Assessing the Impact of Botanical Origins, Harvest Years, and Geographical Variability on the Physicochemical Quality of Serbian Honey.

This study summarized the physicochemical analysis of 609 honey samples originating from the Republic of Serbia. Variations among honey samples from different botanical origins, regions of collections, and harvest years were exposed to descriptive statistics and correlation analysis that differentiated honey samples. Furthermore, most of the observed physicochemical parameters (glucose, fructose, sucrose content, 5-hydroxymethylfurfural (5-HMF) levels, acidity, and electrical conductivity) varied significantly among different types of honey, years, and regions. At the same time, no noticeable difference was found in diastase activity, moisture content, and insoluble matter. Based on the obtained results, 22 honey samples could be considered adulterated, due to the irregular content of sucrose, 5-HMF, acidity, and diastase activity. In addition, 64 honey samples were suspected to be adulterated. Adulterated and non-compliant samples present a relatively low percentage (14.1%) of the total number of investigated samples. Consequently, a considerable number of honey samples met the required standards for honey quality. Overall, these findings provide insights into compositional and quality differences among various types of honey, aiding in understanding their characteristics and potential applications.

Analysis of δ13C and δ15N values in Croatian honey by EA-IRMS and possibility of their application in botanical origin verification.

The aim of this work was to give characteristic stable carbon and nitrogen isotope ratio (δ13Choney, δ13Cprotein and δ15N) ranges and examine their relation with botanical origin of honey. Despite that δ13C parameter has primary purpose to detect honey adulteration, stable isotopes generally have become important parameter for detection its botanical and geographical origin. The data about stable isotopes are scarce in comparison to other well-known parameters in honey, and in Croatia there is no data about stable isotopes in unifloral honey. This research includes six characteristic honey types (black locust, chestnut, lime, rape, winter savory, and sage honey) from Croatia. Large number of differences between honey types were found in the analyzed IRMS parameters. PCA analysis has successfully separated winter savory from all other honey types, except sage honey, whose samples differed from black locust samples. Supplementary Information: The online version contains supplementary material available at 10.1007/s13197-023-05888-9.

Monofloral Corn Poppy Bee-Collected Pollen-A Detailed Insight into Its Phytochemical Composition and Antioxidant Properties.

The aim of this study was to compile a detailed phytochemical profile and assess the antioxidant properties of bee-collected pollen (PBP) obtained from corn poppy (Papaver rhoeas L.) plants. To achieve this, a lipid fraction was prepared for quantifying fatty acids using GC-FID. Extractable and alkaline-hydrolysable PBP fractions (obtained from a defatted sample) were used to determine the qualitative and quantitative profiles of phenolic compounds, phenylamides and alkaloids using UHPLC/Q-ToF-MS. Additionally, various spectrophotometric assays (TAC, FRP, CUPRAC, DPPH⦁) were conducted to evaluate the antioxidant properties. Phenolic compounds were more present in the extractable fraction than in the alkaline-hydrolysable fraction. Luteolin was the predominant compound in the extractable fraction, followed by tricetin and various derivatives of kaempferol. This study presents one of the first reports on the quantification of tricetin aglycone outside the Myrtaceae plant family. The alkaline-hydrolysable fraction exhibited a different phenolic profile, with a significantly lower amount of phenolics. Kaempferol/derivatives, specific compounds like ferulic and 5-carboxyvanillic acids, and (epi)catechin 3-O-gallate were the predominant compounds in this fraction. Regarding phenylamides, the extractable fraction demonstrated a diverse range of these bioactive compounds, with a notable abundance of different spermine derivatives. In contrast, the hydrolysable fraction contained six spermine derivatives and one spermidine derivative. The examined fractions also revealed the presence of seventeen different alkaloids, belonging to the benzylisoquinoline, berberine and isoquinoline classes. The fatty-acid profile confirmed the prevalence of unsaturated fatty acids. Furthermore, both fractions exhibited significant antioxidant activity, with the extractable fraction showing particularly high activity. Among the assays conducted, the CUPRAC assay highlighted the exceptional ability of PBP's bioactive compounds to reduce cupric ions.

