HPLC–MS identification and quantification of flavonol glycosides in 28 wild and cultivated berry species

Berries and red fruits are rich dietary sources of polyphenols with reported health benefits. More than 50 different flavonols (glycosides of quercetin, myricetin, kaempferol, isorhamnetin, syringetin and laricitrin) have been detected and quantified with HPLC–MSⁿ in fruits of blueberry, bilberry, cranberry, lingonberry, eastern shadbush, Japanese wineberry, black mulberry, chokeberry, red, black and white currants, jostaberry, red and white gooseberry, hardy kiwifruit, goji berry, rowan, dog rose, Chinese and midland hawthorn, wild and cultivated species of blackberry, raspberry, strawberry and elderberry. The phenolic constituents and contents varied considerably among the analyzed berry species. Elderberry contained the highest amount of total flavonols (450–568 mg kg⁻¹ FW), followed by berry species, containing more than 200 mg kg⁻¹ FW of total: chokeberry (267 mg kg⁻¹), eastern shadbush (261 mg kg⁻¹), wild grown blackberry (260 mg kg⁻¹), rowanberry (232 mg kg⁻¹), american cranberry (213 mg kg⁻¹) and blackcurrants (204 mg kg⁻¹). Strawberry (10.5 mg kg⁻¹) and white currants (4.5 mg kg⁻¹) contained the lowest amount of total flavonols. Quercetins represent the highest percentage (46–100%) among flavonols in most analyzed berries. In wild strawberry and gooseberry the prevailing flavonols belong to the group of isorhamnetins (50–62%) and kaempferols, which represent the major part of flavonols in currants (49–66%). Myricetin glycosides could only be detected in chokeberry, rowanberry and species from the Grossulariaceae, and Adoxaceae family and Vaccinium genus. Wild strawberry and blackberry contained from 3- to 5-fold higher total flavonols than the cultivated one.     

Trace element content of Boletus tomentipes mushroom collected from Yunnan,China

The contents of As, Cd, Cr, Cu, Fe, Hg, Mg, Mn, Ni, Pb, and Zn in eleven fruiting bodies of Boletus tomentipes were determined. The results showed the values of the studied elements decreased in the order: Mg (208–279 mg kg⁻¹) > Fe (106–137 mg kg⁻¹) > Mn (29.5–46.8. mg kg⁻¹) > Zn (18.7–23.1 mg kg⁻¹), > Cu (11.4–15.8 mg kg⁻¹) > Cr (3.36–4.78 mg kg⁻¹) > Pb (1.38–3.88 mg kg⁻¹) > Ni (1.68–3.01 mg kg⁻¹) > Cd (0.16–0.32 mg kg⁻¹) > As (0.10–0.24 mg kg⁻¹) > Hg (<0.06 mg kg⁻¹).     

Chemical characterization of a traditional honey-based Sardinian product: Abbamele

The first chemical characterization of abbamele, a traditional honey decoction from Sardinia (Italy) is hereby reported. Water content (from 17.7% to 27.7%), electrical conductivity (from 0.19 to 0.81 mS cm⁻¹), pH (from 3.21 to 3.92), free acidity (from 26.1 to 87.6 meq kg⁻¹), invertase activity (from 0 to 1.02 U kg⁻¹), 5-(hydroxymethyl)-2-furaldehyde, HMF (from 881 to 4776 mg kg⁻¹), total polyphenols (from 188 to 984 mg kg⁻¹) and free amino acid contents of thirteen abbamele samples, from industrial and traditional producers, were obtained in an attempt to compare this traditional product with honey and to study the relationship between its main features and the production procedures. The long thermal treatment involved in the production of abbamele has been identified as the main cause of very low (or absent) invertase activity and free amino acid content as well as the very high content of HMF.     

