Iron chelation by the powerful antioxidant flavonoid quercetin

Chelation of the bare and hydrated iron(II) cation by quercetin has been investigated at the DF/B3LYP level in the gas phase. Several complexed species arising from neutral and anionic forms of the ligand have been taken into account. Both 1:1 and 1:2 metal/flavonoid stoichiometries have been considered. Results indicate that among the potential sites of chelation present on quercetin, the oxygen atoms belonging to the 3-hydroxy and 4-oxo, and to the 5-hydroxy and 4-oxo groups, are the preferred ones. Time-dependent density functional theory (TDDFT) calculations, used to reproduce the electronic UV-vis spectra of isolated quercetin and its complexes with Fe2+, were also performed in methanol and dimethylsulfoxide.     

Landscape dynamics of floral resources affect the supply of a biodiversity-dependent cultural ecosystem service

Context

Cultural ecosystem services, many of which depend on biodiversity, are recognized as important but seldom quantified biophysically across landscapes. Furthermore, many ecosystem service models are static, and the supply of cultural ecosystem services may be misrepresented if seasonal shifts in biotic communities are ignored.

Objectives

We modeled landscape dynamics of wildflower blooms in a temperate montane landscape to determine (1) how floral resources (wildflower species richness, abundance, timing, and presence of charismatic species) changed over the growing season, (2) how projected wildflower viewing hotspots varied over space and time, and (3) how spatial shifts in floral resources affected potential public access to wildflower viewing.

Methods

Data were collected at 63 sites across a rural-to-urban gradient in the Southern Appalachian Mountains (USA). Generalized linear models were used to identify factors affecting floral resources at two temporal scales. Floral resources were projected across the landscape and hotspots of wildflower viewing were quantified using overlay analysis.

Results

Floral resources were affected by topoedaphic conditions, climate, and surrounding building density and changed seasonally. Seasonal models revealed locational shifts in ecosystem service hotspots, which changed the proportion of hotspots accessible to the public and identified wildflower-viewing opportunities unnoticed by static models.

Conclusion

Relationships between landscape gradients, biodiversity, and ecosystem service supply varied seasonally, and our models identified cultural ecosystem service hotspots otherwise obscured by simple proxies. Landscape models of biodiversity-based cultural ecosystem services should include seasonal dynamics of biotic communities to avoid under- or over-emphasizing the importance of particular locations in ecosystem service assessments.

     

Characterization of hemiacetal forms of anthocyanidin 3-O-beta-glycopyranosides

The 3-O-beta-glucopyranosides of delphinidin, petunidin, and malvidin (1-3) and cyanidin 3-O-beta-galactopyranoside (4) dissolved in deuterated methanolic solutions without and with acid (5%, CF3COOD) were identified by homo- and heteronuclear NMR techniques. The hemiacetal forms of all the four anthocyanins were characterized as two epimeric 2-hydroxy-hemiacetals on the basis of assignments of both proton and carbon NMR signals together with chemical shift considerations. This is the first report of 13C NMR assignments of two epimeric anthocyanin hemiacetal forms. No 4-hydroxy-hemiacetal form was detected for any of the pigments. For each anthocyanin dissolved in deuterated methanol, the equilibrium between each of the two epimeric hemiacetals and the corresponding flavylium cation was confirmed by the observed positive exchange cross-peaks in the 2D 1H NOESY spectra. The molar proportions of the flavylium cation and the two hemiacetals of 1-4 in deuterated methanol were very similar for all pigments, even during storage for weeks. The majority of the anthocyanins reported to occur in fruits have the same or similar structures as 1-4. These pigments have been proposed to exist predominantly as hemiacetals in slightly acidic to neutral solvents, which is a relevant pH range in plants and in the human gastrointestinal tract.     

Use of partition and redistribution indexes for heavy metal soil distribution after contamination with a multi-element solution

Purpose  

Tessier's sequential extraction method is usually used to study metal parting among different phases in soils. The main objective of this study was to determine the redistribution of trace metals which were added simultaneously to a sandy loam soil by use of the fractional distribution and reduced partition indexes and the risk of assessment code (RAC).     

Chemical characterization and antioxidant properties of coffee melanoidins

Melanoidins, the brown polymers formed through Maillard reaction during coffee roasting, constitute up to 25% of the coffee beverages' dry matter. In this study chemical characterization of melanoidins obtained from light-, medium-, and dark-roasted coffee beans, manufactured from the same starting material, was performed. Melanoidins were separated by gel filtration chromatography and studied by MALDI-TOF mass spectrometry. Results showed that the amount of melanoidins present in the brews increased as the intensity of the thermal treatment increased, while their molecular weight decreased. The antioxidant activity of melanoidins isolated from the different brews was studied by using different methodologies. Melanoidins antiradical activity determined by ABTS(*)(+) and DMPD(*)(+) assays decreased as the intensity of roasting increased, but the ability to prevent linoleic acid peroxidation was higher in the dark-roasted samples. Data suggest that melanoidins must be carefully considered when the relevance of coffee intake in human health is studied.     

