Background: Honey is a natural product that, thanks to its composition, particularly the high sugar content, is highly appreciated as an energy nourishment. In addition to sugars, it contains many other substances (carbohydrates, free amino acids, enzymatic proteins, organic acids, polyphenols) from which the therapeutic properties of honey arise: hydrating and osmotic activity, antimicrobial action, and antioxidant and anti-inflammatory power. Objectives: The present work aims to deepen our knowledge/understanding of the activity of skin protection exerted by honey, as a synergic result of its multiple therapeutic effects. Moreover, this study wants to find possible correlations between biological properties and the chemical-physical traits of honey. Methods: To carry out this research, five varieties of citrus honey, one of acacia honey, one of chestnut honey, and one of multifloral honey were used. The honeys were first characterized by chemical-physical analysis and then were subjected to qualitative melissopalynological analysis. Tests were also carried out to evaluate both their antioxidant power and the effect on collagenase, an enzyme involved in the degradation of collagen present in the extracellular matrix and, therefore, in the processes of skin aging. Finally, honey samples were then used in in vitro experiments to assess their action in stimulating cell viability and proliferation on human keratinocytes. Results: Chemical-physical analysis demonstrated a good water content (about 17%), an important sugar content (with the monosaccharides glucose and fructose being the most represented in all the honey samples), various amino acids (with proline remarkably being the highest in all honeys), and a high concentration of polyphenols and total flavonoids (the maximum in chestnut honey, 762 mg/kg and 514 mg/kg, respectively). Conclusions The results obtained in this work confirm the ethnopharmacological use of honey in wound care, bring new scientific knowledge on the use of honey in dermatology, and highlight two fields of excellence, particularly incitrus and chestnut honey.

Direct methanol fuel cells are regarded nowadays as promising energy sources for portable electronic devices.Numerical models can be very useful for addressing the exploration of the fuel cell performance, without the development of many prototypes, which can be very expensive due to the presence of rear materials.Analytical models are particularly suited for investigating the cell performance with limited computing costs.In this work, a two-dimensional model for assessing the performance of an active-feed direct methanol fuel cell is presented, accounting for electrochemical reactions, mass and heat transfer.

Nuptial and extranuptial nectaries are involved in interactions with different animal functional groups. Nectar traits involved in pollination mutualisms are well known. However, we know little about those traits involved in other mutualisms, such as ant-plant interactions, especially when both types of nectaries are in the same plant organ, the flower. Here we investigated if when two types of nectaries are exploited by distinct functional groups of floral visitors, even being within the same plant organ, the nectar secreted presents distinct features that fit animal requirements. We compared nectar secretion dynamics, floral visitors and nectar chemical composition of both nuptial and extranuptial nectaries in natural populations of the liana Amphilophium mansoanum (Bignoniaceae). For that we characterized nectar sugar, amino acid and specialized metabolite composition by high-performance liquid chromatography. Nuptial nectaries were visited by three medium- and large-sized bee species and extranuptial nectaries were visited mainly by ants, but also by cockroaches, wasps and flies. Nuptial and extranuptial nectar differed regarding volume, concentration, milligrams of sugars per flower and secretion dynamics. Nuptial nectar was sucrose-dominated, with high amounts of γ-aminobutyric acid and β-aminobutyric acid and with theophylline-like alkaloid, which were all exclusive of nuptial nectar. Whereas extranuptial nectar was hexose-rich, had a richer and less variable amino acid chemical profile, with high amounts of serine and alanine amino acids and with higher amounts of the specialized metabolite tyramine. The nectar traits from nuptial and extranuptial nectaries differ in energy amount and nutritional value, as well as in neuroactive specialized metabolites. These differences seem to match floral visitors' requirements, since they exclusively consume one of the two nectar types and may be exerting selective pressures on the composition of the respective resources of interest.