The effect of diets supplemented with thyme essential oils and rosemary extract on the deterioration of farmed gilthead seabream (Sparus aurata) during storage on ice

The effect on quality were assessed for gilthead seabream fed five different diets: control (basal diet); BHT (basal diet with 200 mg kg⁻¹ of butylated hydroxytoluene); rosemary (basal diet with 600 mg kg⁻¹ of rosemary extract - Rosmarinus officinalis); carvacrol (basal diet with 500 mg kg⁻¹ of essential oil of Thymbra capitata, carvacrol chemotype); and thymol (basal diet with 500 mg g⁻¹ of essential oil of Thymus zygis, subspecies gracilis, thymol chemotype). After 18 weeks of experimentation, the animals were stored on ice at 4 °C for 0, 7, 14, and 21 days. Physical-chemical, microbiological and sensory analyses were carried out at each sampling point to determine the degree of deterioration in the gilthead seabream. Lower indices of oxidation were observed in animals who were administered feeds supplemented with BHT, carvacrol and (to a lesser degree) rosemary. Lower bacteria counts were observed for the BHT and thymol groups, in addition to a slower deterioration in terms of sensory perception. Accordingly, the addition of natural antioxidants to the diet may have an added effect on fish quality, delaying post mortem deterioration.     

Comparison of free amino acid,carbohydrates concentrations in Korean edible and medicinal mushrooms

Ten popular species of both edible and medicinal Korean mushrooms were analysed for their free amino acids and disaccharides. The average total free amino acid concentration was 120.79 mg g⁻¹ in edible mushrooms and 61.47 mg g⁻¹ in medicinal mushrooms, respectively. The average total of free amino acids for all mushrooms, edible mushrooms and medicinal mushrooms was 91.13 mg g⁻¹. Agaricus blazei (227.00 mg g⁻¹) showed the highest concentration of total free amino acids; on the other hand, Inonotus obliquus (2.00 mg g⁻¹) showed the lowest concentration among the 10 species of mushrooms. The average total carbohydrates concentration was 46.67 mg g⁻¹ in the 10 species of mushrooms, where the edible mushrooms contained 66.68 mg g⁻¹ and the medicinal mushrooms contained 26.65 mg g⁻¹. The carbohydrates constituents of the 10 mushroom species were mainly mannose (36.23%), glucose (34.70%), and xylose (16.83%).     

Impact of resistance on the efficacy of binary combinations of spinosad, chlorpyrifos-methyl and s-methoprene against five stored-grain beetles

Laboratory experiments were conducted to determine the efficacy of spinosad (a biopesticide), chlorpyrifos-methyl (an organophosphorus compound (OP)) and s-methoprene (a juvenile hormone analogue) applied alone and in binary combinations against five stored-grain beetles in wheat. There were three strains of Rhyzopertha dominica, and one strain each of Sitophilus oryzae, Tribolium castaneum, Oryzaephilus surinamensis and Cryptolestes ferrugineus. These strains were chosen to represent a range of possible resistant genotypes, exhibiting resistance to organophosphates, pyrethroids or methoprene. Treatments were applied at rates that are registered or likely to be registered in Australia. Adults were exposed to freshly treated wheat for 2 weeks, and the effects of treatments on mortality and reproduction were determined. No single protectant or protectant combination controlled all insect strains, based on the criterion of >99% reduction in the number of live F₁ adults relative to the control. The most effective combinations were spinosad at 1 mg kg⁻¹+chlorpyrifos-methyl at 10 mg kg⁻¹ which controlled all strains except for OP-resistant O. surinamensis, and chlorpyrifos-methyl at 10 mg kg⁻¹+s-methoprene at 0.6 mg kg⁻¹ which controlled all strains except for methoprene-resistant R. dominica. The results of this study demonstrate the difficulty in Australia, and potentially other countries which use protectants, of finding protectant treatments to control a broad range of pest species in the face of resistance development.     