The Role of Isoflavones in the Prevention of Breast Cancer and Prostate Cancer.

This narrative review summarizes epidemiological studies on breast cancer and prostate cancer with an overview of their global incidence distribution to investigate the relationship between these diseases and diet. The biological properties, mechanisms of action, and available data supporting the potential role of isoflavones in the prevention of breast cancer and prostate cancer are discussed. Studies evaluating the effects of isoflavones in tissue cultures of normal and malignant breast and prostate cells, as well as the current body of research regarding the effects of isoflavones attained through multiple modifications of cellular molecular signaling pathways and control of oxidative stress, are summarized. Furthermore, this review compiles literature sources reporting on the following: (1) levels of estrogen in breast and prostate tissue; (2) levels of isoflavones in the normal and malignant tissue of these organs in European and Asian populations; (3) average concentrations of isoflavones in the secretion of these organs (milk and semen). Finally, particular emphasis is placed on studies investigating the effect of isoflavones on tissues via estrogen receptors (ER).

Phenolic Compounds as Phytochemical Tracers of Varietal Origin of Some Autochthonous Apple Cultivars Grown in Serbia.

Domesticated international (standard) apple cultivars, together with resistant apple cultivars are the core of the Serbian apple production. Furthermore, autochthonous cultivars are characterized by a good adaptability to the local environmental conditions and represent a valuable source of genetic variability, as well as an important source of the gene pool for further breeding programs. Additionally, they show a higher phenolic content and a stronger antioxidant activity, in comparison to commercial cultivars. Therefore, they are more likely to be used as a functional food. The subjects of this study were seventeen samples of fruits and leaves from autochthonous apple cultivars, five international standard cultivars, and six resistant apple cultivars. The phenolic profile was determined using ultra-high performance liquid chromatography (UHPLC), coupled with a diode array detector and a TSQ Quantum Access Max triple-quadrupole mass spectrometer. A total of twenty compounds were quantified in the samples. Most of the analyzed phenolics were detected in higher amounts in the peel, compared to the mesocarp. The results of the multivariate analysis of variance (MANOVA) indicate that 5-O-caffeoylquinic acid is present in the highest amount in the mesocarp, while in the peel and leaves, quercetin-glycosides were detected in the highest amount. According to the MANOVA: phloretin, phlorizin, 5-O-caffeoylquinic acid, kaempferol, and p-coumaric acid are present in significantly higher levels in the autochthonous cultivars, compared to the standard and resistant ones (in both fruits and leaves). Therefore, these compounds can be used as chemical tracers of the apple varietal origin.

Bioaccessibility of Phenolic Compounds and Antioxidant Properties of Goat-Milk Powder Fortified with Grape-Pomace-Seed Extract after In Vitro Gastrointestinal Digestion.

This study deals with the evaluation of the bioaccessibility and antioxidant properties of phenolic compounds from heat-treated skim goat-milk powder fortified with grape-pomace-seed extract, after in vitro gastrointestinal digestion. Ultra-high performance liquid chromatography coupled to diode array detection and mass spectrometry (UHPLC-DAD MS/MS) analysis confirmed the abundant presence of phenolic acids and flavan-3-ols in the grape-pomace-seed extract (SE) and heat-treated skim goat-milk/seed-extract powder (TME). After in vitro digestion of TME powder and recovery of total quantified phenolics, flavan-3-ols and phenolic acids were 18.11%, 24.54%, and 1.17%, respectively. Low recovery of grape-pomace-seed phenolics indicated strong milk protein-phenolic interactions. Electrophoretic analysis of a soluble fraction of digested heat-treated skim goat milk (TM) and TME samples showed the absence of bands originating from milk proteins, indicating their hydrolysis during in vitro gastrointestinal digestion. The digested TME sample had better antioxidant properties in comparison to the digested TM sample (except for the ferrous ion-chelating capacity, FCC), due to the presence of bioaccessible phenolics. Taking into account the contribution of the digestive cocktail, digested TME sample had lower values of total phenolic content (TPC), in vitro phosphomolybdenum reducing capacity (TAC) and ferric reducing power (FRP), compared to the undigested TME sample. These results could be attributed to low recovery of phenolic compounds. TME powder could be a good carrier of phenolics to the colon; thus, TME powder could be a promising ingredient in the formulation of functional food.

