HPLC-DAD-MS/MS ESI characterization of unusual highly glycosylated acylated flavonoids from cauliflower (Brassica oleracea L. var. botrytis) agroindustrial byproducts

In a recent program to investigate the possible use of vegetable handling and commercialization wastes and residues as a source of potentially bioactive extracts, we have studied cauliflower byproducts. A total of twenty-eight compounds were characterized by HPLC-DAD-MS, of these, twenty-two are produced naturally by the plant. The main compounds found were kaempferol 3-diglucoside-7-glucoside and its combinations with different hydroxycinnamic acids. Moreover, some flavonoids with an unusual high grade of glycosylation have been isolated and tentatively identified for the first time. To our knowledge, the characterization of flavonoids with more than four sugars has not been previously reported. The new products isolated were tentatively identified as kaempferol 3-diglucoside-7-diglucoside, kaempferol 3-triglucoside-7-diglucoside, kaempferol 3-feruloyldiglucoside-7-diglucoside, kaempferol 3-sinapoyltriglucoside-7-glucoside, kaempferol 3-disinapoyltriglucoside-7-glucoside, kaempferol 3-sinapoyltriglucoside-7-diglucoside and kaempferol 3-disinapoyltriglucoside-7-diglucoside.     

Sex pheromone of the oak processionary moth Thaumetopoea processionea. Identification and biological activity

The sex pheromone of the oak processionary moth Thaumetopoea processionea has been characterized from female gland extracts as a mixture of (Z,Z)-11,13-hexadecadienyl acetate (1), (E,Z)-11,13-hexadecadienyl acetate (3) and (Z,Z)-11,13-hexadecadienol (2) in 88:7:5 ratio. The amount of the major compound 1 was 20-30 ng/gland. No trace of (Z,Z)-11,13-hexadecadienal was found in the extract, and therefore, T. processionea appears to be the only "summer" processionary moth lacking this compound as a pheromone compound. The alcohol 2 had also been previously found but is electrophysiologically inactive, and in wind tunnel assays it lowers the number of contacts with the source when mixed with the major compound 1. The major component 1 elicited males to display the complete behavioral sequence, but the amount of chemical needed was unexpectedly high in comparison to the activity displayed by virgin females and gland extracts. (E,E)-11,13-hexadecadienyl acetate (5) inhibits the attractant activity of the major component 1 when mixed with 1 in 1:10 and 1:1 ratios. The main constituent 1 is active in the field, but its tendency to isomerize into the corresponding E,E isomer (5) must be considered if effective formulations are to be prepared.     

Soil penetrometer resistance spatial variability in a Ferralsol at several soil moisture conditions

The penetrometer resistance (PR) spatial variability in a Ferralsol under different soil moisture conditions was characterized through statistical and geostatistical methods. PR measurements were made in a 10-row, 10-columns, 3-m spacing grid at 20–30 cm depth using a hand-pushing penetrometer. Measurements were made for dry soil conditions (before irrigation) as well as 2 and 24 h after irrigation. The soil bulk density (BD) and the relative topographical altitudes (RT) were measured at the same locations. The PR spatial variability is normally distributed for dry soil conditions and after irrigation-water redistribution. A normal distribution fits also to the BD spatial variability. PR mean and coefficients of variations are lower for wet soil conditions and vary notably according to the soil moisture condition. The PR semivariance values are much higher for dry soil conditions than those found for wet soil conditions. However, the semivariogram of PR before irrigation shows almost a pure nugget effect. Irrigation yields a spatial structure in PR measurements. Despite the differences in the shown spatial structure, the range of the PR semivariograms before and 24 h after irrigation is about 8–10 m, which is very similar to the range of the BD semivariogram. The correlation coefficients between PR and the other measured variables are very small before and after irrigation, which could lead to the conclusion that those variables are not related at all. However, according to the co-dispersion coefficients plotted as a function of the separation lag, the correlation between those variables changes according to the separation distance. Particularly, PR and the RT show correlation 24 h after irrigation only for lags between 5 and 12 m. The results pointed out that PR spatial variability depends on soil moisture condition, soil BD and on several local features as microtopography.     

Active label-based packaging to extend the shelf-life of “Calanda” peach fruit: Changes in fruit quality and enzymatic activity

Nectarine fruit after cold storage soften normally, but become dry instead of juicy and can develop flesh browning, bleeding and a gel-like or glassy formation of the flesh near the pit. An experiment was conducted to see if time-resolved reflectance spectroscopy could distinguish these internal disorders non-destructively. The optical parameters of absorption coefficient (μ_a) and reduced scattering coefficient (μ′_s) were measured at 670 nm and 780 nm, on nectarine (Prunus persica cv. Morsiani 90) fruit held at 20 °C after harvest or after 30 d of storage at 0 °C or 4 °C. Each day for 5 d 30 fruit were examined both non-destructively and destructively. Other measurements were firmness with a penetrometer, peel colour on the blush and non-blush side, expressible juice, weight loss, and visual rating of internal browning, bleeding, and gel. The fruit had been sorted at harvest according to the value of μ_a670 so that each batch had a similar spread of fruit maturity. More mature fruit (lower μ_a670 values) developed internal browning and bleeding with more severe symptoms compared to less mature ones (higher μ_a670 values). It was found that μ_a780 could distinguish healthy fruits from the chilling injured ones. Canonical discriminant analysis indicated that fruit without cold storage had low μ_a780, less water loss, low firmness, but high μ_a670 and high expressible juice compared with cool stored fruit. Fruit cool stored at 4 °C had high μ_a780 and less expressible juice, lower water loss and lower firmness compared with fruit cool stored at 0 °C. It was concluded that time resolved reflectance spectroscopy could detect internal woolliness and internal browning in nectarines after storage.     