In the quest for eco-friendly products with biostimulant properties, foliar application of wood distillate (WD) was tested on the growth and yield of chickpea (Citer arietinum L.). WD (pyroligneous acid) is a by-product of plant biomass pyrolysis and is rich in biologically active substances like polyphenols, alcohols, acids and esters. In this work, chickpea plants were sprayed weekly with 100 ml 0.25% (v/v) chestnut (Castanea sativa Mill.) WD during the whole growing period, and at the end physiological and nutritional analyses were performed both on the whole plant and on seeds. While plant height and weight did not change significantly, seeds showed an increase in diameter (+11.2%) and weight (+33.3%), and in the content of starch (+45.9%), total soluble protein (+12.9%), total polyphenol (+16.4%) and antioxidant power (+28.4%). Overall, the content of essential free amino adds increased, except for lysine (-3.4%), phenylala nine (-10.5%) and methionine (-13.7%). Among all the mineral elements analysed, only potassium and magnesium decreased in WD-treated plants, although values were within the common range for chickpea seeds. These results are a clear demonstration of the effectiveness of the use of WD on increasing the nutritional qualities of the edible parts of crop species, thus representing a possible solution to counteract human malnutrition and famine as well as environmental concerns.

Brodifacoum is the most common rodenticide used for the eradication of invasive rodents from islands. It blocks the vitamin K cycle, resulting in hemorrhages in target mammals. Non-target species may be incidentally exposed to brodifacoum, including marine species. A case study conducted on the Italian Marine Protected Area of Tavolara Island was reported after a rodent eradication using the aerial broadcast of a brodifacoum pellet. Brodifacoum presence and effects on non-target marine organisms were investigated. Different fish species were sampled, and a set of analyses was conducted to determine vitamin K and vitamin K epoxide reductase concentrations, prothrombin time, and erythrocytic nuclear abnormalities (ENA) assay. In all the examined organisms, brodifacoum was not detected. The results obtained showed differences in vitamin K and vitamin K epoxide concentrations among the samples studied, with a positive correlation for three species between vitamin K, vitamin K epoxide, and fish weight. The prothrombin time assay showed a good blood clotting capacity in the fish. Higher abnormality values were recorded for four species. The results of this study suggest that it is possible to hypothesize that the sampled fish were not likely to have been exposed to brodifacoum and that consequently there are no negative issues concerning human consumption.

This study examined whether foliar applications of wood distillate (WD) have a protective effect on photosynthesis and the antioxidant power of lettuce when exposed to an ecologically relevant O3 concentration. Seedlings of lettuce (Lactuca sativa L.) were fumigated daily with 60 ppb of O3 for 30 days, five hours per day. Once per week, 50% of the fumigated plants were treated with foliar applications of 0.2% WD, while control plants were treated with water. The results clearly showed the ability of WD to protect lettuce plants from ozone-induced damage. Specifically, WD-treated plants exhibited lower damage to the photosynthetic machinery, assessed through a series of chlorophyll fluorescence parameters, a higher chlorophyll content, higher antioxidant power, as well as antioxidant molecules, i.e., caffeic acid and quercetin, and higher biomass. Counteracting the overproduction of ozone-generated reactive oxygen species (ROS) is speculated to be the main mechanism by which WD protects the plant from ozone-induced damage.

Goji (Lycium barbarum L.) berries are well known for their biological activities and health-promoting antioxidant properties. Environmental and climatic factors can greatly affect accumulation of secondary metabolites, carotenoids and other antioxidants in plants. We determined the content and composition of main functional constituents of goji berries produced in central Italy in relation to the time of harvesting during two ripening seasons by analyzing the main environmental variables involved. The highest flavonoids content (0,19 +/- 0,006 mg QE/g) and antioxidant power (0,03 +/- 0,001 mmol Fe(2+)eq/g) were found at the beginning of the fruiting season. In September, berries show the highest total polyphenols (3,22 +/- 0,09 mg GAE/g) and zeaxanthin contents (339,79 +/- 14,12 mu g/g). Our study focused on some important aspects related to the production of goji fruits with high nutraceutical characteristics in a non-experimental cultivation. Our results could provide reliable information on Goji performance in the European climate to be used for the exploitation of the species suggesting the best harvesting timing in terms of antioxidant power and nutraceutical features of berries. This information could be particularly useful for farmers eager to improve the quality of their products.

