Ab Initio Studies of Cellulose I: Crystal Structure, Intermolecular Forces, and Interactions with Water

We have studied the structural, energetic, and electronic properties of crystalline cellulose I using first-principles density functional theory (DFT) with semiempirical dispersion corrections. The predicted crystal structures of both Iα and Iβ phases agree well with experiments and are greatly improved over those predicted by DFT within the local and semilocal density approximations. The cohesive energy is analyzed in terms of interchain and intersheet interactions, which are calculated to be of similar magnitude. Both hydrogen bonding and van der Waals (vdW) dispersion forces are found to be responsible for binding cellulose chains together. In particular, dispersion corrections prove to be indispensable in reproducing the equilibrium intersheet distance and binding strength; however, they do not improve the underestimated hydrogen bond length from DFT. The computed energy gaps of crystalline cellulose are 5.7 eV (Iα) and 5.4 eV (Iβ), whereas localized surface states appear within the gap for surfaces. The interaction of cellulose with water is studied by investigating the adsorption of a single water molecule on the hydrophobic Iβ(100) surface. The formation of hydrogen bond at the water/cellulose interface is shown to depend sensitively on the adsorption site for example above the equatorial hydroxyls or the CH moieties pointing out of the cellulose sheets. VdW dispersion interactions also contribute significantly to the adsorption energy

Foundations of Character - Developing Character and Values in the Early Years

Foundations of Character takes a deep and insightful look into character and values development during the 'early years' phase of education. It is commonly assumed that the influences on the early years of a child'slife are determinative for the future individual: the evidence from this report suggests that it is more complex. Children's exposure to and engagement in early childhood education is currently a widespread phenomenon in England, with 92% of three year olds and 98% of four year olds benefitting from some free early years education of up to 15 hours per week. This study aimed to explore the developing dispositions, values and attitudes of a sample of young children in the familiar contexts of their homes, early education settings, and primary schools. It was hoped that this exploration would also provide insights into the values of the significant adults in these children's lives, and these adults' views about the development of character and values

N=2* Super-Yang-Mills Theory at Strong Coupling

The planar N=2* Super-Yang-Mills (SYM) theory is solved at large 't Hooft coupling using localization on S(4). The solution permits detailed investigation of the resonance phenomena responsible for quantum phase transitions in infinite volume, and leads to quantitative predictions for the semiclassical string dual of the N=2* theory.Comment: 34 pages, 9 figures; v2: the name of one author change

Bioavailability of soil organic carbon and Fe as influenced by forestry practices in a subtropical coastal catchment

Potential impacts of plantation forestry practices on soil organic carbon and Fe available to microorganisms were investigated in a subtropical coastal catchment. The impacts of harvesting or replanting were largely limited to the soil top layer (0–10 cm depth). The thirty-year-old Pinus plantation showed low soil moisture content (Wc) and relatively high levels of soil total organic carbon (TOC). Harvesting and replanting increased soil Wc but reduced TOC levels. Mean dissolved organic carbon (DOC) and microbial biomass carbon (MBC) increased in harvested or replanted soils, but such changes were not statistically significant (P > 0.05). Total dithionite-citrate and aqua regia-extractable Fe did not respond to forestry practices, but acid ammonium oxalate and pyrophosphate-extractable, bioavailable Fe decreased markedly after harvesting or replanting. Numbers of heterotrophic bacteria were significantly correlated with DOC levels (P < 0.05), whereas Fe-reducing bacteria and S-bacteria detected using laboratory cultivation techniques did not show strong correlation with either soil DOC or Fe content