Deeply inverted electron-hole recombination in a luminescent antibody-stilbene complex

The blue-emissive antibody EP2-19G2 that has been elicited against trans-stilbene has unprecedented ability to produce bright luminescence and has been used as a biosensor in various applications. We show that the prolonged luminescence is not stilbene fluorescence. Instead, the emissive species is a charge-transfer excited complex of an anionic stilbene and a cationic, parallel pi-stacked tryptophan. Upon charge recombination, this complex generates exceptionally bright blue light. Complex formation is enabled by a deeply penetrating ligand-binding pocket, which in turn results from a noncanonical interface between the two variable domains of the antibody.     

Grass-induced changes in properties of soils in urban green areas with emphasis on mobility of metals

Purpose

Green areas in urban parks are special ecosystems because of social and ecological benefits.

Materials and methods

We investigated the ecological impacts of green spaces by comparing the properties of soils, with emphasis on metals, in green spaces and bare soil playgrounds in four urban parks in Murcia City (SE Spain).

Results and discussion

Organic matter (OM) contents in green areas are higher than playground soils due to litter decomposition from grass. Cation exchange capacity in green areas ranged from 10 to 14 compared to 2 cmol₊kg^?1 in playground soils, showing the effect of OM (and clay) contents in green areas due to the presence of vegetation. Soil total metal contents in urban parks are below the environmental threshold values for soils in Spain and other European countries, and come from atmospheric deposition and fertilizers application. Diethylenetriaminepentaacetic acid (DTPA)-extractable soil Cd in green areas (4% of total Cd) is lower than in playground soils (58% of total Cd). We attributed the reduced DTPA- and water-extractable Cd, Co, Cr, Mn, and Mo to the formation of stable complexes between metals and OM produced from the continued decomposition of roots of grasses in green spaces.

Conclusions

Grasses accumulate less metal than soils except in roots where Cr and Zn are higher than soils by as much as 31 and 17%, respectively. We conclude that grasses increased (up to 8×) soil OM content in green areas to significantly increase the ability of soils to accumulate nutrients for plants, and to retain and reduce the mobility and toxicity of metals in soils in urban parks.     

Assessment of the removal efficiency of fish farm effluents by grey mullets: a nutritional approach

A field study was carried out to assess the use of the bottom‐feeding grey mullet (Mugil cephalus) within benthic enclosures as a means to reduce the benthic impacts of a net cage fish farm in the Gulf of Aqaba, Red Sea. Five experimental 1‐m³ net‐cage enclosures were stocked with 12 grey mullets each (fish weights 50, 70 or 144 g). The enclosures had no bottom and the mullets had access to the enclosed organically enriched sediments and to particulate matter (PM) falling from the overlying cages. Sediment traps were used to quantify and qualify the PM falling from the fish farm to the sea floor. Simultaneously, a feeding trial was performed with mullets (50 and 70 g) in experimental tanks. In order to estimate the potential growth rate and to quantify energy and protein requirements, the fish were fed a formulated diet with known composition. After approximately 70 days at sea, mullets in the enclosures had used up all the available food in the sediment and gained up to 0.78 g day^?1 fish^?1. Applying the values for energy and protein requirements for maintenance and growth derived from the experimental trial, estimates indicated that the grey mullets effectively removed 4.2 g organic carbon, 0.70 g nitrogen and 7.5 mg phosphorus kg^?1 mullet m^?2 day^?1 from the organically enriched sediment. Thus deployment of grey mullets may be an efficient means to improve the quality of sediments below intensive net‐cage fish farms.     

Effect of sodium arsenite and sodium chloride on bean plant nutrition (macronutrients)

The effects of different levels of arsenic (As) and salinity on bean plant (Phaseolus vulgaris L., cv. Buenos Aires) nutrition were investigated. We studied the processes of absorption and accumulation of macronutrient elements: nitrogen (N), phosphorus (P), potassium (K), calcium (Ca), and magnesium (Mg). The experiment was performed in soilless culture at two levels of As: 2 and 5 mg AsL^‐1 (added as sodium arsenite, NaAsO₂), and three saline levels [only sodium chloride (NaCl) was added]: 1, 2, and 4 dS‐m^‐1. Sodium arsenite and NaCl significantly affected macronutrients allocation within bean plant at concentration levels used in this study. Arsenite depressed K, Na, and Mg concentrations in root, whereas root N, and Ca levels were increased. Nitrogen, P, K, and Na concentrations were significantly higher in As‐stressed plants compared with controls. The addition of NaCl increased Ca concentration in roots and decreased that of K. Salinity tended to increase leaf concentrations of K, Na, Ca, and Mg; whereas leaf N and P levels decreased with increasing salinity.     

Response of bean micronutrient nutrition to arsenic and salinity

The effects of different levels of arsenic (As) and salinity on bean plant (Phaseolus vulgaris L., cv. Buenos Aires) nutrition were investigated. We studied the processes of absorption and accumulation of chloride (Cl) and micronutrient elements: boron (B), copper (Cu), iron (Fe), manganese (Mn), and zinc (Zn). The experiment was performed in soilless culture at two levels of As: 2 and 5 mg As L^‐1 [added as sodium arsenite (NaAsO₂)], and three saline levels [only sodium chloride (NaCl) was added]: 1, 2, and 4 dSm^‐1. Sodium arsenite and NaCl significantly affected micronutrients allocation within the bean plant at levels used in this study. Arsenite depressed Mn and Cl concentrations in the root, whereas root B, Cu, and Zn levels were increased. Boron, Cu, Fe, and Cl concentrations were significantly higher in As‐stressed plants compared with controls. The addition of NaCl increased the Cl and Mn concentrations in roots and Cl, Fe, and Mn in leaves.