Properties of Reactive Oxygen Species by Quantum Monte Carlo

The electronic properties of the oxygen molecule, in its singlet and triplet states, and of many small oxygen-containing radicals and anions have important roles in different fields of Chemistry, Biology and Atmospheric Science. Nevertheless, the electronic structure of such species is a challenge for ab-initio computational approaches because of the difficulties to correctly describe the statical and dynamical correlation effects in presence of one or more unpaired electrons. Only the highest-level quantum chemical approaches can yield reliable characterizations of their molecular properties, such as binding energies, equilibrium structures, molecular vibrations, charge distribution and polarizabilities. In this work we use the variational Monte Carlo (VMC) and the lattice regularized Monte Carlo (LRDMC) methods to investigate the equilibrium geometries and molecular properties of oxygen and oxygen reactive species. Quantum Monte Carlo methods are used in combination with the Jastrow Antisymmetrized Geminal Power (JAGP) wave function ansatz, which has been recently shown to effectively describe the statical and dynamical correlation of different molecular systems. In particular we have studied the oxygen molecule, the superoxide anion, the nitric oxide radical and anion, the hydroxyl and hydroperoxyl radicals and their corresponding anions, and the hydrotrioxyl radical. Overall, the methodology was able to correctly describe the geometrical and electronic properties of these systems, through compact but fully-optimised basis sets and with a computational cost which scales as $N^3-N^4$, where $N$ is the number of electrons. This work is therefore opening the way to the accurate study of the energetics and of the reactivity of large and complex oxygen species by first principles

Sources of variability in essential oil composition of Ocimum americanum and Ocimum tenuiflorum

Basil has traditionally been used for a long time in medicine and gastronomy. Essential oil is the most important active substance of the drug, which influences the aroma and the effect of the plant. Although the compositions of essential oils vary in different basil cultivars, the main components are oxygenated monoterpenes and phenylpropane derivates. The high chemical variation is most likely caused by interspecific hybridization. Various factors, like genetic background, ontogenesis, morphogenesis, abiotic factors, essential oil extraction method, drying, and storage, are responsible for the variant essential oil composition

Geometric isomers of chloro(6-methyl-1,4,8,11-tetraazacyclotetradecane-6-amine)cobalt(III) tetrachlorozincate(II)

The crystal structures of a pair of cis and trans isomers of the macrocyclic chloropentaamine title complex, as their tetrachlorozincate(II) salts, [CoCl(C11H27N5)][ZnCl4], are reported. The two distinct isomeric forms lead to significant variations in the Co-N bond lengths and, furthermore, hydrogen bonding between the complex ions is influenced by the folded (cis) or planar (trans) conformations of the coordinated ligand

Monitoring of chemical parameters of qualitative pasta samples containing millet flours during storage experiments

Millet has attracted a great deal of interest due to its valuable agricultural, nutritional, and functional properties. In this study the aim was the investigation of millet usability in dry pasta products. Chemical, enzymological, and sensory parameters were measured and monitored in Triticum aestivum, Triticum durum, and millet containing pasta products during a 12-month-long storage period. According to our results, during the storage, millet had a strong effect on different parameters: because of increased acid value, the shelf life was reduced, and millet significantly influenced the pH value and the water soluble polyphenol content. The highest scores were measured in T. durum and T. durum-millet pasta samples in the sensory test, while the T. aestivum-millet mixture pasta got the lowest scores. Also in our experiment we tested how the drying temperature modifies polyphenol oxidase enzyme (PPO) activity right after drying and during storage. The samples containing millet flour had higher PPO activity in all cases after drying, while pasta made with T. durum had the lowest PPO activity. Our results showed that drying temperature has a significant impact on PPO activity

Impacts of Land Abandonment on Vegetation: Successional Pathways in European Habitats

