality control. This review concerns investigations made on the volatile fraction of bee honey by gas chromatography/mass spectrometry. Recent advances in extraction methods, results achieved, and comparisons of alternative dependable methods for determining floral origin of bee honey are discussed. We emphasize solid phase micro-extraction gas chromatography (SPME/GC) methodology and present some of the results obtained to date, plus the advantages and drawbacks of SPME/GS in comparison with other methods.
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A capillary electrophoresis method to determine and quantify some compounds of the polyphenolic fraction of honey has been carried out. A detailed method optimization was performed to separate the phenolic compounds present in honey using a methanol-water extract of Rosemary honey. This manuscript reveals the difficulties presented to carry out the peak identification using UV-vis coupled to capillary electrophoresis as detection system in honey. Honey is a complex mixture of compounds that requires very effective separation techniques to allow the identification of the constituents of the polyphenolic fraction. In order to study this fraction of honey, a capillary electrophoresis method was proposed. The study of the polyphenolic fraction was firstly accomplished in rosemary honey. This honey was spiked individually with 22 commercial standards that have been found previously in honey. Only chrysin, pinocembrin, kaempferol, ferulic acid and p-coumaric acid could be identified, though chrysin and pinocembrin were overlapped. Because of this, only kaempferol and ferulic and p-coumaric acids were quantified. Furthermore, the method was applied in another five extracts of honey from different floral sources and the results obtained were similar. Therefore, other detectors such as the mass spectrometer should be employed to assign without any doubts the identity of the peaks present in the electropherogram of an extract of the polyphenolic fraction of honey.
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The antioxidative effects of honey species and their related products were evaluated using a lipid peroxidation model system. The antioxidant activities of honey species gradually decreased with passage of time. Buckwheat honey was as effective as 1 mM α-tocopherol. Superoxide-scavenging activities of propolis and royal jelly were strongest among the honey species tested. 1,1-Diphenyl-2-picrylhydrazyl radical scavenging ability of sample species were lower than those of 1 mM ascorbic acid and α-tocopherol. Hydroxyl radical scavenging activity was very high in all honeys (over 77% inhibition). From the results of the bacterial test on storage of meat and muscle, each honey exhibited the inhibition of bacterial growth. In particular, propolis and royal jelly exhibited the strongest inhibitory effects against bacterial growth. This suggests that honey species from different floral sources possess strong antioxidative and antibacterial activities and are scavengers of active oxygen species.
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The influence of dietary sunflower honey, propolis, and a flavonoid extract of propolis was examined on drug-metabolizing enzyme activities in rat liver and on microsome-mediated binding of benzo[a]pyrene to DNA. Characterization of flavonoids present in sunflower honey and propolis was achieved in order to assess the relative effects of different components of honey and propolis. Honey and propolis contained the same major flavonoids, pinocembrin, chrysin, galangin, and pinobanksin. The concentration of flavonoids was higher in propolis. Sunflower honey produced no significant changes on phase I and phase II enzyme activities and no modification of in vitro binding of benzo[a]pyrene to DNA. Propolis treatment produced an increase of ethoxyresorufin deethylase, pentoxyresorufin depentylase, ethoxycoumarin deethylase, glutathione transferase, and epoxide hydrolase activities. A flavonoid extract from propolis slightly enhanced only few enzyme activities, ethoxycoumarin deethylase and epoxide hydrolase. The induction pattern was similar to that observed with pinocembrin (a major flavonoid of propolis) administered solely. Binding of benzo[a]pyrene to DNA by microsomes from rats fed with propolis or a flavonoid extract from propolis was not significantly modified. These results contribute to identification of food or foodstuffs that can modify drug-metabolizing enzymes and binding of carcinogens to DNA.
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This study presents a novel packed-column extractor coupled with an absorption system to improve the quality of oleoresin oils for Oolong and green teas, extracted by using carbon dioxide. The effect of various co-solvents on the extract is also examined. In addition, gravimetrical measurement and HPLC chromatographic analysis individually determine the amount of oleoresin oil and the concentration of four major catechins. According to those results, the mean contents in the extract are 7.0- and 10.0-fold higher in an addition of 95% ethanol than in no addition for green tea and Oolong tea, respectively. The ratio of four major catechins to caffeine is the highest in Soxhlet ethanol extraction for both green and Oolong teas.
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Quercetin is a typical flavonoid ubiquitously present in vegetables and fruits, and its antioxidant effect is implied to be helpful for human health. The efficiency of extraction process and acidic hydrolysis parameters for HPLC analysis of quercetin present in glycosides and aglycone forms was investigated. Hydrolysis for 5min in the presence of 2.8M HCl as well as for 10min with 1.1M HCl efficiently released quercetin from rutin. The method developed in this study was applied for quantitative determination of quercetin in some food (onion, apple) and herbal (Hypericum perforatum and Sambucus nigra) products.
