Application of new fungicides under good agricultural practices and their effects on the volatile profile of white wines

Three new commercial fungicides to control downy mildew (Plasmopara viticola), which contain new generation fungicides (benalaxyl, iprovalicarb and piraclostrobin) were applied under Good Agricultural Practices (GAP) in an experimental vineyard producing white grapes (Vitis vinifera) Godello var. Once white grapes were harvested, single vinifications were performed. To evaluate possible modifications in aroma composition of wines, Odour Activity Values (OAVs) were estimated due to this parameter provides information about sensorial changes. Fungicide residual levels found in treated wines with respect to the control wine reduced the varietal aroma of wines attributed to geraniol. However, treated wines showed an increase in the fruity aroma due to several ethyl esters (ethyl hexanoate, ethyl octanoate, and ethyl decanoate) and acetates (3-methyl-1-butyl acetate and 2-phenylethyl acetate) increased their levels and OAVs in presence of fungicide residues; these secondary products of the fermentation process influence strongly the aromatic profile of young wines.     

Decay of fungicide residues during vinification of white grapes harvested after the application of some new active substances against downy mildew

Cyazofamid, famoxadone, mandipropamid and valifenalate are new fungicides recently proposed to control downy mildew (Plasmopara viticola) in vines. In this study, three of them were applied in an experimental vineyard producing white grapes (Vitis vinifera cv. Godello) as commercial formulations: Mildicut (2.5% cyazofamid), Equation Pro (22.5% famoxadone + 30% cymoxanil) and IR-5885 (6% valifenalate + 60% mancozeb), meanwhile mandipropamid was directly applied as an active substance. The last treatments to control this disease were made out under critical agricultural practices, without obeying the preharvest interval. Besides the above products, the control of powdery mildew (Erisiphe necator) and grey mould (Botrytis cinerea) was made by employing standard commercial formulations. Once treated white grapes were harvested, the fate of all these fungicides from vine to wine was studied. Residues of cyazofamid, famoxadone and valifenalate in grapes were higher than their EU MRL, except for mandipropamid. The white wine-making process allowed the dissipation of fungicide residues in high percentages (ca. 95%), except for valifenalate that remained in wine at 32%.     

Changes of the sensorial attributes of white wines with the application of new anti-mildew fungicides under critical agricultural practices

Although the winemaking process could allow the dissipation of residues of fungicides applied under critical agricultural practices (CAP), their residual levels could alter the biosynthesis of volatile compounds. The purpose of this work is to look for changes in the aroma profile of those wines in comparison with wines treated under good agricultural practices (GAP). Four new fungicides (mandipropamid, valifenalate, cyazofamid and famoxadone), used to control downy mildew (Plasmoparaviticola), were applied under CAP in an experimental vineyard producing white grapes (Vitisvinifera) of Godello var. Once grapes were harvested, single vinifications were performed. Possible modifications of sensorial properties of wines were evaluated by a trained sensorial testing panel constituted of 7 experts. The fungicide residues induced an increment of typical fermentative odours associated with esters in treated wines. The critically treated wine was moved to a sweeter balance with a ripe fruit taste, associated with higher viscosity and greater cloudiness.     

Proanthocyanidin profile and antioxidant capacity of Brazilian Vitis vinifera red wines

The free flavan-3-ol and proanthocyanidin (PA) profile and the antioxidant capacity of wines Vitis vinifera L., 2006 and 2007 vintages, from the São Joaquim region, at southern Brazil, are reported here for the first time. Catechin and epicatechin were the two main monomers in the wine samples, followed by gallocatechin and epigallocatechin; and the PA B1 was the main dimer. The terminal units of the PAs were constituted mainly by catechin units, with the co-presence of epicatechin, gallocatechin, epigallocatechin and traces of epicatechin gallate. The epicatechin and epigallocatechin units were the main constituents of the extension units of PAs with the co-presence of catechin and epicatechin gallate. The values for the mean degree of polymerisation ranged from 4.9 to 9.8. The wine samples demonstrated effective scavenging activity against DPPH and ABTS radicals and against lipid peroxidation in vitro. A positive correlation existed between flavan-3-ol content and antioxidant capacity in vitro.     

