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.

Characterization of Sugar and Polyphenolic Diversity in Floral Nectar of Different 'Oblacinska' Sour Cherry Clones.

'Oblacinska' sour cherry, an autochthonous cultivar, is the most planted cultivar in Serbian orchards. Since fruit trees in temperate zone reward insects by producing nectar which 'quality' affects the efficiency of insect pollination, the aim of this study was analyzing of sugars and polyphenolics in floral nectar of 16 'Oblacinska' sour cherry clones with different yielding potential. The contents of sugars and sugar alcohols were analyzed by ion chromatography, while polyphenolic profile was established using liquid chromatography/mass spectrometry technique. Fourteen sugars and six sugar alcohols were detected in nectar samples and the most abundant were fructose, glucose, and sucrose. Eleven polyphenols were quantified using available standards, while another 17 were identified according to their exact masses and characteristic fragmentations. Among quantified polyphenols, rutin, naringenin, and chrysin were the most abundant in nectar. Principal component analysis showed that some polyphenol components (naringin, naringenin, and rutin) together with sugars had high impact of spatial distribution of nectar samples on score plot.

Identification of Phenolic Compounds from Seed Coats of Differently Colored European Varieties of Pea (Pisum sativum L.) and Characterization of Their Antioxidant and In Vitro Anticancer Activities.

To date little has been done on identification of major phenolic compounds responsible for anticancer and antioxidant properties of pea (Pisum sativum L.) seed coat extracts. In the present study, phenolic profile of the seed coat extracts from 10 differently colored European varieties has been determined using ultrahigh-performance liquid chromatography-linear trap quadrupole orbitrap mass spectrometer technique. Extracts of dark colored varieties with high total phenolic content (up to 46.56 mg GAE/g) exhibited strong antioxidant activities (measured by 2,2-diphenyl-1-picrylhydrazyl or DPPH assay, and ferric ion reducing and ferrous ion chelating capacity assays) which could be attributed to presence of gallic acid, epigallocatechin, naringenin, and apigenin. The aqueous extracts of dark colored varieties exert concentration-dependent cytotoxic effects on all tested malignant cell lines (human colon adenocarcinoma LS174, human breast carcinoma MDA-MB-453, human lung carcinoma A594, and myelogenous leukemia K562). Correlation analysis revealed that intensities of cytotoxic activity of the extracts strongly correlated with contents of epigallocatechin and luteolin. Cell cycle analysis on LS174 cells in the presence of caspase-3 inhibitor points out that extracts may activate other cell death modalities besides caspase-3-dependent apoptosis. The study provides evidence that seed coat extracts of dark colored pea varieties might be used as potential cancer-chemopreventive and complementary agents in cancer therapy.

Chemical profile of major taste- and health-related compounds of Oblacinska sour cherry.

BACKGROUND: Oblacinska sour cherry, an autochthonous cultivar, is the most planted cultivar in Serbian commercial orchards. Owing to its long cultivation under different agro-ecological conditions, it is a mixture of different clones. To obtain comprehensive information on Oblacinska sour cherry fruit, the total carbohydrate composition, total phenolic content, total anthocyanin content, antioxidant activity and polyphenolic profiles of 39 clones were investigated. RESULTS: Fructose was found to be the dominant sugar, followed by glucose, sorbitol and sucrose. Rutin and chlorogenic acid were the most abundant polyphenols. Some clones contained pinobanksin, hesperetin and galangin, which, to best knowledge, is the first time these compounds have been reported in sour cherry fruit. CONCLUSION: The data obtained showed huge variation within the germplasm studied, confirming the fact that Oblacinska sour cherry is not a cultivar but a population.

Fatty acid and phenolic profiles of almond grown in Serbia.

Almond production is not typical for Serbia however the existence of natural populations and unexpectedly suitable agro-climatic conditions initiated this kind of study. Total oil content and concentrations of the fatty acids, total phenolic content and radical-scavenging activity were determined in the kernel oil of 20 local almond selections originating from North Serbia and cultivars 'Marcona', 'Texas' and 'Troito'. Sixteen fatty acids were identified and quantified, with the most abundant being oleic acid and linoleic acid. Nine phenolic acids and nineteen flavonoids were quantified using UHPLC-DAD MS/MS. The predominant polyphenol was catechin, followed by chlorogenic acid and naringenin. Based on oleic acid/linoleic acid ratio, levels of unsaturated fatty acids and specific polyphenols, some selections were chosen for growing and could also be recommended for breeding programs. Our investigation demonstrated that this region could be a suitable for growing almonds with chemical compositions competitive with standard cultivars.

Identification and quantification of phenolic compounds in berry skin, pulp, and seeds in 13 grapevine varieties grown in Serbia.