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A solid-phase extraction procedure was applied to remove organic acids from honey. Malic, maleic, citric, succinic and fumaric acids were isolated with an anion-exchange cartridge. The different parameters which affected the extraction procedure were studied and optimised to establish the optimal conditions for maximum recovery of organic acids and minimum extraction of interferences. The optimised procedure used a cartridge which was activated with 10 ml of 0.1 M sodium hydroxide solution (percolation rate 3 ml/min). A 10 ml volume of honey solution was passed at a flow-rate of 0.5 ml/min. The cartridge was washed with 10 ml of water (3 ml/min) and organic acids were eluted with 4 ml of 0.1 M sulfuric acid (0.5 ml/min). This solution was injected directly into the chromatograph. When this procedure was carried out on standard solutions of organic acids, recoveries between 99.2 and 103.4% were found. If this procedure was applied to honey samples these recoveries were also satisfactory and ranged from 62.9 to 99.4%.
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In the past two decades, combining a chromatographic separation system on-line with a spectroscopic detector in order to obtain structural information on the analytes present in a sample has become the most important approach for the identification and/or confirmation of the identity of target and unknown chemical compounds. In most instances, such hyphenation can be accomplished by using commercially available equipment. For most (trace-level) analytical problems encountered today, the combination of column liquid chromatography or capillary gas chromatography with a mass spectrometer (LC–MS and GC–MS, respectively) is the preferred approach. However, it is also true that additional and/or complementary information is, in quite a number of cases, urgently required. This can be provided by, for example, atomic emission, Fourier-transform infrared, diode-array UV–vis absorbance or fluorescence emission, or nuclear magnetic resonance spectrometry. In the present review, the various options are briefly discussed and a few relevant applications are quoted for each combination. Special attention is devoted to systems in which multiple hyphenation, or hypernation, is an integral part of the setup. As regards this topic, the relative merits of various combinations—which turn out to include a mass spectrometer as one of the detectors in essentially all cases—are discussed and the fundamental differences between GC- and LC-based systems are outlined. Finally, the practicability of more extensive hypernation in LC, viz. with up to four spectrometers, is discussed. It is demonstrated that, technically, such multiple hyphenation is possible and that, from a practical point of view, rewarding results can be obtained. In other words, further research in this area is certainly indicated. However, in the foreseeable future, using several separate conventional hyphenated systems will be the commonly implemented solution in most instances.
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Ultra performance liquid chromatography™ (UPLC) takes advantage of technological strides made in particle chemistry performance, system optimization, detector design, and data processing and control. Using sub‐2 µm particles and mobile phases at high linear velocities, and instrumentation that operates at higher pressures than those used in HPLC, dramatic increases in resolution, sensitivity, and speed of analysis can be obtained. This new category of analytical separation science retains the practicality and principles of HPLC while creating a step‐function improvement in chromatographic performance.This review introduces the theory of UPLC, and summarizes some of the most recent work in the field.
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The separation of thirteen flavonoids from honey by micellar electrokinetic capillary chromatography (MECC) is described. All the flavonoids were separated on a fused-silica column (75 cm × 75 μm I.D.) with 0.2 M sodium borate buffer (pH 8.0)-50 mM sodium dodecyl sulphate-10% methanol. These conditions were applied to the separation of flavonoids from lavender, rosemary, citrus and heather honey samples, to establish correlations between the flavonoid profiles and the botanical origin of honey. Citrus honey was characterized by the accumulation of hesperetin, lavender by luteolin, rosemary by 8-methoxykaempferol and heather by some unidentified flavonoids. The influence of the geographical origin on the honey flavonoid pattern was also studied by MECC. Honey samples from Spain, Mexico and Canada were analysed and no significant differences were found.
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A non-parameter method based on the assumption of additive substituent increments on retention is employed for estimation of the effects of the substituents in the flavone ring on the retention in the reversed phase HPLC. The influence of OH-and OCH 3-groups in the positions: 3, 5, 6, 7, 8, 3 0 , 4 0 , and 5 0 on reversed phase HPLC retention is studied in a group of 21 flavones. The multiple linear regressions performed using 15 substituent codes as independent variables and the logarithm of the retention factor (log k) of each solute obtained with isocratic elution as dependent variables, gave a good correlation with R 2 from 0.9884 to 0.9984, and R ¯ 2 from 0.9535 to 0.9937. The regression coefficients confirm that incorporation of an OH-group does not necessarily reduce retention, and OCH 3-groups, depending on the position, can either cause a decrease or increase in retention. The proposed approach was used for prediction of the structure of an unknown flavone. The predicted substituent pattern of an unknown flavone found in an 1035 extract of Teucrium polium is then experimentally confirmed by mass spectrometry and nuclear magnetic resonance of the isolated flavone – cirsiliol.