Influence of some prefermentative treatments on aroma composition and sensory evaluation of white Godello wines

The influence of the static settling time and the addition of ammonium salts on basic parameters, aroma composition and tasting of white Godello wines have been studied. The statistical analysis showed a significant influence of those treatments on several analytical parameters. The static settling time proved to be very influential on total acidity, free sulphur dioxide, esters, terpenols and fatty acids, while the addition of ammonium salts showed a significant effect on higher alcohols and ethyl lactate. According to the odour active value (OAV), 14 out of 47 studied volatile components had OAV >1 in all the analysed wines, while six volatile components showed OAV >1 only for some of them. Ethyl octanoate, isoamyl acetate and ethyl hexanoate showed the highest OAV values. During the tasting session, the two studied factors became relevant, being better valued the wine made with must containing higher limpidity and with the addition of diammonium hydrogen phosphate.     

Odour active aroma compounds of sea fig (Microcosmus sulcatus)

Sea fig is an original shellfish appreciated for its powerful “marine, iodized” flavour. Different methods of analysis by gas chromatography, coupled with olfactometry (GC–O), were studied and compared. Subsequently, odour-active aroma compounds of sea fig extract were analyzed by OSME and CHARM analysis. Twenty-nine olfactive areas were observed by OSME, and 18 by CHARM analysis. Volatile compounds of the extract were analyzed by mass spectrometry and specific detectors associated with the GC. Twenty molecules, responsible for these odours were elucidated. Among them, 12 were directly identified by GC–MS, and the remaining 8 only by GC–O and standard sample injection. Moreover, 10 volatile sulfur-containing compounds were revealed as the major olfactive contributors. The two principal character-impact compounds possessed “marine, fresh” and “fishy, crustaceous” odours. The first could not be identified; however, trimethylamine was attributed to the other, and defined as a key compound of sea fig aroma.     

Antioxidant activities of phenolic rich fractions (PRFs) obtained from black mahlab (Monechma ciliatum) and white mahlab (Prunus mahaleb) seedcakes

The antioxidant activities of phenolic rich fractions (PRFs) from crude methanolic extract (CME), and its fractions using ethyl acetate (EAF), hexane (HF) and water (WF) of black mahlab (Monechma ciliatum) and white mahlab (Prunus mahaleb) seedcakes were investigated. The total phenolic compounds were found to be higher in white mahlab than black mahlab seedcakes. The antioxidant activity determined by the DPPH method revealed that black mahlab PRFs had the highest antioxidant activity, compared to white mahlab fractions. The presence of antioxidants in the two mahlab PRFs reduced the oxidation of β-carotene by hydroperoxides from these extracts/fractions. The effect of the two mahlab PRFs on the oxidative stability of corn oil at 70 °C was tested in the dark and compared with butylated hydroxyanisole (BHA). The CME performed better antioxidant activity in inhibiting the formation of both primary and secondary oxidation products. The qualitative and quantitative characterisation of phenolic compounds was carried out by HPLC/DAD.     

Chemical and sensory characterisation of aroma of Viburnum opulus fruits by solid phase microextraction-gas chromatography-olfactometry

The aroma profile of four cultivars of Viburnum opulus and one cultivar of V. opulus var. sargentii fruits was studied by solid phase microextraction of headspace volatiles and subsequent analysis by gas chromatography, mass spectrometry and olfactometry (SPME-HS-GC-MS-O). In total, 41 compounds were identified, 3-methyl-butanoic acid (63.0-71.8% of identified volatile organic compounds) being the major constituent in the three V. opulus cultivars, while 2-octanone was dominant in one cultivar of V. opulus and in V. opulus var. sargentii, amounting to 28.1% and 25.6% of identified volatile compounds, respectively. Ten odour active compounds were detected and characterised by the trained panel of judges in the course of GC-O by using detection frequency analysis (DFA). 3-Methyl-butanoic and 2-methyl-butanoic acids as well as linalool and ethyl decanoate were found to be the main odour active components for V. opulus aroma.     

