Reversible reduction of oxygen to peroxide facilitated by molecular recognition

Generation of soluble sources of peroxide dianion (O(2)(2-)) is a challenge in dioxygen chemistry. The oxidizing nature of this anion renders its stabilization in organic media difficult. This Report describes the chemically reversible reduction of oxygen (O(2)) to cryptand-encapsulated O(2)(2-). The dianion is stabilized by strong hydrogen bonds to N-H groups from the hexacarboxamide cryptand. Analogous stabilization of peroxide by hydrogen bonding has been invoked recently in crystalline saccharide and protein systems. The present peroxide adducts are stable at room temperature in dimethyl sulfoxide (DMSO) and N,N'-dimethylformamide (DMF). These adducts can be obtained in gram quantities from the cryptand-driven disproportionation reaction of potassium superoxide (KO(2)) at room temperature.     

Genetic variant BDNF (Val66Met) polymorphism alters anxiety-related behavior

A common single-nucleotide polymorphism in the brain-derived neurotrophic factor (BDNF) gene, a methionine (Met) substitution for valine (Val) at codon 66 (Val66Met), is associated with alterations in brain anatomy and memory, but its relevance to clinical disorders is unclear. We generated a variant BDNF mouse (BDNF(Met/Met)) that reproduces the phenotypic hallmarks in humans with the variant allele. BDNF(Met) was expressed in brain at normal levels, but its secretion from neurons was defective. When placed in stressful settings, BDNF(Met/Met) mice exhibited increased anxiety-related behaviors that were not normalized by the antidepressant, fluoxetine. A variant BDNF may thus play a key role in genetic predispositions to anxiety and depressive disorders.     

Steam activation of biochars facilitates kinetics and pH-resilience of sulfamethazine sorption

Purpose

Sulfamethazine (SMT) is increasingly detected in environmental matrices due to its versatile use as antibiotics. We aimed to investigate the benefits and roles of steam activation of biochars with respect to SMT sorption kinetics and equilibrium sorption.

Materials and methods

Biochars were produced from burcucumber plant and tea waste using a pyrolyzer at a temperature of 700 °C for 2 h. The biochar samples were treated with 5 mL min^?1 of steam for an additional 45 min for post-synthesis steam activation. The SMT sorption on the unmodified and steam activated biochars were compared.

Results and discussion

The time taken to reach equilibrium was significantly less for steam activated biochars (～4 h) than non-activated biochars (>24 h). Up to 98 % of SMT could be removed from aqueous solutions by steam activated biochars. The sorption kinetic behaviors were well described by the pseudo-second model and SMT sorption rates of steam activated biochars (k ₂?～?1.11–1.57 mg g^?1 min^?1) were significantly higher than that of the unmodified biochars (k ₂?～?0.04–0.11 mg g^?1 min^?1) because of increased availability of accessible porous structure with averagely larger pore diameters. Moreover, the equilibrium sorption on the unmodified biochars was significantly influenced by increasing solution pH (～30–50 % reduction) because of speciation change of SMT, whereas steam activated biochars manifested much stronger sorption resilience against pH variation (～2–4 % reduction only) because the enhanced porosity offset the effect of unfavorable electrostatic repulsion.

Conclusions

The observed features of steam activated biochars would render their applications more versatile and reliable in field throughout changeable environmental conditions.

     

Influence of redox conditions and rice straw incorporation on nitrogen availability in fertilized paddy soils

Biology and Fertility of Soils - Temporal nitrogen (N) availability in fertilized rice paddies is the result of a balance of processes, mainly the gross rates of N mineralization, microbial and...     

Assessment of shoreline vegetation in relation to use by molting black brant Branta bernicla nigricans on the Alaska coastal plain

To evaluate the importance of large thaw lakes on the Alaska Coastal Plain for molting Pacific black brant Branta bernicla nigricans, distribution and life form of shoreline vegetation were assessed using several scales: satellite imagery, point-intercept transects, cover quadrats, and a parameter for water regime. Brant population and distribution estimates from aerial surveys were used to classify large lakes into high, moderate, and low use. Correlations between brant and abundance of their preferred feeding site — moss flats — were best demostrated by satellite imagery. Intercepts and cover ratings were not correlated, presumably because these techniques were less efficient at assessing area. General observations suggested that the presence of islands, large ice floes, and possibly other physical attributes of the habitat, influenced brant distribution. This area is unique because of low-lying, drained-lake basins that have ideal combinations of moss flats and large water areas where brant seek protection disturbance is vital to the success of this declining species because alternate habitats may not be available elsewhere on the Coastal Plain. in water or on ice floes. Protection of the area from     

Legume cover cropping effects on early growth and soil nitrogen supply in eucalypt plantations in south-western India