Article
Flavonoids and other phenolics of Tunisian honey samples and propolis were analyzed to find correlations between botanical and geographical origin and chemical composition. Flavonoid content of honey was very variable (20−2400 μg/100 g). The richest samples contained the characteristic propolis flavonoids, while those containing fewer flavonoids were devoid of these substances. This is a difference with honeys from temperate areas, in which the poplar-derived flavonoids are present in all honey samples. In Tunisian honeys, and propolis, a new flavonoid, myricetin 3,7,4‘,5‘-tetramethyl ether, was detected. This is characteristic of Cistus spp. leaf exudates. Another minor compound was identified as quercetin 3,7,3‘-trimethyl ether. They were present in high amounts in propolis but were only detected in small amounts in honey. These results show that in border areas, such as Tunisia, where poplars are not always available for propolis collection, other plant sources can be used and their constituents detected in honey. Keywords: Phenolics; honey; propolis; flavonoids; characterization; geographical origin; botanical origin
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Thirty-two aliphatic dicarboxylic acids were identified as methyl esters in the methylated diethyl ether extracts of four unifloral grade New Zealand rewarewa (Knightea excelsa) honeys using combined gas chromatography-mass spectrometry (GC-MS). 2-Methoxybutanedioic acid (O-methylmalic acid) and 4-hydroxy-3-methyl-trans-2-pentenedioic acid are proposed as floral marker substances for New Zealand rewarewa honey. The total level of aliphatic dicarboxylic acids identified in the rewarewa honey samples ranged from 64 to 111 mg/kg with an average level of 88 mg/kg.
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A novel electrochemical route to estimate the antioxidant capacity in honey samples is proposed just using flow injection analysis. The analytical strategy involved the selective oxidation of polyphenolic compounds using two different target potentials, +0.8 and +0.5 V, at two different pHs. An oxidation current obtained at the fixed potential was used as an analytical guide of the antioxidant activity of the target honeys. Chemometrics (correlation and principal component analysis, PCA) demonstrated the significance of the electrochemical protocol versus the traditional spectrophotometric ones in the evaluation of antioxidant capacity and revealed the role of detection potential as a screening variable. The proposed protocol is very simple and fast. However, the most relevant merit of the electrochemical procedure is its inherent versatility which allows the evaluation of the antioxidant activity under predesigned controlled oxidation conditions. In addition, since intercept was statistically zero, its corresponding antioxidant content using just a calibration factor is proposed thus simplifying the calibration-analysis process. As a result, an electrochemical antioxidant index (EAI) is proposed.
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Electrochemical detection of quercetin has been carried out on glassy carbon electrodes modified with carbon nanotubes and Nafion (GC/Nafion-CNT). GC/Nafion-CNT electrodes did not show passivation effect that occurs on the unmodified electrodes and displayed better stability and reproducibility. Quercetin oxidation was most favorable in acidic conditions and current gradually decreased as the solution pH increased. No oxidation was observed when two OH groups in a catechol moiety were fully deprotonated. These electrodes enabled selective determination of quercetin in the presence of interfering species such as ascorbic acid, uric acid, glucose, and catechol in large excess. Quantification of quercetin in a yellow onion has been made and favorably compared with reported values. Good selectivity and high sensitivity obtained by Osteryoung sSquare-wave voltammetry can open new possibilities of direct quercetin determination in vegetables with a minimal sample treatment.
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A comparative study of the recovery of flavonoids (both aglycones and glycosides) by different Amberlite XAD resins has been achieved. No significant differences in the percentages of recovery were found with the chemical nature and physical characteristics of the different resins. A flavonoid recovery higher than 90% is possible in a number of cases. The possibility of fractionating the adsorbed flavonoids by desorption with methanol: water mixtures has also been studied. The polystyrene resins (XAD-2, XAD-4 and XAD-16) were found to be more useful for fractionation purposes than the polyacrylic resins (XAD-7, XAD-8). The results suggest that Amberlite XAD-2 is the most suitable for the recovery and fractionation of flavonoids from plant extracts and foods rich in sugars and other polar compounds such as honey and fruit jams.
Article
Nonaqueous capillary electrophoretic separation of a group of flavonoids (quercetin, myricetin, catechin, epicatechin) and resveratrol in wine was investigated in methanol at high pH. Malonate background electrolyte (pH* 13.5, ionic strength I = 14.2 mmol/L) provided highly repeatable separations of the analytes. Tests of untreated and coated (poly(glycidylmethacrylate-co-N-vinylpyrrolidone)) capillaries showed the analysis to be faster (6.5 min vs. 25 min) and the repeatability better in the coated capillaries. The coating procedure was simple and highly repeatable and the coating was stable during 40-45 runs. Determination of the last migrating peaks (epicatechin, resveratrol and catechin) was achieved merely by evaporating the wine samples and reconstituting the residue in methanol. For determination of the first migrating peaks (quercetin and myricetin) the samples were submitted to solid-phase extraction in C8 cartridges.