The composition of fluids that mediate fertilization in cycads is described for the first time. Using tandem mass spectrometry, proteomes of two stages of fluid production, megagametophyte fluid and archegonial chamber fluid production, are compared in Cycas revoluta . These were compared with the proteome of another sexual fluid produced by ovules, the pollination drop proteins. Cycad ovules produce complex liquids immediately prior fertilization. Compared with the pollination drops that mainly had few proteins in classes involved in defense and carbohydrate modification, megagametophyte fluid and archegonial chamber fluid had larger proteomes with many more protein classes, e.g. proteins involved in programmed cell death. Using high-performance liquid chromatography, megagametophyte fluid and archegonial chamber fluid were shown to have elevated concentrations of smaller molecular weight molecules including glucose, pectin and glutamic acid. Compared to megagametophyte fluid, archegonial chamber fluid had elevated pH as well as higher osmolality.

BACKGROUND:This study aims to evaluate the performance, in terms of accumulation of antioxidant compounds in fruits, of nine local and three commercial Italian tomato cultivars subjected to drought stress. The same local cultivars had been previously studied at morpho-physiological level.METHODS:The present manuscript analyzes drought stress as a tool to increase the amount of secondary metabolites that can enhance fruit quality. Nutraceutical characterization of the fruits was performed by analyzing the content of antioxidants, phenols, flavonoids, lycopene, ascorbic acid (vitamin C), rutin, caffeic acid, and naringenin. At the same time, plant sensitivity to stress during the reproductive phase was monitored in terms of flower abscission, fruit drop, and seed germination.RESULTS:Perina turns out to be the tomato cultivar with the best nutraceutical properties in the absence of stress while the Quarantino cultivar is so for flavonoid content (control plants) and lycopene and vitamin C content (stressed plants). Perina and Quarantino are the cultivars with the best response to drought and Perina has the highest concentrations of bioactives. Quarantino responds most effectively to stress in the reproductive phase.CONCLUSIONS:data confirm that drought stress increases bioactive production in some local cultivars of tomato, which produce higher quality fruits.

Bio-stimulants are showing growing success and are gradually replacing synthetic fertilizers in agriculture. Wood distillate (WD), also known as wood vinegar or pyroligneous acid, is a by-product of biomass pyrolysis and is increasingly used as a bio-stimulant for crop production. This study investigated whether weekly foliar applications of 0.25% and 0.50% WD have a differential effect on the chlorophyll and sugar content as well as biomass production in lettuce (Lactuca sativa L.). Moreover, the additional beneficial effect from the addition of corroborants of plant origin such as 3% soy lecithin and 5% flavonoid-rich wood glycolic extract to WD (BF) was investigated. Moreover, the possible toxicological concern from some potentially toxic elements (PTEs), namely Cd, Cu, Fe, Pb, and Zn, which may be abundant in WD was verified. After four weeks, we found that 0.25% WD not only increases lettuce biomass, which has an economic value, but also has beneficial effects on other qualitative parameters such as sugars and total sweetness. On the other hand, the use of 0.5% WD decreased the content of soluble sugars, suggesting a hormetic-type effect. We did not find evidence of further beneficial effects from the addition to WD of plant-derived corroborants, nor of any enrichment in the content of the investigated PTEs.

Floral nectar is the primary reward directly consumed by floral visitors and its chemical composition affects their behaviour and fidelity. In turn, floral visitors are expected to alter floral nectar composition directly or indirectly through the introduction of external contaminants, such as pollen grains and microorganisms. To understand the effect of exogenous factors on nectar chemistry, we investigated the modifications of nectar sugar and amino acid composition in relation to floral visitors in the perennial herb Gentiana lutea. We quantified nectar contamination by floral visitors through visitor exclusion experiments in the field, estimating pollen and yeast concentration in visited flowers and in uncontaminated nectar at two different flower stages (flower bud and older open flowers). We then assessed changes in the composition and concentration of sugars and both protein and non‐protein amino acid in the nectar. We found clear differences in the chemical composition of flower nectar in relation to flower stage and floral visitation. Nectar sugar and amino acid concentrations were significantly higher in older flowers than in flower buds. In addition, nectar sugar concentration was significantly higher in older flowers where visitors were excluded than in visited flowers. On the contrary, amino acid concentration was comparable between visited and non‐visited older flowers. We also found that pollen contamination enriched the amino acid profile of the host nectar both quantitatively and qualitatively. Finally, nectar exposed to floral visitors showed a higher number of yeast cells than unvisited flowers although too low to cause the observed changes in the glucose:fructose ratio, suggesting the presence of fructose‐related bacteria. Our results show that the chemical composition of floral nectar is altered by several endogenous and exogenous factors in a complex process of ecological relations, and suggest that the modulation of floral visitation through nectar is not solely related to the plant itself.