Changes in traditional agricultural systems in Europe in recent decades have led to widespread abandonment and colonization of various habitats by shrubs and trees. We combined several vegetation databases to test whether patterns of changes in plant diversity after land abandonment in different habitats followed similar pathways. The impacts of land abandonment and subsequent woody colonization on vegetation composition and plant traits were studied in five semi-natural open habitats and two arable habitats in six regions of Europe. For each habitat, vegetation surveys were carried out in different stages of succession using either permanent or non-permanent plots. Consecutive stages of succession were defined on a physiognomic basis from initial open stages to late woody stages. Changes in vegetation composition, species richness, numbers of species on Red Lists, plant strategy types, Ellenberg indicator values of the vegetation, Grime CSR strategy types and seven ecological traits were assessed for each stage of the successional pathway. Abandonment of agro-pastoral land-use and subsequent woody colonization were associated with changes in floristic composition. Plant richness varied according to the different habitats and stages of succession, but semi-natural habitats differed from arable fields in several ecological traits and vegetation responses. Nevertheless, succession occurred along broadly predictable pathways. Vegetation in abandoned arable fields was characterized by a decreasing importance of R-strategists, annuals, seed plants with overwintering green leaves, insect-pollinated plants with hemi-rosette morphology and plants thriving in nutrient-rich conditions, but an increase in species considered as endangered according to the Red Lists. Conversely, changes in plant traits with succession within the initially-open semi-natural habitats showed an increase in plants thriving in nutrient-rich conditions, stress-tolerant plants and plants with sexual and vegetative reproduction, but a sharp decrease in protected species. In conclusion, our study showed a set of similarities in responses of the vegetation in plant traits after land abandonment, but we also highlighted differences between arable fields and semi-natural habitats, emphasizing the importance of land-use legacy

Effective User Experience in Online Technical Communication Courses: Employing Multiple Methods within Organizational Contexts to Assess Usability

In teaching online technical communication courses, shaping an electronic interface requires extensive consideration of the user experience, both for students and for faculty members who design and teach the courses. Technical communication faculty members should provide strong examples of effective user experiences and should be leaders in making the interfaces of online learning management systems as usable as possible. Principles of usability designed for general web sites may or may not apply to learning management systems designed for educational purposes. In order to create effective online technical communication courses, one needs to consider both usability concerns and pedagogical concerns. To assess the usability and pedagogical effectiveness of online courses, faculty members may use indirect means such as heuristic analyses. In addition, they may use direct means such as usability testing, student feedback, and analytic tools. Each approach has advantages as well as limitations. Faculty members will gain the richest information through using multiple approaches. In assessing usability and pedagogical effectiveness, faculty members also need to consider the situational constraints and resources in their unique contexts. Understanding and adapting their approaches to use resources well and to work within constraints will benefit their abilities to enhance their student users' experiences with online courses

Novel one-dimensional structures and solution behaviour of copper(II) bromide and chloride complexes of a new pentapyridyldiamine ligand

Copper(II) bromide and chloride complexes of the new heptadentate ligand 2,6-bis(bis(2-pyridylmethyl)amino)methylpyridine (L) have been prepared. For the bromide complexes, chains of novel, approximately C-2-symmetric, chiral [Cu-2(L)Br-2](2+) 'wedge-shaped' tectons are found. The links between the dicopper tectons and the overall chirality and packing of the chains are dictated by the bromide ion content, not the counter anion. In contrast, the chloride complexes exhibit linked asymmetric [Cu-2(L)Cl-3](+) tectons with distinct N3CuCl2 and N4CuCl2 centres in the solid. The overall structures of the dicopper bromide and chloride units persist in solution irrespective of the halide. The redox chemistry of the various species is also described

The 2010 ILSO-ISRU Field Test at Mauna Kea, Hawaii: Results from the Miniaturised Mossbauer Spectrometers Mimos II and Mimos IIA

For the advanced Moessbauer instrument MIMOS IIA, the new detector technologies and electronic components increase sensitivity and performance significantly. In combination with the high energy resolution of the SDD it is possible to perform X-ray fluorescence analysis simultaneously to Moessbauer spectroscopy. In addition to the Fe-mineralogy, information on the sample's elemental composition will be gathered. The ISRU 2010 field campaign demonstrated that in-situ Moessbauer spectroscopy is an effective tool for both science and feedstock exploration and process monitoring. Engineering tests showed that a compact nickel metal hydride battery provided sufficient power for over 12 hr of continuous operation for the MIMOS instruments

Precision spectroscopy of the 3s-3p fine structure doublet in Mg+

We apply a recently demonstrated method for precision spectroscopy on strong transitions in trapped ions to measure both fine structure components of the 3s-3p transition in 24-Mg+ and 26-Mg+. We deduce absolute frequency reference data for transition frequencies, isotope shifts and fine structure splittings that are in particular useful for comparison with quasar absorption spectra, which test possible space-time variations of the fine structure constant. The measurement accuracy improves previous literature values, when existing, by more than two orders of magnitude