Polyphenolic and Chemical Profiles of Honey From the Tara Mountain in Serbia.

This study presents a detailed characterization of 27 honey samples from the Tara Mountain region in Serbia using different comprehensive techniques and methods. The types of the honey samples were defined as monofloral (4 samples), honeydew (5 samples) and polyfloral (18 samples) honey based on determined polyphenol content, antioxidant activity, electrical conductivity and melissopalynological analyses. Physicochemical parameters such as pH (4.13-4.94), diastase activity (24.20-41.70 DN), acidity (14.60-29.70 meq/kg), content of 5-(hydroxymethyl)furfural (in range below 5, up to 16.90 mg/kg), sucrose (0.20-3.90 g/100 g), and moisture content (15.01-19.23%) confirmed the required quality of the honey samples. Sensory analysis revealed honey characteristics favorable to consumers. Analyses of 19 phenolic compounds using ultra-high-performance liquid chromatography with a diode-array detection and triple quadrupole mass spectrometry (UHPLC-DAD-MS/MS) revealed six phenolic acids and 13 other compounds from the group of flavonoids and their glycosides. In all the samples the highest content was determined for p-coumaric acid, followed by caffeic acid and pinocembrin. Besides total phenolic content and radical scavenging activity, antimicrobial activity was also examined. Most honey samples showed bactericidal activity against Staphylococcus aureus and bacteriostatic activity against Escherichia coli, while none of the honey samples inhibited the growth of Candida albicans. Chemometric analyses were applied for an in-depth study of the results to further evaluate the characteristics of the honey samples studied. Principal component analysis (PCA) was used for assessing the differences in physicochemical parameters, polyphenols content and antioxidant capacity between honey samples. The unrooted cluster tree was used to group the samples based on the melissopalynological analyses.

Polyphenolics and Chemical Profiles of Domestic Norwegian Apple (Malus × domestica Borkh.) Cultivars.

Using modern analytical techniques, a comprehensive study of the chemical composition of fruits from apple cultivars grown in Western Norway during 2019 and 2020 was done. Metals, sugars, organic acids, antioxidant tests, and polyphenol content have been observed. In all investigated samples, the most dominant sugars were glucose, fructose, and sucrose. Among 11 tested organic acids, the dominant was malic acid, followed by citric and maleic acid. The most common metal was potassium, followed by magnesium and zinc. The quantification of polyphenols showed that among the 11 quantified polyphenols, chlorogenic acid, quercetin 3-O-rhamnoside, quercetin 3-O-glucoside, quercetin, and phlorizin were the most abundant. A detailed study of the polyphenolic profile of nine investigated apple samples provided 30 identified polyphenolic compounds from the class of hydroxybenzoic and hydroxycinnamic acids, flavonoids, and dihydrochalcones. In addition to the identified 3-O-caffeoylquinic acid, its two isomers of 5-O-caffeoylquinic acid and three esters were also found. Present polyphenols of the tested apples provided significant data on the quality of Norwegian apples, and they contribute to the distinguishing of these apple samples.

Hieracium waldsteinii (Asteraceae) and Onosma stellulata (Boraginaceae) as a Source of Antioxidant and Antimicrobial Agents.

The current study aimed to phytochemically characterize (including a detailed phenolic profile) two endemic Balkan's species (Hieracium waldsteinii and Onosma stellulata) and determine their possible application as a source of natural antioxidant and antimicrobial agents. The main phenolic compound in both species (in all examined parts) was chlorogenic acid. Eriodictyol, genistein and naringenin were quantified only in H. waldsteinii while isorhamnetin-3-O-rutinoside and sinapic acid were characteristic for O. stellulata. The highest antioxidant activity (98 mg AAE/g dry weight for TAC assay) was ascribed to the flower extract of H. waldsteinii while the lowest results (∼4.3 mg AAE/g dry weight for FRP assay) were exhibited by the extracts obtained from the plant's stem. Antimicrobial assays showed moderate antibacterial, i. e., moderate/strong activity against several tested fungi (in particular Trichoderma viride). Correlation analysis revealed strong positive connection between phenolic compounds and reducing power of extracts as well as between total phenolic and flavonoid content and the obtained minimal inhibitory concentration recorded in antibacterial assays.