The Mediterranean basin hosts a high diversity of plants and bees, and it is considered one of the world’s biodiversity hotspots. Insect pollination, i.e., pollen transfer from male reproductive structures to conspecific female ones, was classically thought to be a mutualistic relationship that links these two groups of organisms, giving rise to an admirable and complex network of interactions. Although nectar is often involved in mediating these interactions, relatively little is known about modifications in its chemical traits during the evolution of plants. Here, we examine how the current sucrose-dominated floral nectar of most Mediterranean plants could have arisen in the course of evolution of angiosperms. The transition from hexose-rich to sucrose-rich nectar secretion was probably triggered by increasing temperature and aridity during the Cretaceous period, when most angiosperms were radiating. This transition may have opened new ecological niches for new groups of insects that were co-diversifying with angiosperms and for specific nectar-dwelling yeasts that originated later (i.e., Metschnikowiaceae). Our hypothesis embeds recent discoveries in nectar biology, such as the involvement of nectar microbiota and nectar secondary metabolites in shaping interactions with pollinators, and it suggests a complex, multifaceted ecological and evolutionary scenario that we are just beginning to discover.

In the Valdichiana area (Tuscany, Italy) an ancient native landrace of elephant garlic (Allium ampeloprasum L.), locally known as “Aglione della Valdichiana”, has long been cultivated. The aim of this study was to check whether there are differences in the mineral and nutraceutical profiles of the Aglione della Valdichiana cultivated conventionally and organically. Based on the analysis by ICP-MS of a wide array of major, minor, essential, and non-essential trace elements as well as rare earth elements, and the evaluation of the content of polyphenols, flavonoids, antioxidants, soluble proteins, soluble sugars, and starch, as well as the weight and water content, it was concluded that differences in the mineral and nutraceutical profiles of organically and conventionally grown bulbs were very limited. Only a statistically (p < 0.05) higher concentration of Cd (+2620%), Co (+113%), Mn (+55%), Rb (+180%), and Sb (+180%), as well as glucose (+37%) in conventionally cultivated bulbs emerged. Cadmium was the only element slightly higher than in the “reference plant,” but with a negligible risk (three orders of magnitude lower) for human health based on consumption. It is concluded that we failed to find evidence of healthier food or a higher nutraceutical quality for organically cultivated elephant garlic.

In this study, the release of Cu 2+ and Zn 2+ was investigated and modeled in the epiphytic lichen Evernia prunastri. Samples were incubated with solutions containing these metals at ecologically relevant concentrations (10 and 100 μM) and then transplanted to a remote area and retrieved after 1, 2, 3, 6, 12, and 18 months. The results showed that, after 12 months, all samples faced similar metal reductions of ca. 80–85%, but after this period, all the involved processes seem to be no longer capable of generating further reductions. These results suggest that the lichen E. prunastri can provide information about environmental improvements after exposure to high or very high pollution levels in a relatively short period of time.

Background: A diet rich in fruits and vegetables contributes to lowering the risk of chronic diseases. The fruits of Malus x domestica are a rich dietary source of bioactive compounds, namely vitamins and antioxidants, with recognized action on human health protection. Tuscany is known for its rich plant biodiversity, especially represented by ancient varieties of fruit trees. Particularly noteworthy are the many ancient Tuscan varieties of apple trees. Methods: Sugar quantification via HPLC and spectrophotometric assays to quantify the antioxidant power and total polyphenol content revealed interesting differences in 17 old varieties of Malus x domestica Borkh. recovered in Siena (Tuscany). Results: The quantification of antioxidants, polyphenols, and the main free sugars revealed that their content in the old fruits was often superior to the widespread commercial counterparts ('Red Delicious' and 'Golden Delicious'). Such differences were, in certain cases, dramatic, with 8-fold higher values. Differences were also present for sugars and fibers (pectin). Most ancient fruits displayed low values of glucose and high contents of xylitol and pectin. Conclusions: The results reported here suggest the possible use of ancient apple varieties from Siena for nutraceutical purposes and draw attention to the valorization of local old varieties.