Efficacy of diflubenzuron plus methoprene against Sitophilus oryzae and Rhyzopertha dominica in stored sorghum

The efficacy of diflubenzuron (1 mg kg⁻¹)+methoprene (1 mg kg⁻¹) against Sitophilus oryzae (L.) and Rhyzopertha dominica (F.) in sorghum was evaluated in a silo-scale trial in southeast Queensland, Australia. Sorghum is normally protected from a wide range of insects by mixtures of grain protectants. The chitin synthesis inhibitor diflubenzuron was evaluated as a potential new protectant for S. oryzae in combination with the juvenile hormone analogue methoprene, which is already registered for control of R. dominica. Sorghum (ca 200 t) was treated after harvest in 2000 and assessed for treatment efficacy and residue decline during 6.5 months storage. The reproductive capacity of S. oryzae and R. dominica was greatly reduced in bioassays of treated sorghum throughout the trial, and efficacy remained relatively stable during the trial. An initial exposure of S. oryzae adults to treated sorghum for 2 weeks reduced F₁ progeny production of all strains by 80.8-98.8%, but a second exposure of 4 weeks reduced F₁ progeny production by 98.5-100%. In addition, the reproductive capacity of any S. oryzae progeny produced was greatly reduced. Exposure of R. dominica adults to treated sorghum for 2 weeks reduced F₁ progeny production of all strains by 99.6-100%, including a methoprene-resistant strain. The results indicate that S. oryzae or R. dominica adults invading sorghum treated with diflubenzuron (1 mg kg⁻¹)+methoprene (1 mg kg⁻¹) would be incapable of producing sustainable populations.     

Comparison of the cell wall composition for flesh and skin from five different plums

Cell walls were isolated from flesh and skin of five plum varieties corresponding to three species (Prunus domestica L., Prunus salicina Lindl. and Prunus insititia Lindl.) using the alcohol-insoluble solids (AIS) procedure. Yields varied from 83 to 114 g kg⁻¹ dry weight in the flesh and from 192 to 361 g kg⁻¹ dry weight in the skins. Their main sugars were uronic acid (224–322 mg g⁻¹ AIS), cellulosic glucose (139–170 mg g⁻¹ AIS), galactose and arabinose. Galactose and arabinose ratio were variable between the varieties. The degrees of methylation were high (62–84).     

Chemical composition of cultivated seaweed Ulva clathrata (Roth) C. Agardh

Samples of cultivated Ulva clathrata were collected from a medium scale system (MSS, 1.5 × 1.5 m tank), or from a large scale system (LSS, 0.8 ha earthen pond). MSS samples were dried directly while the LSS sample was washed in freshwater and pressed before drying. Crude protein content ranged 20–26%, essential amino acids accounting for 32–36% of crude protein. The main analysed monosaccharides were rhamnose (36–40%), uronic acids (27–29%), xylose (10–13%) and glucose (10–16%). Some notable variations between MSS and LSS samples were observed for total dietary fibre (26% vs 41%), saturated fatty acids (31% vs 51%), PUFAS (33% vs 13%), carotenoids (358 vs 169 mg kg⁻¹ dw) and for Ca (9 vs 19 g kg⁻¹), Fe (0.6 vs 4.2 g kg⁻¹), Cu (44 vs 14 mg kg⁻¹), Zn (93 vs 17 mg kg⁻¹) and As (2 vs 9 mg kg⁻¹). The chemical composition of U. clathrata indicates that it has a good potential for its use in human and animal food.     

Use of Fourier transform infrared spectroscopy for rapid comparative analysis of Bacillus and Micrococcus isolates

The identification of foodborne microorganisms and their endospores in food products are important for food safety. The present work compares Bacillus (Bacillus licheniformis, Bacillus circulans and Bacillus subtilis) and Micrococcus (Micrococcus luteus) species with Fourier transform infrared (FTIR) spectroscopy. Our results show that there are several characteristic peaks belonging to both the Micrococcus and Bacillus species which can be used for the identification of these foodborne bacteria and their endospores. For Micrococcus species, a new band was observed at 1338 cm⁻¹ which may be due to acetate oxidation via the carboxylic acid cycle. The bands at 1313 cm⁻¹ and 1256 cm⁻¹ can be explained by an exopolymer formation and the other bands at 1074 cm⁻¹ and 550 cm⁻¹, may be due to the glycogen-like storage material in Micrococcus spp. There are also characteristic peaks at 993 cm⁻¹ and 801 cm⁻¹ for these bacterial species. Different Bacillus species also showed characteristic peaks at 1000–500 cm⁻¹ region. Dipicolinic acid (DPA) bands at ∼728 cm⁻¹ and ∼703 cm⁻¹ seen only in B. circulans were the marker of an endospore formation.     