Growth and soil N supply in young Eucalyptus tereticornis stands at two sites in Kerala, India, were examined in response to cover cropping with three legume species (Pueraria phaseoloides, Stylosanthes hamata, and Mucuna bracteata). The effects of legume residues on soil N supply were investigated in a long-term (392 day) laboratory incubation using leaching micro-lysimeters. Residues from the eucalypt and legume species had different rates of net N release during the laboratory incubation. Net N release was significantly related to residue N concentration (R² =0.94), the C:N ratio (R² =0.91), the lignin:N ratio (R² =0.83), and the (lignin + soluble polyphenol):N ratio (R² =0.95). Nitrogen release rates declined in the order Mucuna > Pueraria > Eucalyptus > Stylosanthes. There was no net N release from Stylosanthes residues during the 392-day laboratory incubation, whereas Mucuna and Pueraria released N throughout the incubation period. Net N release from mixtures of legume and eucalypt residues was not additive in the early phase of the incubation, probably because eucalypt residues initially immobilized a portion of the legume-derived N in addition to the soil-derived N. Legume establishment had no significant effect on tree growth at one site (Kayampoovam), but resulted in depressed tree growth at the lower rainfall site (Punnala) at 18 months. There were no significant treatment effects on growth at Punnala after that time. Cover cropping with legumes during the early phase of forest plantation growth may be a useful mechanism to enhance soil N supply and optimize the synchrony between N supply and tree N uptake. Although these effects did not translate into improved plantation growth in the 3 years of this study, improved soil organic matter and N fertility may help ensure sustainable productivity over several rotations in the future. This study showed that the effect of legumes on N dynamics varies markedly with legume species. This, together with other factors (e.g. competition with trees, N fixation capacity), will be important in selecting suitable species for cover cropping in forest plantations.     

Surface cast production by the earthworm Aporrectodea nocturna in a pre-alpine meadow in Switzerland

Field and laboratory experiments were carried out to describe the effects of Aporrectodea nocturna on soil characteristics in a pre-alpine meadow and to support the development of a model of cast production. In the prealpine meadow, increased cast production, first observed about 20 years ago around a newly planted hedge, was recorded to a distance of maximal 170 m from the hedge. Numbers of A. nocturna between 130 and 165 m from the hedge decreased from 164 to 16 individuals m^-2. In the same area cast production steadily decreased from about 1.5 kg m^-2 week^-1 to nil, the plant community structure changed and the microbial biomass decreased, but the root biomass and the moisture content did not change. Laboratory experiments demonstrated that high cast production was not a specific feature of the A. nocturna population nor of the soil in the meadow. Diapause of A. nocturna was terminated in the laboratory during September. A model of cast production potential by the earthworm A. nocturna was established using laboratory determinations of the relationships with body weight, temperature, and water potential. The model was shown to predict cast production in the field given the assumption that the water potential was 0 MPa. According to the model, 81% of surface cast production was by juveniles, and 19% by adults of A. nocturna.     

Application of Fourier transform midinfrared spectroscopy to the discrimination between Irish artisanal honey and such honey adulterated with various sugar syrups

A collection of authentic artisanal Irish honeys (n = 580) and certain of these honeys adulterated by fully inverted beet syrup (n = 280), high-fructose corn syrup (n = 160), partial invert cane syrup (n = 120), dextrose syrup (n = 160), and beet sucrose (n = 120) was assembled. All samples were adjusted to 70 degrees Bx and scanned in the midinfrared region (800-4000 cm(-1)) by attenuated total reflectance sample accessory. By use of soft independent modeling of class analogy (SIMCA) and partial least-squares (PLS) classification, authentic honey and honey adulterated by beet sucrose, dextrose syrups, and partial invert corn syrup could be identified with correct classification rates of 96.2%, 97.5%, 95.8%, and 91.7%, respectively. This combination of spectroscopic technique and chemometric methods was not able to unambiguously detect adulteration by high-fructose corn syrup or fully inverted beet syrup.     

Photocatalytic Removal of the Antibiotic Cefotaxime on TiO<Subscript>2</Subscript> and ZnO Suspensions Under Simulated Sunlight Radiation

This study presents the main results about the removal of the antibiotic cefotaxime (CTX) under simulated sunlight radiation using heterogeneous photocatalysis with titanium dioxide (TiO₂) and zinc oxide (ZnO) in aqueous solutions. The effects of pH and catalyst initial load on pollutant removal were assessed considering the response surface methodology and a central composite circumscribed experimental design, which allowed to determine the optimized conditions that lead to a higher substrate elimination. Experimental results indicated that evaluated parameters have a significant effect on antibiotic removal in both TiO₂ and ZnO suspensions. In addition, the role of photogenerated holes, hydroxyl, and superoxide anion radicals on CTX degradation was evaluated to clarify the reaction mechanism. Finally, analysis of the dissolved organic carbon content in solutions and the antibacterial activity of treated samples showed that photocatalytic treatments were able to reduce a considerable portion of the organic matter present in the systems and its antimicrobial activity.