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Apitherapy has become the focus of attention as a form of folk and preventive medicine for treating certain conditions and diseases as well as promoting overall health and well-being. In apitherapy, honey is the therapeutic agent used for dressing surgical wounds, burns or skin ulcers, as well as for dyspepsia, peptic ulcer, etc., because of its antioxidant activity. Therefore, it is important to determine the antioxidants in honey by analytical techniques. In the present study, the antioxidant activities of honeys from different floral sources were investigated by electron spin resonance (1,1-diphenyl-2-picrylhydrazyl (DPPH) and H2O2/NaOH/DMSO scavenging systems), liquid chromatography with coulometric array detection (LC-ED), and liquid chromatography with electrospray mass spectrometry (LC-MS). The antioxidant activities of some unifloral honeys (acacia, Chinese milk vetch, buckwheat and manuka) were evaluated using the radical scavenging systems. It was shown that DPPH radical scavenging activity was significantly different among the honeys, with buckwheat and manuka honeys having significantly higher scavenging activity than acacia honey. In addition, only manuka honey had specific scavenging activity for superoxide anion radicals. The compound responsible for this activity in manuka honey was identified by LC-ED and LC-MS. Careful examination of the LC-ED chromatographic patterns of manuka and other honey samples revealed a distinct peak in the chromatogram of manuka honey to be methyl syringate (MSYR). The radical scavenging activity of MSYR was specific for superoxide anion radicals, similar to the case of manuka honey. Copyright © 2005 Society of Chemical Industry
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The electrophoretic behaviour of 13 flavonoids commonly found in medicinal plants has been studied. The performance of two modes of separation, capillary zone electrophoresis (CZE) and micellar electrokinetic capillary chromatography (MEKC), was assessed and compared. MEKC was found to be more effective for separation of the analytes. The effect of structure on the electrophoretic behaviour of the flavonoids is also discussed.
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In this study, the multivariate partial least squares projections to latent structures (PLS) technique was used for modeling the RP-HPLC retention data of 17 chalcones, which were determined with methanol-water mobile phases of different compositions. The PLS model was based on molecular descriptors which can be calculated for any compound utilizing only the knowledge of its molecular structure. The PLS analysis resulted in a model with the following statistics: r=0.976, Q=0.933, s=0.076, and F=43.63. The adequacy of the developed model was assessed by means of crossvalidation and also, by PLS modeling of the retention data of several chalcones reported by Walczak et al. [J. Chromatogr. 353, 123, (1986)], which were obtained using stationary phases of different polarity (-NH2, DIOL,-CN, ODS, C8). The structural interpretation of the developed PLS model was accomplished by means of comparative correlations between the nonempirical descriptors used in the model and the solvation parameters developed by Abraham. The results obtained in this work provides evidence for the great potential of the topological approach for the development of quantitative structure-retention relationship (QSRR) models.
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Seven phenolic acids related to the botanical origins of nine monofloral Eucalyptus honeys from Australia, along with two abscisic isomers, have been analyzed. The mean content of total phenolic acids ranges from 2.14 mg/100 g honey of black box (Eucalyptus largiflorens) honey to 10.3 mg/100 g honey of bloodwood (Eucalyptus intermedia) honey, confirming an early finding that species-specific differences of phytochemical compositions occur quantitatively among these Eucalyptus honeys. A common profile of phenolic acids, comprising gallic, chlorogenic, coumaric and caffeic acids, can be found in all the Eucalyptus honeys, which could be floral markers for Australian Eucalyptus honeys. Thus, the analysis of phenolic acids could also be used as an objective method for the authentication of botanical origin of Eucalyptus honeys. Moreover, all the honey samples analyzed in this study contain gallic acid as the main phenolic acid, except for stringybox (Eucalyptus globoidia) honey which has ellagic acid as the main phenolic acid. This result indicates that the species-specific differences can also be found in the honey profiles of phenolic acids. Furthermore, the analysis of abscisic acid in honey shows that the content of abscisic acid varies from 0.55 mg/100 g honey of black box honey to 4.68 mg/100 g honey of bloodwood honey, corresponding to the contents of phenolic acids measured in these honeys. These results have further revealed that the HPLC analysis of honey phytochemical constituents could be used individually and/or jointly for the authentication of the botanical origins of Australian Eucalyptus honeys.