Sensory,microbiological and chemical assessment of the freshness of red mullet (Mullus barbatus) and goldband goatfish (Upeneus moluccensis) during storage in ice

The shelf life of red mullet and goldband goatfish during ice storage were studied in terms of sensory, microbiological and chemical changes. The sensory acceptability limit was 8 days for goldband goatfish (Upeneus moluccensis) and 11 days for red mullet (Mullus barbatus) stored in ice. The TVC level was correlated with sensory assessment. The TVC exceeded 7 log cfu g⁻¹ after 8 days for goldband goatfish, and 11 days for red mullet. At the end of storage period, pH, TVB-N, TBA, FFA and PV for red mullet were 7.84, 47.19 mg/100 g, 0.69 mg MA kg⁻¹, 1.17% oleic acid and 1.58 meq O₂/kg and for goldband goatfish they were 7.53, 43.97 mg/100 g, 0.74 mg MA kg⁻¹, 1.62% oleic acid and 1.68 meq O₂/kg, respectively. In red mullet, agmatine, serotonin, histamine and dopamine became the dominant amines, reaching 7.30, 5.97, 2.52 and 2.31 mg/100 g, respectively. Also the dominant amines for goldband goatfish were 4.37, 3.88, 3.38 and 2.00 mg/100 g for histamine, agmatine, dopamine and putrescine, respectively.     

Study of the content of cadmium,chromium and lead in bivalve molluscs of the Pacific Ocean (Maule Region,Chile)

The concentration of Cd, Cr and Pb in the following species Ameghinomya antiqua, Aulacomya atra and Mytilus chilensis, bivalves from Iloca, Constitución and Pelluhue, coastal towns located in the Maule Region, Chile was determined. Representative tissue samples of each species were analysed by using atomic absorption spectroscopy with flame. Validation of methodology was carried out using a certified reference material (TORT-1). The ranges of concentrations found for Cd, Cr and Pb in the 3 species were, respectively, 0.21–4.32, 0.38–12.62 and 0.43–31.10 mg kg⁻¹ dry weight. In relation to the results obtained and the average of each individual metal in the different species of bivalves, Pb concentrations were found in higher levels rather than those of other metals reported by other authors in a similar work, this element constitutes a potential health hazard for the consumers of shellfish. The results were statistically evaluated for possible correlations in the content of metals in different species and in different sites of origin.     

Change in anthocyanin concentrations in red apricot fruits during ripening

Here we report on accumulation patterns of anthocyanins and of β-carotene during fruit maturation, between 82 and 125 days after flowering, of two apricot (Prunus armeniaca L.) cultivars, A3576 and A3751. Both cultivars displayed an intense red colour of the skin but differed in their genetic background. The pigments were extracted from skin and flesh, separately, and analysed using HPLC-DAD-MS. Out of three anthocyanins detected here, the major compound, cyanidin-3-O-rutinoside was present at 75%. The two minor compounds were cyanidin-3-O-glucoside and peonidin-3-O-rutinoside. This is the first time that peonidin-3-O-rutinoside has been detected in apricot fruit. During maturation, A3751 accumulated anthocyanins in both skin and flesh, whereas anthocyanins were present only in the skin of A3576. The skin anthocyanin content was higher in A3751 (296 mg kg⁻¹) than in A3576 (41 mg kg⁻¹). Maximum anthocyanin levels were attained after 108 and 118 days of flowering in A3751 and A3576, respectively, in conjunction with loss of firmness and red colour acquisition on the un-blushed side of the fruit. At the end of ripening, the β-carotene flesh concentration reached 5 mg kg⁻¹ in A3576 and 15 mg kg⁻¹ in A3751. A significant effect of environment was observed on the anthocyanin content in the two cultivars.     