Phenolic profile of 13 grapevine varieties was determined, with respect to three different parts of berries: skin, seed and pulp. Identification and quantification of the phenols was done using ultra-high performance liquid chromatography (UHPLC) coupled with a diode array detector and a triple-quadrupole mass spectrometer. The most abundant phenols in grape seeds were found to be flavan-3-ols, most of which are gallocatechin gallate and catechin. The skins were characterized mostly by flavonols, i.e. quercetin and myricetin. Characterization of anthocyanins in the berry skin by UHPLC coupled with Linear Trap Quadrupole and OrbiTrap mass analyzer revealed a total of twenty derivatives of malvidin, delphinidin, petunidin, cyanidin, and peonidin. To the extent of our knowledge this is the first work that shows the presence of malvidin 3,5-O-dihexoside in the berry skin of 'Merlot', 'Cabernet Franc', 'Shiraz' 'Sangiovese', 'Pinot Noir' and 'Prokupac', untypical for Vitis vinifera Linneo species.

Analysis and characterisation of phytochemicals in mulberry (Morus alba L.) fruits grown in Vojvodina, North Serbia.

In this study, the polyphenolic profile of 11 Morus alba fruits grown in the Vojvodina region was investigated. Ultra high performance liquid chromatography (UHPLC) coupled with Linear Trap Quadrupole and OrbiTrap mass analyzer, and UHPLC coupled with a diode array detector and a triple-quadrupole mass spectrometer were used for the identification and quantification of the polyphenols, respectively. A total of 14 hydroxycinnamic acid esters, 13 flavonol glycosides, and 14 anthocyanins were identified in the extracts with different distributions and contents according to the sampling. The total phenolic content ranged from 43.84 to 326.29 mg GAE/100g frozen fruit. The radical scavenging capacity (50.18-86.79%), metal chelating ability (0.21-8.15%), ferric ion reducing power (0.03-38.45 µM ascorbic acid) and superoxide anion radical scavenging activity (16.53-62.83%) were assessed. The findings indicated that mulberry polyphenolics may act as potent superoxide anion radical scavengers and reducing agents.

Polyphenolic Profile of Pear Leaves with Different Resistance to Pear Psylla (Cacopsylla pyri).

The European pear psylla, Cacopsylla pyri L. (Hemiptera: Psyllidae), is one of the most serious arthropod pests of pear. Since proper control of this pest is essential, better understanding of the complex plant-pest relationship is mandatory. This research deals with constitutive polyphenolic profiles in leaves of 22 pear cultivars of diverse origin (P. communis, P. pyrifolia, and P. pyrifolia × P. communis) and different resistance to psylla. The study was designed to show which differences in the polyphenolic profile of leaves from resistant and susceptible pear cultivars could be utilized as information in subsequent breeding programs. The results demonstrated that the leaves of Oriental pear cultivars contained much higher amounts of p-hydroxybenzoic acid, ferulic acid, aesculin, and naringin, that, together with detected 3-O-(6″-O-p-coumaroyl)-hexoside, apigenin, apigenin 7-O-rutinoside, and hispidulin, indicated a clear difference between the species and might represent phenolics responsible for psylla resistance.

Mineral content of bee pollen from Serbia.

In this study we analysed mineral composition of bee pollen of different plant origin collected across Serbia using inductively coupled plasma - optical emission spectrometry. The most abundant elements were potassium, calcium, and magnesium. The samples were also exceptionally rich in iron and zinc, which are very important as nutrients. Judging by our findings, mineral composition of bee pollen much more depends on the type of pollen-producing plant than on its geographical origin.

Chemical composition of two different extracts of berries harvested in Serbia.

Total phenolic content (TPC), total anthocyanin content (TAC), free and total ellagic acid content, sugars, minerals, and radical-scavenging activity were determined in nine berries harvested in Serbia. More than 30 phenolic compounds were identified; among them, 11 polyphenols and cis,trans-abscisic acid were quantified using UHPLC coupled with an LTQ-Orbitrap XL mass analyzer. For the first time chrysin, naringenin, pinocembrin, and galangin were quantified in some of the investigated berry species. The extraction efficiency of the two extraction systems, methanol and acetone, was investigated. It was found that acetone is a better extracting solvent for TPC, whereas more TAC was extracted by methanol. TPC in acetone extracts ranged from 177.51 to 459.71 mg gallic acid equiv/100 g frozen weight. TAC ranged from 5.39 to 96.94 mg cyanidin-3-glucoside/100 g frozen weight in methanol extracts. The amounts of both free and total ellagic acid were found to be higher in the acetone extract in comparison to the methanol extract.

Physicochemical, antioxidant and sensory properties of peach wine made from redhaven cultivar.

Physicochemical, sensory, and health-related characteristics of peach wine produced from Redhaven variety and selected white wines produced from various grape varieties were determined and compared. The alcohol content, titratable acidity, and total extract of peach wine was significantly lower compared with that of white wines, while its pH value was higher. The content of total phenolics (TPC) and flavonoids (TFC) of peach wine (402.53 mg/L GAE and 332.67 mg CAE/L, respectively) have been found significantly higher in comparison with that of white wines (TPC range 243.67-319.00 mg/L GAE, TFC range 129.67-175.17 mg CAE/L). The main phenolic compounds found in peach wine were chlorogenic acid, caffeic acid, and catechin (3.59, 0.87, and 0.60 mg/L, respectively). Antioxidant capacities were strongly correlated with total phenolics with correlation coefficients over 0.99. The highest antioxidant capacity was ascribed to peach wine. The results of sensory analysis indicated that the peach wine was very well accepted by the regular consumers of wine and can be a very interesting product in the market.