Inhibitory effect of sour orange (Citrus aurantium) juice on Salmonella Typhimurium and Listeria monocytogenes

The sour orange (Citrus aurantium) juice is commonly used as flavoring and acidifying agent for vegetable salads and appetizers in Turkey. It was aimed to determine the survival and growth pattern of Salmonella Typhimurium and Listeria monocytogenes in sour orange juice. Different concentrations of neutralized and un-neutralized juice samples were inoculated with each of the test microorganisms (∼6 log CFU/mL) separately and then incubated at 4 °C and 37 °C for seven days. It was detected both of the test microorganisms could survive and even grow in neutralized juice samples at 37 °C for two days. However, none of them could survive at the end of seventh day of incubation at 37 °C. Low incubation temperature (+4 °C) increased the survival of the tested microorganisms. Also, it was detected that L. monocytogenes were less resistant to the variable conditions than S. Typhimurium. It was concluded that the antimicrobial effect of sour orange juice mainly depends on the low pH value of the product. However, incubation time and temperature are also effective on the survival of the tested pathogens.     

Antioxidant activity of hydrolysates obtained from scallop (Patinopecten yessoensis) and abalone (Haliotis discus hannai Ino) muscle

Scallop (Patinopecten yessoensis) and abalone (Haliotis discus hannai Ino) muscle were hydrolysed with commercially available food-grade proteases. The resulting hydrolysates showed DPPH and hydroxyl radicals scavenging abilities, reducing power, and ferrous ion chelating capacity. The antioxidant activities of hydrolysate of abalone foot muscle (HAFM) increased with increasing incubation time during the whole hydrolysis process in 180 min. Whereas, the antioxidant activities of hydrolysate of scallop adductor muscle (HSAM) increased at initial stage and peaked after 25-30 min of hydrolysis, and then gradually decreased thereafter. Compared with HAFM, HSAM with comparable hydrolysis time contained more free amino acids (FAA) and small-sized peptides (below 500 Da), which may account for the differences in antioxidant activities versus hydrolysis time curves of the two hydrolysates. The above results indicate that limited hydrolysis of proteins can increase their antioxidant activity, whereas extensive hydrolysis can decrease it.     

Contribution to the characterisation of honey-based Sardinian product abbamele: Volatile aroma composition,honey marker compounds and antioxidant activity

Sardinian abbamele is a typical product obtained from the honey recuperation from combs (traditional procedure) or by concentration of the honey diluted in water (industrial procedure). Seven abbamele samples were obtained to study the volatiles’ composition, the presence of honey marker compounds and their relationship with the production procedures. The long thermal treatment applied in abbamele production caused very high (1007.0–4405.8 mg/kg) HMF content (HPLC-DAD), while glucose and fructose amounts were quite similar to the honey ones (HPLC-RI). Total antioxidant activity (FRAP assay) of the samples ranged between 13.3 and 71.2 mmol Fe²⁺/kg, while antiradical activity (DPPH assay) ranged between 3.8 and 23.3 mmol TEAC/kg. Such high antioxidant values were linearly correlated with total phenol amount (1297.8–4469.5 mg GAE/kg) determined by Folin–Ciocalteau method. Thermally derived furan derivatives and terpenes were abundant among the headspace volatiles (HS-SPME), particularly limonene (0.5–76.0%) that probably originated from citrus rinds’ addition during abbamele production. GC and GC–MS analyses of USE isolates revealed HMF predominance as well as the honey marker compounds (if/when existing) such as methyl syringate (up to 49.2%), marker of Asphodelus microcarpus honey. High isophorone percentage (up to 30.9%) determined by HS-SPME followed by minor percentage of 4-ketoisophorone and norisoprenoids in one sample indicated Arbutus unedo L. honey use in the production. HPLC-DAD analysis confirmed the presence of specific honey markers: two samples showed high methyl syringate concentrations (150.4–120.1 mg/kg) while homogentisic acid and other specific markers of A. unedo honey were found in one sample. The compared GC–MS and HPLC-DAD data proved to be useful to obtain information about the use of specific honey in the production and to verify citrus addition.     