Analysis of Phenolic Compounds for the Determination of Grafts (in) Compatibility Using In Vitro Callus Cultures of Sato-Zakura Cherries.

The aim of this study was to prove that under in vitro conditions, the adhesiveness of the callus between rootstock and scion, the development of callus cells at the points of fusion, and the presence of phenolic components are closely related to the level of (in) compatibility of the grafting combinations between Sato-zakura cherry cultivars ('Amanogawa', 'Kanzan', and 'Kiku-shidare-zakura') and commercial rootstocks. Prunus avium, Prunus 'Colt', Prunus mahaleb and Prunus serrulata were used as compatible and Prunus serotina and Pyrus communis 'Pyrodwarf' were used as two potentially incompatible rootstocks. The results indicated the significant manifestations of the early signs of the incompatibility on the callus junction. Phenols, as well as tissue senescence, were very precisely localized by toluidine blue and alcian blue as well as safranin staining, which can indicate the early signs of the callus incompatibility in some grafting unions. In the callus unions of Prunus avium with 'Amanogawa' and 'Kiku-shidare-zakura' the results of chemical analyses indicated that the existence of several flavonols, flavones and phenol acids could be involved in the incompatibility process in grafted combination. The detection of flavonol astragalin in the unions can be a biomarker of compatibility between scion and the rootstock, while some polyphenols, such as neochlorogenic acid, sinapic acid, ellagic acid, caffeic acid, baicalein, naringenin, apigenin and luteolin can be used as the indicators of graft incompatibility. p-coumaric acid and ferulic acid could be used for detection of delayed incompatibility.

Phytochemical Profile and Antioxidant Properties of Bee-Collected Artichoke (Cynara scolymus) Pollen.

The current study intended to determine, for the first time, phenolic and fatty acid profile, antioxidant and certain nutritional properties of monofloral bee-collected artichoke (Cynara scolymus) pollen. Based on UHPLC-DAD MS-MS analysis the main phenolics in extractable fraction were different flavonol glycosides (in particular Isorhamnetin-3-O-glucoside, 49.2 mg/kg of dry weight) while ferulic acid was the predominant phenolic compound (39.4 mg/kg of dry weight) in the alkaline hydrolyzable fraction. Among fatty acids (FAs), results of GC-FID analysis revealed prevalence of unsaturated FAs with cis-5,8,11,14,17-eicosapentaenoic acid (EPA) and oleic acid as the main ones- 28.4% and 24.9%, respectively. Based on the FA composition, nutritional analysis proved that artichoke bee-collected pollen had balanced ω-6 and ω-3 FAs content. To determine the antioxidant properties of pollen, five different assays were applied. It was proved that bioactive compounds in artichoke pollen possessed significant ability to quench DPPH radical as well as ABTS radical cation. In addition, in vitro phosphomolybdenum assay confirmed that artichoke pollen is an excellent source of different antioxidants. Pollen extracts exhibited moderate ferric reducing power as well as low ferrous chelating ability. Some further antioxidant studies (preferably in vivo) should be performed to confirm the observed results.

Skimmed Goat's Milk Powder Enriched with Grape Pomace Seed Extract: Phenolics and Protein Characterization and Antioxidant Properties.

The aim of this research was phenolics and protein characterization and antioxidant properties evaluation of skimmed thermally treated goat's milk powder enriched with different concentration of grape pomace seed extract (SE). The dominant phenolics in SE were phenolic acids, flavan-3-ols and procyanidins. Different electrophoretic techniques together with UHPLC-MS/MS analysis revealed the presence of phenolics-protein interactions in the samples, mainly procyanidins with whey protein/caseins complexes. Addition of SE into thermally treated goat's milk significantly improved antioxidant properties of goat's milk such as TAC, FRP, DPPH• and ABTS•+ scavenging activity. Gallic acid, catechin, and procyanidins mostly contributed to these activities. The schematic representation of phenolics-casein micelles interactions in thermally treated goat's milk enriched with SE was given. The addition of SE into thermally treated goat's milk can be a promising strategy in food waste recovery and to enhance the beneficial health effects of goat's milk-based functional foods.