Ethyl-carbamate determination by gas chromatography–mass spectrometry at different stages of production of a traditional Brazilian spirit

Ethyl carbamate (EC), which is probably carcinogenic to humans, can be produced during the alcoholic fermentation of sugar-cane juice to give cachaça. The stages to produce cachaça are obtainment of sugar-cane juice, sugar-cane fermentation to wine, and obtainment of distilled fractions and residue. In order to investigate the presence of EC in the wine and in the fractions of the distillation process, as well as in the vinasse (the residue left after distillation), gas chromatography–mass spectrometry was employed. After the fermentation phase, the wine showed an average content of 122 mg L⁻¹ of EC. Average EC content in distilled fractions was 59.7 mg L⁻¹ for head, 52 μg·L⁻¹ for heart and 1.57 mg L⁻¹ for tail. EC content was 53.1 mg L⁻¹ for vinasse. The results showed that it is essential to separate the head and tail fractions to ensure cachaça quality, with respect to EC content.     

Elemental composition of cephalopods from Portuguese continental waters

Essential and contaminant elements concentrations were determined in the muscle tissue of octopus (Octopus vulgaris), squid (Loligo vulgaris) and cuttlefish (Sepia officinalis), caught off the Portuguese coast in 2004–2005. As expected, the largest concentrations found correspond to Cl, S, K, Na, P and Mg (average values between 629 mg (100 g)⁻¹, for Cl, and 435 mg kg⁻¹, for Mg, in octopus and squid, respectively). Above average concentrations of Zn, Cu, Fe and Sr were also found. The highest total Hg concentration was found in cuttlefish (0.36 mg kg⁻¹); however, this value did not exceed the recommended limit proposed by EU (0.5 mg kg⁻¹). Lead levels observed in all samples were always significantly lower than the EU limit (1.0 mg kg⁻¹). Regarding Cd, the 1.0 mg kg⁻¹ limit was only exceeded in two octopus samples. It may be concluded that the cephalopods studied do not constitute cause for concern, in terms of toxic elements, and could be safely used for daily intake of essential elements. Nevertheless, the squid contribution for elemental DI is minor in comparison to the other two species.     

Antioxidant potential of solvent extracts of Kappaphycus alvarezii (Doty) Doty – An edible seaweed

Various solvent extracts of Kappaphycus alvarezii, an edible red seaweed (family Solieriaceae) were screened for total phenol content and antioxidant activity using 1,1-diphenyl-2-picrylhydrazyl (DPPH), ferrous ion chelating activity, reducing power and antioxidant activity assays in a linoleic acid system with ferrothiocyanate reagent (FTC). The total phenol content of different extracts of K. alvarezii varied from 0.683 ± 0.040% to 2.05 ± 0.038%. The radical-scavenging activity of ethanol extract was, as IC₅₀ 3.03 mg ml⁻¹, whereas that of the water extract was IC₅₀ 4.76 mg ml⁻¹. Good chelating activity was recorded for methanol extract (IC₅₀ 3.08 mg ml⁻¹) wherein 67.0 ± 0.924% chelation was obtained using 5.0 mg ml⁻¹ of extract. The reducing power of the samples was in the following order: BHT > methanol > ethanol > ethyl acetate > water > hexane. But, in the linoleic acid system, the ethanol extract proved superior to the synthetic antioxidants butylated hydroxytoluene (BHT). Hence, these extracts could be considered as natural antioxidants and may be useful for curing diseases arising from oxidative deterioration.     