In this work, two hypotheses have been tested: 1) that lichen transplants "travelling" in smokers' cars accumulate relevant amounts of nicotine and heavy metals from cigarette smoke, and 2) that such exposure affects their vitality. Lichen samples (Evernia prunastri) were exposed for two months inside the cabin of 10 volunteer's cars, equally distributed between smokers and non-smokers. Travelling in a smoker's car for two months increased the content of nicotine and heavy metals (Al, As, Cd, Cr, Cu, Ni, Pb and Sb) in the lichen. Exposed to Control (EC) ratios revealed an indoor uptake also for Cu and Sb in non-smoker's cars, caused by traffic pollution. A smoke factor, calculated as the ratio between values of smokers' and non-smokers' cars, indicated a 85.6-fold contribution for nicotine and contributions in the range 1.2 (Pb) to 2 (Ni) for heavy metals; in addition, after travelling in smokers' cars, lichens showed a remarkable (60%) reduction of their vitality, as indicated by the potential quantum yield of primary photochemistry. The study demonstrated that the effects of indoor pollution by cigarette smoke can be detected using lichen transplants.

How long does it take a lichen to respond to changes (worsening or improvement) of atmospheric conditions is still discussed. We selected and removed lichen thalli (Flavoparmelia caperata) from sites subject to different intensities of pollution around a landfill in Central Italy and exposed them in a remote unpolluted area for 12 months. The content of elements of toxicological concern (As, Cd, Cr, Cu, Pb, Zn) and several physiological parameters in lichen thalli (chlorophyll a fluorescence emission, chlorophyll content and integrity, membrane lipid peroxidation, content of secondary metabolites and ergosterol content) were investigated before and after the recovery and hence compared with those of native (and clean) samples of the remote area. In an opposite trial, heavy metals content was investigated in samples taken from the remote area and exposed around the landfill. Values of the transplants were then compared with those of native samples at the landfill. From chemical point of view, the content of heavy metals decreased (by ca. 25%) in lichen thalli taken from the landfill and exposed in the remote area, however background values were never reached. On the other hand, lichen thalli taken from the remote area and exposed around the landfill accumulated up to ca. 80% of the content of in situ samples. The rate of accumulation was higher than the rate of element loss referred to the same temporal interval. The recovery of physiological parameters, especially those typical of the mycobiont or of the whole lichen symbiosis, was much faster than heavy metal detoxification, and after 12 months transplanted lichens already reflected the new environmental conditions at the remote site.

Background and Aims Gymnosperms are either wind-pollinated (anemophilous) or both wind- and insect-pollinated (ambophilous). Regardless of pollination mode, ovular secretions play a key role in pollen capture, germination and growth; they are likely also involved in pollinator reward. Little is known about the broad-scale diversity of ovular secretions across gymnosperms, and how these may relate to various reproductive functions. This study analyses the sugar and amino acid profiles of ovular secretions across a range of ambophilous (cycads and Gnetales) and anemophilous gymnosperms (conifers) to place them in an evolutionary context of their possible functions during reproduction. Methods Ovular secretions from 13 species representing all five main lineages of extant gymnosperms were sampled. High-performance liquid chromatography techniques were used to measure sugar and amino acid content. Multivariate statistics were applied to assess whether there are significant differences in the chemical profiles of anemophilous and ambophilous species. Data were compared with published chemical profiles of angiosperm nectar. Chemical profiles were placed in the context of phylogenetic relationships. Key results Total sugar concentrations were significantly higher in ovular secretions of ambophilous species than wind-pollinated taxa such as Pinaceae and Cupressophyta. Ambophilous species had lower amounts of total amino acids, and a higher proportion of non-protein amino acids compared with anemophilous lineages, and were also comparable to angiosperm nectar. Results suggest that early gymnosperms likely had ovular secretion profiles that were a mosaic of those associated with modern anemophilous and ambophilous species. Ginkgo, thought to be anemophilous, had a profile typical of ambophilous taxa, suggesting that insect pollination either exists in Gingko, but is undocumented, or that its ancestral populations were insect-pollinated. Conclusions Chemical profiles of ovular secretions of ambophilous gymnosperms show a clear signal of pollinator-driven selection, including higher levels of carbohydrates than anemophilous taxa, lower levels of amino acids, and the presence of specific amino acids, such as β-alanine, that are known to influence insect feeding behaviour and physiology.