Polyphenol bioaccessibility and antioxidant properties of in vitro digested spray-dried thermally-treated skimmed goat milk enriched with pollen.

The aim of research was to determine polyphenols bioaccessibility and antioxidant properties of thermally-treated skimmed goat milk enriched with sunflower bee-collected pollen through in vitro digestion. HPLC analysis confirmed that pollen-enriched milk contained flavonols as the main phenolic fraction (80.7-76.2%) followed by phenolic acids (14.2-17.4%). Among individual compounds quercetin-3-O-glucoside (155.1-197.2 µg/L) and p-coumaric acid (29.5-30.7 µg/L) were the main quantified flavonols and phenolic acids, respectively. After digestion of milk/pollen sample, total polyphenols recovery was 30.71% with higher phenolic acids recovery (40.1%) compared to flavonols (28.3%) indicating strong interactions between caprine milk casein micelles and pollen polyphenols. Applied antioxidant assays (phosphomolybdenum, ABTS•+scavenging activity and ferrous-ion-chelating capacity) have confirmed complexity of prepared product- it had high ability to quench ABTS•+ radicals and to form chelating complexes with Fe2+ ions. Digestion provoked 20% reduction in total antioxidant capacity compared to the initial sample. TTSG milk/pollen powder could be good functional ingredient.

Elemental Analysis and Phenolic Profiles of Selected Italian Wines.

The study of the chemical composition of wines is nowadays a topic of great interest because of the importance of this market, especially in Italy, and also considering the numerous cases of falsification of famous and very expensive wines. The present paper focused on the analysis of metals and polyphenols in Italian wines belonging to different provenance and types. At this purpose 20 elements were quantified by inductively coupled plasma optical emission spectrometry (ICP-OES) and ICP mass spectrometry (ICP-MS). Regarding polyphenols, a total of 32 were quantified, among 6 were anthocyanins. Furthermore, in 4 samples (1 rosè and 3 red wines) 42 anthocyanins and related compounds were identified by ultra-high performance liquid chromatography (UHPLC)-Orbitrap MS technique (among these, 6 were also quantified). Non-anthocyanins were determined using UHPLC coupled with a diode array detector and triple-quadrupole mass spectrometer (UHPLC-DAD-QqQ-MS). Total phenolic content (TPC) and radical scavenging activity (RSA) were measured using spectrophotometric methods. The results obtained by elemental techniques were submitted to principal components analysis (PCA) allowing to get information on both geographical and botanical origin of the examined wine samples. Some polyphenols have been detected in higher concentrations only in a certain type of wine, as for example in the case of Grechetto wine. Most of the identified anthocyanin derivatives (pyranoanthocyanins) are formed during the aging of wine by reaction with the other wine components.

Comparative Study on the Phenolic Fingerprint and Antioxidant Activity of Strawberry Tree (Arbutus unedo L.) Leaves and Fruits.