Antidiabetic effect of Ficus racemosa Linn. stem bark in high-fat diet and low-dose streptozotocin-induced type 2 diabetic rats: A mechanistic study

The present study was designed to investigate the effects of the ethanol extract of Ficus racemosa (FRE) on biochemical parameters in type 2-like diabetes, induced by a combination of standardised high-fat diet and low-dose streptozotocin (25 mg kg⁻¹, i.p.) in rats. To elucidate the mode of action of FRE, its effects on a battery of targets involved in glucose homeostasis was evaluated. FRE (200 and 400 mg kg⁻¹, p.o.), in a dose-dependent manner, altered the biochemical parameters and significantly improved glucose tolerance and HDL-c levels. In different bioassays, FRE showed inhibition of PTP-1B (IC₅₀ 12.1 μg/mL) and DPP-IV (42.5%). FRE exhibited 82.6% binding to PPAR-γ. Furthermore FRE exhibited stimulation of glucose uptake by skeletal muscles (hemi-diaphragm). Bergenin was quantified in bioactive-FRE by high-performance liquid chromatography (0.15% w/w). This is the first report demonstrating the effectiveness of F. racemosa stem bark in type 2 diabetes and targets involved in it.     

Flow injection spectrophotometry using natural reagent from Morinda citrifolia root for determination of aluminium in tea

A flow injection (FI) spectrophotometric method with using natural reagent extracted from Morinda citrifolia root has been developed for determination of aluminium. The extract contained anthraquinone compounds which could react with Al³⁺ to form reddish complexes which had maximum absorption wavelength at 499.0 nm. The extract could be used as a reagent in FI system without further purification to obtain pure compound. A sensitive method for determination of aluminium in concentration range of 0.1-1.0 mg L⁻¹, with detection limit of 0.05 mg L⁻¹ was achieved. Relative standard deviations of 1.2% and 1.7% were obtained for the determination of 0.1 and 0.6 mg L⁻¹ Al³⁺ (n = 11). Sample throughput of 35 h⁻¹ was achieved with the consumption of 3 mL each of carrier and reagent solutions per injection. The developed method was successfully applied to tea samples, validated by the FAAS standard method. The method is simple, fast, economical and could be classified as a greener analytical method.     

Selected arsenic species: As(III), As(V) and dimethylarsenic acid (DMAA) in Xerocomus badius fruiting bodies

The aim of the study was to determine the content of As(III), As(V) and DMAA (dimethylarsinic acid) in Xerocomus badius fruiting bodies collected from selected Polish forests from areas subjected to very low or high anthropopressure and some commercially available samples obtained from the Polish Sanitary Inspectorate. The arsenic species determination was provided by two independent HPLC–HG-AAS hyphenated systems. The results show high levels (up to 27.1, 40.5 and 88.3 mg kg⁻¹ for As(III), As(V) and DMAA, respectively) of arsenic and occurrence of different species in mushrooms collected from areas subjected to high anthropopressure and two commercially available samples. For mushroom samples collected from areas not subjected to high anthropopressure and two commercially available samples the arsenic species level was below 0.5 mg kg⁻¹ for each arsenic form. Therefore, the accumulation of arsenic by mushrooms may lead to high (toxic for humans) arsenic concentrations, and arsenic species levels should be monitored in mushroom foodstuffs.     

Fish and food safety: Determination of formaldehyde in 12 fish species by SPME extraction and GC–MS analysis

The formaldehyde (FA) content in different fish products was evaluated using a solid phase microextraction (SPME)-GC–MS method based on fiber derivatisation with pentafluorobenzyl-hydroxyl-amine hydrochloride. LOD and LOQ values of 17 and 28 μg kg⁻¹, respectively were calculated. Fish quality was assessed by the analysis of 12 species (sea-fish, freshwater-fish and crustaceans), revealing variable FA levels. Fresh, deep frozen, canned, boiled and roasted fish were analysed; cooking always produced a decrease in the analyte content. Fish belonging to the Gadidae family were the samples with the highest FA concentration (from 6.4 ± 1.2 mg kg⁻¹ to 293 ± 26 mg kg⁻¹), in four cases out of 14 exceeding the value of 60 mg kg⁻¹ proposed by the Italian Ministry of Health. Storage on ice was also investigated, showing moderate FA production also at temperature around 0 °C. FA contents lower than 22 mg kg⁻¹ were finally found in all the other samples.