Analysis of free and bound aroma compounds of pomegranate (Punica granatum L.)

Volatile aroma compounds were isolated from pomegranate arils by high vacuum distillation (HVD) and solvent extraction with diethyl ether. The HVD distillate exhibited a fresh-fruity and characteristic pomegranate aroma while the total ether extract was devoid of this note in its concentrate. Gas chromatography–mass spectroscopy (GC–MS) analysis revealed the presence of 3-octen-1-yl acetate, trans-3-hexen-1-ol, hexanol and 2-methyl pentanol only in the high vacuum distillate. Ether extract was dominated by 2-heptanol, 2-nonanol and 3-methyl-2-butanol. Based on olfactometric analysis of the HVD isolate, 3-octen-1-yl acetate was identified as the key odorant of pomegranate. Chemical synthesis of this compound, further confirmed its structure. Among the bound aroma compounds, 2-phenylethanol (40%), alpha-terpineol (4.53%) and 2-heptanol (6.35%) were identified as the major compounds existing as glycoconjugates. Identification of the character impact compound and the occurrence of glycosidic precursors in pomegranate are being reported here for the first time.     

Antioxidant and antidiabetic activity of Dangyuja (Citrus grandis Osbeck) extract treated with Aspergillus saitoi

Dangyuja is a citrus fruit of Cheju Island in Korea, which is known to have a high content of flavanone glycosides, such as naringin and neohesperidin. Flavanone glycosides of Dangyuja (Citrus grandis Osbeck) extract were converted into their aglycones by naringinase and hesperidinase, and into their hydroxylated forms by Aspergillus saitoi.Dangyuja extract treated with A. saitoi had significantly higher antioxidant and antidiabetic activity than both its glycosides and aglycones in oxygen radical absorption capacity (ORAC) and supercoiled DNA strand scission assay, rat intestinal α-glucosidase and porcine pancreatic α-amylase inhibition, suggesting that the fermentation of flavanone aglycones of Dangyuja extract with A. saitoi can increase antioxidant and antidiabetic activity, compared to their glycosides and aglycones. This result suggests that Dangyuja extract prepared with enzymatic and microbial treatments could be used for the development of pharmaceutical foods to control the blood glucose level of diabetic patients by inhibiting α-amylase and α-glucosidase in the intestinal tract.     

Composition,antimicrobial, antiradical and spasmolytic activity of Ferula heuffelii Griseb. ex Heuffel (Apiaceae) essential oil

The essential oil from underground parts of Ferula heuffelii from N.E. Serbia, was analysed using GC and GC–MS. The main compounds of the essential oil were elemicin (35.4%) and myristicin (20.6%). The essential oil exhibited the best antimicrobial activity against two strains of Candida albicans (MIC = 7.0 and 13.7 μg/ml), as well as against Micrococcus luteus (MIC = 13.7 μg/ml), Staphylococcus epidermidis (MIC = 17.6 μg/ml), Bacillus subtilis (MIC = 21.1 μg/ml) and Micrococcus flavus (MIC = 28.2 μg/ml). In the DPPH radical scavenging assay, essential oil showed substantial activity with SC₅₀ = 22.43 μl/ml. The essential oil was also tested for antispasmodic activity. It inhibited spontaneous contraction of isolated rat ileum dose-dependently, and at the concentration of 86.64 μg/ml exhibited 50% of the maximum effect of atropine. After incubation with 75.00 μg/ml of essential oil, acetylcholine did not induce contractions of ileum, and at 250.00 μg/ml, the essential oil almost completely abolished the spasmodic effect of potassium chloride (80 mM).     