The strawberry tree (Arbutus unedo L., Ericaceae family) is an evergreen Mediterranean shrub whose leaves and fruits are used in traditional medicine due to their antioxidant, antimicrobial, antidiabetic, diuretic, and antiproliferative properties. The health benefits are mainly attributed to the presence of phenolic compounds. The aim of this study was to compare the phenolic profiles, total phenolic content (TPC), and radical scavenging activity (RSA) of A. unedo leaves and fruits collected at two locations in Croatia. Phenolic profiles were identified using an ultra-high-performance liquid chromatograph (UHPLC) coupled with a hybrid mass spectrometer (LTQ Orbitrap MS). TPC was determined by Folin-Ciocalteu's assay, while RSA was investigated using DPPH reagent. A total of 64 phenolics (60 and 42 compounds in leaves and fruits, respectively) were identified. Hyperoside and flavan-3-ols were predominant compounds in leaves, while gallocatechin and catechin were the major compounds found in fruits. To the authors' knowledge, 16 and 5 phenolics in leaves and fruits, respectively, were reported for the first time. Principal component analysis (PCA) showed that UHPLC-LTQ Orbitrap MS could be used to identify which phenolics were able to discriminate samples regarding plant tissue and geographical origin. TPC in leaves and fruits were in the ranges of 67.07-104.74 and 16.78-25.86 mg gallic acid equivalents (GAE)/g dried weight (dw), respectively. RSA for leaves and fruits were in the ranges of 408.92-430.98 and 74.30-104.04 µmol Trolox equivalents (TE)/g dw, respectively. The number of identified phenolics was lower in fruits compared to leaves. Such a large number of bioactive phenolics identified and the strong antioxidant activity pointed to A. unedo as a promising health-promoting plant and natural food preservative.

Distribution of polyphenolic and sugar compounds in different buckwheat plant parts.

The aim of this study was to provide information on the phenolic and sugar profiles of different parts of the buckwheat plant, which can define that buckwheat is a functional food, with a high nutritional value and very useful for human health. Therefore, the extracts of buckwheat leaf, stem, and flower, as well as buckwheat grain were analysed for the content of polyphenol and antioxidant tests. The identification of a notable number of phenolic compounds and quantification of sugars in different parts of buckwheat indicates that buckwheat is a highly valuable plant. A total of 60 phenolic compounds were identified (18 cinnamic acid derivatives, 14 flavonols, 13 flavan-3-ols (including proanthocyanidins), 10 hydroxybenzoic acid derivatives, and 5 flavones) using ultra-high-performance liquid chromatography (UHPLC), coupled with a hybrid mass spectrometer which combines the Linear Trap Quadrupole (LTQ) and OrbiTrap mass analyzer. The highest number of phenolic compounds was found in the analysed buckwheat flower sample, and then in the leaf, followed by the grain and the stem. In addition, the sugar profile of buckwheat leaf, stem, flower and grain, as well as the buckwheat pollen and the nectar was analysed. Hence, 16 sugars and 5 sugar alcohols were detected by the high-performance anion exchange chromatography (HPAEC) with a pulsed amperometric detector (PAD). Sucrose was found in a significant amount with the highest content in buckwheat leaf. Trisaccharides had similar accumulation in the sample extracts, while disaccharides dominated in buckwheat leaf, followed by nectar and pollen. The sugar alcohols showed the highest content in buckwheat grain, where erythritol was predominant. The obtained results show that buckwheat is very rich in phenolic compounds and sugars. In addition to grain, the other parts of the buckwheat plant can be used as a very good source of different classes of phenolic compounds. This study provides useful information on the distribution of phytochemicals in different parts of the buckwheat plant, which contribute to the maintaining of the status of buckwheat as a functional food.

Chemical composition and antimicrobial activity of Osage orange (Maclura pomifera) leaf extracts.

The main goal of this study was to establish the chemical profile of Osage orange (Maclura pomifera) leaf extracts, obtained by conventional maceration technique, and to examine its antimicrobial activity. The identification and quantification of the extract compounds were done using ultra-high-performance liquid chromatography, with a diode array detector coupled with triple-quadrupole mass spectrometer and gas chromatography-mass spectrometry techniques. Thirty-one polyphenolic compounds were detected and identified in the ethanolic extracts, whereby 5-O-caffeoylquinic acid was found to be the dominant compound. Among other compounds, pentacosane and palmitic acid were the most abundant compounds in the dichloromethane extract. The preliminary antimicrobial activity screening shows that Gram-positive bacteria tend to be more sensitive to the investigated extracts. The highest antimicrobial activity was determined against Enterococcus faecalis ATCC 19433 and Listeria monocytogenes ATCC 35152. From these results, Osage orange leaves can be considered as plant material with significant antimicrobial properties.

Polyphenols as Possible Agents for Pancreatic Diseases.