Optothermistor as a breakthrough in the quantification of lycopene content of thermally processed tomato-based foods: verification versus absorption spectrophotometry and high-performance liquid chromatography

This study reports on the first use of the "optothermistor" as a novel, precise, fast, and low-cost detector of lycopene in a wide range of commercially available processed-tomato products. The quantitative performance of the new device was evaluated by comparing data obtained to that acquired by conventional methods, namely, absorption spectrophotometry and high-performance liquid chromatography (HPLC); the linear correlation was high (R = 0.98). The variation of data obtained with the optothermistor in a series of consecutive measurements performed with the same loading of the sample was better than 1%. However, the repeatability (RSD 0.5-9.0%, n = 3-5) achieved with the optothermistor by independent analyses (multiple loading) is comparable to that of HPLC and spectrophotometry. Results of the studies performed on the 19 products derived from tomatoes demonstrated that the optothermistor is suitable for selective, accurate, precise, and simple determination of lycopene (range = 7-75 mg/100 g of product weight) without the need for a sample pretreatment step. The estimated sensitivity of the present optothermistor is 2 mg of lycopene/100 g of product.     

Consequences of spatial heterogeneity for ecosystem services in changing forest landscapes: priorities for future research

Changes in key drivers (e.g., climate, disturbance regimes and land use) may affect the sustainability of forest landscapes and set the stage for increased tension among competing ecosystem services. We addressed two questions about a suite of supporting, regulating and provisioning ecosystem services in each of two well-studied forest landscapes in the western US: (1) How might the provision of ecosystem services change in the future given anticipated trajectories of climate, disturbance regimes, and land use? (2) What is the role of spatial heterogeneity in sustaining future ecosystem services? We determined that future changes in each region are likely to be distinct, but spatial heterogeneity (e.g., the amount and arrangement of surviving forest patches or legacy trees after disturbance) will be important in both landscapes for sustaining forest regeneration, primary production, carbon storage, natural hazard regulation, insect and pathogen regulation, timber production and wildlife habitat. The paper closes by highlighting five general priorities for future research. The science of landscape ecology has much to contribute toward understanding ecosystem services and how land management can enhance—or threaten—the sustainability of ecosystem services in changing landscapes.     

Biocatalytic synthesis of butein and sulfuretin by Aspergillus alliaceus

Aspergillus alliaceus UI315 was examined for its potential to catalyze biotransformation reactions of chalcones that mimic plant biosynthetic processes. 3-(4' '-Hydroxyphenyl)-1-(2',4'-dihydroxyphenyl)propenone (4,2',4'-trihydroxychalcone, isoliquiritigein) (1) was efficiently transformed to two major metabolites that were isolated chromatographically and identified by spectroscopic methods as 3-(3' ',4' '-dihydroxyphenyl)-1-(2',4'-dihydroxyphenyl)propenone (butein) (7) and 2-[(3,4-dihydroxyphenyl)methylene]-6-hydroxy-3(2H)benzofuranone (7,3',4'-trihydroxyaurone, sulfuretin) (10). Inhibition experiments suggested that initial C-3 hydroxylation of 1 to 7 was catalyzed by a cytochrome P450 enzyme system. A second A. alliaceus enzyme, partially purified and identified as a catechol oxidase, catalyzed the oxidation of the catechol butein (7) likely through an ortho-quinone (8) that cyclized to the aurone product 10. This work showed that A. alliaceus UI315 contains oxidative enzyme systems capable of converting phenolic chalcones such as 1 into aurones such as 10 in a process that mimics plant biosynthetic pathways.     

Interactions of soy protein fractions with high-methoxyl pectin

A protein-binding technique was employed to visualize, using scanning electron microscopy, the soy protein as well as the association between HMP and soy protein fractions. Image analysis indicated that at pH 7.5 and 3.5 soy protein isolate showed a bimodal distribution of sizes with an average [ d(0.5)] of about 0.05 microm, but at pH 3.8 the proteins formed larger aggregates than at high pH. Addition of HMP at pH 3.8 changed the surface charge of the particles from +20 to -15 mV. A small addition of HMP caused bridging of the pectin between soy protein aggregates and destabilization. With sufficient HMP, the suspensions showed improved stability to precipitation. The microscopy images are the first direct evidence of the interactions between soy proteins with high-methoxyl pectin (HMP).