Biological aging of sherry wines under periodic and controlled microaerations with Saccharomyces cerevisiae var. capensis: Effect on odorant series

Wine aged for 2 years in cellar conditions and a batch of non aged wine were subjected to biological aging with S. cerevisiae var. capensis under controlled microaeration. Another batch of the non aged wine and 4 year aged wine in cellar conditions were used as control and named initial and final control wines, respectively. Thirty-five aroma compounds were quantified by GC–MS, and grouped in nine odorants series to compare the microaerated wines with the control wines. Fruity, balsamic, floral, herbaceous, fatty and roasty series increases their values, while solvent and phenolic diminishes by the effect of yeast metabolism. Roasty and spicy series show the higher values in wines previously aged in cellar conditions for 2 and 4 years probably due to the contact of the wine with the wood. The roasty series is dependent of compounds such as 2,3-butanedione, 2,3-pentanodione, 4-ethylguaiacol and some lactones, whereas the spicy series is only dependent on 4-ethylguaiacol. The similarity obtained for some odorant series in wines aged under controlled conditions and wines aged for 4 years in cellar, suggest that the biological aging time can be shortened using a first step for wine aging in stainless-steel under controlled and periodic microaerations and a second step in an oak cask under cellar conditions.     

Phytochemicals and antioxidant activity of different parts of bambangan (Mangifera pajang) and tarap (Artocarpus odoratissimus)

Mangifera pajang (family: Anacardiaceae; local name: bambangan) and Artocarpus odoratissimus (familiy: Moraceae; local name: tarap) are popular edible fruits in Sabah, Malaysia. The flesh, kernel and peel from M. pajang; seed and flesh from A. odoratissimus were analysed for total antioxidant activity, total polyphenol, total flavonoid and total anthocyanins contents. M. pajang kernel extract displayed the highest free radical scavenging and ferric reducing activities. Total phenolic content of the samples were in the range of 5.96–103.3 mg gallic acid equivalent/g. M. pajang kernel and M. pajang flesh contained the highest and lowest total flavonoid content with the values of 10.98 and 0.07 mg rutin equivalent/g, respectively. The antioxidant activities of extracts were significantly correlated with the total phenolic and flavonoid content (but not the anthocyanins content). The phytochemicals and antioxidant properties of M. pajang and A. odoratissimus, especially their by-products (kernel/seed), indicate that they may impart health benefits when consumed and should be regarded as a valuable source of antioxidant-rich nutraceuticals.     

Control of the lesser grain borer (Rhyzopertha dominica (F.), Coleoptera: Bostrichidae) by treatments with residual formulations of Metarhizium anisopliae (Metschnikoff) Sorokin (Deuteromycotina: Hyphomycetes)

Treatments with conidia of the entomopathogenic fungus Metarhizium anisopliae formulated in invert emulsion (water-in-oil formulation) or in wheat flour were applied to Rhyzopertha dominica adults infesting Cicer arietinum grains. The application rates were 4.1×10⁵ conidia/cm² of treated area using a concentration of 1.8×10⁷ conidia/ml of the invert emulsion and 8.2×10⁶ conidia/cm² of treated area using a concentration of 6.5×10⁸ conidia/g of the wheat flour formulation. Results have indicated significant mortality (P<0.05) when newly emerged R. dominica adults were introduced and then treated with the invert emulsion and wheat flour formulations (86.7-93.3%, control treatment 10.0-26.7% mortality). When treated grains were left until the emergence of F₁ adults, there was also significant mortality (P<0.05) in both treatments (28.3-60.0%, control treatment 1.7-8.3% mortality). This indicates a residual effectiveness of the treatment with the two formulations against R. dominica adults which extended to >2 months (equivalent to the duration of the insect life-cycle at 23±2°C and 75±5% r.h.). Infestation rate of C. arietinum grains by R. dominica at 23±2°C and 75±5% r.h. was significantly reduced in the treatments with the fungal conidia formulated in invert emulsion (0.7%) or in wheat flour (1.0%) when compared with the control treatment (19.0-23.3%). The preventive treatments significantly retarded R. dominica development (P<0.05) by 8-12 days compared with the control treatment. The infection with the fungus thus delayed adult emergence of R. dominica by 8-12 days. Overall results give promise for control of R. dominica with M. anisopliae mixed with wheat flour or introduced into invert emulsion.