Pancreatic cancer (PC) is very aggressive and it is estimated that it kills nearly 50% of patients within the first six months. The lack of symptoms specific to this disease prevents early diagnosis and treatment. Today, gemcitabine alone or in combination with other cytostatic agents such as cisplatin (Cis), 5-fluorouracil (5-FU), irinotecan, capecitabine, or oxaliplatin (Oxa) is used in conventional therapy. Outgoing literature provides data on the use of polyphenols, biologically active compounds, in the treatment of pancreatic cancer and the prevention of acute pancreatitis. Therefore, the first part of this review gives a brief overview of the state of pancreatic disease as well as the procedures for its treatment. The second part provides a detailed overview of the research regarding the anticancer effects of both pure polyphenols and their plant extracts. The results regarding the antiproliferative, antimetastatic, as well as inhibitory effects of polyphenols against PC cell lines as well as the prevention of acute pancreatitis are presented in detail. Finally, particular emphasis is given to the polyphenolic profiles of apples, berries, cherries, sour cherries, and grapes, given the fact that these fruits are rich in polyphenols and anthocyanins. Polyphenolic profiles, the content of individual polyphenols, and their relationships are discussed. Based on this, significant data can be obtained regarding the amount of fruit that should be consumed daily to achieve a therapeutic effect.

Phenolic Profiles of Leaves, Grapes and Wine of Grapevine Variety Vranac (Vitis vinifera L.) from Montenegro.

Vranac, an old autochthonous red grapevine variety of Montenegro, was first mentioned in a historical document published in the 15th century. As currently the study of indigenous varieties is of particular importance, the subject of this work was detailed characterization of phenolic compounds in the autochthonous grapevine variety Vranac, from the Montenegrin Podgorica subregion. Phenolic profiles of leaves, berries (skin, seeds, and pulp were examined separately) and young monovarietal wine were determined using ultra-high performance liquid chromatography (UHPLC) with linear trap quadrupole (LTQ)-Orbitrap XL mass spectrometry (MS). Total phenolic content (TPC) and radical scavenging activity (RSA) were higher for the grape seeds extracts, followed by extracts of grape skins and pulps. As expected, the total anthocyanin content (TAC) was higher in grape skin than in wine. A total of one hundred twenty nine compounds (forty two phenolic acids and their derivatives, twenty three flavan-3-ols, twenty one flavanols, five stilbenes and thirty eight anthocyanins) were identified in the investigated extracts. To our best knowledge, this is the first report of tentative identification of (epi)catechin 3-O-coumarate in grape seed and chalcan-flavan 3-ol dimers in wine and grape seed.

Establishing the chromatographic fingerprints of flavan-3-ols and proanthocyanidins from rose hip (Rosa sp.) species.

The profile of flavan-3-ols and proanthocyanidins in five different Rosa species (R. canina, R. glutinosa, R. rubiginosa, R. multiflora, and R. spinosissima) was estimated on high performance thin layer chromatography cellulose plates. Differences in flavanol and proanthocyanidin profiles of the extracts were evident, among which Rosa spinosissima stood out with catechin as the only detected flavanol and red zones as indication of anthocyanins. Furthermore, the elution solvent for thin layer chromatography with mass spectrometry analyses of glycosylated flavan-3-ols and proanthocyanidins was optimized, enabling identification of catechin, (epi)catechin hexoside, proanthocyanidin dimer, and proanthocyanidin dimers and trimers hexosides. A total of 15 flavanols and their derivatives were identified using ultra-high-performance liquid chromatography with linear trap quadrupole-Orbitrap mass analyzer and epicatechin, gallocatechin, and proanthocyanidin trimer were identified only using this technique. However, proanthocyanidin trimer trihexoside was identified only by thin-layer chromatography with mass spectrometry. To establish the relationships between the flavanols and proanthocyanidins composition of rose hip and their origin, principal component analysis was performed on the entire set of liquid chromatography/mass spectrometry data. Both principal components' scores plots showed that Rosa spinosissima could be considered as an outlier. Our study demonstrated that flavanol and proanthocyanidin profiles of different rose hips depend on the geographical origin rather than on the cultivar and genotype.